EP3122853A1 - Flüssige kationische formulierung und verfahren zu deren herstellung - Google Patents
Flüssige kationische formulierung und verfahren zu deren herstellungInfo
- Publication number
- EP3122853A1 EP3122853A1 EP15712344.9A EP15712344A EP3122853A1 EP 3122853 A1 EP3122853 A1 EP 3122853A1 EP 15712344 A EP15712344 A EP 15712344A EP 3122853 A1 EP3122853 A1 EP 3122853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- concentrate
- formulation
- cationic
- acrylic polymer
- thickening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 238000009472 formulation Methods 0.000 title claims abstract description 61
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 58
- 239000007788 liquid Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000012141 concentrate Substances 0.000 claims abstract description 61
- 230000008719 thickening Effects 0.000 claims abstract description 29
- 239000002979 fabric softener Substances 0.000 claims abstract description 23
- 229920000058 polyacrylate Polymers 0.000 claims description 34
- 239000000375 suspending agent Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000010924 continuous production Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- -1 1-hydroxyprop-2-yloxy Chemical group 0.000 claims description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 125000001137 3-hydroxypropoxy group Chemical group [H]OC([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical group OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 4
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000012669 liquid formulation Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LVKKFNORSNCNPP-UHFFFAOYSA-N 2,2-bis(prop-2-enoylamino)acetic acid Chemical compound C=CC(=O)NC(C(=O)O)NC(=O)C=C LVKKFNORSNCNPP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005399 allylmethacrylate group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
Classifications
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2096—Heterocyclic 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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
Definitions
- the present invention relates to a thickening concentrate for the continuous preparation of a liquid cationic formulation of household cleaners or softeners and to a process for the continuous production of a liquid cationic formulation of household cleaners or softeners in which a thickening concentrate according to the invention is used.
- the present invention relates to a formulation which is obtainable by the process according to the invention.
- Liquid cationic formulations of household cleaners or fabric softeners are often aqueous or alcoholic formulations.
- additives which influence the viscosity to the formulation.
- these may be polymers.
- WO 99/06455 A describes thickening agents for acidic compositions comprising cationic homopolymers in a proportion of 50 to 600 ppm of crosslinking agent. Suitable polymers are also described, for example, in WO 2004/050812 A1.
- liquid formulations In the preparation of liquid formulations, however, it has been found that continuous metering of a corresponding polymer into the liquid cationic formulation is not possible or difficult, especially when present in solid form. Usually, liquid formulations are therefore produced in a batch mixer. In batch production, however, a constant quality over different batches can only be ensured with great effort, so that a consistent quality of the liquid cationic formulation is only possible within limits. Even within a batch, different concentrations of polymers can occur and thus quality differences.
- thickeners cationic acrylic polymers have emerged. These are usually present as a solid, for example in the form of a powder. Since the continuous metering of a powder is difficult to realize, solids are usually first dissolved in a suitable solvent or suspended in a suspending agent and then added as a solution or suspension to a liquid formulation. As solvents or suspending agents, preference is given to using those liquids which are also present in the actual formulation in order to obtain good intermixability.
- WO 2013/016029 A1 discloses a process for the preparation of a composition comprising a rheological properties adjusting agent.
- a rheology additive is dispersed in an anhydrous but water-miscible liquid carrier material such as a surfactant, a humectant, a polymer, an oil, or mixtures thereof. It will be in Water-swellable polymers, non-water-soluble crystalline polymers or mixtures thereof used as a rheological additive.
- a thickening concentrate for the continuous production of a liquid cationic formulation of household cleaners or fabric softeners which comprises a cationic acrylic polymer as thickener and a propylene oxide structure suspending agent for the acrylic polymer.
- a first aspect of the invention is therefore a thickening concentrate for the continuous preparation of a liquid cationic formulation of household cleaners or fabric softeners which comprises a cationic acrylic polymer as thickening agent and at least one suspending agent for the acrylic polymer of the following general formula (A)
- R 2 is a hydrogen atom, a methyl group, a 2-hydroxypropoxy group, a 3-hydroxypropoxy group or together with R is a ring-closing carbonyl group,
- R 3 is hydrogen, 1-hydroxyprop-2-yloxy or 2-hydroxypropoxy.
- R is a hydrogen atom or together with R 2 with ring closure a
- R 2 is a hydrogen atom, a methyl group, a 3-hydroxypropoxy group or together with R is a ring-closing carbonyl group.
- the suspending agent is selected from the group consisting of dipropylene glycol (preferably with the CAS No. 25265-71 -8), 1-butanol, 1-propanol and ⁇ -butyrolactone and mixtures thereof.
