EP2614134A1 - Microcapsule containing detergent or cleaning agent - Google Patents
Microcapsule containing detergent or cleaning agentInfo
- Publication number
- EP2614134A1 EP2614134A1 EP11752566.7A EP11752566A EP2614134A1 EP 2614134 A1 EP2614134 A1 EP 2614134A1 EP 11752566 A EP11752566 A EP 11752566A EP 2614134 A1 EP2614134 A1 EP 2614134A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- microcapsules
- meth
- oil
- cleaning agent
- amps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
Definitions
- the invention is in the field of detergents and cleaners and relates to detergents or cleaners containing special microcapsules, as well as to processes for producing detergents or cleaners containing microcapsules.
- a variety of detergents contain sensitive ingredients, such as e.g. Fragrances.
- the disadvantage is that such ingredients that are used in such agents, often lose their activity during storage and / or before the desired application time or at least greatly reduced, for example by chemical reactions due to interaction with other ingredients of the detergent or cleaning agent and / or by physical influences. For this reason, an encapsulation of ingredients may be indicated.
- microencapsulation systems based on natural or artificial polymers. These can enclose an active substance or its solution and then be physically or chemically crosslinked in the shell or precipitated by a coacervation process with another polymer. Furthermore encapsulations exist by liposomes, eg. B. "nanotopes" from Ciba-Geigy or sponge-like particles such as "microsponges” from the company Advanced Polymer Systems. For example, microencapsulated molded bodies are used to increase the stability of pharmaceutical active substances, to influence the taste, to target organ-specific active substance delivery and to avoid incompatibility with other auxiliaries and active ingredients. In addition, microcapsules are used in adhesive technology.
- perfume capsules with gelatin from which perfume oils are released by mechanical destruction.
- spherical carrier particles z As alginate, gelatin or polyvinyl alcohol (PVAI), in which a Wrkstoff, living cells or enzymes can be embedded. These capsules can z. B. be prepared by a Vertropfungsver-. In general, microcapsules are particles with diameters of ⁇ 1 mm. In addition to inclusion in capsules of various sizes, substances can also be adsorbed on suitable carrier materials or chemically modified.
- Microcapsules are known from the prior art, which may contain liquid, solid or gaseous substances as core material.
- material for the capsule walls for example, phenolic Formaldehyde polymers, melamine-formaldehyde polymers, polyurethane, gelatin, polyamides or polyureas in use.
- microcapsules of melamine-formaldehyde resins have proven useful in detergents or cleaners, since they are particularly stable.
- the capsule dispersions accumulating in the production of these microcapsules basically still comprise residual free formaldehyde whose presence in the further processing or in the end product which is released to the consumer is undesirable.
- formaldehyde scavengers There are therefore suggestions in the patent literature to lower the formaldehyde content by using formaldehyde scavengers.
- EP-A 0 415 273 describes the preparation and use of mono- and polydispersed solid ball particles of melamine-formaldehyde condensate. For binding of the liberated in the condensation formaldehyde, the use of ammonia, urea or ethylene urea is proposed.
- the object of the present invention was therefore to provide microcapsule-containing detergents or cleaning compositions which contain microcapsules which are associated with the lowest possible formaldehyde input or in which the use of formaldehyde for microcapsules is preferably dispensed with altogether.
- a first object of the present invention is a washing or cleaning agent comprising
- surfactants and / or builders in particular in a total amount of 0.01 to 80 wt .-%, based on the total agent
- microcapsules whose capsule walls comprise a resin which is converted by reaction a) at least one aromatic alcohol or its ethers or derivatives with
- the washing or cleaning agents according to the invention have the advantage that they have at most a very low formaldehyde content, since their production is accompanied at most by a very low, but in particular no formaldehyde entry.
- the washing or cleaning agents according to the invention enable the targeted release of active substances, in particular fragrances, which are stored in the capsules.
- the capsules are stable within the detergent or cleaning agent matrix and can be opened by targeted stimulus, in particular mechanical force.
- the microcapsules deposit on the material to be cleaned and, after drying the product, e.g. be easily opened by friction. In this way, a targeted drug release succeeds, so that the performance profile of the entire agent is increased.
- the scent effect is of particular importance, since the product performance is judged in many cases by the consumer proportionally to the fragrance.
- the release of the active substances, in particular fragrances can also take place in a diffusive manner, in which the active substances, in particular fragrances, migrate through the polymeric shell material and are then slowly released.
- the present washing or cleaning agent in particular allows a long-lasting release of active ingredient, in particular a long-lasting scenting of the goods to be cleaned and a targeted release of active ingredient, in particular fragrance release, even after long periods by using the microencapsulated active ingredients, especially fragrances.
- microcapsules usable according to the invention are in the washing or cleaning agent in amounts of preferably 0.0001 to 50 wt .-%, advantageously 0.001 to 40 wt .-%, more preferably 0.005 to 30 wt .-%, more preferably 0 , 01 to 20 wt .-%, more preferably 0.05 to 10 wt .-% and in particular 0.1 to 5 wt .-%, based on the total agent.
- microcapsules contain in particular liquid, preferably comprising
- liquid detergent ingredients such as preferably surfactants, in particular nonionic surfactants, silicone oils, paraffins
- liquid non-pharmaceutical additives or excipients e.g. Oils such as almond oil or cooling substances,
- fragrances perfume oils
- Preferred aromatic alcohols ii) a) in the context of the present invention are aryloxyalkanols, arylalkanols and oligoalkanol aryl ethers. Also preferred are aromatic compounds in which at least one free hydroxy group, particularly preferably at least two free hydroxy groups, are directly aromatically bonded, it being particularly preferred if at least two free hydroxy groups are bonded directly to an aromatic ring and very particularly preferred are arranged in meta position to each other.
