EP4351774A1 - Compositions contenant des microcapsules dégradables neutres en couleur - Google Patents

Compositions contenant des microcapsules dégradables neutres en couleur

Info

Publication number
EP4351774A1
EP4351774A1 EP22733388.7A EP22733388A EP4351774A1 EP 4351774 A1 EP4351774 A1 EP 4351774A1 EP 22733388 A EP22733388 A EP 22733388A EP 4351774 A1 EP4351774 A1 EP 4351774A1
Authority
EP
European Patent Office
Prior art keywords
weight
layer
barrier layer
oil
stability
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.)
Pending
Application number
EP22733388.7A
Other languages
German (de)
English (en)
Inventor
Andreas Bauer
Marc-Steffen Schiedel
Stefan Urlichs
Manuela Materne
Hubert Smyrek
Christian GIESEN
Andreas Gerigk
Christian Kind
Claudia Meier
Jeanette HILDEBRAND
Michael BIEDENBACH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP21179043.1A external-priority patent/EP4101529A1/fr
Priority claimed from EP21179039.9A external-priority patent/EP4101528A1/fr
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP4351774A1 publication Critical patent/EP4351774A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the invention relates to detergents and cleaning agents and cosmetics which contain biodegradable microcapsules with environmentally friendly wall materials.
  • Microencapsulation is a versatile technology. It offers solutions for numerous innovations - from the paper industry to household products, microencapsulation increases the functionality of a wide variety of active substances. Encapsulated active ingredients can be used more economically and improve the sustainability and environmental compatibility of many products.
  • microcapsule walls based on the natural product gelatine and therefore completely biodegradable have long been used in carbonless paper.
  • a process for gelatine encapsulation that was developed as early as the 1950s is disclosed in US Pat. No. 2,800,457. Since then, a multitude of variations in terms of materials and process steps have been reported.
  • biodegradable or enzymatically degradable microcapsule walls are used in order to use enzymatic degradation as a method for releasing the core material.
  • Such microcapsules are described, for example, in WO 2009/126742 A1 or WO 2015/014628 A1.
  • microcapsules are not suitable for many industrial applications and household products. This is because microcapsules based on natural substances do not meet the diffusion tightness, chemical resistance and temperature resistance required for e.g.
  • organic polymers such as melamine-formaldehyde polymers (see e.g. EP 2 689 835 A1, WO 2018/114056 A1, WO 2014/016395 A1, WO 2011/075425 A1 or WO 2011/120772 A1); polyacrylates (see e.g. WO 2014/032920 A1, WO 2010/79466 A2); polyamides; Polyurethane or polyureas (see e.g. WO 2014/036082 A2 or WO 2017/143174 A1) are used.
  • the capsules made from such organic polymers have the required diffusion tightness, stability and chemical resistance. However, these organic polymers are enzymatically or biologically degradable only to a very small extent.
  • WO 2014/044840 A1 describes a process for preparing two-layer microcapsules having an inner polyurea layer and an outer gelatin-containing layer.
  • the polyurea layer is produced by polyaddition on the inside of the gelatine layer obtained by coacervation.
  • the capsules obtained in this way have the necessary stability and tightness for use in detergents and cleaning agents due to the polyurea layer and, in addition, due to the gelatin they are sticky so that they can be attached to surfaces. Concrete stability and resistance are not mentioned.
  • a disadvantage of polyurea capsules is the unavoidable side reaction of the core materials with the diisocyanates used to produce the urea, which have to be admixed to the oil-based core.
  • microcapsules based on biopolymers are also described in the prior art, which, by adding a protective layer, achieve improved impermeability or stability with respect to environmental influences or a targeted setting of a delayed release behavior.
  • WO 2010/003762 A1 describes particles with a core-shell-shell structure.
  • the core of each particle is a poorly water-soluble or water-insoluble organic substance.
  • the shell directly encasing the core contains a biodegradable polymer and the outer shell contains at least one metal or semimetal oxide. With this structure, a biodegradable shell is obtained.
  • the microcapsules are nevertheless used in foods, cosmetics or pharmaceuticals, but cannot be used for the high-demand areas according to the invention due to a lack of tightness.
  • the unpublished PCT/EP2020/085804 describes microcapsules with a multilayer structure of the shells, which are essentially biodegradable and yet have sufficient stability and tightness to be able to be used in high-demand areas. This is achieved in that a stability layer makes up the main part of the capsule shell, which consists of naturally occurring and easily biodegradable materials, in particular such as gelatine or alginate or of materials that are ubiquitously present in nature.
  • This stability layer is combined with a barrier layer, which can consist of materials known for microencapsulation, such as melamine-formaldehyde or meth(acrylate). It has been possible to design the barrier layer with a previously unimaginable small wall thickness and still ensure adequate tightness. The proportion of the barrier layer in the overall wall is thus kept very low, so that the microcapsule wall has a biodegradability of at least 40%, measured according to OECD 301 F.
  • microcapsules with a multilayer shell structure consisting of a readily biodegradable (outer) stability layer and a thin (inner) barrier layer can be improved by using emulsion stabilizers after the inner barrier layer has been produced.
  • emulsion stabilizers are regularly used to stabilize the core material emulsion
  • treating the surface of the barrier layer encasing the core material with an emulsion stabilizer, in particular a copolymer containing certain acrylic acid derivatives leads to improved deposition of the stability layer and thus to a greater average layer thickness of the stability layer (see examples 2 to 4).
  • Such microcapsules are particularly suitable for use in detergents and cleaning agents and cosmetic preparations. It has further been found that these microcapsules are particularly suitable for the encapsulation of perfume compositions as described herein.
  • the invention relates to agents selected from detergents and cleaning agents and cosmetic preparations that contain biodegradable microcapsules comprising a core material and a shell, the shell consisting of at least one barrier layer and one stability layer, the barrier layer surrounding the core material , wherein the stability layer comprises at least one biopolymer and is arranged on the outer surface of the barrier layer, and wherein an emulsion stabilizer is arranged at the transition from barrier layer to stability layer.
  • the barrier layer and the stability layer differ in their chemical composition or their chemical structure.
  • the core material preferably comprises at least one fragrance and can be, for example, a perfume (oil) composition.
  • perfume oil composition and “perfume composition” can be used synonymously within the scope of this invention.
  • the core material comprises at least one perfume composition, the perfume composition comprising, based on the total weight of all fragrances contained in the perfume composition: a) ⁇ 10% by weight of fragrances with a CLogP of ⁇ 2.5 and a boiling point of >200° C; b) >15% by weight of at least one fragrance with a CLogP of >4.0 and a boiling point of ⁇ 275°C; and c) >30% by weight of at least one fragrance with a vapor pressure of >5 Pa at 20°C.
  • the perfume composition comprising, based on the total weight of all fragrances contained in the perfume composition: a) ⁇ 10% by weight of fragrances with a CLogP of ⁇ 2.5 and a boiling point of >200° C; b) >15% by weight of at least one fragrance with a CLogP of >4.0 and a boiling point of ⁇ 275°C; and c) >30% by weight of at least one fragrance with a vapor pressure of >5 Pa at 20°C.
  • the perfume composition can comprise, based on the total weight of all the fragrances contained in the perfume composition: a) ⁇ 8% by weight of fragrances with a CLogP of ⁇ 2.5 and a boiling point of >200°C; b) >20% by weight of at least one fragrance with a CLogP of >4.0 and a boiling point of ⁇ 275°C; and/or c) >40% by weight of at least one fragrance with a vapor pressure of >5 Pa at 20°C.
  • the agent is a washing or cleaning agent, it preferably contains at least one other component selected from surfactants, builders, enzymes and agents that enhance sap.
  • the agent is a cosmetic agent, it can also contain at least one other component, which can be selected from surfactants and skin-care substances, for example.
  • the emulsion stabilizer is a polymer or copolymer made from certain acrylic acid derivatives, N-vinylpyrrolidone; and/or styrene.
  • the polymer or copolymer consists of one or more monomers selected from:
  • Ri, R2 and R3 are selected from: hydrogen and an alkyl group having 1 to 4 carbon atoms, where Ri and R2 are especially hydrogen and R3 is especially hydrogen or methyl; and R 4 is -OX or -NR5R6, where X is hydrogen, an alkali metal, an ammonium group or a C1-C18 alkyl optionally substituted by -SO3M or -OH, where M is hydrogen, an alkali metal or ammonium, where the C1-C18 alkyl optionally substituted by -SO3M or -OH is preferably methyl, ethyl, n-butyl, (2-)ethylhexyl, 2-sulfoethyl or 2-sulfopropyl, where R5 and R6 independently represent hydrogen or an optionally substituted by -SO3M substituted C1-C10 alkyl wherein at least one of Rs and R6 is not hydrogen, preferably Rs is H and R62 is methyl-propan-2-y
  • R4 can be -OX, where X is hydrogen, C1-C10 alkyl, an alkali metal or an ammonium group, preferably C1-C10 alkyl, more preferably methyl, n-butyl, or Ethylhexyl, especially 2-ethylhexyl.
  • ethylhexyl typically includes or refers to 2-ethylhexyl and/or 3-ethylhexyl, preferably 2-ethylhexyl.
  • the emulsion stabilizer is preferably an acrylate copolymer containing 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • a suitable copolymer is available, for example, under the trade name Dimension PA 140.
  • the barrier layer is made up of one or more components selected from the group consisting of an aldehyde component, an aromatic alcohol, an amine component, an acrylate component and an isocyanate component, and the stability layer comprises at least one biopolymer.
  • Another advantage is that the improved structural absorption of the stability-providing layer by the barrier layer through the addition of the emulsion stabilizer ensures the structural (covalent) connection of all wall-forming components, so that the individual layers can be inseparably connected and viewed as a monopolymer.
  • the biodegradable capsule Due to the robustness and tightness of the biodegradable capsule, it can be used in a large number of products in the field of detergents and cleaning agents as well as cosmetics. Another advantage of the microcapsules described is the light coloring of dispersions of these microcapsules.
  • the dispersions containing biodegradable microcapsules as described herein have a color locus with an L* value of at least 50 in the L*a*b* color space.
  • the invention relates to the use of detergents and cleaning agents according to the first aspect in a method for conditioning textiles or for cleaning textiles and/or hard surfaces.
  • the invention relates to the cosmetic use of agents according to the first aspect.
  • FIG. 1 shows a light micrograph of various microcapsule dispersions, each on the left, magnified 50 times and 500 times, taken with an Olympus BX 50 microscope.
  • FIG. 2 shows two microscopic photographs of the microcapsule dispersions Slurry 2 and MK1 with auxiliary lines for determining the thickness of the stability layer of the microcapsules and details of the measured thicknesses.
  • 3 shows a diagram of the course of the biological degradation according to OECD 301 F over 60 days after washing the microcapsule dispersions according to the invention and references.
  • A) the degradation of Slurry 2 and Slurry 3 is shown as well as the degradation of ethylene glycol and walnut shell flour as positive controls.
  • B) Slurry 2 and Slurry 3 are shown in comparison with the MK1 reference capsule.
  • FIG. 4 shows a diagram of the storage stability of various microcapsule dispersions as described in Example 5.