- a thickening concentrate according to the invention is in the form of a suspension which can be used in a continuous production process of liquid cationic formulations of fabric softeners or household cleaners.
- the thickening concentrate according to the invention may contain a suspending agent. It is also possible according to the invention that a mixture of two or more different suspending agents is contained in the thickening concentrate.
- the suspending agents according to the invention and mixtures thereof are suitable for suspending cationic acrylic polymers such that the suspension is not substantially thickened, so that continuous metering is possible for preparing the liquid cationic formulation of household cleaners or fabric softeners.
- the suspension of the suspending agent according to the invention and the cationic acrylic polymer is not necessarily sedimentation stable. However, there is a slight resuspendability of the acrylic polymer in said suspending agents.
- the suspending agents according to the invention have a high flash point and are not toxic. A low flashpoint and toxicity would preclude the production of liquid cationic formulations of household cleaners or softeners, since these would be excluded from household use.
- the suspending agent is inexpensive to obtain.
- the suspending agent can be used in technical purity.
- the thickening concentrate is stable to small amounts of water.
- the concentrate may contain water in an amount of 5% by weight or less, more preferably 3% by weight or less, based on the total weight of the concentrate.
- the concentrate comprises the suspending agent in an amount of 70% by weight to 99% by weight, in particular in an amount of 75% by weight to 90% by weight, based on the total weight of the concentrate.
- the concentrate contains 1 to 30 wt .-%, in particular 10 to 25 wt .-% of cationic acrylic polymer, based on the total weight of the concentrate.
- a thickening concentrate is obtained, which can be metered into liquid cationic formulations of household cleaners or fabric softeners using continuous production processes known in the prior art.
- the suspending agent is compatible with the components of the liquid cationic formulation.
- the concentrate can therefore be added in any desired amount, so that the viscosity of the cationic formulation can be adjusted as required. If the concentrate has more than 30% by weight of cationic acrylic polymer, the concentrate itself already has a high viscosity. The flowability is impaired. An addition, for example by means of a pump is then difficult. Thus, even in this case, a continuous production is no longer possible because a continuous metering is no longer possible due to the high viscosity of the thickening concentrate. If the concentrate has less than 1% by weight of cationic acrylic polymer, economical preparation of the cationic formulation of household cleaners or fabric softeners is no longer possible.
- the final product should preferably contain the thickening concentrate in a proportion of 1% by weight or more, based on the total weight of the formulation. If the proportion of cationic acrylic polymer in the concentrate is less than 1% by weight, the proportion of thickener in the end product is very low, so that a change in the viscosity is not or almost undetectable. Preferably, therefore, the concentrate has the acrylic polymer in an amount of 10% by weight. This allows economical addition of the concentrate with high variability in adjusting the viscosity of the liquid cationic formulation of household cleaners or fabric softeners.
- the weight ratio of the suspending agent to the acrylic polymer is in the range of 4: 1 to 1: 3. It has been found that in this weight ratio, the thickening concentrate can be used well in continuous production processes known in the art. In conventional continuous production processes, the thickening concentrate is pumped by means of a pump into a liquid cationic formulation of household cleaners or fabric softeners which do not yet have a thickener in their formulation. In order to obtain a uniform dosage, the thickening concentrate should preferably be pumpable. To ensure this, the viscosity of the concentrate is preferably 10000 mPas or less, in particular 7500 mPas Or less. In this range of viscosity, it is ensured that the concentrate can be pumped with a commercial pump to a liquid cationic formulation of household cleaners or fabric softeners in a continuous manufacturing process.
- the cationic acrylic polymer is in the form of solid particles.
- the particles are preferably spherical particles, which in particular have a spherical shape.
- the average particle size (average volume diameter) of the solid particles is in particular in the range of 100 to 900 ⁇ , preferably in the range of 200 to 800 ⁇ , more preferably in the range of 250 to 750 ⁇ . If the solid particles are in spherical form, the diameter of the sphere corresponds to the particle size. For all other spherical forms, the particle size corresponds to the size of the particles with the greatest spatial extent.
- the particle size can be determined by means of scanning electron micrographs (SEM).
- the cationic acrylic polymer is hygroscopic. With a particle size of 100 ⁇ or less, in particular of 200 ⁇ or less, especially of 250 ⁇ or less so much water can be accumulated on the surface of the particles that a stable suspension is no longer obtained. Rather, it then comes to a swelling of the cationic acrylic polymer, so that after mixing with a suspending agent according to the invention no meterable suspension, but a highly viscous, rubbery mass is obtained. On the other hand, if the particle size is more than 900 ⁇ m, these large and therefore also heavy particles can sediment faster than particles having a size of 900 ⁇ m or less, in particular of 800 ⁇ m or less, especially of 750 ⁇ m or less.