- the aromatic alcohols are selected from the phenols, the cresols (o-, m- and p-cresol), the naphthols (o and ß-naphthol) and thymol, and from the ethylphenols, propylphenols, fluorophenols and methoxyphenols.
- Aromatic alcohols which are preferred according to the invention are furthermore those which are used in the production of polycarbonate plastics (for example for compact discs, plastic bowls, baby bottles) and epoxy resin paints (for example for cans and foil packaging), in particular 2.2 Bis (4-hydroxyphenyl) propane (bisphenol A).
- the aromatic alcohol is selected from the phenols having two or more hydroxyl groups, preferably from catechol, resorcinol, hydroquinone and 1, 4-naphthohydroquinone, phloroglucinol, pyrogallol, hydroxyhydroquinone, in particular resorcinol and / or phloroglucinol as aromatic Alcohols are preferred.
- compositions according to the invention are preferred in which the at least one aromatic alcohol ii) a) is selected from the phenols, the cresols (o-, m- and p-cresol), the naphthols (o and ß-naphthol), thymol, catechol , Resorcinol, hydroquinone and 1,4-naphthohydroquinone, phloroglucinol, pyrogallol, hydroxyhydroquinone.
- the at least one aromatic alcohol ii) a) is selected from the phenols, the cresols (o-, m- and p-cresol), the naphthols (o and ß-naphthol), thymol, catechol , Resorcinol, hydroquinone and 1,4-naphthohydroquinone, phloroglucinol, pyrogallol, hydroxyhydroquinone.
- the detergents or cleaners contain microcapsules, in the preparation of which the aromatic alcohol is used as ether, the ether being in particular a derivative of the respective free form of the aromatic alcohol ii) a) to be reacted according to the invention.
- the free alcohol can also be present; then there is a mixture.
- the molar ratio between the free form of the aromatic alcohol to be reacted according to the invention and the said additional component (ether form of an aromatic alcohol) may be between 0: 100, preferably 1: 1, or 1: 2 or 1: 4.
- the advantage of mixing the aromatic alcohol with an ether form is that it can influence the reactivity of the system. In particular, with the appropriate choice of ratio, a system can be created whose reactivity balances with the storage stability of the system.
- esters are preferred.
- aldehydes ii) b) having at least 2 carbon atoms both aliphatic and aromatic aldehydes are preferred according to the present invention.
- Particularly preferred aldehydes are one or more selected from the following group: valeraldehyde, caproic aldehyde, caprylaldehyde, decanal, succinic dialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-1-propanol, 2-methylpropionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8 'Apo- ⁇ -caroten-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, g
- the aldehydic component may have at least one or two, particularly preferably two, three or four, in particular two free aldehyde groups per molecule, it being preferred if at least glyoxal, glutaric and / or Succindialdehyd is present, particularly preferred is glutaric dialdehyde.
- the molar ratio of a) the at least one aromatic alcohol or (ether or derivative thereof) to b) of the at least one aldehydic component is generally between 1: 1 and 1: 5, more preferably between 1 and 2 and 1 to 3, and most preferably resorcinol is about 1 to 2.6.
- the weight ratio of components a) + b) to c), i. the ratio of the weight sum of a) + b)) to the weight of component c) is generally between 1: 1 and 1: 0.01, more preferably between 1: 0.2 and 1: 0.05.
- compositions according to the invention are preferred in which the aldehydic component ii) b) is selected from valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succinic dialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-1-propanal, 2-methylpropionaldehyde, acetaldehyde, acrolein, aldosterone, Antimycin A, 8'-apo- ⁇ -caroten-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glyceraldehyde, glycolaldehyde, glyoxal, glycosyl xylic acid, h
- the optionally used (meth) acrylate polymers may be homo- or copolymers of methacrylate monomers and / or acrylate monomers.
- the term "(meth) acryl" in this invention means both methacrylates and acrylates.
- the (meth) acrylate polymers are e.g. Homopolymers or copolymers, preferably copolymers, of one or more polar-functionalized (meth) acrylate monomers, such as sulfonic acid-containing, carboxylic acid-containing, phosphoric acid group-containing, nitrile-containing, phosphonic acid-containing, ammonium group-containing, amine group-containing or nitrate group-containing (meth) acrylate monomers.
- the polar groups can also be present in salt form.
- the (meth) acrylate polymers are suitable as protective colloids and can be advantageously used in the production of microcapsules.
- (meth) acrylate copolymers may consist of two or more (meth) acrylate monomers (eg, acrylate + 2-acrylamido-2-methylpropanesulfonic acid) or one or more (meth) acrylate monomers and one or more of ( Meth) acrylate monomers of various monomers (eg methacrylate + styrene).
- Examples of (meth) acrylate polymers are homopolymers of sulfonic acid group-containing (meth) acrylates (for example, 2-acrylamido-2-methyl-propanesulfonic acid or salts thereof (AMPS), commercially available as Lupasol ® PA 140, BASF), or copolymers thereof , copolymers of acrylamide and (meth) acrylic acid, copolymers of alkyl (meth) acrylates and N-vinylpyrrolidone or ethoxylates (commercially available as Luviskol ® K15, K30 or K90, BASF), copolymers of (meth) acrylates with polycarbosilane polystyrenesulfonates, Copolymers of (meth) acrylates with vinyl ethers and / or maleic anhydride, copolymers of (meth) acrylates with ethylene and / or maleic anhydride, copolymers of (meth) acrylates with isobut
- Preferred (meth) acrylate polymers are homopolymers or copolymers, preferably copolymers, of 2-acrylamido-2-methylpropanesulfonic acid or its salts (AMPS).