  • FIG. 5 shows the diagram of the development of the L*a*b* of the microcapsule dispersions Slurry 3 and 3A over a period of 8 days.
  • Barrier layer refers to the layer of a microcapsule wall that is essentially responsible for the tightness of the capsule shell, i. H. Prevents the core material from escaping.
  • Biodegradability refers to the ability of organic chemicals to be broken down biologically, i.e. by living beings or their enzymes. In the ideal case, this chemical metabolism proceeds completely up to mineralization, but it can also stop in the case of transformation products that are stable in degradation.
  • the tests of the OECD test series 301 (A-F) demonstrate rapid and complete biodegradation (ready biodegradability) under aerobic conditions. Different test methods are available for readily or poorly soluble as well as for volatile substances.
  • the manometric respiration test (OECD 301 F) is used within the scope of the application.
  • the basic biodegradability inherent biodegradability
  • OECD 302 C the measurement standard OECD 302 C.
  • microcapsule walls are referred to, measured according to OECD 301 F biodegradability of at least 40% within 60 days. From a limit value of at least 60% degradation within 60 days measured according to OECD 301 F, microcapsule walls are also referred to as rapidly biodegradable.
  • a “biopolymer” is a naturally occurring polymer, such as a polymer found in a plant, fungus, bacterium, or animal.
  • the biopolymers also include modified polymers based on naturally occurring polymers.
  • the biopolymer can be obtained from the natural source or it can be artificially produced.
  • Tightness against a substance, gas, liquid, radiation or similar is a property of material structures. According to the invention, the terms “tightness” and “tightness” are used synonymously. Tightness is a relative term and always refers to given framework conditions.
  • Emmulsion stabilizer are additives used to stabilize emulsions.
  • the emulsion stabilizers can be added in small amounts to the aqueous or oily phase (of emulsions), whereby they are enriched in the interface in a phase-oriented manner and, on the one hand, facilitate the breakdown of the inner phase by reducing the interfacial tension and, on the other hand, increase the breakdown resistance of the emulsion.
  • (meth)acrylate designates both methacrylates and acrylates.
  • microcapsules is understood according to the invention as meaning particles containing an inner space or core which is filled with a solid, gelled, liquid or gaseous medium and surrounded (encapsulated) by a continuous shell (shell) of film-forming polymers. These particles preferably have small dimensions.
  • microcapsules core-shell capsules or simply “capsules” are used interchangeably.
  • Microencapsulation is a manufacturing process in which small and very small portions of solid, liquid or gaseous substances are surrounded by a shell made of polymer or inorganic wall materials.
  • the microcapsules obtained in this way can have a diameter of a few millimeters to less than 1 ⁇ m. However, it can be preferred that the diameter is greater than 100 nm or greater than 500 nm.
  • the microcapsule according to the invention has a multi-layer “shell”.
  • the shell encasing the core material of the microcapsule is also regularly referred to as the “wall” or “shell”.
  • microcapsules according to the invention with a multilayer shell can also be referred to as multilayer microcapsules or multilayer microcapsule system, since the individual layers can also be viewed as individual shells. "Multi-layered” and “multi-layered” are therefore used synonymously.
  • Stability layer refers to the layer of a capsule wall that is essentially responsible for the stability of the capsule shell, i. H. usually makes up the main part of the shell.
  • “Wall builders” are the components that make up the microcapsule wall.
  • the biodegradable microcapsules which are used according to the first aspect of the invention in detergents and cleaning agents and cosmetics, comprising a core material and a shell, the shell consisting of at least one barrier layer and a stability layer, the barrier layer surrounding the core material, the Stability layer comprises at least one biopolymer, and is arranged on the outer surface of the barrier layer, and wherein an emulsion stabilizer is arranged at the transition from barrier layer to stability layer.
  • This arrangement can consist of an intermediate layer of emulsion stabilizer, which can be continuous or discontinuous, covering part or all of the inner barrier layer.
  • only individual molecules of the emulsion stabilizer can be arranged on the surface of the barrier layer in such a way that they mediate a bond between the stability layer and the barrier layer.
  • the emulsion stabilizer acts here as a mediator.
  • the microcapsule shells according to the invention have a significantly increased thickness of the stability layer due to the use of the emulsion stabilizer.
  • the proportion of natural components in the capsule is further increased compared to the multilayer microcapsules described above.
  • the surface of the barrier layer is brought into contact with the emulsion stabilizer before the stability layer is formed.
  • the capacity of the surface for the structural connection of the stability layer is increased.
  • the emulsion stabilizer attaches itself to the non-polar surface of the barrier layer, in particular a melamine-formaldehyde layer, and thus offers the biopolymers of the stability layer a framework for deposition on the surface. This not only increases the mean layer thickness of the stability layer produced with the biopolymer, but also incorporates the emulsion stabilizer at the interface between the stability layer and the barrier layer. Proceeding from this theory, in principle any emulsion stabilizer can be used as a mediator for the production of the microcapsules according to the invention.
  • the emulsion stabilizer is a polymer or copolymer consisting of one or more monomers selected from: (1) Acrylic acid derivatives of general formula (I)
  • Ri, R2 and R3 are selected from: hydrogen and an alkyl group having 1 to 4 carbon atoms, where Ri and R2 are especially hydrogen and R3 is especially hydrogen or methyl; and R4 is -OX or -NR5R6, where X is hydrogen, an alkali metal, an ammonium group or a C1-C18 alkyl optionally substituted by -SO3M or -OH, for example C1-C10 alkyl, where M is hydrogen, a alkali metal or ammonium, where the C1-C18 alkyl optionally substituted by -SO3M or -OH, for example C1-C10 alkyl, is preferably methyl, ethyl, n-butyl, (2-)ethylhexyl, 2-sulfoethyl or 2-sulfopropyl, where Rs and R6 are independently hydrogen or a C1-C10 alkyl optionally substituted by -SO3M, where at least one of Rs and R
  • R1, R2 and R3 can be ethyl, n-propyl, i-propyl and n-butyl.
  • Ri and R2 are hydrogen and R3 is hydrogen or methyl.
  • R3 is an acrylate (hydrogen) or methacrylate (methyl).
  • the C1-C18 alkyl groups optionally substituted by -OH or -SO3M for X are preferably selected from methyl, ethyl, C2-4 -hydroxyalkyl, C2-4 -sulfoalkyl and C4-C18 alkyl groups.
  • the C 2-4 hydroxyalkyl groups can be selected from ethyl, n-propyl, i-propyl and n-butyl.
  • Examples of unsubstituted C 4-18 -alkyl groups are the n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, ethylhexyl, octyl, decyl, dodecyl or stearyl groups to name.
  • the n-butyl and ethylhexyl are particularly suitable.
  • the ethylhexyl is in particular 2-ethylhexyl.
  • 2-Sulfoethyl and 3-Sulfopropyl can be mentioned in particular as C.sub.2-4-Sulfoalkyl groups.
  • R4 is -NR5R6 where Rs is H and R62 is methyl-propan-2-yl-1-sulfonic acid.
  • R 1 , R 2 and R 3 are in particular hydrogen.
  • R4 is -OX and X is hydrogen.
  • R 1 , R 2 and R 3 are in particular hydrogen (acrylic acid).
  • R3 is methyl (methacrylate).
  • the acrylic acid derivatives is R4-OX and X is methyl.
  • R 1 , R 2 and R 3 are in particular hydrogen (methyl acrylate).
  • R4 is -OX and X is 2-ethylhexyl.
  • R 1 , R 2 and R 3 are in particular hydrogen (ethyl hexacrylate).
  • R4 is -OX and X is n-butyl.
  • R 1 , R 2 and R 3 are in particular hydrogen (n-butyl acrylate).
  • R4 is -OX and X is 2-sulfoethyl.
  • R 1 , R 2 and R 3 are in particular hydrogen (sulfoethyl acrylate).
  • R4 is -OX and X is 3-sulfopropyl.
  • Ri and R2 are hydrogen and R3 is methyl (sulfopropyl (meth)acrylate).
  • R4 is -OX, where X is hydrogen, C1-C10 alkyl, an alkali metal or an ammonium group, preferably C1-C10 alkyl, more preferably methyl, n-butyl, or ethylhexyl, especially 2 -ethylhexyl.
  • n is an integer of at least 3.
  • n can be greater than 5, 10, 20, 30, 40, 50, 60, 70, 80, or 100, for example. In one embodiment, n ranges from 5 to 5000. In one embodiment, n ranges from 10 to 1000
  • the group of these polymers and copolymers represents a useful generalization of the copolymers present in Dimension PA 140.
  • the emulsion stabilizer is preferably an acrylate copolymer which contains at least two different monomers of the formula (I).
  • the copolymer contains AMPS, optionally in combination with (meth)acrylic acid and/or at least one alkyl (meth)acrylate.
  • the copolymer contains AMPS and one or more monomers selected from acrylate, methacrylate, methyl acrylate, ethyl hexacrylate, n-butyl acrylate, N-vinylpyrrolidone and styrene.
  • the copolymer contains AMPS, acrylate, methyl acrylate, and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and ethyl hexacrylate. According to one embodiment, the copolymer contains AMPS, methyl acrylate, N-vinylpyrrolidone and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and ethyl hexacrylate. According to one embodiment, the copolymer contains AMPS, methyl acrylate, N-vinylpyrrolidone and styrene.
  • the copolymer contains AMPS, methyl acrylate and styrene. According to one embodiment, the copolymer contains AMPS, methacrylate and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and n-butyl acrylate.
  • the emulsion stabilizer is a copolymer as defined in EP0562344B1, which is incorporated herein by reference.
  • the emulsion stabilizer is a copolymer containing a) AMPS, sulfoethyl or sulfopropyl (meth)acrylate or vinyl sulfonic acid, in particular in a proportion of 20 to 90%; b) a vinylically unsaturated acid, in particular with a proportion of 0 to 50%; c) methyl or ethyl acrylate or methacrylate, C 2-4 -hydroxyalkyl acrylate or N-vinylpyrrolidone, in particular with a proportion of 0 to 70% and d) styrene or C 4 -is-alkyl acrylate or C 4-18 -alkyl methacrylate, in particular with a share of 0.1 to 10%.
  • the emulsion stabilizer is a copolymer containing a) 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl or sulfopropyl (meth)acrylate or vinylsulfonic acid, in particular with a proportion of 40 to 75% b) acrylic acid or methacrylic acid, in particular with a proportion from 10 to 40% c) methyl or ethyl acrylate or methacrylate, C 2-4 -hydroxyalkyl acrylate or N-vinylpyrrolidone, in particular with a proportion of 10 to 50% and d) 0.5 to 5% styrene or C 4 -i8-alkyl acrylate or methacrylate, in particular with a proportion of 0.5 to 5%.
  • the emulsion stabilizer is a copolymer containing a) 40 to 75% of 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl or sulfopropyl (meth)acrylate or vinylsulfonic acid, in particular with a proportion of 40 to 75% b) acrylic acid or methacrylic acid, 10 to 30% c) methyl or ethyl acrylate or methacrylate or N-vinylpyrrolidone, in particular in a proportion of 10 to 50% and d) styrene or C 4 -is-alkyl acrylate or methacrylate, in particular in a proportion from 0.5 to 5%.
