CN107109297B - Dumpable liquid fabric conditioner composition - Google Patents
Dumpable liquid fabric conditioner composition Download PDFInfo
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- CN107109297B CN107109297B CN201580073218.2A CN201580073218A CN107109297B CN 107109297 B CN107109297 B CN 107109297B CN 201580073218 A CN201580073218 A CN 201580073218A CN 107109297 B CN107109297 B CN 107109297B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract
A kind of dumpable liquid fabric condition composition, it includes: a) cationic fabric softens active matter；B) particle is viscosified, it has 25 to 5000 microns of volume average particle sizes, the particle includes the water-swellable polymer of the crosslinking based on the particle less than 50 weight % and at least the absorbed water of 50 weight %, the amount of polymer are at least 0.1 weight % of the fabric-conditioning compositions based on the particle；And c) other water, the composition is in 106s‑1There is viscosity in the range of 60 to 3500mPas at 25 DEG C.
Description
Technical field
The present invention relates to the dumpable liquid fabric conditioner compositions comprising viscosity modifying polymer.
Background technique
Consumer Preferences is fabric conditioner in 25 DEG C and 106s-1It is lower that there is at least viscosity of 30mPas.Opsonic activity
The concentration of object (cation) is higher, recommended dose is lower, then composition intrinsic viscosity will higher and effective distribution will problem.
The viscosity of liquid composition can be increased by the way that thickening polymer is added, otherwise it will too for Consumer Preferences
It is dilute.A kind of such additive be with it is water-swellable when diameter < 10 micron polymer gel.These particles show strong glue
Body interaction simultaneously increases viscosity to reduce dispersibility as cost.It is if fruit product will be distributed from washing machine drawer, then this bad
Dispersibility will lead to main problem, and be recognized as in hand washing unsatisfactory.Undesirable dispersibility will lead to not
Good fabric-conditioning.
A kind of fabric-conditioning liquid of structuring includes multiple phases, wherein cation softening active matter is (usually quaternized
Close object) it suspends in water.The dispersion of water and immiscible softening active matter is usually (such as more with the double-deck micro-structure of structuring
Layer vesica) exist.Gained liquid shows complicated flow behavior (non-newtonian flow) and liquid, and intracorporal to be short to moderate orderly.
GB1428062 discloses fabric softening compositions, and it includes cationic softener compounds and tool not soluble in water
There is the particulate matter of 1 to 50 micron of average particle size.It is said that the addition of this insoluble granule substance will enhance institute's softening fabrics
Property.It is exemplary to have glass beads and microballoon, starch and other low swollen materials.According to introduction, should be avoided with high swelling power
The particulate matter of (> 15), because such swelling will detract beneficial effect.So a large amount of solid particle is deposited on clothes
It is undesirable.
WO2010/079100 discloses the fabric conditioner composition comprising cationic polymer thickeners, shows low
Water-soluble polymer score and higher cross-linking level, this causes the dirt of the weight efficiency and reduction significantly improved to sink again
Product.These polymer cannot provide the particle that desired dispersibility improves comprising too small.
Summary of the invention
According to the present invention, a kind of dumpable liquid fabric condition composition is provided, it includes:
A) cationic fabric softens active matter；
B) particle is viscosified, with 25 to 5000 microns of volume average particle sizes, the particle includes few based on particle
In the water-swellable polymer of the crosslinking of 50 weight % and at least absorbed water of 50 weight % based on particle, polymer
Amount is at least 0.1 weight % of fabric-conditioning compositions；With
C) other water,
The composition is in 106s-1There is viscosity in the range of 60 to 3500mPas at 25 DEG C.
According to the present invention, a kind of method provided for improving the liquor (liquor) of fabric is additionally provided comprising will
The step of composition according to the present invention is dispersed in water.
Specific embodiment
Composition
The composition is dispersible, drumped liquid fabric conditioner composition.It is dispersible to refer to when water is added,
Grain separates in entire liquid and forms dispersion.Good dispersibility is characterized in that particle is good in a liquid, uniform
Separation and isolated speed.
The appropriate method of dispersibility assessment is described below.This provides dispersion index (DI) based on 1 to 5 point of scale.
Composition 17ml to be tested is poured into the 1000ml cold running water in 2000ml beaker from container.30 seconds
Afterwards, it visually assesses gained mixture and is graded based on 1-5 points of scale, half point is used when appropriate.The scale is defined as follows:
Grade 1: solution is evenly dispersed and without agglomerate (lump) or fritter (bit).
Grade 2: product dispersion provides uniform dispersion, only a small amount of small agglomerate or fritter.
Grade 3: product dispersion mainly provides small agglomerate or fritter, but favorable dispersibility and provides slight haziness/coloured
Solution.
Class 4: product resolves into several medium and/or large-sized agglomerate and without finely divided；Water keeps substantially limpid nothing
Color.
Class 5: product does not decompose when entering in water.It usually forms one or two large crumb in clear water.
If desired, mixture can be stirred by carrying out 5 rotations with grafter with rate of once per second, then use
Identical equal is assessed again.
Fabric conditioner of the invention is dispersed in water before the use or in use process.
The composition is in 25 DEG C and 106s-1It is lower have preferably 80 to 1000mPas, more preferably 120 to 500mPas,
Viscosity even more preferably in the range of 180 to 350mPas.Any suitable viscosimeter can be used, for example, Haake
VT550 or Thermo Fisher RS600.
For the composition preferably substantially free from conventional thickening polymer, this means can use 0 to 1 in the composition
The conventional thickening polymer of weight %, preferably 0 to 0.05 weight %, more preferable 0 to 0.01 weight %, most preferably 0 weight %.
In the context of the present invention, conventional thickening polymer refers to the length dimension (long-length for reaching long in solution phase
Scale the polymer molecule of extension) is (for example, modified cellulosic materials such as hydroxyethyl cellulose (HEC), carboxymethyl cellulose
Sodium (SCMC) or xanthan gum), the associative thickener that is connected between surfactant micellar or liquid crystal farmland is (for example, hydrophobically modified
Polyacrylate (hydrophobic base swellable emulsions-HASE)) and occupy as described in Krieger-Dougherty equation enough phases
Volume is to increase the little particle microgel (for example, polyacrylate (carbomer)) of solution phase viscosity.The micro- of Conventional thickeners coagulates
Glue particle is more much smaller than particle used in the present invention in the composition (< 10 microns), and shows strong gel phase interaction
With this will further enhance its ability for preparing viscosity dispersion but has the shortcomings that disperse to be deteriorated as viscosity increases.
Composition of the invention, which not only has to improve, to be thickened and improves the benefit dispersed when being diluted with water, but also because big
Thickening particle and have environment and sustainable benefit.In the composition, most of quality in these particles are water, this
By the consumer benefit needed for allowing composition to deliver without the use of unnecessary chemicals.In addition, if any particle
It deposits on the fabric improved, then they will have low-down quality and influence when dry.
Viscosify particle
The particle is added in the basal liquid with low intrinsic viscosity and relevant good dispersion, so as to only
It wants it to keep undiluted and the enhancing of its viscosity is provided.The particle is formed from the cross-linked polymer of water-swellable, and because absorbing
Some water in composition and be swollen to a certain extent.Such swellable particles will fill more spaces.
These thickening particles have 10 to 400 microns of average dry granularity.However, in presence of water, polymer will
Swelling so that particle have 25 to 5000 microns, preferably 25 to 1000 microns, it is 50 to 500 microns more preferable, even 60 to
The volume average particle sizes of 300 microns or 100 to 225 microns, especially 140 to 200 microns.Unless otherwise indicated, all
Granulometry value is addressed with the granularity after being swollen in presence of water.Generally, it is preferred to polymer will absorb about 50 times
In the water of their own weight to form thickening particle.This be lower than there is no cation and swelling in pure water there is a situation where.
In such a situation, same polymer may absorb up to 450 times of its own weight.The amount of particle in preferred composition
Water is obtained less than in composition 50% by absorbing.
All grain graininess are calculated with bulk averaged value.Dry particle refers to the residual humidity in particle lower than 10 weight %
(as passed through the weight loss determining in an oven at 105 DEG C after drying 2 hours).