- AMPS 2-acrylamido-2-methylpropanesulfonic acid or its salts
- copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts for example copolymers with one or more comonomers from the group of (meth) acrylates, vinyl compounds such as vinyl esters or styrenes, of unsaturated di- or polycarboxylic acids such as maleic acid esters , or the salts of amyl compounds or allyl compounds.
- polar-functionalized (meth) acrylate monomers 1) vinyl compounds, for example vinyl esters such as vinyl acetate, vinyl laurate, vinyl propionate or vinyl esters of neononanoic acid, or aromatic vinyl compounds such as styrene comonomers, for example styrene, alpha-methylstyrene or polar-functionalized styrenes such as styrenes with hydroxyl, amino, nitrile, carboxylic acid, Phosphonic acid, phosphoric acid, nitro or sulfonic acid groups and their salts, wherein the styrenes are preferably polar functionalized in the para position.
- vinyl esters such as vinyl acetate, vinyl laurate, vinyl propionate or vinyl esters of neononanoic acid
- aromatic vinyl compounds such as styrene comonomers, for example styrene, alpha-methylstyrene or polar-functionalized styrenes such as
- Unsaturated di- or polycarboxylic acids e.g. Maleic acid esters such as dibutyl maleate or di-tylmaleinate, as salts of allyl compounds e.g. Sodium allylsulfonate, as salts of amyl derivatives e.g. Natriumamylsulfonat.
- esters of acrylic acid and methacrylic acid these are esters of acrylic acid and methacrylic acid, the ester groups e.g. are saturated or unsaturated, straight-chain, branched or cyclic hydrocarbon radicals which may contain one or more heteroatoms such as N, O, S, P, F, Cl, Br, I.
- hydrocarbon radicals are straight-chain, branched or cyclic alkyl, straight-chain, branched or cyclic alkenyl, aryl such as phenyl or heterocylyl such as tetrahydrofurfuryl.
- Suitable (meth) acrylate comonomers are, for example: a) acrylic acid, C 1 -C 3 -alkyl-acrylic acid, such as methacrylic acid, b) (meth) acrylamides, such as acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, N Butoxymethyl-acrylamide, N-isobutoxymethyl-acrylamide, N-butoxymethyl-methacrylamide, N-isobutoxymethyl-methacrylamide, N-methylol-acrylamide, N-methylol-methacrylamide; c) heterocyclyl (meth) acrylates such as tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate or carbocyclic (meth) acrylates such as isobornyl acrylate and isobornyl methacrylate, d) urethane (meth) acrylates such as diurethane
- alkyl groups may optionally be substituted with one or more halogen atoms (eg fluorine, chlorine, bromine or iodine), eg trifluoroethyl acrylate, or with one or more amino groups, eg diethylaminoethyl acrylate, or with one or more alkoxy groups such as methoxypropyl acrylate, or with one or more aryloxy
- C 2 -C 4 alkenyl acrylates such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, sec-butenyl, iso-butenyl, tert.
- hexenyl eg n-hexenyl, iso-hexenyl or cyclohexenyl
- heptenyl eg 2-ethylhexenyl
- CC H -hydroxyalkyl acrylates such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-iso-butyl, hydroxy tert-butyl, hydroxy-n-pentyl, hydroxyiso-pentyl, hydroxyhexyl (eg hydroxy-n-hexyl, hydroxy-iso-hexyl or hydroxy-cyclohexyl), hydroxyheptyl, hydroxyoctyl ( eg 2-ethylhexyl), hydroxynonyl, hydroxy decyl (eg hydroxy-2-propylheptyl or hydroxyiso-decyl), hydroxyundecyl, hydroxydodecyl, hydroxytridecyl (eg hydroxyiso-tridecyl), and hydroxytetradecyl,
- Examples are i) monoalkylene glycol acrylates, such as acrylates of ethylene glycol, propylene glycol (eg 1, 2 or 1, 3-propanediol), butylene glycol (eg 1, 2, 1, 3 or 1, 4-butanediol, pentylene glycol (eg 1, 5-pentanediol) or hexylene glycol (for example 1,6-hexanediol) in which the second hydroxyl group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid, or ii) polyalkylene glycol acrylates such as polyethylene glycol acrylates, polypropylene glycol acrylates, polybutylene glycols.
- monoalkylene glycol acrylates such as acrylates of ethylene glycol, propylene glycol (eg 1, 2 or 1, 3-propanediol), butylene glycol (eg 1, 2, 1, 3 or 1, 4-butane
- kolacrylate Polypentylenglykolacrylate or Polyhexylenglykolacrylate whose second hydroxy group may optionally be etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid;
- Examples of (poly) alkylene glycol units having etherified hydroxy groups are C 1 -C 3 -alkyloxy (poly) alkylene glycols (eg C 1 -C 3 -alkyloxy-polyalkylene glycol acrylates), examples of (poly) alkylene glycol units having esterified hydroxy groups are sulfonium ( poly) alkylene glycols (for example sulfonium (poly) alkylene glycol acrylates) and salts thereof, (poly) alkylene glycol diacrylates, such as 1,4-butanediol diacrylate or 1,6-hexanediol diacrylate or (poly) alkylene glycol methacrylate acrylates, such as 1,4-butanediol methacrylate acrylate or 1, 6-Hexandiolmethacrylatacrylat;
- the polyalkylene glycol acrylates may carry an acrylate group (eg polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, polypentylene glycol monoacrylate or polyhexylene glycol monoacrylate) or two or more, preferably two, acrylate groups such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, polypentylene glycol diacrylate or polyhexylenglycol diacrylate;
- the polyalkylene glycol acrylates may also contain two or more different polyalkylene glycol blocks from each other, for example blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol;
- the degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks is generally in the range from 1 to 20, preferably in the range from 3 to 10, particularly preferably in the range from 3 to 6.