  • a suitable copolymer is available, for example, under the trade name Dimension PA 140 (from Solenis).
  • the emulsion stabilizer does not consist of or include N-vinyl pyrrolidone, polyvinyl pyrrolidine homopolymer, or polyvinyl pyrrolidine copolymer.
  • the proportion of the emulsion stabilizer used in the components used for the microencapsulation can be in the range from 0.1 to 15% by weight.
  • the proportion of the emulsion stabilizer used can be 0.1% by weight, 0.2% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt% -%, 12% by weight, 13% by weight, 14% by weight or 15% by weight.
  • the emulsion stabilizer is used with a proportion of the components used for the microencapsulation in the range from 0.25% by weight to 5% by weight. In a particularly preferred embodiment, the proportion of the emulsion stabilizer used is in the range from 0.5% by weight to 4% by weight.
  • the proportion of the emulsion stabilizer based on the total weight of the microcapsule wall is in the range from 0.5 to 15.0% by weight.
  • the proportion of the emulsion stabilizer used can be 0.5% by weight, 1.0% by weight, 1.5% by weight, 2.0% by weight, 2.5% by weight, 3% by weight -%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt% , 12% by weight, 13% by weight, 14% by weight or 15% by weight.
  • the proportion of the wall-forming components of the microcapsule shell is in the range from 1% by weight to 11% by weight. %. In a particularly preferred embodiment, the proportion of the emulsion stabilizer used is in the range from 2% by weight to 7% by weight.
  • the barrier layer preferably contains, as a wall former, one or more components selected from the group consisting of an aldehyde component, an aromatic alcohol, an amine component, an acrylate component. Production processes for producing microcapsules with these wall materials are known to those skilled in the art. A polymer selected from a polycondensation product of an aldehyde component with one or more aromatic alcohols and/or amine components can be used to produce the barrier layer.
  • the small wall thickness of the barrier layer can be achieved in particular with a melamine-formaldehyde layer containing aromatic alcohols or m-aminophenol. Consequently, the barrier layer preferably comprises an aldehyde component, an amine component and an aromatic alcohol.
  • amine-aldehyde compounds in the barrier layer in particular melamine-formaldehyde, has the advantage that these compounds form a hydrophilic surface with a high proportion of hydroxyl functionality, which thus ensures basic compatibility with the components of the first layer ( Stability layer) such as biodegradable proteins, polysaccharides, chitosan, lignins and phosphazenes but also inorganic wall materials such as CaC03 and polysiloxanes.
  • polyacrylates in particular from the components styrene, vinyl compounds, methyl methacrylate, and 1, 4-butanediol acrylate, methacrylic acid, by initiation, for example, with t-butyl hydroperoxide in a free-radically induced polymerization (polyacrylates) are generated as a microcapsule wall that has a hydrophilic surface with a high Form proportion of hydroxy functionality, which are therefore just as compatible with the components of the stability layer according to the invention.
  • a wall former of the barrier layer is an aldehyde component.
  • the aldehyde component of the barrier layer is selected from the group consisting of formaldehyde, glutaraldehyde, succinaldehyde, furfural and glyoxal. Microcapsules have already been successfully produced with all of these aldehydes (see WO 2013 037 575 A1), so it can be assumed that capsules with a similar density as with formaldehyde are obtained with them.
  • the proportion of the aldehyde component for wall formation based on the total weight of the barrier layer should be in the range from 5% by weight to 50% by weight.
  • the proportion of the aldehyde component can be 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight or 15% by weight 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%. Outside these limits, it is considered that a sufficiently stable and dense thin film cannot be obtained.
  • the concentration of the aldehyde component in the barrier layer is preferably in the range from 10% by weight to 30% by weight.
  • the concentration of the aldehyde component in the barrier layer is particularly preferably in the range from 15% by weight to 20% by weight.
  • melamine, melamine derivatives and urea or combinations thereof come into consideration as the amine component in the barrier layer.
  • Suitable melamine derivatives are etherified melamine derivatives and methylolated melamine derivatives. Melamine in the methylolated form is preferred.
  • the amine components can be used, for example, in the form of alkylated mono- and polymethylol-urea precondensation products or partially methylolated mono- and polymethylol-1,3,5-triamono-2,4,6-triazine precondensation products such as Dimension SD® (from Solenis).
  • the amine component is melamine.
  • the amine component is a combination of melamine and urea.
  • the aldehyde component and the amine component can be present in a molar ratio ranging from 1:5 to 3:1.
  • the molar ratio can be 1:5, 1:4.5, 1:4, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.8, 1:1.6, 1:1.4, 1:1.35,1; 1.3, 1:1.2, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1.
  • the molar ratio is preferably in the range from 1:3 to 2:1.
  • the molar ratio of the aldehyde component and the amine component can particularly preferably be in the range from 1:2 to 1:1.
  • the aldehyde component and the amine component are generally used in a ratio of about 1:1.35.
  • This molar ratio allows complete reaction of the two reactants and results in a high tightness of the capsules.
  • aldehyde-amine capsule walls with a molar ratio of 1:2 are also known. These capsules have the advantage that the proportion of the highly crosslinking aldehyde, in particular formaldehyde, is very low. However, these capsules are less tight than the capsules with a ratio of 1:1.35. Capsules with a ratio of 2:1 have an increased tightness, but have the disadvantage that the aldehyde component is partly unreacted in the capsule wall and the slurry.
  • the proportion of the amine component(s) (e.g. melamine and/or urea) in the barrier layer is in the range from 20% by weight to 85% by weight, based on the total weight of the barrier layer.
  • the proportion of the amine component can be 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%.
  • the proportion of the amine component in the barrier layer, based on the total weight of the barrier layer is in the range from 40% by weight to 80% by weight.
  • the proportion of the amine component is particularly preferably in the range from 55 to 70% by weight.
  • the aromatic alcohol With the aromatic alcohol, it is possible to greatly reduce the wall thickness of the barrier layer made up of the amine component and the aldehyde component in order to still obtain a layer that has the necessary tightness and is stable enough, at least in combination with the stability layer.
  • the aromatic alcohols give the wall increased tightness, since their highly hydrophobic aromatic structure makes it difficult for low-molecular substances to diffuse through.
  • particularly suitable aromatic alcohols are phloroglucinol, resorcinol or m-aminophenol.
  • the aromatic alcohol is selected from the group consisting of phloroglucinol, resorcinol and aminophenol.
  • the aromatic alcohol is used in a molar ratio to the aldehyde component in the range from (alcohol:aldehyde) 1:1 to 1:20, preferably in the range from 1:2 to 1:10 .
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 1.0% by weight to 20% by weight.
  • the proportion of the aromatic alcohol can be 1.5% by weight, 2.0% by weight, 2.5% by weight, 3.0% by weight, 4.0% by weight, 5, 0 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt% 13 wt% -%, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight,
  • the aromatic alcohols Due to their aromatic structure, the aromatic alcohols give the capsule wall a color that increases with the proportion of aromatic alcohol. Such coloring is undesirable in a number of applications.
  • the aromatic alcohols are susceptible to oxidation, which leads to a change in color over time. As a result, the undesired coloration of the microcapsules can hardly be compensated for with a dye. For this reason, the aromatic alcohols should not be used above 20.0% by weight. Below 1.0% by weight, no effect on the tightness can be detected.
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 5.0% by weight to 15.0% by weight.
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 6% by weight to 16.0% by weight. In particular, the proportion of the aromatic alcohol in the barrier layer is in the range from 10% by weight to 14.0% by weight.
  • the aldehyde component of the barrier layer can be used together with an aromatic alcohol such as resorcinol, phloroglucinol or m-aminophenol as the wall-forming component(s), i.e. without the amine component(s).
  • an aromatic alcohol such as resorcinol, phloroglucinol or m-aminophenol
  • the barrier layer contains melamine, formaldehyde and resorcinol. In one embodiment, the barrier layer of the microcapsules contains melamine, urea, formaldehyde and resorcinol. In a preferred embodiment, the barrier layer contains melamine in the range from 25 to 40% by weight, formaldehyde in the range from 15 to 20% by weight and resorcinol in the range from 10 to 14% by weight and optionally urea in the range from 25 to 35% by weight. The proportions relate to the amounts used to form the wall of the layer and are based on the total weight of the barrier layer without protective colloid.
  • an emulsion stabilizer is preferably used as a protective colloid to encapsulate the core material with the barrier layer composed of an aldehyde component, an amine component and an aromatic alcohol.
  • the emulsion stabilizer used as protective colloid can be a polymer or copolymer as defined above as a mediating agent.
  • the protective colloid is a copolymer AMPS) Dimension® PA 140, from Solenis ) or its salts. In one embodiment, the same copolymer is used as the protective colloid and as the mediator.
  • melamine, melamine derivatives and urea or combinations thereof come into consideration as the amine component in the barrier layer.
  • Suitable melamine derivatives are etherified melamine derivatives and methylolated melamine derivatives. Melamine in the methylolated form is preferred.
  • the amine components can be used, for example, in the form of alkylated mono- and polymethylol-urea precondensation products or partially methylolated mono- and polymethylol-1,3,5-triamono-2,4,6-triazine precondensation products such as Dimension SD® (from Solenis).
  • the amine component is melamine.
  • the amine component is a combination of melamine and urea.
  • the stability layer forms the main component of the microcapsule shell and thus ensures high biodegradability according to OECD 301 F of at least 40% within 60 days.
  • a mural for Biopolymers suitable for the stability layer are proteins such as gelatin, whey protein, plant storage protein; polysaccharides such as alginate, gum arabic-modified gum, chitin, dextran, dextrin, pectin, cellulose, modified cellulose, hemicellulose, starch or modified starch; phenolic macromolecules such as lignin; polyglucosamines such as chitosan, polyvinyl esters such as polyvinyl alcohols and polyvinyl acetate; Phosphazenes and polyesters such as polylactide or polyhydroxyalkanoate.
  • the biopolymers can be selected appropriately for the respective application in order to form a stable multi-layer shell with the material of the stability layer.
  • the biopolymers can be selected in order to achieve compatibility with the chemical conditions of the area of application.
  • the biopolymers can be combined in any way in order to influence the biodegradability or, for example, the stability and chemical resistance of the microcapsule.
  • the shell of the microcapsules has a biodegradability of 50% according to OECD 301F. In a further embodiment, the shell of the microcapsule has a biodegradability of at least 60% (OECD 301 F). In another embodiment, the biodegradability is at least 70% (OECD 301 F). The biodegradability is measured over a period of 60 days. In the extended degradation process ("enhanced ready biodegredation"), the biodegradability is measured over a period of 60 days (see Opinion on an Annex XV dossier proposing restrictions on intentionally-added microplastics of June 11, 2020 ECHA/RAC/RES- 0-0000006790- 71-01/F).
  • the microcapsules are preferably freed from residues by washing before the biodegradability is determined.
  • replica microcapsules for this test are made with an inert, non-biodegradable core material such as perfluorooctane (PFO) in place of the perfume oil.