Polymer in particle is insoluble in water.In the context of the present invention, " water is insoluble in " to be defined as
Solubility is lower than 1x10 at 20 DEG C in demineralized water-3Weight %, it is preferably lower than 1x10-4Weight %, it is again more preferably less than
1x10-8To 1x10-6The material of weight %.
Polymer material should be chosen such that particle and the other materials in composition are not reactive；In other words,
It is inert in the environment of composition.
Although the polymer in formed particle be it is insoluble, polymer raw material may contain some soluble constituents,
These components are mostly derived from incomplete crosslinking.The amount of soluble constituent is preferably shorter than 15 weight % of polymer weight, more preferably low
In 10 weight %, most preferably less than 7.5 weight %.
It is present in for the preferred swellable polymer beads in composition of the invention containing at least one cation mono
In the polymers capable of swelling of the crosslinking of body and optional nonionic or anionic monomer；Wherein the polymer has such as this paper institute
State lower than 15 weight % extract (solvable) polymer content and relative to polymer be 500ppm to 10,000ppm crosslinking
Agent concentration, the polymer are obtained by gel polymerisation.In a preferred embodiment, based on the total of hydration prepolymer
The content that extracts of poidometer, polymer is preferably shorter than 10%, more preferably less than 7.5%.
The polymers capable of swelling being preferably crosslinked will form (i.e. when with such as hydration of suitable solvent simultaneously) poly- under hygrometric state
Close object gel.
The polymer can be homopolymer or copolymer.
The polymer for being ready to use in manufacture particle is advantageously prepared using gel polymerisation.Such polymerization will generate
Dry particle with required big granularity.The polymeric acceptor generated by gel polymerisation can be broken into lesser fragment, and
If necessary, being classified to obtain the three dimensional polymeric composition granule in required particle size range, such as pass through sieving.Skillfully
Technical staff will can utilize other polymerizations for generating the polymer beads in required particle size range to obtain with hydration simultaneously
When big thickening particle.
Cross-linked polymer has the three-dimensional network for wherein caning absorb water.It is penetrated into network with dampening, when in the presence of cationic material
When material, the volume of particle will increase to 10 to 100 times of particle initial volume.Gained particle is thickening particle.In base composition
In comprising these particles for being filled with water will bring the increase of composition viscosity.
It include institute for the same basic composition comprising conventional smaller particle size cationic polymer thickeners
The overall performance for stating the fabric softening compositions of particle will be improved.Particularly, it has been found that when they have higher aging
Stability and more preferably rheological characteristic.
The cationic crosslinked polymers capable of swelling being suitable for the invention in composition can by gel polymerisation, pass through polymerization
It is prepared by following components:
At least one cationic monomer,
Optionally other nonionics and/or anionic monomer,
In the presence of crosslinking agent and optional chain transfer agent.
The total electrical charge of polymer is preferably cationic, but non-ionic polymers may be also suitable.Cation is poly-
Closing object must be containing at least one cationic monomer.In other words, when polymer contains anion and/or non-ionic monomer,
The amount of cationic charge should be greater than the amount of anionic charge.
Gel polymerisation is a kind of well-known polymerization technique comprising polymeric water-soluble monomer is in an aqueous medium to obtain
Gel is obtained, then the gel is generally cut out or is sliced and dry to obtain the polymer for being in powder type.Resulting polymers
Can using it is preceding in advance be added in water or another solvent in.It also can be used as powder use.
Gel polymerisation method preparation can be used in cross-linked polymer comprising following steps:
In the presence of crosslinking agent and optional chain transfer agent aqueous media, be usually that at least one sun is added in water
Ion monomer and optional other nonionics and/or anionic monomer；
Start to polymerize；
Obtain gel；
It is solid particle, usually powder by gel conversion.
Gained gel is converted into powder by conventional methods, such as blocking and/or by that will coagulate by cutting gelinite
Colloid is extruded through coarse aperture, optionally cuts gel before or after extrusion, and pass through desiccant gel block.It can also make
Use jet grinding.
The polymers capable of swelling of crosslinking can be used as powder or be added in softening compositio as liquid dispersion.Additional amount
Between preferably 0.1 weight % and 10 weight %, between more preferable 0.2 and 7%.The amount is in drying corresponding to not yet absorb water
The polymer of powder type.
The polymerization is usually usually by redox couple, the radical polymerization of such as sodium peroxydisulfate and sodium pyrosulfite induction
It closes.
Relative to the total amount of monomer, crosslinker concentration is in the range of 500 weight ppm to 10000 weight ppm.
Be the non-limiting list of crosslinking agent below: methylene-bisacrylamide (MBA), gathers glycol diacrylate
Ethylene glycol dimethacrylate, diacrylamine, triallylamine, glyoxal, glycidol ether type compound such as second two
Allow to be crosslinked known to alcohol diglycidyl ether, Allyl pentaerythritol, trimethylolpropane allyl ether or professional
Any other measure.
Preferred crosslinking agent is methylene-bisacrylamide (MBA), triallylamine and Allyl pentaerythritol.
When crosslinking agent used is methylene-bisacrylamide, relative to monomer, concentration is preferably between 500 weight ppm
And 5000 between weight ppm.
When crosslinking agent used is triallylamine, relative to monomer, concentration is preferably between 1000 weight ppm and 10000
Between weight ppm.
Following monomer and season are preferably selected from for the suitable cationic monomer in the preparation of the polymers capable of swelling of crosslinking
Ammonium or salinization derivative: dimethylaminopropyl Methacrylamide, dimethylaminopropylacryl amide, diallyl
Amine, amide, propenoic acid dialkyl aminoalkyl ester, methacrylates, dialkyl amino
Base alkyl acrylamide and dialkyl aminoalkyl-Methacrylamide.
It has been found that certain cationic monomers have optimum performance in terms of dispersibility.Accordingly, it is preferred that cation mono
Body is selected from dimethylaminoethyl methacrylate and its quaternized or salinization derivative and/or dimethylaminopropyl methyl-prop
Acrylamide and its quaternized or salinization derivative.
In a most preferred embodiment, cationic monomer is dimethylaminoethyl methacrylate chloromethanes salt
Or dimethylaminoethyl methacrylate quaternary ammonium salt.
Polymerization following components preparation can be passed through for the cross-linked polymer in composition of the invention:
The cationic monomer of more than 50 moles %, preferably more than 70 moles of %, most preferably more than 80 moles of %；
Optionally, other nonionics and/or anionic monomer；
It is single in the presence of amount is 500ppm to crosslinking agent between 10000ppm for the total weight relative to monomer
The total amount of body is 100%.
These percentages are based on the total amount of monomer.However, the amount of crosslinking agent and the amount of chain-transferring agent are relative to total
The weight ppm of the weight of monomer, that is, the monomer relative to above-mentioned 100 moles of %.
Can in polyblend using chain-transferring agent such as isopropanol, sodium hypophosphite, mercaptoethanol to control polymeric chain
Length and crosslink density.
When having used chain-transferring agent, relative to the total amount of monomer, concentration is in 10 weight ppm to 1000 weight ppm's
In range.
Be used to prepare for the cross-linked polymer in composition of the invention preferred non-ionic monomer be selected from acrylamide,
Methacrylamide, N- alkyl acrylamide, n-vinyl pyrrolidone, N- vinyl formamide, N- vinyl acetamide, second
Vinyl acetate, vinyl alcohol, acrylate and allyl alcohol.Preferred non-ionic monomer is acrylamide.
It is used to prepare and is selected from acrylic acid, first for the preferred anionic monomer of the cross-linked polymer in composition of the invention
Base acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the monomer such as 2- acrylamide for realizing sulfonic acid or phosphonic acids function
Base -2- methyl propane sulfonic acid (ATBS), the anionic monomer are acid either partially or completely salinization.Preferred anion
Monomer be acrylic acid and 2- acrylamido -2- methyl propane sulfonic acid (ATBS), the anionic monomer be acid either part or
Complete salinization.
Optionally, the cross-linked polymer contains the monomer with hydrophobic property.
The water-swellable cationic polymer being preferably crosslinked passes through the dimethylaminoethyl acrylate methyl base quaternized by chloromethanes
The gel polymerisation of amino ethyl ester (cationic monomer), acrylamide (non-ionic monomer) and methylene-bisacrylamide (crosslinking agent)
It obtains.