- C 1 -C 4 -alkyl methacrylates such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert.
- alkyl groups may optionally be substituted by one or more halogen atoms (eg fluorine, chlorine, bromine or iodine), eg trifluoroethyl methacrylate, or with one or more amino groups, eg diethylaminoethyl methacrylate, or with one or more alkoxy groups, such as methoxypropyl methacrylate, or with one or more halogen atoms (eg fluorine, chlorine, bromine or iodine), eg trifluoroethyl methacrylate, or with one or more amino groups, eg diethylaminoethyl methacrylate, or with one or more alkoxy groups, such as methoxypropyl methacrylate, or with one or
- C 2 -C 4 alkenyl methacrylates such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, sec-butenyl, iso-butenyl, tert.
- hexenyl eg n-hexenyl, iso-hexenyl or cyclohexenyl
- heptenyl eg 2-ethylhex
- alkylene glycol methacrylates containing one or more alkylene glycol units examples are i) monoalkylene glycol methacrylates, such as methacrylates of ethylene glycol, propylene glycol (eg 1, 2 or 1, 3-propanediol), butylene glycol (eg 1, 2, 1, 3 or 1, 4-butanediol, pentylene glycol (eg 1, 5-pentanediol) or hexylene glycol (eg 1,6-hexanediol) in which the second hydroxy group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid, or ii) polyalkylene glycol methacrylates such as polyethylene glycol methacrylates, polypropylene glycol methacrylates, polybutylene glycol methacrylates, polypentylene glycol methacrylates or polyethyleneglycol methacrylates whose second hydroxy group may optionally be
- Examples of (poly) alkylene glycol units having etherified hydroxy groups are C 1 -C 3 -alkyloxy (poly) alkylene glycols (for example C 1 -C 3 -alkyloxyalkylene glycol methacrylates), examples of (poly) alkylene glycol units having esterified hydroxyl groups are sulfonium (poly) alkylene glycols (for example sulfonium (poly) alkylene glycol methacrylates) and salts thereof or (poly) alkylene glycol dimethacrylates such as 1,4-butanediol dimethacrylate;
- the polyalkylene glycol methacrylates may carry one methacrylate group (eg polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, poly (pentylene glycol mono methacrylate or polyhexylenglycol monomethacrylate) two or more, preferably two, methacrylate groups, such as polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, polypentylene glycol di-methacrylate or poly (ethylene glycol) dimethacrylate;
- methacrylate group eg polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, poly (pentylene glycol mono methacrylate or polyhexylenglycol monomethacrylate
- methacrylate groups such as polyethylene glycol dimethacrylate, polypropylene
- the polyalkylene glycol methacrylates may also contain two or more different polyalkylene glycol blocks, e.g. Blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol (e.g., Bisomer PEM63PHD (Cognis), CAS 58916-75-9);
- the degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks is generally in the range of 1 to 20, preferably in the range of 3 to 10, more preferably in the range of 3 to 6.
- Examples of preferred (meth) acrylate comonomers are 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, ammonium sulfatoethyl methacrylate, pentapropylene glycol methacrylate, acrylic acid, hexaethylene glycol methacrylate, hexapropylene glycol acrylate, hexaethylene glycol acrylate, hydroxyethyl methacrylate, polyalkylene glycol methacrylate (CAS No.
- Bisomer PEM63PHD methoxy polyethylene glycol methacrylate, 2-propylheptyl acrylate (2-PHA), 1,3-butanediol dimethacrylate (BDDMA), triethylene glycol dimethacrylate (TEGDMA), hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGDMA), glycidyl methacrylate (GMA ) and / or allyl methacrylate (ALMA).
- the AMPS copolymers generally have a proportion of AMPS units of greater than 50 mol%, preferably in the range of 60-95 mol%, particularly preferably from 80 to 99 mol%, the proportion of comonomers is generally smaller 50 mol%, preferably in the range of 5 to 40 mol%, particularly preferably from 1 to 20 mol%.
- the copolymers can be obtained by processes known per se, for example in the batch or in the semibatch process. For example, first appropriate amounts of water and monomers are passed into a temperature-controlled reactor and placed under an inert gas atmosphere. The original then stirred, brought to reaction temperature (preferably in the range of about 70 - 80 ° C) and initiator added, preferably in the form of an aqueous solution.
- Suitable initiators are known initiators for free-radical polymerizations, for example sodium, potassium or ammonium peroxodisulfate, or the H 2 O 2 -based mixtures, for example mixtures of H 2 O 2 with citric acid.
- the maximum temperature is waited for and as soon as the temperature in the reactor decreases either a) the addition of the remaining monomers and then a post-reaction (semibatch process), or b) directly the post-reaction (batch process). Thereafter, the resulting reaction mixture is cooled to room temperature and the copolymer isolated from the aqueous solution, for example by extraction with organic solvents such as hexane or methylene chloride and then distilling off the solvent. Thereafter, the copolymer may be washed with organic solvent and dried.