  • PFO perfluorooctane
  • the capsule dispersion is prepared by centrifuging three times and redispersing in dist. water washed. To do this, the sample is centrifuged (e.g. for 10 min at 12,000 rpm). After sucking off the clear supernatant, it is filled up with water and the sediment is redispersed by shaking.
  • biodegradability such as rapidly degradable ethylene glycol or natural walnut shell flour with the typical gradual degradation of a complex mixture of substances.
  • the microcapsule according to the invention shows a similar, preferably better, biodegradability over a period of 28 or 60 days than the walnut shell flour.
  • Residues in the microcapsule dispersions are substances that are used in the manufacture of the microcapsules and have a non-covalent interaction with the shell, such as deposition aids, preservatives, emulsifiers/protective colloids, excess ingredients. These residues have a proven impact on the biological Degradability of microcapsule dispersions. For this reason, washing is necessary before determining biodegradability.
  • the capsules were packed using the method described in Gasparini et al. 2020 based on Py-GC-MS for polymer-encapsulated fragrances.
  • This method incorporates a multi-step purification protocol for polymers from complex samples such as microcapsule dispersions and enables quantification of residual volatile components suspected to be non-covalently bound into the 3D polymer network and therefore amenable to other standard methods (e.g. SPME-GC -MS or TGA) are not quantifiable.
  • a high biodegradability value according to the invention is achieved on the one hand by the wall-forming agents used and on the other hand by the structure of the shell according to the invention. Because the use of a certain percentage of biopolymers does not automatically lead to a corresponding biodegradability value. This depends on how the biopolymers are present in the shell.
  • the stability layer contains gelatin as a biopolymer.
  • the stability layer contains alginate as a biopolymer.
  • the stability layer contains gelatin and alginate as biopolymers.
  • both gelatin and alginate are suitable for the production of microcapsules according to the invention with high biodegradability and high stability.
  • an emulsion stabilizer in particular a copolymer containing AMPS, leads to a strong increase in the layer thickness of the stability layer (see Examples 1-4).
  • Other suitable combinations of natural components in the first layer (stability layer) are gelatin and gum arabic.
  • the stability layer contains one or more curing agents.
  • Curing agents according to the invention are aldehydes such as glutaraldehyde, formaldehyde and glyoxal and tannins, enzymes such as transglutaminase and organic anhydrides such as maleic anhydride, epoxy compounds, polyvalent metal cations, amines, polyphenols, maleimides, sulfides, phenol oxides, hydrazides, isocyanates, isothiocyanates, N-hydroxysulfosuccinimide derivatives, carbodiimide - Derivatives, and polyols.
  • the curing agent is preferably glutaraldehyde due to its very good crosslinking property.
  • the curing agent glyoxal is preferred because of its good crosslinking properties and, compared to glutaraldehyde, lower toxicological classification. Through the use of hardening agents, a higher tightness of the stability layer is achieved. However, curing agents lead to reduced biodegradability of the natural polymers.
  • the barrier layers do not contain any isocyanates.
  • Some isocyanates such as methylenediphenyl isocyanate (MDI), hexamethylene diisocyanate (HDI) or toluene-2,4-diisocyanate (TDI) have a certain toxicity and should be viewed critically from the point of view of occupational safety. Furthermore, side reactions with components of the core material can also occur in the case of isocyanates.
  • MDI methylenediphenyl isocyanate
  • HDI hexamethylene diisocyanate
  • TDI toluene-2,4-diisocyanate
  • the barrier layers according to the invention contain no silane monomers, silane oligomers or silicates.
  • these components can be disadvantageous for the formation of the capsule according to the invention.
  • silicates such as TEOS and TMOS (tetraethyl orthosilicate or methyl orthosilicate) enter into side reactions with their components, for example fragrances, when added to an oil phase and thus the properties of the oil phase, i.e. the core material (e.g. the fragrance oil), for example influence negatively.
  • TEOS and TMOS are to be classified as critical for reasons of occupational safety and are preferably not used according to the invention.
  • the barrier layers do not contain a silicone-melamine-polyurethane copolymer.
  • Side reactions with the core material, i.e. the oil phase, in particular the fragrances contained therein, can also occur with silicone-melamine-polyurethane copolymers.
  • a silicone-melamine-polyurethane copolymer is also to be classified as critical with regard to occupational safety.
  • the proportion of the hardening agent in the stability layer is less than 25% by weight.
  • the proportions of the components of the layers relate to the total weight of the layer, i.e. the total dry weight of the components used for production, without taking into account the components used in production that are not or only slightly incorporated into the layer, such as surfactants and protective colloids. Above this value, the biodegradability according to the invention according to OECD 301 F cannot be guaranteed.
  • the proportion of the curing agent in the stability layer can be, for example, 1.0% by weight, 2.0% by weight, 3.0% by weight, 4.0% by weight, 5.0% by weight, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% %, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23% by weight or 24 % by weight.
  • the proportion of the curing agent in the stability layer is preferably in the range from 1 to 15% by weight.
  • This proportion leads to effective cross-linking of the gelatine and, in a quantitative reaction, results in as little residual monomer as possible being formed.
  • the range from 9 to 12% by weight is particularly preferred, it ensures the required degree of crosslinking and a stable coating of the barrier layer in order to buffer the otherwise sensitive barrier layer and has only a small amount of residual aldehyde, which can be removed in a subsequent alkaline setting of the slurry via an aldol reaction is dismantled.
  • the stability layer contains gelatin and glutaraldehyde. According to another embodiment, the stability layer contains gelatin, alginate and glutaraldehyde. In an additional embodiment, the stability layer contains gelatin and glyoxal. According to a further embodiment, the stability layer contains gelatin, alginate and glyoxal.
  • the exact chemical composition of the stability layer is not critical. However, the effect according to the invention is preferably achieved with polar biopolymers.
  • the use of the emulsion stabilizer according to the invention on the surface of the barrier layer significantly increases the average thickness of the stability layer.
  • the mean thickness of the stability layer is at least 1 ⁇ m.
  • the mean thickness of the stability layer can be 1 ⁇ m, 1.2 ⁇ m, 1.4 ⁇ m, 1.6 ⁇ m, 1.8 ⁇ m, 2 ⁇ m, 2.2 ⁇ m, 2.4 ⁇ m, 2.6 ⁇ m, 2.8 ⁇ m , 3pm, 3.5pm, 4pm, 4.5pm, 5pm, 5.5pm, 6pm, 6.5pm, 7pm, 7.5pm, 8pm, 8.5pm, 9 pm, 9.5 pm, or 10 pm.
  • the stability layer often has an elliptical shape in cross section, so the thickness of the stability layer varies across the microcapsule surface. Therefore, an average thickness of the microcapsules is calculated. Above this, the deposition varies from microcapsule to microcapsule. This is taken into account by determining the average thickness of a plurality of microcapsules and calculating the average from this. Thus, the average thickness referred to here is, strictly speaking, an average average thickness.
  • the layer thickness of the stability layer can be determined in two ways. First of all, the light microscopic approach should be mentioned here, i.e. the direct, optical measurement of the observed layer thickness using a microscope and appropriate software. A large number of microcapsules of a dispersion are measured and, due to the variance within the capsules, at least the diameter of each individual microcapsule.
  • a second possibility is the measurement of the particle size distribution by means of laser diffraction.
  • the modal value of a particle size distribution without the layer to be measured can be compared to the modal value of a particle size distribution with the layer to be measured.
  • the increase in this mode reflects the increase in the hydrodynamic diameter of the main fraction of microcapsules measured. Forming the difference from the two measured modal values ultimately results in twice the layer thickness of the layer.
  • the average thickness of the stability layer is at least 2 gm.
  • stability layers with an average thickness of 6 gm or more can be formed.
  • the mean thickness of the stability layer is at least 3 ⁇ m.
  • the microcapsules according to the invention are very tight. According to one embodiment, the microcapsules are tight enough to ensure that at most 50% by weight of the core material used escapes after storage for a period of 4 weeks at a temperature of 0 to 40.degree.
  • the microcapsules according to the invention have a tightness that ensures that at most 80% by weight of the core material used escapes after storage for a period of 12 weeks at a temperature of 0 to 40° C., preferably at most 75% by weight and more preferably at most 70% by weight. In various embodiments, the microcapsules according to the invention still contain at least 20% by weight, preferably at least 25% by weight and in particular at least 30% by weight of the core material used after storage for a period of 12 weeks at a temperature of 0 to 40°C.
  • the microcapsules according to the invention after storage for a period of 4 weeks at a temperature of 0 to 40° C., still contain at least 50% by weight of the core material used.
  • the tightness also depends on the type of core material.
  • the tightness of the microcapsules according to the invention was determined according to the invention for the fragrance oil Weiroclean from Kitzing, since the chemical properties of this fragrance oil are representative of microencapsulated fragrance oils. Weiroclean has the following components (with proportion based on the total weight):
  • the core material is hydrophobic.
  • the core material can be solid or liquid. In particular, it is liquid. It is preferably a liquid hydrophobic core material.
  • the core material is a fragrance or the core material comprises at least one fragrance. Fragrance or perfume oils optimized for microencapsulation for the detergent and cleaning agent sector, such as the fragrance formulation Weiroclean (from Kurt Kitzing GmbH), are particularly preferred.
  • the fragrances can be used in the form of a solid or liquid formulation, but especially in liquid form.
  • Perfumes that can be used as the core material are not subject to any particular restrictions.
  • individual fragrance compounds of natural or synthetic origin for example of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used.
  • Perfume compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate and jasmacyclate.
  • DMBCA dimethylbenzylcarbinyl acetate
  • the ethers include, for example, benzyl ethyl ether and ambroxan
  • the aldehydes include the abovementioned e.g. the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde (3-(4-propan-2-ylphenyl)butanal), Lilial and bourgeonal, the ketones e.g.
  • Suitable perfume aldehydes can be selected from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal or cyclamenaldehyde (3-(4-isopropylphenyl)-2- methylpropanal), Nympheal (3-(4-isobutyl-2-methylphenyl)propanal), Ethylvanillin, Florhydral (3-(3- isopropylphenyl)butanal]), Trifernal (3-phenylbutyraldehyde), Helional (3-(3,4- methylenedioxyphenyl)-2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3-
  • Suitable perfume ketones include but are not limited to methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4- on), Calone
  • the core materials can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • fragrances such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • clary sage oil chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • fragrances that can be included in the present invention in the agents according to the invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champaca blossom oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, Geranium Oil, Gingergrass Oil, Guaiac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calamus Oil, Chamomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Copaiva Balm Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lavender Oil, Lemongrass Oil, Lime Oil, Mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, oliban
  • At least one perfume composition which is in particular liquid, is used as the core material.
  • the perfume composition encapsulated in the microcapsules described preferably comprises, based on the total weight of all the fragrances contained in the perfume composition: a) ⁇ 10% by weight, preferably ⁇ 8% by weight, of fragrances with a CLogP of ⁇ 2.5 and a boiling point from >200°C; b) >15% by weight, preferably >20% by weight, of at least one fragrance with a CLogP of >4.0 and a boiling point of ⁇ 275°C; and c) >30% by weight, preferably >40% by weight, of at least one fragrance with a vapor pressure of >5 Pa at 20°C.