The polymer content that water can extract be the polymer that can be extracted when polymer is dispersed in water quality with
Ratio between the gross mass of polymer.
The method for the polymer content that the water of measurement cross-linked polymer can extract is based on the basic principle of colloidal titration,
It is chemist and well known to those skilled in the art.
The method includes by the water-soluble portion (" can extract " polymer) of polymer and water-insoluble be partially separated with
The filtrate for containing only water-soluble portion is obtained, and then passes through the water-soluble polymer content in colloidal titration measurement filtrate.Water can
The polymer content of extraction is the ratio in filtrate between the quality of polymer and the gross mass of polymer.
Step 1: polymer extraction
The step includes separatin non-soluble polymer (swellable particles) and water-soluble polymer: Xiang Han 800ml deionized water
Beaker in be added 0.5g (m0, unit g) polymer.Mixture is gently mixed 6 hours with magnetic stirring apparatus.Then 8g is added
NaCl is to complete to extract.Salting liquid is stirred for 1 hour.Then it is sieved through with 100 μm and filters the polymeric blends, then in 15 points
Filtrate is recycled after clock to measure its weight (M0, unit g).Then " water can extract " polymer content in filtrate is titrated.
Step 2: polymer titration
Titration principle is the known colloidal titration for measuring the charge density of cationic polymer.Colloidal titration as follows into
Row: it is made by the way that polyvinyl potassium sulfate (PVSK) polymer that molecular weight is 243,300g/mol to be dissolved in deionized water
Standby PVSK solution, to obtain concentration as the solution of 0.0025N (N/400).
The hydrochloric acid solution of 0.1N is prepared in deionized water.
Titration is carried out to the 30g polymer solution (filtrate) through being acidified with hydrochloric acid (pH=4) and is indicated with 2 to 3 drop blues
Agent coloring.PVSK solution is slowly added to until color is from Lan Bianzi (balance).
Then according to (i) balance when measure PVSK volume, (ii) polymer composition, (iii) polymer weight and
(iv) reagent molar concentration calculates the polymer content (percentage of " extractable matter ") that water can extract by following formula:
Veq: the volume for the PVSK solution being added when balance, units/ml.
The concentration (N=1) of PVSK in N/400:PVSK solution.
M0: the quality for the total filtrate recycled in step 1, unit of gram.
“m0": the quality of the polymer in water, unit of gram are added in step 1.
X corresponds to the weight percent of the cationic monomer based on the total amount of monomer.
Y corresponds to the molecular weight of cationic monomer.
Professional would know how the amount for changing crosslinking to obtain with sufficiently low water-soluble polymer score and institute
The final polymer of the rheological characteristic needed.
For example, as it is known that the increase of crosslinker concentration will lead to the reduction of extractable polymer content when other parameters are identical.
Vice versa.
Cationic fabric softens active matter
Composition of the invention contains cationic fabric softening active matter.
Fabric-conditioning compositions of the invention can be diluted or concentration.Cut back usually contains supreme about 8 weight
The softening active matter of %, preferably 2 to 8 weight % are measured, and enriched product can contain about 8 to about 50 weight %, preferably 8 to 25 weights
Measure the active matter of %.Composition with the active matter of about 25 weight % incessantly is defined as " super concentration ", specifically depends on
In active system, and it is also intended to and is covered by the present invention.Fabric-softening active matter can be for example with 0.5 weight % of composition
To 35 weight %, preferably 2 weight % to 30 weight %, more preferable 5 weight % to 25 weight %, most preferably 8 weight % to 20 weights
The amount for measuring % uses.
It is quaternary ammonium compound (QAC) for the preferred softening active matter in rinse conditioner compositions of the invention.For
Preferred quaternary ammonium compound in composition of the invention is so-called " ester quat " comprising ester linkage.Particularly preferred material is
Triethanolamine (TEA) quaternary ammonium compound of ester linkage comprising mono-, two- and three -ester linked components mixtures.Most preferably,
The quaternary ammonium compound of the ester linkage is the triethanolamine quaternary ammonium compound of the ester linkage comprising unsaturated fatty chain.
Fabric-softening active matter generally, based on TEA includes mono-, two- and three -ester forms the mixture of compound,
In two -ester linked components account for the 70 weight % that are no more than of fabric softening compound, preferably more than 60%, such as fabric-softening
Close the 55% or 45% of object, and at least 10% monoesters linked component, such as 11% monoesters.Preferred hardening type active matter
With 18 to 22 monoesters: 58 to 62 diester: the typical case of 18 to 22 3 esters is single: the distribution of two: three esters, such as 20:60:20.Soft TEA season
Ammonium salt could generally have 25 to 45%, preferably 30 to 40% monoesters: 45 to 60%, preferably 50 to 55% diester: 5 to
25%, the list of preferably 10 to 15% 3 ester: two: three esters distribution；Such as 40:50:10.
First group of quaternary ammonium compound (QAC) suitable for the present invention is indicated by formula (I):
Wherein each R is independently selected from C5-35Alkyl or alkenyl group；R1Indicate C1-4Alkyl, C2-4Alkenyl or C1-4Hydroxyl alkane
Base group；T is usually O-CO (that is, via ester group of its carbon atom bonding to R), but can or be CO-O (that is, via its oxygen
Ester group of the atomistic binding to R)；N is the number selected from 1 to 4；M is the number selected from 1,2 or 3；X-For anionic counter-ion, such as
Halide or alkyl sulfate, for example, chloride or Methylsulfate.Two -ester modifications (that is, m=2) of Formulas I be it is preferred simultaneously
Usually there are the mono- and three -ester analogs being associated with.Such material is especially suitable in the present invention.
Especially preferred reagent is the preparation of two -ester rich in triethanol ammonium Methylsulfate, otherwise known as " TEA ester quaternary ammonium
Salt ".
Commercial examples include StepantexTMUL85 (coming from Stepan), PrapagenTMTQL (come from Clariant) and
TetranylTMAHT-1 (coming from Kao) (both for two-[hardened tallow esters] of triethanol ammonium Methylsulfate), AT-1 (three
Two-[butter esters] of ethyl alcohol ammonium methyl sulphate) and L5/90 (two-[palm esters] of triethanol ammonium Methylsulfate) (the two is equal
From Kao) and RewoquatTM(diester of triethanol ammonium Methylsulfate has and is derived from C WE1510-C20And C16-C18No
The fatty acyl residue of saturated fatty acid) (coming from Evonik).
What is be also suitable for has soft quaternary ammonium active object such as Stepantex VK90, Stepantex VT90, SP88 (to come from
Stepan), Ceca Noramine, Prapagen TQ (come from Clariant), Dehyquart AU-57 (coming from Cognis),
Rewoquat WE18 (coming from Degussa) and Tetranyl L190P, Tetranyl L190SP and Tetranyl L190S are (
From Kao).
Second group of QAC suitable for the present invention is indicated by formula (II):
Wherein each R1Group is independently selected from C1-4Alkyl, hydroxyalkyl or C2-4Alkenyl group；And wherein each R2
Group is independently selected from C8-28Alkyl or alkenyl group；And wherein n, T and X-As hereinbefore defined.
This second group preferred material includes bis- [the tallowoyloxy] -3- trimethyl ammonium propane chlorides of 1,2-, 1,2- bis-
Bis- [oleoyl the oxygroup] -3- trimethyl ammonium propane chlorides of [hardened tallowoyloxy] -3- trimethyl ammonium propane chloride, 1,2- and
Bis- [the stearoyl-oxy] -3- trimethyl ammonium propane chlorides of 1,2-.Such material is in 4,137,180 (Lever of US
Brothers it is described in).Preferably, these materials also include a certain amount of corresponding monoesters.
Third group QAC suitable for the present invention is indicated by formula (III):
(R1)2-N+-[(CH2)n-T-R2]2X- (III)
Wherein each R1Group is independently selected from C1-4Alkyl or C2-4Alkenyl group；And wherein each R2Group is only
On the spot it is selected from C8-28Alkyl or alkenyl group；And n, T and X-As hereinbefore defined.The preferred material of this third group includes bis- (2-
Tallowoxyloxyethyl) alkyl dimethyl ammonium chloride and its hardening pattern.