- the reaction mixture obtained can also be further processed directly, in which case it is advantageous to add a preservative to the aqueous copolymer solution.
- the AMPS copolymers are useful as protective colloids in the preparation of the microcapsules useful in the present invention.
- compositions according to the invention are those in which the (meth) acrylate polymer is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid or salts thereof with one or more further (meth) acrylate monomers selected from the group of (meth) acrylates, the vinyl compounds, the unsaturated di- or polycarboxylic acids and the salts of amyl compounds or allyl compounds.
- the molar ratio of the at least one aromatic alcohol ii) a) to the at least one aldehydic component ii) b) which has at least two carbon atoms per molecule is between 1: 2 and 1: 3.5 , preferably between 1 to 2.4 and 1 to 2.8, and more preferably at 1 to 2.6.
- Preferred washing or cleaning agents according to the invention comprise microcapsules which have the following components ii) a), ii) b), and ii) c):
- Ph oroglucin glutaric dialdehyde, AMPS / hydroxypropyl methacrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / hydroxypropyl acrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / hydroxybutyl methacrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / hydroxybutyl acrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / polyethylene glycol monomethacrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / polyethylene glycol monoacrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / polypropylene glycol monomethacrylate copolymer
- Ph oroglucin glutaric dialdehyde, AMPS / polypropylene glycol monoacrylate copolymer
- Resorcinol glutaric dialdehyde, AMPS / polypropylene glycol monoacrylate copolymer
- Resorcinol, succinic aldehyde, AMPS / polypropylene glycol monoacrylate copolymer
- Resorcinol, glyoxal, AMPS / polypropylene glycol monoacrylate copolymer
- Resorcinol glutaric dialdehyde, AMPS / methoxy polyethylene glycol monomethacrylate copolymer
- Resorcinol succinic aldehyde, AMPS / methoxy polyethylene glycol monomethacrylate copolymer
- Resorcinol, glyoxal, AMPS / methoxy polyethylene glycol monomethacrylate copolymer Resorcinol, succinic aldehyde, AMPS / methoxy polyethylene glycol monomethacrylate copolymer
- Resorcinol glutaric dialdehyde, AMPS / methoxy polyethylene glycol monoacrylate copolymer
- Resorcinol succinic aldehyde, AMPS / methoxy polyethylene glycol monoacrylate copolymer
- Resorcinol, glyoxal, AMPS / methoxy polyethylene glycol monoacrylate copolymer Resorcinol, glyoxal, AMPS / methoxy polyethylene glycol monoacrylate copolymer.
- one or more nitrogen-containing or silicon dioxide-containing agents can additionally be used for the preparation of the microcapsules which can be used according to the invention.
- the nitrogenous agents may be polymerized into the resin (e.g., to round off the property profile of the resin) or used for aftertreatment.
- heterocyclic compounds having at least one nitrogen atom as heteroatom which is adjacent to either an amino-substituted carbon atom or a carbonyl group, such as pyridazine, pyrimidine, pyrazine, pyrrolidone, aminopyridine and compounds derived therefrom.
- Advantageous compounds of this type are aminopyridine and compounds derived therefrom. Suitable in principle are all aminopyridines, for example melamine, 2,6-diaminopyridine, substituted and dimeric aminopyridines and mixtures prepared from these compounds.
- polyamides and dicyandiamide, urea and its derivatives, and pyrrolidone and compounds derived therefrom are also advantageous.
- Suitable pyrrolidones are, for example, imidazolidinone and compounds derived therefrom, such as, for example, hydantoin, whose derivatives are particularly advantageous, especially advantageous of these compounds are allantoin and its derivatives. Also particularly advantageous are triamino-1, 3,5-triazine (melamine) and its derivatives.
- the aftertreatment is a "sheer" aftertreatment of the surface in order to arrive at this preferred embodiment of the microcapsules which can be used according to the invention
- said nitrogenous agent is not uniform in structure involved in the entire capsule wall but concentrated predominantly on the outer surface of the capsule walls.
- Action can also be carried out with silica gel (esp. amorphous hydrophobic silica gel) or with aromatic alcohols a), these are preferably used as feasting.
- microcapsules which can be used according to the invention are introduced, in particular in the form of microcapsule dispersions which contain one or more of the microcapsules which can be used according to the invention, into the washing or cleaning agent according to the invention.
- the preparation of the microcapsules or microcapsule dispersions contained in the detergents or cleaning agents according to the invention is preferably carried out by the at least one aromatic alcohol to be reacted and the at least one aldehydic component to be reacted according to the invention having at least two C atoms per molecule, optionally in the presence of at least one ( Meth) acrylate polymer, optionally in the presence of at least one substance to be encapsulated (core material), are brought together and reacted and by subsequent increase in temperature, the curing of the capsules. It is particularly preferred that the pH is increased in the course of the process.
- the pH is then at most 4, more preferably between 3 and 4, for example between 3.2 to 3.5.
- the yield and quality of the present invention can be used microcapsules or microcapsule dispersions are influenced.
- too low a temperature may cause the capsule wall to be made less dense. This is apparent to those skilled in a reduced yield and deposition of nuclear material as a condensate in the filter of the dryer.
- the alkalinity can likewise be of importance for the quality of the microcapsules which can be used according to the invention.
- the pH value in the context of litigation influences the tendency to gel the batch. If the particle formation (step b) above) is carried out at a pH of 9 or lower, the batch could gel.
- an alkali metal salt preferably alkali metal carbonate, in particular sodium carbonate, is used to adjust the alkalinity. Sodium carbonate is preferred because it reduces the risk of gelling.