  • the CLogP value is the liquid-liquid partition coefficient for the n-octanol-water system and a measure of the relationship between lipophilicity and hydrophilicity of a substance.
  • a value greater than 1 denotes a more lipophilic substance, a value below 1 a substance that is more soluble in water than in n-octanol.
  • the ClogP value can be calculated for each substance using suitable programs that are commercially available. Unless otherwise stated, the values given herein are determined using the EPI SUITETM program (v4.11) with the KOWWINTM v1.68 module.
  • boiling point was determined using the EPI SUITETM program (v4.11) with the MPBPWIN v.1.43 module (adapted Stein and Brown Method).
  • the vapor pressure at 20°C was determined using the program EPI SUITETM (v4.11) with the module MPBPWIN v.1 .43 (modified grain method).
  • fragrances include, but are not limited to:
  • group b) fragrances include, but are not limited to:
  • group c) fragrances include, but are not limited to:
  • Mixtures of fragrances are preferably used, for example at least two or more different fragrances from groups b) and/or at least two or more different fragrances from group c).
  • the proportion of fragrances from group a) can also be less than 6, less than 5, less than 4, less than 3, less than 2 or less than 1% by weight.
  • the perfume composition may contain no fragrances from group a).
  • the perfume composition contains fragrances from group a), but in amounts below the upper limits given here.
  • the fragrances of groups b) and c) together can make up at least 60, preferably at least 65, at least 70, at least 75, at least 80, at least 85 or at least 90% by weight of the total fragrances in the perfume composition.
  • fragrances in the perfume composition relate to the sum of all fragrances in the perfume composition, unless stated otherwise. Alternatively, they can also relate to the total weight of the perfume composition, for example if it contains formulation auxiliaries.
  • further fragrances can be used as components of the perfume composition as long as features a)-c) are met.
  • additional fragrances are not subject to any particular restrictions.
  • individual fragrance compounds of natural or synthetic origin for example of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used.
  • the core materials can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • clary sage oil chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
  • the tightness of the capsule wall can be influenced by the choice of shell components.
  • the microcapsules have a tightness that allows leakage of at most 45% by weight, at most 40% by weight, at most 35% by weight, at most 30% by weight, at most 25% by weight, at most 20% by weight of the core material used when stored over a period of 4 weeks at a temperature of 0 to 40 °C.
  • the microcapsules still contain at least 55% by weight, preferably at least 60% by weight, more preferably at least 65% by weight, even more when stored for a period of 4 weeks at a temperature of 0 to 40°C preferably at least 70% by weight, even more preferably at least 75% by weight, even more preferably at least 80% by weight of the core material used.
  • microcapsules are stored in a model formulation that corresponds to the target application.
  • the microcapsules are also storage stable in the product in which they are used. For example in detergents, fabric softeners or cosmetic products.
  • the guide formulations for these products are known to those skilled in the art.
  • the pH around the microcapsules during storage is in the range of 2 to 12.
  • microcapsule shells according to the invention have at least two layers, i.e. they can be, for example, two-layered, three-layered, four-layered, or five-layered.
  • the microcapsules preferably have two or three layers.
  • the microcapsule has a third layer which is arranged on the outside of the stability layer.
  • This third layer can be used to tailor the surface properties of the microcapsule for a specific application. Mention should be made here of the improvement in the adhesion of the microcapsules to a wide variety of surfaces and a reduction in agglomeration.
  • the third layer also binds residual aldehyde quantities, thereby reducing the content of free aldehydes in the capsule dispersion. Furthermore, it can provide additional (mechanical) stability or further increase the tightness.
  • the third Layer containing a component selected from amines, organic salts, inorganic salts, alcohols, ethers, polyphosphazenes and noble metals.
  • Precious metals increase the tightness of the capsules and can give the microcapsule surface additional catalytic properties or the antibacterial effect of a silver layer.
  • Organic salts especially ammonium salts, lead to cationization of the microcapsule surface, which means that it adheres better to e.g. textiles.
  • alcohols When incorporated via free hydroxyl groups, alcohols also lead to the formation of H bridges, which also allow better adhesion to substrates.
  • An additional polyphosphazene layer or a coating with inorganic salts, e.g. silicates leads to an additional increase in impermeability without affecting biodegradability.
  • the third layer contains activated melamine.
  • the melamine catches possible free aldehyde components of the stability and/or barrier layer, increases the tightness and stability of the capsule and can also influence the surface properties of the microcapsules and thus the adhesion and agglomeration behavior.
  • the proportion of the barrier layer in the shell is at most 30% by weight.
  • the proportion of the barrier layer in the shell can be, for example, 30% by weight, 28% by weight, 25% by weight, 23% by weight, 20% by weight. 18 wt%, 15 wt%. 13%, 10%, 8%, or 5% by weight.
  • the proportion is at most 25% by weight based on the total weight of the shell.
  • the proportion of the barrier layer is particularly preferably not more than 20% by weight.
  • the proportion of the stability layer in the shell, based on the total weight of the shell is at least 40% by weight.
  • the proportion of the stability layer in the shell can be, for example, 40% by weight, 43% by weight, 45% by weight, 48% by weight, 50% by weight. 53 wt%, 55 wt%. 58 wt%, 60 wt%, 63 wt%, 65 wt%, 68 wt%, 70 wt% 75 wt%, 80 wt%, 85 wt% -%, or 90% by weight.
  • the proportion of the stability layer is at least 50% by weight, particularly preferably at least 60% by weight.
  • the proportion of the third layer in the shell, based on the total weight of the shell is at most 35% by weight.
  • the proportion of the third layer in the shell can be, for example, 35% by weight, 33% by weight, 30% by weight, 28% by weight, 25% by weight, 23% by weight. %, 20% by weight. 18 wt%, 15 wt%. 13%, 10%, 8%, or 5% by weight.
  • the proportion of the third layer is preferably at most 30% by weight, particularly preferably at most 25% by weight.
  • the size of the microcapsules according to the invention is in the range customary for microcapsules.
  • the diameter can be in the range from 100 nm to 1 mm. The diameter depends on the exact capsule composition and the manufacturing process.
  • the peak maximum of the particle size distribution is regularly used as a parameter for the size of the capsules.
  • the peak maximum of the particle size distribution is preferably in the range from 1 ⁇ m to 500 ⁇ m.
  • the peak maximum of the particle size distribution can be, for example, at 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 10 pm, 15 pm, 20 gm, 30 gm, 40 mhh, 50 mhh, 60 mhh, 70 mhh, 80 mhh, 90 mhh, 100 mhh, 120 mhh, 140 mhh, 160 mhh, 180 gm 200 mhh, 250 mhh, 300 gm 350 mhh, 400 mhh , 450 gm or 500 gm lie.
  • the microcapsules have a peak maximum of the particle size distribution of 10 ⁇ m to 100 ⁇ m.
  • the peak maximum of the particle size distribution is in the range of 10 ⁇ m to 50 ⁇ m.
  • the use of the emulsion stabilizer to coat the barrier layer represents a new use to be distinguished from the usual use of the emulsion stabilizer, namely the stabilization of the core material droplets.
  • these biodegradable capsules Due to the robustness and tightness of these biodegradable capsules, they can be used advantageously in detergents and cleaning agents or in cosmetics, these agents being fabric softeners, textile care products, solid detergents, for example granules or powders, liquid detergents, household cleaners, bathroom and toilet detergents - Detergents, hand dishwashing detergents, machine dishwashing detergents, hand soaps, shampoos, shower gels, creams and the like include but are not limited to these.
  • the detergents or cleaning agents of the invention preferably comprise at least one ingredient selected from the group consisting of surfactants, enzymes, builders and agents that enhance absorption.
  • the detergents and cleaning agents can also contain anionic, nonionic, cationic, amphoteric or zwitterionic surfactants or mixtures thereof. Furthermore, these agents can be in solid or liquid form.
  • the surfactants include, in particular, at least one anionic surfactant and/or at least one nonionic surfactant.
  • Suitable nonionic surfactants are, in particular, ethoxylation and/or propoxylation products of alkyl glycosides and/or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • Corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives mentioned with regard to the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical can also be used.
  • Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali metal ions as cations.
  • Soaps that can be used are preferably the alkali metal salts of saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in a form that is not completely neutralized.
  • the usable surfactants of the sulfate type include the salts of the sulfuric acid half esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants with a low degree of ethoxylation.
  • Useful sulfonate-type surfactants include linear alkyl benzene sulfonates having from 9 to 14 C- Atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding mono-olefins with sulfur trioxide, and alpha-sulfofatty acid esters, which are formed in the sulfonation of fatty acid methyl or ethyl esters.
  • Cationic surfactants are preferably selected from the ester quats and/or the quaternary ammonium compounds (QAC) of the general formula ( RI)(R")(R III ) (RI IV )N + X ⁇ , in which R' to R IV are identical or different C1-22-alkyl radicals, C7-28- arylalkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic bond as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, e.g.
  • QAC quaternary ammonium compounds
  • X ⁇ represents halide ions, sulfate ions, hydroxide ions or similar anions.
  • QAVs can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups are particularly easy to achieve, and tertiary amines with two long radicals and one methyl group can also be quaternized with the aid of methyl chloride d be carried out under mild conditions.
  • Eligible QAVs are, for example, benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkon B (m,p-dichlorobenzyldimethyl-Ci2-alkylammonium chloride, benzoxonium chloride (benzyldodecyl-bis-(2-hydroxyethyl)-ammonium chloride), cetrimonium bromide (N -hexadecyl-N,N-trimethyl-ammonium bromide), benzetonium chloride (N,N-dimethyl-N[2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]-ethoxy]-ethyl]-benzyl - ammonium chloride), dial
  • Preferred esterquats are methyl N-(2-hydroxyethyl)-N,N-di(tallowoyloxyethyl)ammonium methosulfate, bis(palmitoyl)ethyl hydroxyethyl methyl ammonium methosulfate or methyl N,N -bis(acyl-oxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate.
  • Commercially available examples are those marketed by the Stepan company under the Stepantex® trademark
  • the amounts of the individual ingredients in the detergents and cleaning agents are based on the intended use of the composition in question and the person skilled in the art is generally familiar with the order of magnitude of the amounts of the ingredients to be used or can find them in the relevant specialist literature.
  • the surfactant content selected will be higher or lower, for example.
  • the surfactant content, for example of detergents is from 10 to 50 wt%, preferably from 12.5 to 30 wt% and more preferably from 15 to 25 wt%.
  • the detergents and cleaning agents can contain, for example, at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular
  • Methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and Mixed polymers of these, which can also contain small proportions of polymerizable substances without carboxylic acid functionality as polymerized units.
  • polyphosphonic acids in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid
  • polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid detergents and cleaning agents. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances can be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% to 8% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions according to the invention. Laundry aftertreatment agents, such as fabric softeners, can optionally also be free from organic builders.
  • water-soluble inorganic builder materials are alkali metal silicates and polyphosphates, preferably sodium triphosphate.