The iodine number of quaternary ammonium fabric conditioning materials is preferably 0 to 80, more preferable 0 to 60, most preferably 0 to 45.The visual feelings of iodine number
Condition selection.Iodine number is 0 to 5, preferably 0 to 1 to be substantially saturated in material composition for use in the present invention.Such material is claimed
For " hardening " quaternary ammonium compound.
Preferred iodine number range is 20 to 60, preferably 25 to 50, more preferable 30 to 45.A kind of material of the type is
" soft " triethanolamine quaternary ammonium compound, preferably triethanolamine di-alkyl ester methyl sulfate.Such ester linkage triethanolamine season
Ammonium compounds includes unsaturated fatty chain.
As used in context of the invention, iodine number refers to through such as Johnson and Shoolery, Anal.Chem.,34, degree of unsaturation present in the material that NMR spectroscopy method measures described in 1136 (1962).
The softening compound of another type is the non-ester quaternary material indicated by formula (IV):
Wherein each R1Group is independently selected from C1-4Alkyl, hydroxyalkyl or C2-4Alkenyl group；Each R2Group is independent
Ground is selected from C8-28Alkyl or alkenyl group；X-As hereinbefore defined.
Composition of the invention optionally contains non-cationic softener material, is preferably oiliness sugar derivatives.Oiliness
Sugar derivatives is the liquid or soft solid derivative of cyclic polyols (CPE) or reduced sugar (RSE), and the derivative is because described more
35 to 100% hydroxyl group is esterified or is etherified and generates in first alcohol or in the sugar.There are two the derivative has or more
It is multiple to be attached separately to C8-C22The ester or ether group of alkyl or alkenyl chain.
Advantageously, CPE or RSE does not have the crystallization property of any substance at 20 DEG C.On the contrary, it is preferred at 20 DEG C
In liquid as herein defined or soft solid state.
Liquid or soft solid (as defined hereinafter) CPE or RSE suitable for the present invention because of starting cyclic polyol or
35 to 100% hydroxyl group is esterified or is etherified by group, makes CPE or RSE in required liquid or soft solid in reduced sugar
State and generate.These groups usually contain degree of unsaturation, branching or mixing chain length.
In general, CPE or RSE has 3 or more esters or ether group or their mixture, for example, 3 to 8, especially
It is 3 to 5.It is preferred that two or more of CPE or RSE ester or ether group are connected to C independently of one another8To C22Alkyl or alkene
Base chain.The C8To C22Alkyl or alkenyl group can be branching or linear carbon chain.
Preferably, the hydroxyl group quilt of 35 to 85%, most preferably 40-80%, even more preferably 45-75%, such as 45-70%
Esterification or etherificate.
Preferably, CPE or RSE contains at least 35% three esters or more advanced ester, for example, at least 40%.
CPE or RSE is attached separately to the chain of ester or ether group at least one unsaturated bond at least one.
This provides the cost effective manner for making CPE or RSE in liquid or soft solid.Preferably, such as rapeseed oil, cottonseed are derived from
Oil, soybean oil, oleic acid, butter, palmitoleic acid, linoleic acid, erucic acid or the unsaturated vegetable fatty acid in other sources it is main not
The aliphatic chain of saturation is connected to ester/ether group.
These chains are hereinafter referred to as (CPE or RSE) ester or ether chain.
The ester or ether chain of CPE or RSE is preferably mainly unsaturated.Preferred CPE or RSE includes four tallow acid of sucrose
Ester, four vegetable seed oleate of sucrose, four oleate of sucrose, soybean oil or cottonseed oil four ester of sucrose, four oleate of cellobiose, sugarcane
Sugared trioleate, three vegetable seed oleate of sucrose, five oleate of sucrose, five vegetable seed oleate of sucrose, six oleate of sucrose, sucrose six
Vegetable seed oleate, the TSE sucrose tri ester of soybean oil or cottonseed oil, five-ester and six esters, glucose trioleate, four oleate of glucose,
The -ester of sucrose four-, three-, five-or six of xylose trioleate or any mixture with main unsaturated fatty acid chain.
Most preferred CPE or RSE is with those of monounsaturated fatty acids chain, that is, any of them how unsaturated degree has passed through part
Hydrogenation removes.However, some CPE or RSE based on polyunsaturated fatty acid chain, such as four linoleate of sucrose can be used, it is preceding
The condition of mentioning is that most of how unsaturated degree hydrogenate removal by part.
The preferred liquid CPE or RSE of topnotch be among the above it is any those, but wherein how unsaturated degree has passed through part
Hydrogenation removes.Preferably 40% or more, more preferable 50% or more, most preferably 60% or more fatty acid chain contains insatiable hunger
And key.In most cases, 65% to 100%, such as 65% to 95% contains unsaturated bond.
Present invention preferably uses CPE.Inositol is a preferred embodiment of cyclic polyols.Particularly preferred inositol derivative.
In the context of the present invention, term cyclic polyols cover the carbohydrate of form of ownership.In fact, the present invention is especially
It is preferable to use carbohydrates.The example of CPE or RSE preferred carbohydrate derived from it is monosaccharide and disaccharides.
The example of monosaccharide includes xylose, arabinose, galactolipin, fructose, sorbose and glucose.Particularly preferred grape
Sugar.The example of disaccharides includes maltose, lactose, cellobiose and sucrose.Particularly preferred sucrose.One example of reduced sugar is to lose
Water sorbierite.
Liquid or soft solid CPE can be by the way that well known to a person skilled in the art methods to prepare.These include using acylated with acid chloride
Cyclic polyols or reduced sugar；It is transesterification to cyclic polyols or reduction sugar fatty acid ester using various catalyst；With acid anhydrides acyl
Change cyclic polyols or reduced sugar and with fatty-acylation cyclic polyols or reduced sugar.See, for example, US 4 386 213 and AU
14416/88 (being P&G's).
It is preferred that CPE or RSE has 3 or more, preferably 4 or more esters or ether group.If CPE is two
Sugar, then preferably the disaccharides has 3 or more esters or ether group.Particularly preferred CPE is the ester of the esterification degree with 3 to 5,
For example, sucrose three, four and five-ester.
When cyclic polyols are reduced sugar, it is advantageous that each ring of CPE has an ether or ester group, preferably exists
C1At position.The suitable example of such compound includes methyl glucose derivatives.
The example of suitable CPE includes the alkyl glucoside that the ester of alkyl (poly-) glucoside, the especially degree of polymerization are 1 to 2
Ester.
The length of (and saturation, if there is) chain unsaturated in CPE or RSE is C8-C22, preferably C12-C22.It can wrap
Include one or more C1-C8Chain, but these are less preferably.
Liquid or soft solid CPE or RSE suitable for the present invention are characterized in that: such as passing through T2Relaxation time NMR institute
Measurement, the material have between 50:50 and 0:100 at 20 DEG C, are being preferably between 43:57 and 0:100, optimal selected introductions
Between 40:60 and 0:100, such as consolidating between 20:80 and 0:100: liquor ratio.T2NMR relaxation time is commonly used to characterization soft solid
Consolidating in product such as fat and margarine: liquor ratio.For purposes of the invention, T2Any group of signal less than 100 μ s
Dividing is considered as solid component, and T2Any component of >=100 μ s is considered as liquid component.
For CPE and RSE, prefix (for example, four and five) only indicates average esterification degree.Compound is from monoesters to complete ester
The material blends of the ester of change exist.Used herein is average esterification degree to define CPE and RSE.
The HLB of CPE or RSE is generally between 1 and 3.
When it is present, based on the total weight of composition, CPE or RSE are preferably with 0.5-50 weight %, more preferable 1-30 weight
Amount %, such as 2-25%, such as 2-20% amount be present in composition.
For in composition of the invention CPE and RSE include four oleate of sucrose, five eruciate of sucrose, four mustard of sucrose
Five oleate of acid esters and sucrose.
Fabric softener (and other non-quaternary ammonium salts soften compound) based on siloxanes
Composition of the invention can also contain the fabric softener based on siloxanes.Preferably, fabric-softening siloxanes is
Dimethyl silicone polymer.