- Suitable cationic acrylic polymers which can be used as thickeners according to the invention are described, for example, in WO 03/102043 A1 on pages 1 to 4, to the content of which reference is made in their entirety.
- the cationic acrylic polymers of the invention are therefore preferably made
- the cationic monomer preferably corresponds to a compound according to the following compound (I) in which independently
- Ri is hydrogen or methyl
- R2 is hydrogen or C1 to C4-alkyl
- R 3 is C 1 -C 4 -alkylene
- R4, R5 and R6 are each independently hydrogen or C1 to C4 alkyl
- Y is Cl, Br, I, hydrogen sulfate or methosulfate
- the respective alkyl groups may be linear or branched.
- the crosslinking agent b) preferably comprises at least two ethylenically unsaturated units.
- Suitable preferred crosslinking agents are divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, ⁇ , ⁇ '-methylenebisacrylamide and polyol polyallyl ethers such as polyallylsucrose and pentaerythritol triallyl ether , Particularly preferred crosslinking agents are
- Tetraallylammonium chloride Tetraallylammonium chloride, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid and ⁇ , ⁇ '-methylenebisacrylamide.
- Tetraallylammonium chloride and ⁇ , ⁇ '-methylenebisacrylamide as crosslinking agent. It is also possible to use mixtures of the crosslinking agents.
- the cationic acrylic polymer comprises at least one crosslinking agent b) in a proportion of 50 to 1200 ppm, preferably 500 to 1000 ppm and more preferably 700 to 900 ppm, each based on the weight of component a).
- the chain transfer agent c) is preferably selected from the group comprising mercaptans, malic acid, lactic acid, formic acid, isopropanol and hypophosphites.
- the content of chain transfer agent c) is preferably from 10 to 50,000 ppm, preferably from 100 to 10,000 ppm, in each case based on the weight of component a).
- the cationic acrylic polymer is formed from the formula (Ia) shown below as a cationic monomer: in which independently
- R1 is hydrogen or methyl
- R2 is hydrogen or methyl
- R 3 is C 1 -C 2 -alkylene
- the at least one crosslinking agent is selected from the group consisting of divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, ⁇ , ⁇ ' -Methylenbisacrylamid and Polyolpolyallylether, and in an amount of 50 to 1200 ppm, preferably in an amount of 50 to 1000 ppm, more preferably in an amount of 700 to 900 ppm, each based on the weight of component a), and
- At least one chain transfer agent selected from the group consisting of malic acid, lactic acid, formic acid, isopropanol and hypophosphites in an amount of 1,000 to 9,000 ppm, preferably in an amount of 2,000 to 5,000 ppm, each based on the weight of Component a) is included.
- the present invention relates to a process for the continuous preparation of a liquid cationic formulation of household cleaners or fabric softeners.
- the process is characterized in that a concentrate according to the invention with a liquid, aqueous premix is added.
- This premix is a solution that includes the active ingredients of the formulation. Thickeners are not included in the premix.
- the premix is thus the formulation, but without thickener.
- the concentrate according to the invention is metered into a stream of the premix. A mixing between the premix and the concentrate according to the invention takes place on the basis of the flow properties of the premix or of the concentrate.
- the liquid, aqueous premix and the concentrate according to the invention in the stream by means of a circulating pump or a static mixer, preferably mixed by means of a static mixer with each other.
- the process of the invention relates to a continuous production process in which a thickening concentrate in the form of a premix is added to the formulation. This allows continuous production with consistent quality.
- the amount of concentrate added to the formulation can be changed at any time so that it can respond quickly and easily to changing customer requests or other changes in formulation.
- the pH of the formulation is preferably 6 or less, more preferably 4 or less.
- the formulation is preferably an acidic cationic formulation. If the formulation according to the invention is a household cleaner, the pH is preferably in the range from 2 to 5, in particular from 3 to 4. If the formulation according to the invention is a fabric softening agent, the pH is preferably in the range from 1 to 6, particularly preferably from 1, 5 to 3.5.
- the object underlying the present invention is achieved by a liquid cationic formulation of household cleaners or fabric softeners, which is obtainable by the process according to the invention.
- a liquid cationic formulation of household cleaners or fabric softeners which is obtainable by the process according to the invention.