  • Crystalline or amorphous alkali metal aluminosilicates in particular can be used as water-insoluble, water-dispersible inorganic builder materials, if desired, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. -%, are used.
  • the crystalline detergent grade sodium aluminosilicates, particularly zeolite A, P and optionally X are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • suitable aluminosilicates do not have any particles with a particle size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • Those in laundry or Alkali metal silicates which can be used as builders in detergents preferably have a molar ratio of alkali metal oxide to S1O2 below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O:SiC> 2 ratio of 1:2 to 1:2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x 0 2x+i yH 2 0 are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
  • beta and delta sodium disilicates Na 2 Si 2 O 5 -yH 2 O
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10:1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
  • builder substances are preferably present in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • Laundry aftertreatment agents such as fabric softeners, are preferably free of inorganic builders.
  • an agent according to the invention further comprises at least one enzyme.
  • the enzyme can be a hydrolytic enzyme or other enzyme at a concentration useful for the effectiveness of the composition.
  • One embodiment of the invention is thus represented by agents which comprise one or more enzymes. All enzymes that can develop a catalytic activity in the agent according to the invention can preferably be used as enzymes, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ⁇ -glucosidase, pectinase, carrageenase, perhydrolase, oxidase , oxidoreductase or a lipase, and mixtures thereof.
  • the agent advantageously contains enzymes in each case in an amount of 1 ⁇ 10 ⁇ 8 to 5% by weight, based on active protein. Increasingly preferred is each enzyme in an amount of from 1 x 10 7 -3% by weight, from 0.00001-1% by weight, from 0.00005-0.5% by weight, from 0.0001 to 0 1% by weight and particularly preferably from 0.0001 to 0.05% by weight in agents according to the invention, based on active protein.
  • the enzymes particularly preferably show synergistic cleaning performance against certain soiling or stains, ie the enzymes contained in the agent composition support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent according to the invention.
  • the amylase(s) is preferably an ⁇ -amylase.
  • the hemicellulase is preferably a pectinase, a pullulanase and/or a mannanase.
  • the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and/or a cellobiohydrolase.
  • the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
  • the proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their optimum pH is usually in the clearly alkaline range.
  • the enzyme contained in the agent according to the invention is a protease.
  • the enzymes used here can be naturally occurring enzymes or enzymes which have been modified by one or more mutations based on naturally occurring enzymes in order to positively influence desired properties such as catalytic activity, stability or disinfecting performance.
  • the enzyme is present in the agent according to the invention in the form of an enzyme product in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the agent.
  • the active protein content is preferably in the range from 0.00001 to 1% by weight, in particular 0.0001 to 0.2% by weight, based on the total weight of the agent.
  • the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the Biuret method.
  • the active protein concentration is determined via a titration of the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88 , 24 (1966), pp. 5890-5913).
  • a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
  • the enzymes to be used can also be packaged together with accompanying substances, for example from the fermentation.
  • the enzymes are preferably used as enzyme liquid formulation(s).
  • the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
  • Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
  • the agent according to the invention can have one or more enzyme stabilizers.
  • Lifting agents are agents which improve the opening of the microcapsules onto surfaces, in particular textile surfaces.
  • This category of agents includes, for example, the esterquats already mentioned above.
  • Further examples are so-called SRPs (soil repellent polymers), which can be nonionic or cationic, in particular polyethyleneimines (PEI) and ethoxylated variants thereof and polyesters, in particular esters of terephthalic acid, especially those of ethylene glycol and terephthalic acid or polyester / polyether of polyethylene terephthalate and polyethylene glycol.
  • PKI polyethyleneimines
  • anionic and nonionic silicones also fall under this group.
  • Exemplary compounds are also disclosed in patent specification EP 2638 139 A1.
  • the detergents and cleaning agents can contain other ingredients which further improve the performance and/or aesthetic properties of the composition, depending on the intended use.
  • they can be bleaches, bleach activators, bleach catalysts, esterquats, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotopes, foam inhibitors, antiredeposition agents, solvents, optical brighteners, graying inhibitors, shrinkage inhibitors, Wrinkle inhibitors, dye transfer inhibitors, color stabilizers, wetting improvers, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing aids, repellents and impregnating agents, pearlescent agents, polymers, swelling and non-slip agents and UV absorbers, without being limited thereto be.
  • Suitable ingredients and framework compositions for detergent compositions are disclosed, for example, in EP 3 110 393 B1.
  • Processes for producing core/shell microcapsules are known to those skilled in the art.
  • an oil-based core material that is insoluble or sparingly soluble in water is emulsified or dispersed in an aqueous phase containing the wall-forming agents.
  • a wide variety of units are used, from simple stirrers to high-performance dispersers, which distribute the core material into fine oil droplets.
  • the wall formers are separated from the continuous water phase on the oil droplet surface and can then be crosslinked.
  • This mechanism is used in the in situ polymerization of amino and phenoplast microcapsules and in the coacervation of water-soluble hydrocolloids.
  • free-radical polymerization uses oil-soluble acrylate monomers to form the wall.
  • methods are used in which water-soluble and oil-soluble starting materials are reacted at the phase boundary of the emulsion droplets that form the solid shell.
  • Examples of this are the reaction of isocyanates and amines or alcohols to form polyurea or polyurethane walls (interfacial polymerization), but also the hydrolysis of silicate precursors with subsequent condensation to form an inorganic capsule wall (sol-gel process).
  • the barrier layer serving as a diffusion barrier is provided as a template.
  • the sensitive templates are preferably provided with an electrically negative charge by means of suitable protective colloids (eg poly-AMPS) in such a way that neither Ostwald ripening nor coalescence can occur.
  • the wall-forming agent for example a suitable pre-condensate based on aminoplast resin, can form a very thin shell (layer) with the stirring speed now greatly reduced.
  • the thickness of the shell can be further reduced, in particular by adding an aromatic alcohol, for example m-aminophenol will.
  • an aromatic alcohol for example m-aminophenol will.
  • the use of the emulsion stabilizer made it possible to further increase the separation of the biopolymers.
  • the method comprises at least the following steps: a) producing an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming component(s) of the inner barrier layer with the addition of protective colloids; b) deposition and curing of the wall-forming component(s) of the barrier layer, the wall-forming component(s) of the barrier layer preferably being an aldehyde component, an amine component and an aromatic alcohol, particularly preferably formaldehyde, melamine and resorcinol; c) adding an emulsion stabilizer, wherein the emulsion stabilizer is as defined herein; d) addition of the wall-forming component(s) of the stability layer, followed by deposition and curing, the wall-forming component(s) of the stability layer comprising at least one biopolymer, preferably a protein and/or a polysaccharide, particularly preferably gelatin and alginate, and a curing agent, are preferably glutaralde
  • a thickener such as Jaguar HP105 (Solvay) can be beneficial.
  • the thickening agent serves in particular to adjust the viscosity.
  • An increase in viscosity for example up to a viscosity of 2500 mPas (measured with Brookfield, RT, S3) can stabilize the microcapsule dispersion and thus improve the stirrability and storage.
  • the addition of the emulsion stabilizer is preferably done slowly over at least two minutes.
  • the microcapsule dispersion is agitated.
  • a paddle stirrer for example, can be used for stirring.
  • the stirring speed is preferably in the range of 150 to 250 rpm. Above 250 rpm there is a risk of air entering the microcapsule dispersion. Mixing may not be sufficient below 150 rpm.
  • the temperature is preferably in the range of 15°C to 35°C.
  • the temperature can be 15°C, 18°C, 20°C, 23°C, 25°C, 28°C, 30°C, 33°C, or 35°C.
  • the temperature is particularly preferably 25.degree.
  • the microcapsule dispersion is stirred until a homogeneous mixture is formed. In one embodiment, the microcapsule dispersion is stirred for at least 5 minutes after addition. In a preferred embodiment, the microcapsule dispersion is stirred for at least 10 minutes after addition.
  • steps a) and b) can be carried out as follows: a) Production of an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming component(s) of the inner barrier layer, optionally with the addition of protective colloids ; b) Deposition and curing of the wall-forming component(s) of the inner barrier layer, the wall-forming component(s) of the inner barrier layer being in particular an aldehyde component, an amine component and an aromatic alcohol.
  • This process can be carried out either sequentially or as a so-called one-pot process.
  • sequential method only steps a) and b) are carried out in a first method until microcapsules are obtained with only the inner barrier layer as the shell (intermediate microcapsules). A portion or the total amount of these intermediate microcapsules is then subsequently transferred to a further reactor. The further reaction steps are then carried out in this.
  • one-pot process all process steps are carried out in a batch reactor. The implementation without changing the reactor is particularly time-saving.
  • the overall system should be matched to the one-pot process.
  • the right choice of the solids content, the right temperature control, the coordinated addition of formulation components and the sequential addition of the wall-forming agents is possible in this way.
  • the method comprises the production of a water phase by dissolving a protective colloid, in particular a polymer based on acrylamidosulfonate and a methylated pre-polymer, in water.
  • a protective colloid in particular a polymer based on acrylamidosulfonate and a methylated pre-polymer
  • the pre-polymer is preferably produced by reacting an aldehyde with either melamine or urea.
  • methanol can be used.
  • the water phase can be thoroughly mixed by stirring and setting a first temperature, the first temperature being in the range from 30.degree. C. to 40.degree.
  • An aromatic alcohol in particular phloroglucinol, resorcinol or aminophenol can then be added to the water phase and dissolved therein.
  • an oil phase can be produced in the method according to the invention by mixing a fragrance composition or a phase change material (PCM) with aromatic alcohols, in particular phloroglucinol, resorcinol or aminophenol.
  • aromatic alcohols in particular phloroglucinol, resorcinol or aminophenol.
  • reactive monomers or diisocyanate derivatives can also be incorporated into the fragrance composition.
  • the first temperature can then be set.
  • a further step can be the production of a two-phase mixture by adding the oil phase to the water phase and then increasing the speed.
  • the emulsification can then be started by adding formic acid. A regular determination of the particle size is recommended. Once the desired particle size has been reached, the two-phase mixture can be stirred further and a second temperature can be set to harden the capsule walls. The second temperature can be in the range from 55°C to 65°C.
  • a melamine dispersion can then be added to the microcapsule dispersion and a third temperature set, the third temperature preferably being in the range from 75° C. to 85° C.
  • Another suitable step is the addition of an aqueous urea solution to the microcapsule dispersion.
  • the emulsion stabilizer is then added to the microcapsule dispersion before this is added to a solution of gelatine and alginate to produce the stabilization layer.
  • the microcapsule dispersion can then be cooled to a fourth temperature, the fourth temperature being in the range of 20°C to 30°C. It can then be cooled to a fifth temperature, the fifth temperature being in a range from 4°C to 17°C, in particular at 8°C.
  • the pH of the microcapsule dispersion would then be adjusted to a value in the range 4.3 to 5.1 and glutaraldehyde or glyoxal added.
  • the reaction conditions in particular temperature and pH, can be chosen differently depending on the crosslinker.
  • the person skilled in the art can derive the respectively suitable conditions from the reactivity of the crosslinker, for example.