Fabric-softening siloxanes includes but is not limited to: 1) nonfunctionalized siloxanes such as dimethyl silicone polymer (PDMS) or alkane
Base (or alkoxy) functional silicone；2) there are one or more different types of functional group such as amino, phenyl, polyethers, propylene
The functionalized silicone or copolymer of acid esters, silane, carboxylic acid, quaternary nitrogen etc..
Suitable siloxanes can be selected from polydialkysiloxane, preferably dimethyl silicone polymer, more preferable aminofunctional
Siloxanes, anion siloxanes and carboxy-functionalized siloxane.
Amino silicone can also be used, for example, Arristan 64 (coming from CHT) or Wacker CT45E (come from
Wacker)。
For silicone emulsion, granularity can in the range of about 1nm to 100 microns, preferably from about 10nm to about 10 microns,
Including microemulsion (< 150nm), standard lotion (about 200nm to about 500nm) and huge lotion (about 1 micron to about 20 microns).
Poly- alkyl wax emulsion, such as polyethylene wax can also be used, as the softening agent in composition of the invention.
Softening agent and aliphatic complexing agent altogether
Softening agent altogether can be used.When employed, based on the total weight of composition, they usually with 0.1 to 20%, especially
It is 0.5 to 10% amount presence.Preferably softening agent includes aliphatic ester and fatty N-oxides altogether.Adoptable aliphatic
Ester include aliphatic monoesters such as glycerin monostearate, aliphatic sugar ester as disclosed in WO 01/46361 (Unilever) that
A bit.
Composition of the invention may include aliphatic complexing agent.
The aliphatic complexing agent being particularly suitable includes fatty alcohol and fatty acid.In these, most preferably fatty alcohol.
It is without being bound by theory, it is believed that aliphatic complex materials will be by being complexed with the mono-ester component of fabric-conditioning agent material
And improve the viscosity characteristics of composition, to provide the composition with higher diester and three ester linkage composition levels.Diester and
Three ester linkage components are more stable and initial viscosity will not be negatively affected as mono-ester component.
It is also believed that the monoesters linked component of higher level present in the composition comprising the quaternary material based on TEA may
Keep composition unstable by vacancy flocculation (depletion flocculation).Material is complexed by using aliphatic
Material to be complexed with monoesters linked component, and vacancy flocculation will substantially reduce.
In other words, if raised levels of aliphatic complexing agent of the presently claimed invention is by the monoesters of " neutralization " quaternary material
Linked component.This generates the softening that will also improve composition from the diester in situ of monoesters and fatty alcohol.
Preferred fatty acid includes that hardened tallow fatty acid (can be with trade name PristereneTMIt is obtained from Croda).It is excellent
The fatty alcohol of choosing includes that hardened tallow alcohol (can be with trade name StenolTMAnd HydrenolTMFrom BASF and with trade name
LaurexTMCS is obtained from Huntsman).
Total weight based on composition, aliphatic complexing agent preferably exist with the amount higher than 0.3 to 5 weight %.It is more excellent
Selection of land, aliphatic component exist with 0.4 to 4% amount.The mono-ester component of quaternary ammonium fabric softener material is to aliphatic complexing agent
Weight ratio is preferably 5:1 to 1:5, more preferable 4:1 to 1:4, most preferably 3:1 to 1:3, for example, 2:1 to 1:2.
Nonionic surfactant
The composition can also include nonionic surfactant.In general, can include for the purpose of stabilized composition
These nonionic surfactants.Suitable nonionic surfactant include ethylene oxide and/or propylene oxide and fatty alcohol,
The addition product of fatty acid and fatty amine.It can be used any alkoxylate material of concrete type described hereinafter as nonionic table
Face activating agent.
Suitable surfactant is the substantially water-soluble surfactant of logical formula (V):
R-Y-(C2H4O)z-CH2-CH2-OH (V)
Wherein R is selected from primary, secondary and branched alkyl and/or acyl group hydrocarbyl group；Primary, secondary and branched-chain alkenyl hydrocarbyl group；And
The phenols hydrocarbyl group that primary, secondary and branched-chain alkenyl replaces；The hydrocarbyl group have 8 to about 25, preferably 10 to 20, such as 14 to
The chain length of 18 carbon atoms.
In the general formula for ethoxylated non-ionic surface active agent, Y is usual are as follows:
- O- ,-C (O) O- ,-C (O) N (R)-or-C (O) N (R) R-
Wherein R has above for meaning given by formula (V), or can be hydrogen；Z is at least about 8, preferably at least about 10
Or 11.
Preferably, nonionic surfactant has about 7 to about 20, more preferable 10 to 18, such as 12 to 16 HLB.Base
In the Genapol of cocounut oil chain and 20 EO groupsTMC200 (Clariant) is a reality of suitable nonionic surfactant
Example.
If it exists, nonionic surfactant is so based on the total weight of composition with 0.01 to 10 weight
Measure %, the amount of more preferable 0.1 to 5 weight % exists.A kind of preferred nonionic surfactant includes ethylene oxide and/or ring
The addition product of Ethylene Oxide and fatty alcohol, fatty acid and fatty amine.These are preferably selected from (a) alkoxide and (b) aliphatic material
The addition product of material, the alkoxide are selected from ethylene oxide, propylene oxide and their mixture, the aliphatic material choosing
From fatty alcohol, fatty acid and fatty amine.
Suitable surfactant is the substantially water-soluble surfactant of logical formula (VI):
R-Y-(C2H4O)z-CH2-CH2-OH (VI)
Wherein R be selected from primary, secondary and branched alkyl and/or acyl group hydrocarbyl group (as Y=-C (O) O, R ≠ acyl group alkyl base
Group)；Primary, secondary and branched-chain alkenyl hydrocarbyl group；And the phenols hydrocarbyl group that primary, secondary and branched-chain alkenyl replaces；The hydrocarbyl group
Chain length with 10 to 60, preferably 10 to 25, such as 14 to 20 carbon atoms.
In the general formula for ethoxylated non-ionic surface active agent, Y is usual are as follows:
- O- ,-C (O) O- ,-C (O) N (R)-or-C (O) N (R) R-
Wherein R has above for meaning given by formula (VI), or can be hydrogen；Z is at least about 6, preferably at least about
10 or 11.
Lutensol based on cocounut oil chain and 25 EO groupsTMAT25 (BASF) is suitable nonionic surfactant
One example.Other suitable surfactants include Renex 36 (Trideceth-6) (from Croda)；Tergitol
15-S3 (comes from Dow Chemical Co.)；Dihydrol LT7 (comes from Thai Ethoxylate ltd)；Cremophor
CO40 (comes from BASF)；With Neodol 91-8 (coming from Shell).
Other optional member
The composition may include those skilled in the art by the other compositions of known fabric conditioner liquid.In this way
Material in, can be mentioned that: defoaming agent, essence and fragrance (both free oil and encapsulating material), insect repellent, shading or toning
Dyestuff, pH buffer, fragrance carrier, hydrotropic agent, anti-redeposition agents, detergent, gathers preservative (for example, bactericide)
Electrolyte, nonshrink aqua, anti wrinkling agent, antioxidant, dyestuff, colorant, sun-screening agent, corrosion inhibitor, drape imparting agents, resist it is quiet
Electric agent, chelating agent and ironing aids.Product of the invention can contain pearling agent and/or opacifiers.A kind of preferred chelating agent is
HEDP is etidronic acid or 1- hydroxyl ethane 1, the abbreviation of 1- di 2 ethylhexyl phosphonic acid.
Product form
The composition is that softening compositio is added in the rinsing suitable for laundry processes.The composition is drumped
Liquid.
The liquid composition has about 2.0 to 6, preferably from about 2.2 to 4.5, most preferably from about 2.5 to 2.8 pH.The present invention
Composition can also contain pH adjusting agent, preferred hydrochloric acid or lactic acid.
The composition is preferably the instant liquid for including water phase.Water phase may include water-soluble substances, such as mineral salt or
Short chain (C1-4) alcohol.
The composition is preferred in the rinse cycle of home textiles washing operation, wherein can be by it with undiluted shape
State is directly appended in washing machine (such as by distributor drawer)；Or it for top-loaded formula washing machine, is directly appended to
In roller.The composition can be also used in the operation of family's hand-wash laundry.