- the formulation according to the invention preferably comprises the thickening concentrate in a proportion of 1% by weight or more, based on the total weight of the formulation. With a small amount of concentrate in the formulation, an influence on the viscosity is barely detectable. The use of the thickening concentrate would therefore not be economical here.
- Formulation of household cleaners or fabric softeners means domestic cleaners, such as bathroom cleaners, toilet cleaners, hard surface cleaners, as well as fabric softeners.
- the liquid cationic formulation according to the invention furthermore comprises customary constituents known in the prior art.
- the suspension agent for the acrylic polymer according to the invention is therefore soluble in water or the alcoholic solution.
- the formulation is a fabric softener.
- This comprises the thickening concentrate according to the invention in a proportion of 1% by weight or more.
- the thickening concentrate according to the invention comprises customary constituents, such as one or more fabric softening compounds, fragrance compositions and other additives, for example alcohols, amphoteric or nonionic surfactants, pH buffer substances, enzymes, fungicides or antioxidants.
- a fabric softener usually comprises a fabric softening compound. It is preferred that the fabric softening compound is selected from the group of quaternary ammonium compounds, polysiloxanes, fabric softening clays and mixtures thereof. These compounds are effective and commercially available fabric softening compounds.
- the fabric softener contains a quaternary ammonium compound as fabric softening compound.
- the quaternary ammonium compound is a compound of the following general formula (B):
- R 4 is an aliphatic alk (en) yl radical having 1 1 to 21 carbon atoms with 0, 1, 2 or 3
- R 5 is H, OH or O (CO) R 7 ,
- R 6 is independently of R 5 is H, OH or 0 (CO) R 8 , wherein R 7 and R 8 are each independently an aliphatic alk (en) ylrest having 1 1 to 21 carbon atoms with 0, 1, 2 or 3 Double bonds is,
- n, n and p can each independently have the value 1, 2 or 3 and
- X " may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these anions.
- the thickening concentrates from 1 a) and 1 b) were pumpable and could be used in a continuous process for the preparation of liquid formulations by means of commercially available metering pumps.
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Abstract
Description
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102014205661.6A DE102014205661A1 (de) | 2014-03-26 | 2014-03-26 | Flüssige kationische Formulierung und Verfahren zu deren Herstellung |
PCT/EP2015/056274 WO2015144713A1 (de) | 2014-03-26 | 2015-03-24 | Flüssige kationische formulierung und verfahren zu deren herstellung |
Publications (2)
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EP3122853A1 true EP3122853A1 (de) | 2017-02-01 |
EP3122853B1 EP3122853B1 (de) | 2019-05-08 |
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EP15712344.9A Active EP3122853B1 (de) | 2014-03-26 | 2015-03-24 | Flüssige kationische formulierung und verfahren zu deren herstellung |
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Country | Link |
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US (1) | US10030213B2 (de) |
EP (1) | EP3122853B1 (de) |
DE (1) | DE102014205661A1 (de) |
WO (1) | WO2015144713A1 (de) |
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IT1293509B1 (it) | 1997-07-30 | 1999-03-01 | 3V Sigma Spa | Addensanti per composizioni acquose acide |
MXPA04011844A (es) | 2002-06-04 | 2005-03-31 | Ciba Sc Holding Ag | Formulaciones de polimeros acuosas. |
US7138366B2 (en) * | 2002-11-01 | 2006-11-21 | Colgate-Palmolive Company | Aqueous composition comprising oligomeric esterquats |
DE60320672T2 (de) | 2002-11-29 | 2009-06-10 | Ciba Holding Inc. | Wäscheweichspülmittel enthaltend homo- und/oder copolymere |
JP5431619B2 (ja) * | 2010-04-01 | 2014-03-05 | ザ プロクター アンド ギャンブル カンパニー | 柔軟仕上げ剤 |
ES2428231T5 (es) * | 2010-06-24 | 2021-07-20 | Procter & Gamble | Composiciones líquidas no acuosas estables que comprenden un polímero catiónico en forma de partículas |
EP2551337A1 (de) | 2011-07-27 | 2013-01-30 | The Procter & Gamble Company | Verfahren zur Herstellung einer rheologiemodifikatorhaltigen Zusammensetzung |
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2014
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2015
- 2015-03-24 EP EP15712344.9A patent/EP3122853B1/de active Active
- 2015-03-24 WO PCT/EP2015/056274 patent/WO2015144713A1/de active Application Filing
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US20160362635A1 (en) | 2016-12-15 |
WO2015144713A1 (de) | 2015-10-01 |
DE102014205661A1 (de) | 2015-10-01 |
US10030213B2 (en) | 2018-07-24 |
EP3122853B1 (de) | 2019-05-08 |
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