- the (meth) acrylate polymer and the substance to be encapsulated can then be added to the resulting precondensate.
- the stirring speed is increased, whereby it may then be at 3000 to 5000 rpm, in particular at 3500 to 4500 rpm, above all at 4000 rpm ,
- the thus increased stirring speed is maintained until the viscosity values of the mixture decrease, wherein after the onset of a viscosity decrease, the stirring speed is lowered, preferably to 500 to 2500 rpm, more preferably to 1000 to 2000 rpm.
- An earlier lowering of the stirring speed can also lead to undesirable gelling of the approach.
- the curing of the capsules Temperature increase takes place.
- This phase after the beginning of the described decrease in viscosity and before curing of the capsules is also referred to as rest phase in the present invention.
- the quiescent phase may preferably serve to achieve the preforming of sufficiently stable capsule walls, in other words, to make the capsule walls so stable that no more core material escapes.
- microcapsules generally have diameters in the range of 1 to 1000 ⁇ .
- microcapsule also includes nanocapsules, ie capsules with a diameter ⁇ 1 ⁇ m.
- the capsules preferably have diameters in the range from 1 to 100 ⁇ m, preferably from 2 to 50 ⁇ m.
- the wall thickness can be, for example 0.05 to 10 ⁇ .
- the loading of the capsules can generally be carried out with gaseous, liquid and solid substances. Preference is given to using hydrophobic materials.
- liquid substances in particular fragrances, liquid washing and cleaning agent ingredients, such as preferably surfactants, in particular nonionic surfactants, silicone oils, paraffins, liquid non-pharmaceutical additives or active ingredients, e.g. Oils such as almond oil and mixtures of the aforementioned.
- surfactants in particular nonionic surfactants, silicone oils, paraffins, liquid non-pharmaceutical additives or active ingredients, e.g. Oils such as almond oil and mixtures of the aforementioned.
- fragrances perfume oils
- fragrances or fragrances or perfume oils all known substances and mixtures can be used.
- perfume compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol type ester-type odoriferous compounds are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrally
- Ethers include, for example, Benz ylethyl ether and ambroxane, to the aldehydes z.
- the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes, such as unions and pinene.
- mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller 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.
- Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champacell blossom oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, Gingergrass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamomedicine, cassia oil, pine oil, copalvabalam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, Tangerine oil, Melissa oil, Musk grain oil, Myrrh oil, Clove oil, Neroli oil, Niaouli oil
- fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
- These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amyl cinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate , Benzyl formate, benzyl valerate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol
- the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
- Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phela- landren, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
- fragrance compounds of the aldehyde type are hydroxycitronellal (CAS 107-75-5), helional (CAS 1205-17-0), citral (5392-40-5), bourgeonal (18127-01 -0) , Triplal (CAS 27939-60-2), Ligustral (CAS 68039-48-5), Vertocitral (CAS 68039-49-6), Florhydral (CAS 125109-85-5), Citronellal (CAS 106-23-0) , Citronellyloxyacetaldehyde (CAS 7492-67-3).
- the perfume to be encapsulated does not comprise 2-methyl undecanal, decanal, benzene acetaldehyde and 3-phenylprop-2-enal.
- the microcapsules may preferably also contain one or more (preferably liquid) skin-care and / or skin-protecting active substances.
- Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage. Skin-care active substances are preferably selected from the following substances:
- waxes such as carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
- hydrocarbons such as squalene and / or squalane
- Higher fatty acids preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and others.
- Higher fatty alcohols preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.
- esters preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol stearates, glycerol monostearates, glyceryl distearates, glycerol tristers, alkyl lactates, alkyl citrates and / or alkyl tartrates and others.
- esters preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol
- lipids such as cholesterol, ceramides and / or sucrose esters and others.
- vitamins such as vitamins A, C and E, vitamin C esters, including vitamin C alkyl esters and others.
- Germicides for cosmetic use both synthetic and, for example, salicylic acid and / or other natural as well as neem oil and / or others, m) silicones
- the washing or cleaning agent according to the invention contains, in addition to the microcapsules described, further ingredients, namely at least surfactants and / or builders.
- detergents or cleaning agents are described in more detail.
- detergents or cleaning agents and textile aftertreatment agents such as fabric softener, air freshener, conditioning wipes for use in tumble dryer, hygiene rinse, etc.
- Fabric washing agent is the name given to those needed to wash textile products, e.g. in the form of powders, granules, beads, tablets, pastes, gels, tissues, pieces or liquids of present formulations, which are preferably used in aqueous solutions, especially in washing machines.
- Fabric softeners are textile aftertreatment agents for the care of textiles and preferably contain active ingredients which result in a soft feel of the treated textiles, in particular cationic active substances (preferably cationic surfactants, for example quaternary ammonium compounds), fatty acid derivatives and / or silicone oils.
- Fragrance scavengers are perfume-containing textile aftertreatment agents for the care of textiles, which bring about a particularly pleasant scent of the textiles.
- Conditioning wipes for use in the tumble dryer are impregnated with Wrkstoffen (especially fabric softeners) nonwovens or sheets.
- Hygienic rinse aids are textile aftertreatment agents for the care of textiles, which comprise at least one antimicrobial agent, e.g. quaternary ammonium compounds such as e.g.