The preparation of composition of the invention
Composition of the invention can be prepared by preparing fabric-conditioning compositions and adding particle.Alternatively, can will polymerize
Object is added in composition with dry state and allows hydrated in-situ.Function composition is preferably with routine well known by persons skilled in the art
Prepared by mode, and then merge with preformed particle of the present invention to form composition of the invention.In an embodiment
In, composition of the invention is made by least merging cationic softener active constituent in water with preformed particle
It is standby.
Composition of the invention can be prepared usually by merging the melt comprising the fabric-softening active matter with water phase.
Polymer can be merged with water phase, or can by it after melt and water phase merge again afterwards investment (post dose) to combining
In object.
It is a kind of preferred the preparation method is as follows:
1. heating water to about 40 to 80 DEG C.
2. any micro constitutent is added, such as defoaming agent, chelating agent and preservative.
3. being melted softening active matter and optional fatty alcohol together to form eutectic.
4. the eutectic is added into heated water.
5. if desired, acid is added to preferred pH.
6. dyestuff and fragrance is added.
7. cooling.
Be formed by particle can after put into or be added in batch water.
The present invention will be further described in conjunction with following non-limiting example and in conjunction with attached drawing, and attached drawing briefly describes are as follows:
Fig. 1 is the figure for showing the size distribution of embodiment 1；
Fig. 2 is the figure for showing the size distribution of embodiment A；
Fig. 3 is the figure for showing the size distribution of embodiment 2；
Fig. 4 is the figure for showing the size distribution of embodiment B；
Fig. 5 is to show polymer 1 and compare with Flosoft 270LS thickening polymer there is no cation
Comparison figure；With
Fig. 6 is the figure for showing the gained size distribution of embodiment C.
Embodiment
The embodiment of the present invention is by digital representation.Comparative example is indicated by letter.
Embodiment 1: the synthesis that cationic polymer-polymer 1 passes through gel polymerisation
Monomer solution is prepared by the way that following component is added and stirred in glass beaker:
- 9.0 parts of acrylamide solutions (weight concentration 50%, the monomer have the molecular weight of 71g/mol), i.e., 4.5 parts
Acrylamide
- 71.0 parts through with the quaternized dimethylaminoethyl methacrylate of chloromethanes (weight concentration 75%, the list
Body has the molecular weight of 207.7g/mol), i.e. 53.25 parts of monomers
- 20.0 parts of deionized waters
The methylene-bisacrylamide (ppm relative to monomer weight) of -800ppm
The sodium formate (ppm relative to monomer weight) of -7550ppm
PH:[3.4 to 3.8 is adjusted with phosphoric acid]
By weight, the quaternized dimethylaminoethyl methacrylate that polymer composition (monomer ratio) is 92.0%
With 8.0% acrylamide.After stirring 30 minutes, cooling monomer solution is transferred in Dewar bottle, is then blown with nitrogen to 10 DEG C
15 minutes are swept to remove oxygen.Polymerization is by being added sodium peroxydisulfate (20ppm/ total monomer weight) and Mohr's salt (10ppm/ monomer
Total weight) redox couple carried out with adiabatic method.Pre-dilution while being added mono- with 500ppm/ to 25g/L the salt in water
The azobis isobutyronitrile of body total weight dispersion.
The temperature of solution is spontaneously rose to 75 DEG C after 2 hours, is then kept for 2 hours at 75 DEG C.Gained mixture is
Viscogel.Then the piece that the gel is cut into 2 to 5mm is simultaneously dried 24 hours at 80 DEG C in an oven.It then will be through drying
Slice injection mill or grind to provide dry powder.Then the powder is filtered, it is straight to be removed by making pellet through sieves
Particle of the diameter less than 10 microns.As determined by the weight loss in drying oven at 105 DEG C after 2 hours, the powder
Residual moisture < 10.0%.
Drying is measured under 2.0 bar pressures (normal pressure) using Malvern Mastersizer Scirocco 2000
The granularity of powder is fallen between 10 and 60 microns.
Examples 1 and 2 and A and B: fabric conditioner composition
Fabric-conditioning compositions are prepared using the ingredient in table 1.
Table 1
| Material | Embodiment 1 | Embodiment A | Embodiment 2 | Embodiment B |
| Stepantex SP88 | 12 | 12 | 12 | 12 |
| Lutensol AT25 | 1 | 1 | 1 | 1 |
| HEDP | 0.005 | 0.005 | 0.005 | 0.005 |
| Fragrance | 1.15 | 1.15 | 1.15 | 1.15 |
| CaCl2 | 0.0025% | 0.0025% | 0.0025% | 0.0025% |
| Polymer 1* | 0.5 | 0 | 0.5 | 0 |
| Flosoft 270LS | 0 | 0.5 | 0 | 0.5 |
| HCl | 0.04 | 0.04 | 0.04 | 0.04 |
| Microcomponent and water | To 100% | To 100% | To 100% | To 100% |
Embodiment 1 and A are prepared by following procedure:
Batch water is heated to 50 DEG C；
In lower addition polymer of milling (polymer 1 or Flosoft 270LS, substantially such as institute's public affairs in WO2010/079100
The polymer opened)；
Microcomponent is added, followed by melts active matter (SP88, a kind of ester linkage TEA quaternary ammonium material from Stepan
Material and Lutensol AT25, a kind of nonionic from BASF) and CaCl2；
Mill admixture is simultaneously cooled to 36 DEG C, and free oil spice composition is added and simultaneously remixes the final stage time.
Embodiment 2 and B are prepared by following procedure:
Batch water is maintained at 50 DEG C；
Microcomponent, followed by Lutensol AT25 is added；
In lower addition polymer 1 or the Flosoft 270LS of milling；
The SP88 of melting is added, further mills and CaCl is added2；
Mill admixture is simultaneously cooled to 36 DEG C, and free oil flavors are added at this temperature and remix the final stage time.
The disperse properties of example composition 1 and 2 and A and B
The method for measuring dispersibility
Instrument: TA Instruments DHR2 rheometer (or rheometer of any similar capabilities).
Measure geometry equipment: concentric circles cartridge type system, by rotor (cross bladed blade band side rib perpendicular blade) and stator (band
Collet cylinder) composition.The axial depth of internal diameter and 35mm of the cylinder with 26mm；Collet is connected to outer loop water-bath with will be warm
Degree control is at 25 DEG C.The sword diameter of cross bladed blade is 20mm, while sword height is 20mm.
Method: measure geometry equipment is installed on instrument, cross bladed blade arrangement above the cylinder base portion at 0.5mm, with
Displacement volume at the top of sword is about 9cm3.The volume is partly full of by test fabric conditioning composition.Experimental arrangement is by three parts group
At:
I) rheometer is started with 54rad/s, record viscosity per second, is recorded 300 seconds in total.After 20 seconds, set to measure geometry
The isometric water of standby middle injection (volume with composition) simultaneously records decentralized signal and terminated to 300 seconds.
Ii) it cannot be guaranteed that product is completely dispersed in water at this time, therefore by making rheometer rerun 300 seconds with 90rad/s
Carry out mixing to completion.
Iii it) is read now by measuring 300 seconds again with 54rad/s to obtain the final viscosity under the conditions of original measurement.
Data analysis: take step (i) viscosity number be more than the final viscosity value of acquirement in step (iii) 90% time
For T90 point (the time spent in reaching 90% dispersion).Adjustment time is to consider the time before addition water.
As a result
T90 distributed test result is shown in Table 2.Lesser number shows that mixture quickly reaches complete equipilibrium.In addition,
It is shown in table 2 as used cup hammer viscosimeter in 106s-1Shear rate and 25 DEG C at the viscosity that measures.
Table 2
| Embodiment 1 | Embodiment A | Embodiment 2 | Embodiment B | |
| Viscosity | 330 | 259 | 214 | 189 |
| T90 | 30 | 326 | 30 | 143 |
Known polymer using sample made from polymer 1 than the prior art reaches balance when mixing (dispersion) with water
The time spent in want much shorter.In both cases, despite the fact that being, two kinds of compositions comprising bulky grain Tackified polymeric
Viscosity be higher than prior art Flosoft 270LS composition.