  • the added amount of glutaraldehyde or glyoxal influences the crosslinking density of the first layer (stability layer) and thus, for example, the tightness and degradability of the microcapsule shell. Accordingly, the person skilled in the art can vary the amount in a targeted manner in order to adapt the property profile of the microcapsule.
  • a melamine suspension consisting of melamine, formic acid and water can be produced to produce the additional third layer.
  • the melamine suspension is then added to the microcapsule dispersion.
  • the pH of the microcapsule dispersion would be adjusted to a value in the range of 9 to 12, especially 10 to 11.
  • the microcapsule dispersion can be heated to a temperature in the range from 20° C. to 80° C. for curing in step e). As shown in Example 8, this temperature has an impact on the color stability of the microcapsules.
  • the temperature can be at 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75° C, or 80 °C.
  • the temperature is in the range of 30°C to 60°C. According to a preferred embodiment, the temperature is in the range of 35°C to 50°C.
  • the microcapsule dispersion is maintained at the heating temperature for a period of at least 5 minutes.
  • the time period can be 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes.
  • the microcapsule dispersion is held at the heating temperature for a period of at least 30 minutes.
  • the microcapsule dispersion is held at the heating temperature for a period of at least 60 minutes.
  • Microcapsules are usually in the form of microcapsule dispersions. Despite the use of aromatic alcohol in the barrier layer of the microcapsule shell, the microcapsule dispersions containing the microcapsules described herein exhibit little coloration.
  • the L*a*b* color model is standardized in EN ISO 11664-4 "Colorimetry -- Part 4: CIE 1976 L*a*b* Color space".
  • the L*a*b* color space (also: CIELAB, CIEL*a*b*, Lab colors) describes all perceivable colors. It uses a three-dimensional color space in which the lightness value L* is perpendicular to the color plane (a*,b*). The a-coordinate gives the chromaticity and chroma between green and red, and the b-coordinate gives the chromaticity and chroma between blue and yellow.
  • the properties of the L*a*b* color model include device independence and perception-relatedness, i.e. colors are defined as they are perceived by a normal observer under standard lighting conditions, regardless of how they are produced or how they are reproduced.
  • the microcapsule dispersions according to the invention have a color locus with an L* value of at least 50 in the L*a*b* color space.
  • the L* value can be 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, or 80.
  • the invention Microcapsule dispersions have a color locus with an L* value of at least 50 in the L*a*b* color space.
  • the color point is particularly preferably at least 60.
  • the microcapsule dispersions produced using the production process according to the invention are particularly color-stable.
  • the color locus of the microcapsule dispersion has an L* value of at least 50 in the L*a*b* color space after storage.
  • the L* value after storage can be, for example, 51, 52, 53, 54, 55, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70 , 71 , 72, 73, 74, 75, 76, 77, 78, 79, 80.
  • the microcapsule dispersions according to the invention have a color locus with an L* value of at least 60 after storage in the L*a*b* color space.
  • the color point is particularly preferably at least 65.
  • the microcapsule dispersion may contain a thickening agent such as Jaguar HP105 (Solvay).
  • the thickening agent serves in particular to adjust the viscosity.
  • An increase in viscosity for example up to a viscosity of 2500 mPas (measured with Brookfield, RT, S3), can stabilize the microcapsule dispersion and thus improve the stirrability and storage.
  • the storage time is at least four weeks, preferably at least six weeks and in particular at least eight weeks.
  • Example 1 Production of reference microcapsules not according to the invention with a melamine-formaldehyde formulation
  • Dimension SD was stirred into deionized water and then Dimension PA140 was added and stirred until a clear solution formed.
  • the solution was warmed to 30-35°C in a water bath.
  • the perfume oil was added at 1100 rpm while stirring with a dissolver disk.
  • the pH of the oil-in-water emulsion was adjusted to 3.3-3.8 with 10% formic acid. Thereafter, the emulsion was stirred further for 30 min at 1100 rpm until a droplet size of 20-30 ⁇ m was reached or correspondingly prolonged until the desired particle size of 20-30 ⁇ m (peak max) was reached.
  • the particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method) determined.
  • the speed was reduced in such a way that thorough mixing was ensured. This speed was used for stirring at 30 to 40° C. for a further 30 minutes. The emulsion was then heated to 60° C. and stirred further. The melamine suspension was adjusted to a pH of 4.5 with formic acid (10%) and metered into the reaction mixture. The batch was kept at 60° C. for 60 min and then heated to 80° C. After stirring at 80° C. for 60 min, the urea solution was added.
  • microcapsule dispersion was filtered through a 200 ⁇ m mesh filter.
  • the obtained MF reference microcapsule MK2 was examined by light microscopy.
  • a typical shot of the MK2 is shown in Figure 1F.
  • the pH, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L* value of the color locus were determined. The result is shown in Table 2.
  • Slurry 2 and Slurry 5 are shown in Table 3.
  • Table 3 List of substances used to produce Slurry 2 and 5
  • reaction mixture 1 Dimension PA140 and Dimension SD with addition of deionized water 1 were weighed into a beaker and premixed with a 4 cm dissolver disk. The beaker was fixed in the water bath and stirred with the dissolver disc at 500 rpm and 30° C. until a clear solution formed.
  • the quantity of perfume oil was added slowly and the speed adjusted (1100 rpm) so that the desired particle size was achieved. Then the pH of this mixture was acidified by the addition of Formic Acid Feed 1. It was emulsified for 20-30 minutes or extended accordingly until the desired particle size of 20-30 ⁇ m (peak max) was reached. The particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method). After the particle size had been reached, the speed was reduced in such a way that gentle mixing was ensured.
  • the resorcinol solution was then stirred in and preformed with gentle stirring for 30 - 40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60°C over a period of 15 min and this temperature was maintained for a further 30 min.
  • the melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes. Thereafter, the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 120 minutes.
  • reaction mixture 1 was then added and the heat source switched off and the reaction mixture 1 is cooled to room temperature.
  • sodium sulfate was dissolved in tap water while stirring with a paddle stirrer at 40-50°C.
  • Sodium alginate and pigskin gelatin are slowly sprinkled into the heated water.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring.
  • the pH was adjusted to 3.9 by slow dropwise addition of formic acid 2, after which the heat source was removed.
  • the batch was then cooled to room temperature. After reaching room temperature, the reaction mixture was cooled with ice.
  • the melamine suspension which had been acidified to a pH of 4.5 using 20% formic acid, was then metered in slowly.
  • the reaction mixture was then heated to 60° C. and held for 60 min when this temperature was reached. After this holding time, the heat source was removed and the microcapsule suspension was gently stirred for 14 hours. After 14 hours had elapsed, the microcapsule suspension was adjusted to a pH of 10.5 by adding sodium hydroxide solution 2.
  • microcapsule MK1 obtained was examined under a light microscope. Typical recordings are shown in Figure 1E.
  • pH value the pH value, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L* value of the color locus were determined. The result is shown in Table 5.
  • the core material was added slowly, adjusting the speed (e.g. 1100 rpm) to achieve the desired particle size.
  • preforming was carried out for 30-40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60° C. over a period of 15 minutes and this temperature was maintained for a further 30 minutes. The melafin suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes.
  • the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 90 minutes.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring.
  • the pH was adjusted to 3.7 by slow dropwise addition of the formic acid addition 2, after which the heat source was removed and the batch was naturally cooled to room temperature.
  • the reaction mixture was cooled with ice.
  • the temperature had reached 8° C., the ice bath was removed and the pH was increased to 4.7 with addition 1 of sodium hydroxide solution.
  • 50% glutaraldehyde was added. Care was taken to ensure that the temperature did not exceed 16-20° C. before the 50% glutaraldehyde was added.
  • the melamine suspension which had been acidified to a pH of 4.5 using 20% formic acid, was then added to addition 2 over a period of about 2 minutes.
  • the microcapsule suspension was then gently stirred at room temperature for 14 h. After 14 hours had elapsed, the microcapsule suspension was adjusted to a pH of 10.5 by adding sodium hydroxide solution 2 over a period of about 15 minutes.
  • Example 3 Preparation of inventive microcapsule dispersions Slurry 3 and Slurry 6 and the non-inventive reference microcapsule dispersion MK4
  • reaction mixture 1 Dimension PA140 and Dimension SD with addition of water 1 were weighed into a beaker and premixed with a 4 cm dissolver disk. The beaker was fixed in the water bath and stirred with the dissolver disc at 500 rpm and 30° C. until a clear solution formed. Once the Dimension SD / Dimension PA140 solution was clear and had reached 30-40°C, the core material was slowly added, adjusting the speed (eg 1100 rpm) to achieve the desired particle size. Then the pH of this mixture was acidified by the addition of Formic Acid Feed 1. It was emulsified for 20-30 minutes or extended accordingly until the desired particle size of 20-30 ⁇ m (peak max) was reached. The particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method). After the particle size had been reached, the speed was reduced in such a way that gentle mixing was ensured.
  • the resorcinol solution was then stirred in and preformed with gentle stirring for 30 - 40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60°C over a period of 15 min and this temperature was maintained for a further 30 min.
  • the melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes. Thereafter, the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 120 minutes.
  • reaction mixture 1 was cooled to room temperature.
  • sodium sulfate was dissolved in tap water while stirring with a paddle stirrer at 40-50°C.
  • Sodium alginate and pigskin gelatin are slowly sprinkled into the heated water.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring.
  • the pH was adjusted to 3.9 by slow dropwise addition of formic acid 2, after which the heat source was removed.
  • the batch was then cooled to room temperature. After reaching room temperature, the reaction mixture was cooled with ice.
  • the ice bath was removed and the pH was increased to 4.7 with addition 1 of sodium hydroxide solution. Then the glyoxal solution was added. Care was taken to ensure that the temperature before the glyoxal solution was added did not exceed 16-20 °C.
  • the melamine suspension addition 2 which had been acidified to a pH of 4.5 using 20% formic acid, was then metered in slowly. The reaction mixture was then heated to 60° C. and held for 60 min when this temperature was reached. After this holding time, the heat source was removed and the microcapsule suspension was gently stirred for 14 hours. After 14 hours had elapsed, the microcapsule suspension was adjusted to a pH of 10.5 by adding sodium hydroxide solution 2.
  • the core material was added slowly, adjusting the speed (e.g. 1100 rpm) to achieve the desired particle size.
  • preforming was carried out for 30-40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60° C. over a period of 15 minutes and this temperature was maintained for a further 30 minutes. The melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes. Thereafter, the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 90 minutes.
  • the reaction mixture was cooled to a temperature of 8°C with ice and the temperature was kept at 8°C.
  • the pH value is increased to 4.7 by adding sodium hydroxide solution 1.
  • 40% glyoxal was then added at a temperature of 8° C. and then the melamine suspension, acidified to a pH of 4.5 using 20% formic acid, was metered in over a period of about 2 minutes.
  • the ice bath is removed and the reaction mixture is heated to 40°C and maintained at this temperature for 1 hour.
  • the resulting microcapsules Slurry 3 and Slurry 6 according to the invention were examined under a light microscope. Typical recordings are shown in Figures 1B and 1D.