- detergents includes all cleaners for hard or soft surfaces, but preferably hard surface, in particular dishwashing detergents (comprising hand dishwashing detergents and machine dishwashing detergents), all-purpose cleaners, toilet cleaners, sanitary cleaners and glass cleaners. All washing or cleaning agents may e.g. in the form of powders, granules, beads, tablets, pastes, gels, tissues, pieces or liquids. They can be single-phase or multi-phase. They may also be present in sachets, so-called pouches, in one variant the microcapsules in the film materials used for the pouch, e.g. PVA, are embedded.
- dishwashing detergents comprising hand dishwashing detergents and machine dishwashing detergents
- All washing or cleaning agents may e.g. in the form of powders, granules, beads, tablets, pastes, gels, tissues, pieces or liquids. They can be single-phase or multi-phase. They may also be present in sachets, so-called pouch
- the detergents or cleaners according to the invention contain surfactants and / or builders in addition to the microcapsules as a compelling component.
- Suitable surfactants are, in particular, anionic surfactants, nonionic surfactants, cationic, zwitterionic and / or amphoteric surfactants. However, it is particularly preferred if the washing or cleaning agent according to the invention contains anionic, nonionic and / or cationic surfactants. In particular, the use of a mixture of anionic and nonionic surfactants is advantageous.
- the washing or cleaning agent according to the invention preferably contains 0.05 wt .-% to 50 wt .-%, advantageously 1 to 40 wt .-%, more preferably 3 to 30 wt .-% and in particular 5 wt .-% to 20 wt .-% surfactant (s), in particular from the Groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic and / or amphoteric surfactants.
- surfactant in particular from the Groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic and / or amphoteric surfactants. This corresponds to a preferred embodiment of the invention and enables optimum cleaning performance.
- the washing or cleaning agent according to the invention contains anionic surfactant, advantageously in amounts of from 0.1 to 25% by weight, more preferably 1 to 20% by weight, in particular in amounts of from 3 to 15% by weight. , relative to the entire remedy.
- anionic surfactant is alkylbenzenesulfonate, preferably linear alkylbenzenesulfonate (LAS).
- washing or cleaning agent according to the invention contains alkylbenzenesulfonate, advantageously in amounts of 0.1-25% by weight, more preferably 1-20% by weight, in particular in amounts of 3-15% by weight, based on the total Means, so is a preferred embodiment of the invention.
- Particularly suitable anionic surfactants are also the alkyl sulfates, especially the fatty alcohol sulfates (FAS), such as C 2 -C 8 fatty alcohol sulfate.
- FAS fatty alcohol sulfates
- C 8 -C 8 -alkyl sulfates can preferably be used; C 3 -alkyl sulfate and C 3 are particularly preferred.
- Particularly suitable fatty alcohol sulfates are derived from lauryl and myristyl alcohol, so are fatty alcohol sulfates with 12 or 14 carbon atoms.
- the long-chain FAS types (C 6 to C 8 ) are very suitable for washing at higher temperatures.
- Other anionic surfactants which can preferably be used are, for example, alkanesulfonates (for example C13-C18 secondary alkanesulfonate), methyl ester sulfonates (for example ⁇ -C12-C18 methyl ester sulfonate) and ⁇ -olefin sulfonates (for example ⁇ -C14-C18 olefinsulfonate) and alkyl ether sulfates (for example C12). C14 fatty alcohol 2EO ether sulfate) and / or soaps. Further suitable anionic surfactants will be described below. However, FAS and / or LAS are particularly suitable.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- the washing or cleaning agent according to the invention contains nonionic surfactant, advantageously in amounts of from 0.01 to 25% by weight, more preferably from 1 to 20% by weight, in particular in amounts of from 3 to 15% by weight. , relative to the entire remedy.
- nonionic surfactant advantageously in amounts of from 0.01 to 25% by weight, more preferably from 1 to 20% by weight, in particular in amounts of from 3 to 15% by weight.
- alkylpolyglycol ethers in particular in combination with anionic surfactant, such as preferably LAS.
- nonionic surfactants are alkylphenol polyglycol ethers (APEO), (ethoxylated) sorbitan fatty acid esters (sorbitans), alkyl polyglucosides (APG), fatty acid glucamides, fatty acid ethoxylates, amine oxides, ethylene oxide-propylene oxide block polymers, polyglycerol fatty acid esters and / or fatty acid alkanolamides.
- APEO alkylphenol polyglycol ethers
- APG alkyl polyglucosides
- fatty acid glucamides fatty acid ethoxylates
- amine oxides amine oxides
- ethylene oxide-propylene oxide block polymers polyglycerol fatty acid esters and / or fatty acid alkanolamides.
- suitable nonionic surfactants will be described below.
- Sugar-based nonionic surfactants, such as APG in particular, are particularly preferred
- the builders according to the invention include, in particular, zeolites, polycarboxylates, citrates (such as sodium citrate), soda, sodium bicarbonate, phosphates, sodium silicates (water glass), phosphonates, alkaline amorphous disilicates and crystalline layered silicates.
- Builders are in the detergent or cleaning agent according to the invention preferably in amounts of 0.1 to 80 wt .-%, advantageously 1 to 60 wt .-%, in a further advantageous manner, 5 to 50 wt .-%.
- the washing or cleaning agent according to the invention contains a builder system (ie at least 2 builder-builders), preferably a zeolite-containing builder system, preferably comprising zeolite in amounts of> 1% by weight, more preferably> 5% by weight. %, more preferably> 10% by weight, in particular> 15% by weight, based on the total agent.
- a builder system ie at least 2 builder-builders
- a zeolite-containing builder system preferably comprising zeolite in amounts of> 1% by weight, more preferably> 5% by weight. %, more preferably> 10% by weight, in particular> 15% by weight, based on the total agent.