The particle size Lambda characterization of example composition 1 and 2 and A and B
Granularity is characterized using Malvern Mastersizer Scirocco 2000.
Fig. 1 shows the size distribution of embodiment 1.Lower peak is since there are the vesicas of cationic softener material.
As can be seen that the diameter for the cross-linked polymer particle being swollen in composition most (by volume %) is more than 100 microns.
Fig. 2 shows the corresponding datas of embodiment A.It is the same manner as in Example 1, there is short grained the first of instruction cation
Peak, followed by the second peak show that most polymers exist in the composition with the particle less than 12 microns.
Fig. 3 shows the data of embodiment 2.Figure line is the average value measured three times.
Fig. 4 shows the data of embodiment B.Single measured value and average value three times are all shown between different measurements
Difference very little.The same with embodiment A, main peak is present in 0.5 to 1 micron and 4 to 12 microns.
Fig. 5 is shown in polymer 1 there is no the cation of fabric-conditioning compositions and in the case where other components and right
Than the comparison with Flosoft 270LS thickening polymer.With being with 0.2 weight lower than 1 micron corresponding compared with the curve of small peak
Measure % prior art Flosoft polymer in water, and have it is corresponding higher than the curve at 100 microns of larger peak be with
The polymer 1 of 0.5 weight % in water.Different concentration does not influence the position at peak.
In order to confirm that some peaks seen in fabric-conditioning compositions are not due to the presence of polymer, preparation is not present
The comparative example C of any polymer.In other respects, identical as embodiment 2 and B.Fig. 6 shows gained size distribution.
The comparative example C of non-polymer confirms that the low granularity peak found in the embodiments of the present invention and comparative example is group
Close other components in object rather than the result of cross-linked polymer particle.
Embodiment 3: fabric-conditioning compositions 3 and D
The fabric softener base formulation based on ester quat is prepared, it includes 20 weights of the weight of total base composition
The partially hardened TEAQ (Stepantex SP88 (coming from Stepan)) of % is measured, remaining is microcomponent and water.By 50% (with most
The stereometer of whole composition) fabric softener base formulation merge with the polymer gel of 50 volume % to generate composition 3,
The polymer gel includes big polymer viscosified particle (polymer 1) of the invention.The concentration of polymer 1 in 50 volume %
By the polymer of 2 weight % supplied.Therefore, composition 1 includes that the fabric of 50 volume % of the volume of final composition is soft
The polymer gel of agent preparation and 50 volume %.
Composition D is prepared in an identical manner, but uses the prior art thickening polymer (Flosoft of pre-hydrated
270LS comes from SNF) replace polymer 1.Thickening polymer part accounts for 50 volume % of final composition.In 50 volume %
The polymer supplied of the concentration of polymer by 2 weight %.
Ingredient used in composition is shown in Table 3.
Table 3: composition 3 and D show the amount (weight %) of component
| Material | Composition 3 | Composition D |
| Stepantex SP88 | 10 | 10 |
| Flosoft 270LS | - | 1.0 |
| Polymer 1 | 1.0 | - |
| Microcomponent and water | To 100 weight % | To 100 weight % |
The disperse properties of composition 3 and D
The method for measuring dispersibility
By 17ml composition to be tried from standard ComfortTMBottle cap pours into the 1000ml cold running water in 2000ml beaker
In.After 30 seconds, visual assessment gained mixture is simultaneously graded based on 1-5 points of scale, and half point is used when appropriate.Scale definition
It is as follows:
Grade 1: solution is evenly dispersed and without agglomerate or fritter.
Grade 2: product dispersion provides uniform dispersion, only a small amount of small agglomerate or fritter.
Grade 3: product dispersion mainly provides small agglomerate or fritter, but favorable dispersibility and provides slight haziness/coloured
Solution.
Class 4: product resolves into several medium and/or large-sized agglomerate and without finely divided；Water keeps substantially limpid nothing
Color.
Class 5: product does not decompose when entering in water.It usually forms one or two large crumb in clear water.
If desired, mixture can be stirred by carrying out 5 rotations with grafter with rate of once per second, then use
Identical equal is assessed again.As a result it is given in Table 4.
Table 4: example composition 3 and the viscosity of D and dispersed score
As can be seen that composition 3 according to the present invention has significantly than the analogous composition D comprising conventional thickening polymer
Improved disperse properties.
Embodiment 4: prior art polymer viscosifier of the fabric-conditioning compositions E into G
The fabric softener base formulation based on ester quat is prepared with conventional thickener polymers, it includes total bases
The partially hardened TEAQ (Stepantex SP88 (coming from Stepan)) of 12 weight % of the weight of composition, remaining is micro group
Point and water.
Composition is prepared by merging polymer and water phase, then addition melt and microcomponent.These composition institutes
It is shown in Table 5 with ingredient.
Table 5: composition E to G shows the amount (weight %) of component
| Material | Composition E | Composition F | Composition G |
| Stepantex SP88 | 12 | 12 | 12 |
| Flosoft 270LS | 0.5 | - | - |
| Luvigel Star | - | 0.1 | 0.07 |
| Microcomponent and water | To 100 weight % | To 100 weight % | To 100 weight % |
The disperse properties of composition E to G
As a result it is given in Table 6.
Table 6: the viscosity of composition E to G and dispersed score
This illustrates when being added in fabric-conditioning compositions, the viscosity of the polymer viscosifier applied to the prior art
The undesirable compromise between dispersibility.As can be seen that composition viscosity is higher, dispersed poorer grade.
Embodiment 4 to 6
The fabric softener base formulation based on ester quat is prepared, it includes 20 weights of the weight of total base composition
The partially hardened TEAQ (Stepantex VT90 (coming from Stepan)) of % is measured, remaining is microcomponent and water.
By the cross-linked polymeric of the fabric softener base formulation of 60% (in terms of the volume of final composition) and 40 volume %
Object gel (polymer 1 comes from SNF) merges to generate composition 4 to 6.The concentration of polymer 1 in 40 volume % is 2 weights
Measure the polymer of % supplied.As shown in table 7, by the weight % for accounting for composition, change 2 weight % polymer in composition
Amount.
Table 7: composition 4 to 6 (weight %)
| Material | Composition 4 | Composition 5 | Composition 6 |
| Stepantex SP88 | 12 | 12 | 12 |
| Polymer 1 | 0.4 | 0.5 | 0.6 |
| Microcomponent and water | To 100 weight % | To 100 weight % | To 100 weight % |
The disperse properties of composition 4 to 6
As a result it is given in Table 8.
Table 8: the viscosity of composition 4 to 6 and dispersed score
The dispersibility which demonstrate the present invention in certain viscosity range improves.
The property of composition 5 is compared with the property of composition G and the property of the property of composition 6 and composition F
Compare, it is shown that the dispersibility that composition according to the present invention improves under similar viscosity.
Embodiment 7 and H
The fabric softener base formulation based on ester quat is prepared, it includes 20 weights of the weight of total base composition
The partially hardened TEAQ (Stepantex SP88 (coming from Stepan)) of % is measured, remaining is micro constitutent and water.
The polymer of the fabric softener base formulation of 50% (in terms of the volume of final composition) and 50 volume % is solidifying
Glued and to generate example composition 7, which includes that (polymer 1, comes from big polymer beads of the invention
SNF).The polymer supplied of the concentration of polymer 1 in 50 volume % by 1 weight %.Therefore, composition 7 includes most
The fabric-softening agent formulation of 50 volume % of the volume of whole composition and the polymer gel of 50 volume %.
Composition H is fabric conditioner that can be commercially available from Unilever (Indonesia) with trade name Molto,
It contains conventional thickening polymer rather than polymer 1.
The distribution drawer property of composition 7 and H
The method for measuring dispersibility
Using standard weights analysis with index method, using BRIX function, the distributor drawer of front-loading washing machine is obtained
In remaining residue precise measurements.
(i) the distributor drawer of washing machine is pre-weighed, and fabric-conditioning is added into the fabric conditioner compartment of drawer
Agent composition (35g).
(ii) washing machine setting is recycled to " rinsing ".
(iii) it when siphon is completed, takes out machine drawer and weighs, to record the weight of remaining residue.