  • the pH value, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L* value of the color locus were determined. The result is shown in Table 10.
  • Example 4 Microscopic determination of the thickness of the stability layer
  • the thickness of the stability layer can be determined in two ways. First of all, the light microscopic approach should be mentioned here, i.e. the direct, optical measurement of the observed layer thickness using a microscope and appropriate software.
  • a second possibility is the measurement of the particle size distribution by means of laser diffraction.
  • the modal value of a particle size distribution of the pure barrier template (cf. example 1) can be compared to the modal value of a particle size distribution for a microcapsule according to the invention.
  • the increase in this reading should reflect the increase in hydrodynamic diameter (due to the application of the stability layer) of the main fraction of measured microcapsules. Forming the difference between the two measured modal values ultimately results in twice the layer thickness of the stability layer.
  • the layer thickness of the stability layer was determined by light microscopy on an Olympus BX50 microscope.
  • the OLYMPUS Stream Essentials software was used for the measurement
  • a highly diluted sample of the capsule slurry according to the invention was prepared with tap water. A drop of this dispersion was placed on a slide and covered with a coverslip.
  • the layer thickness of the stability layer could be measured at three characteristic points using the ruler function.
  • microcapsules of the present invention Due to the elliptical shape of the stability layer, several layer thickness measurements were taken per focused microcapsule to reflect the variance in the layer thickness.
  • the microcapsules of the present invention have a larger layer thickness at two opposite vertices and a smaller layer thickness at the remaining two opposite vertices. To reduce this measurement error when specifying a layer thickness for the stability layer, an average value was prepared for 10 individual microcapsules.
  • Table 11 Results of the layer thickness measurement of the stabilization layer using Slurry 3 as an example
  • the light microscope images of the prepared layer thickness measurement for slurry 3 and a comparison of the microcapsule MK1 are shown in FIG. 2 as an example.
  • the result of measuring 10 capsules of Slurry 3 is shown in Table 11. This result was confirmed for slurry 3 by means of laser diffraction and the difference in the modal value of the particle size distribution compared to a microcapsule without the stability layer.
  • microcapsules To determine the stability of microcapsules, they were stored in a model fabric softener formulation at 40° C. for a period of up to 4 weeks and the concentration of the fragrances diffused from the interior of the capsule into the surrounding formulation was determined using HS-GC/MS. Based on the measured values, the residual proportion of the perfume oil still in the capsule was calculated.
  • microcapsule dispersions Slurry 2, Slurry 3, Slurry 5, Slurry 6 and MK1, MK2 and MK4 were carefully homogenized and stored in the heating cabinet at a concentration of 1% by weight in the model formulation at 40° C., sealed airtight.
  • the non-encapsulated fragrance with an analogous concentration of fragrance in the model formulation serves as a comparison.
  • the samples were removed from the heating cabinet and an aliquot was weighed into a 20 ml headspace vial. The vial was then immediately sealed.
  • the microcapsules according to the invention show a stability comparable to the MF reference MK2 after storage for 4 weeks in a model formulation. Furthermore, it is found that the microcapsules according to the invention with an increased layer thickness of the stability layer slurry 2 and 3 have improved stability over a storage period of 4 weeks compared to the reference capsules MK1 and MK4 (cf. FIGS. 4B and 4C).
  • a change in concentration of 16 individual ingredients of the encapsulated fragrance was considered for the calculation of the capsule stability.
  • a reduction in stability results in the escape of the encapsulated fragrance, which can then be detected by gas chromatography using headspace SPME. Since all capsule dispersions were adjusted to a defined oil content of 15% by weight, a direct comparison of the capsule samples examined is possible. Individual ingredients (or their individual signals recorded by gas chromatography) which, due to fluctuations caused by measurement technology, indicate higher concentrations than were theoretically possible in comparison with the reference standard, were only taken into account in the evaluation up to the theoretical maximum concentration.
  • This test is used to assess the rapid biodegradability of the microcapsules.
  • the standard test concentration of the samples to be examined is 1000 mg/l ⁇ 2.
  • the measuring heads and the controller measure the oxygen consumption in a closed system. Through the consumption of oxygen and the simultaneous binding of carbon dioxide that is produced caustic soda biscuits creates a negative pressure in the system.
  • the measuring heads register and save this pressure over the set measuring period.
  • the stored values are read into the controller using infrared transmission. They can be transferred to a PC and evaluated using the Achat OC program.
  • OxiTop Control measuring system WTW incl. Controller OxiTop OC 110 with
  • Wastewater treatment plant ethylene glycol z.A., Merck Reference sample with COD 1000 mg/l 02 walnut shell flour, Senger Naturrohstoffe
  • microcapsule dispersions Slurry 2 and Slurry 3 were produced according to the descriptions of Examples 2 to 3, with the difference that the completely persistent perfluorooctane (degradation rate ⁇ 1%) was used as the core material instead of the perfume oil. This eliminates any influence of the core material on the test result. 6.3.2 Sample preparation
  • the microcapsule slurries were washed after preparation by centrifuging and redispersing in water three times in order to separate off dissolved residues.
  • a sample of 20-30 ml_ is centrifuged for 10 minutes at 12,000 revolutions per minute. After the clear supernatant has been suctioned off, 20-30 ml of water are added and the sediment is redispersed by shaking.
  • ethylene glycol 711.6 mg were dissolved in a 1 l volumetric flask and filled up to the mark. This corresponds to a COD of 1000 mg/l O2.
  • Ethylene glycol is considered to be readily biodegradable and serves as a reference here.
  • Walnut shell flour consists of a mixture of biopolymers, particularly cellulose and lignin, and serves as a solid-based biobased reference. Due to the slow degradation of walnut shell flour, the course of the test can be followed over the entire 60-day period. For this purpose, 117.36 g of walnut shell flour were dispersed homogeneously in 1 l of water with stirring. Aliquots of this mixture were taken with stirring for COD determination. The required quantity was calculated based on the average COD value of 1290 ⁇ 33 mg/l O2 and transferred to the OxiTop bottles while stirring.
  • Activated sludge was removed from the outlet of the activated sludge tank of a factory or municipal wastewater treatment plant using a 20 l bucket. After 30 minutes of settling, the supernatant water was discarded.
  • the concentrated organic sludge in the bucket was then permanently aerated for 3 days with the help of the aquarium pump and an air stone.
  • the COD value of the samples to be examined was determined using the COD LCK 514 cuvette test.
  • the sample is diluted with water until the COD value of 1000 mg/l O2 is reached.
  • microcapsule dispersions Slurry 2 and Slurry 3 show very good biodegradability in the OECD301 F test. After 14 days (slurry 3) or 26 days (slurry 2), the requirements of the OECD/ECHA are met, as there is a degree of degradation of >60%.
  • the course of degradation of the ethylene glycol reference sample indicates a healthy inoculum and also shows the functionality of the instrument over the entire duration of the experiment.
  • the walnut shell flour is characterized by the typical, gradual degradation process, which was expected for a complex mixture of biopolymers. Due to the continuous increase in biol. Degradability over the entire test period of 60 days can also be used to conclude that the inoculum is healthy.
  • the color of the microcapsule dispersions Slurry 2 and 3 as the color locus in the L*a*b* color space was determined using the following test protocol.
  • the portable spectrophotometer "spectro-colored/8°C" from Dr. Long used in conjunction with glass measuring cells for liquids. Furthermore, the measurement took place in the associated measurement setup, which darkens the sample during the measurement (and thus minimizes the influence of scattered light).
  • a calibration was performed against a black and white standard (LZM268 standard set).
  • the corresponding capsule dispersion is filled undiluted into a round glass cuvette (approx. 5-6 mL).
  • the measuring range is set to a defined layer thickness and any air inclusions in the dispersion are removed using the associated PTFE stamp.
  • the color measurement was carried out as part of a triple determination, with the cuvette being rotated by approx. 30° after each individual measurement. The mean value and standard deviation are then calculated.
  • Table 15 Determination of the color locus of slurry 2 and 3 in the L*a*b* color space after production and after storage
  • Slurry 3 In order to determine the influence of the heat treatment in the last curing step on the color stability, the manufacturing process of Slurry 3 was modified. It was on the heating of Reaction mixture dispensed at 40 °C for 1 h before stirring for 14 h at room temperature. The resulting microcapsule dispersion is referred to as Slurry 3A.
  • Slurries 3 and 3A were prepared in parallel and the color locus of samples of both microcapsule dispersions was determined directly thereafter according to the protocol described in Example 7. On the following days 1, 2, 3, 4 and 8, samples were taken from slurries 3 and 3A and the color locus of these samples was again determined. Three samples per microcapsule dispersion and day were measured and the mean for the three L*a*b* coordinates.
  • FIG. 5 shows the development over time of the L*a*b* coordinates of the two microcapsule dispersions slurry 3 and 3A.
  • the diagrams clearly show that the heat-treated microcapsule dispersion Slurry 3 has a constant colour.
  • the non-heat-treated microcapsule dispersion shows a greater change in color with a value of AL* of about 10, of D a* of about 5 and of Ab* of about 8.
  • the perfume used corresponded to the definition described herein, particularly preferably the definition for the at least one perfume composition of the core material, the perfume composition comprising, based on the total weight of all the fragrances contained in the perfume composition: a) ⁇ 10% by weight of fragrances with a CLogP of ⁇ 2.5 and a boiling point of >200°C; b) >15% by weight of at least one fragrance with a CLogP of >4.0 and a boiling point of ⁇ 275°C; and c) >30% by weight of at least one fragrance with a vapor pressure of >5 Pa at 20°C.
  • Washing program detergent: main wash at 40°C (without fabric softener);
  • Fabric softener main wash at 40°C with unscented detergent + fabric softener Spin speed: 1200rpm Water hardness: 12°dH Type of drying: Line
  • Drying conditions 50-60% rel. Humidity in a clean and odorless room

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

Selon un premier aspect, l'invention concerne une composition choisie parmi des détergents, des agents de nettoyage et des compositions cosmétiques, ladite composition contenant des microcapsules biodégradables comprenant un matériau de noyau et une coque, la coque étant constituée d'au moins une couche barrière et d'une couche de stabilité, la couche barrière entourant le matériau de noyau, la couche de stabilité comprenant au moins un biopolymère et étant située sur la surface extérieure de la couche barrière, et un stabilisateur d'émulsion étant situé au niveau de la transition entre la couche barrière et la couche de stabilité. L'invention concerne également l'utilisation de la dite composition.
EP22733388.7A 2021-06-11 2022-06-10 Compositions contenant des microcapsules dégradables neutres en couleur Pending EP4351774A1 (fr)

Applications Claiming Priority (3)

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EP21179043.1A EP4101529A1 (fr) 2021-06-11 2021-06-11 Milieu contenant des microcapsules dégradables de couleur neutre avec composition de parfum
EP21179039.9A EP4101528A1 (fr) 2021-06-11 2021-06-11 Milieu contenant des microcapsules dégradables de couleur neutre
PCT/EP2022/065834 WO2022258808A1 (fr) 2021-06-11 2022-06-10 Compositions contenant des microcapsules dégradables neutres en couleur

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