(iv) demineralized water is added rinsing residue to the fixed volume of 100ml.
(v) residue and water are mixed using disposable pipette, it is ensured that adhere to the residue of drawer side surface
It is mixed with water.
(vi) then aqueous mixture is transferred in 125ml powder glass bottle using disposable pipette, is sealed against
And shake mixing.
(vii) relative to reference standard, the refractive index of composition is measured.
Every kind of composition is tested in duplicate.
For each sieving sample (35% solution of the composition in demineralized water), preparation is represented in distributor drawer and is remained
The reference substance of 100% remaining residue.
As a result it is given in Table 9.
Table 9
As can be seen that composition 7 has the distribution property substantially improved than the similar products comprising conventional thickening polymer.
Claims (14)
1. a kind of dumpable liquid fabric condition composition, the composition includes:
A) cationic fabric softens active matter；
B) particle is viscosified, with 35 to 1000 microns of volume average particle sizes, the particle includes few based on the particle
In the water-swellable polymer of the crosslinking of 50 weight % and at least absorbed water of 50 weight % based on the particle, polymerization
The amount of object is at least 0.1 weight % of the fabric-conditioning compositions；With
C) other water,
The composition is in 106s-1There is viscosity in the range of 60 to 3500mPas, wherein in the particle at 25 DEG C
The polymer be insoluble in water and the particle is inert, wherein the polymer contains at least one cation
Monomer and optional nonionic and/or anionic monomer.
2. composition according to claim 1, wherein the particle has 50 to 500 microns of volume average particle sizes.
3. composition according to claim 2, wherein the particle has 60 to 300 microns of volume average particle sizes.
4. composition according to any one of claim 1-3, wherein the polymer has extracting lower than 15%
Polymer content and the crosslinker concentration for being 500ppm to 10,000ppm relative to the polymer.
5. composition according to any one of claim 1-3, wherein the polymer is obtained by gel polymerisation.
6. composition according to claim 5, wherein the cationic monomer is quaternized with theirs selected from following monomer
Or salinization derivative: dimethylaminopropyl Methacrylamide, dimethylaminopropylacryl amide, diallylamine, first
Base diallylamine, propenoic acid dialkyl aminoalkyl ester, methacrylates, dialkyl aminoalkyl
Acrylamide and dialkyl aminoalkyl-Methacrylamide.
7. composition according to claim 6, wherein the cationic monomer is selected from dimethylamine second
Ester and derivative and their quaternized or salinization derivative, and/or dimethylaminopropyl Methacrylamide and derivative
And their quaternized or salinization derivative.
8. composition according to claim 4, wherein the crosslinking agent is selected from methylene-bisacrylamide (MBA), second two
Alcohol diacrylate, polyethylene glycol dimethacrylate, diacrylamine, triallylamine, glyoxal, glycidol ether chemical combination
Object.
9. composition according to any one of claim 1-3, wherein the polymer includes nonionic selected from the following
Monomer: acrylamide, Methacrylamide, N- alkyl acrylamide, n-vinyl pyrrolidone, N- vinyl formamide, N-
Vinyl acetamide, vinyl acetate, vinyl alcohol, acrylate and allyl alcohol.
10. composition according to any one of claim 1-3, wherein cationic fabric softening active matter is ester bond
The quaternary ammonium compound of conjunction.
11. composition according to claim 10, wherein the quaternary ammonium compound of the ester linkage is to include unsaturated fat
The triethanolamine quaternary ammonium compound of the ester linkage of chain.
12. composition according to any one of claim 1-3, wherein the cationic fabric softens active matter with total group
The amount for closing 2 to 25 weight % of object exists.
13. a kind of method of the offer for improving the liquor of fabric, the method includes will be according to claim 1 to any in 12
The step of composition described in is dispersed in water.
14. according to the method for claim 13, wherein the composition is added to the distribution drawer of washing machine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14197882 | 2014-12-15 | ||
| EP14197882.5 | 2014-12-15 | ||
| PCT/EP2015/077633 WO2016096347A1 (en) | 2014-12-15 | 2015-11-25 | Pourable liquid fabric conditioner compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107109297A CN107109297A (en) | 2017-08-29 |
| CN107109297B true CN107109297B (en) | 2019-08-16 |
Family
ID=52101154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580073218.2A Expired - Fee Related CN107109297B (en) | 2014-12-15 | 2015-11-25 | Dumpable liquid fabric conditioner composition |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3234086B1 (en) |
| CN (1) | CN107109297B (en) |
| BR (1) | BR112017012522A2 (en) |
| TR (1) | TR201815223T4 (en) |
| WO (1) | WO2016096347A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11053465B2 (en) | 2018-06-04 | 2021-07-06 | The Procter & Gamble Company | Methods of treating fabrics and related compositions |
| CN113227338A (en) * | 2018-12-11 | 2021-08-06 | 联合利华知识产权控股有限公司 | Fabric conditioner composition |
| US20230183608A1 (en) * | 2020-05-27 | 2023-06-15 | Conopco, Inc., D/B/A Unilever | Method of preparing a liquid fabric conditioner |
| EP4247925B1 (en) * | 2020-11-18 | 2024-09-04 | Unilever IP Holdings B.V. | Fabric conditioner |
| CN117716010A (en) * | 2021-07-26 | 2024-03-15 | 联合利华知识产权控股有限公司 | Method for preparing fabric conditioner |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114600A (en) * | 1989-04-21 | 1992-05-19 | Bp Chemicals Limited | Fabric conditioners |
| CN1742076A (en) * | 2002-12-16 | 2006-03-01 | 高露洁-棕榄公司 | Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers |
| CN102272282A (en) * | 2009-01-06 | 2011-12-07 | 荷兰联合利华有限公司 | Improvements relating to fabric conditioners |
| WO2014092691A1 (en) * | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Fabric conditioning composition |
| WO2014092690A1 (en) * | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Fabric conditioning composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3861870A (en) | 1973-05-04 | 1975-01-21 | Procter & Gamble | Fabric softening compositions containing water-insoluble particulate material and method |
| GB1567947A (en) | 1976-07-02 | 1980-05-21 | Unilever Ltd | Esters of quaternised amino-alcohols for treating fabrics |
| DE3027611A1 (en) | 1980-07-21 | 1982-02-18 | Bayer Ag, 5090 Leverkusen | DI- AND OLIGO-1,2,4-TRIAZOLIDINE-3,5-DIONE AND METHOD FOR THE PRODUCTION THEREOF |
| EP0311154B1 (en) | 1987-04-10 | 1994-01-19 | The Procter & Gamble Company | Novel solid, nondigestible, fat-like compounds |
| GB9930435D0 (en) | 1999-12-22 | 2000-02-16 | Unilever Plc | Fabric softening compositions |
-
2015
- 2015-11-25 CN CN201580073218.2A patent/CN107109297B/en not_active Expired - Fee Related
- 2015-11-25 TR TR2018/15223T patent/TR201815223T4/en unknown
- 2015-11-25 EP EP15798483.2A patent/EP3234086B1/en not_active Not-in-force
- 2015-11-25 WO PCT/EP2015/077633 patent/WO2016096347A1/en active Application Filing
- 2015-11-25 BR BR112017012522A patent/BR112017012522A2/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5114600A (en) * | 1989-04-21 | 1992-05-19 | Bp Chemicals Limited | Fabric conditioners |
| CN1742076A (en) * | 2002-12-16 | 2006-03-01 | 高露洁-棕榄公司 | Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers |
| CN102272282A (en) * | 2009-01-06 | 2011-12-07 | 荷兰联合利华有限公司 | Improvements relating to fabric conditioners |
| WO2014092691A1 (en) * | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Fabric conditioning composition |
| WO2014092690A1 (en) * | 2012-12-11 | 2014-06-19 | Colgate-Palmolive Company | Fabric conditioning composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TR201815223T4 (en) | 2018-11-21 |
| BR112017012522A2 (en) | 2018-02-27 |
| WO2016096347A1 (en) | 2016-06-23 |
| EP3234086A1 (en) | 2017-10-25 |
| CN107109297A (en) | 2017-08-29 |
| EP3234086B1 (en) | 2018-09-26 |
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