- a reasonable upper limit of zeolite may e.g. at 40 wt .-%, 30 wt .-% or 20 wt .-%, based on the total agent. This corresponds to a preferred embodiment of the invention.
- Preferred is combination of zeolite with soda.
- the washing or cleaning agent according to the invention contains a soluble builder system, preferably comprising soda, silicate, citrate and / or polycarboxylates, advantageously in amounts of from 0.1 to 50% by weight, based on the total agent , This corresponds to a preferred embodiment of the invention.
- a soluble builder system preferably comprising soda, silicate, citrate and / or polycarboxylates, advantageously in amounts of from 0.1 to 50% by weight, based on the total agent.
- insoluble builders such as, in particular, zeolite, e.g. ⁇ 5 wt .-% to 0.1 wt .-% are included, especially in such a case, no insoluble builder is included.
- the washing or cleaning agent according to the invention may contain phosphates, phosphate preferably being present in amounts of from 1 to 40% by weight, in particular from 5 to 30% by weight, based on the total agent. According to another preferred embodiment, however, the washing or cleaning agent according to the invention is free of phosphates.
- the detergents or cleaners according to the invention which can be in the form of, in particular, pulverulent solids, in densified particle form, as homogeneous solutions or suspensions, can furthermore in principle contain all known ingredients customary in such agents.
- the agents according to the invention may in particular be builders, surfactants, bleaching agents, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, fluorescers, grayness inhibitors, anti-shrinkage agents, anti-wrinkling agents, Color transfer inhibitors, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, glass corrosion inhibitors, disinfectants tion aids antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slipping agents, neutral filler salts and UV absorbers, foam regulators and dyes and fragrances.
- the detergents and cleaning agents according to the invention may also contain so-called free, non-microencapsulated perfume oils (fragrances). This corresponds to a particularly preferred embodiment of the invention.
- the composition of these perfume oils may be the same as or different from that of the encapsulated perfume oils. Based on the total washing or cleaning agent, it may preferably contain from 0.0001 to 15% by weight, advantageously from 0.001 to 10% by weight, in particular from 0.01 to 5% by weight, of fragrances.
- Another object of the invention is a process for the preparation of a solid detergent or cleaning agent, characterized
- compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step and granulation are preferred.
- compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
- the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses pressed.
- it can be advantageous if at least one layer is pre-compressed. Obtained so easily break-resistant, yet sufficiently soluble under conditions of use tablets.
- the spatial form of the tablets is arbitrary and may be round, oval or angular, although intermediate forms are possible. Corners and edges are advantageously rounded.
- Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
- the microcapsules of the invention may e.g. be subsequently suspended in the otherwise "ready" composition.
- Another object of the invention is a process for the preparation of a liquid detergent or cleaning agent, characterized by the stirring of a microcapsule dispersion, comprising microcapsules whose capsule walls comprise a resin, which by reaction
- microcapsule dispersion into the liquid washing or cleaning agent matrix or by continuous addition of the microcapsule dispersion into a liquid washing or cleaning agent matrix and mixing via static mixing elements, wherein the microcapsule dispersion has preferably been previously mixed with surfactant in each case.
- microcapsules In the preparation of the washing or cleaning agents according to the invention in general, whether solid or liquid, it is advantageous to introduce the microcapsules to be introduced in the form of a microcapsule slurries (aqueous dispersion of the microcapsules). It has proved to be very advantageous to provide the microcapsule slurry for stabilization with surfactant, wherein as a surfactant cationic, anionic and / or nonionic surfactant is used, preferably nonionic surfactant, in particular ethoxylated oxoalcohol is suitable.
- Such stabilized microcapsule slurries are easier to process. Otherwise, the processability of the microcapsule slurries can be made more difficult by reversible flocculation.
- Anionic surfactants can advantageously be used in amounts of from 1 to 40% by weight, for example from 2 to 30% by weight, in particular from 3 to 20% by weight, for stabilizing the dispersions,% by weight, based on the total dispersion.
- Cationic surfactants may advantageously be used in amounts of 0.001 to 4 wt .-%, for example 0.01 to 3 wt .-% and in particular 0.1 to 2 wt .-% for stabilizing the dispersions, wt .-% based on the entire dispersion.
- Nonionic surfactants may advantageously be used in amounts of from 0.01 to 20% by weight, for example from 0.1 to 15% by weight, in particular from 1 to 10% by weight, for stabilizing the dispersions,% by weight based on the total dispersion.
- Suitable anionic surfactants are, for example, alkylbenzenesulfonates, preferably secondary C 10 -C 13 -n-alkyl- benzenesulfonate, alkanesulfonates, methyl ester sulfonates, ⁇ -olefin sulfonates, alkyl sulfates, preferably fatty alcohol sulfate, alkyl ether sulfates, preferably fatty alcohol ether sulfate and sulfosuccinates.
- Suitable cationic surfactants are, for example, quaternary ammonium compounds, in particular quaternary ammonium compounds having one or two hydrophobic alkyl radicals, quaternary phosphonium salts or tertiary sulfonium salts. Particular preference is given to so-called ester quats. Esterquat is the collective name for cationic surfactant compounds having preferably two hydrophobic groups linked via ester linkages to a quaternized di (tri) ethanolamine or an analogous compound.
- nonionic surfactants for stabilizing aqueous microcapsule dispersions has proved to be particularly advantageous.
- Particularly advantageous are fatty alcohol ethoxylates, oxoalcohol ethoxylates, alkylphenol polyglycol ethers, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triacylglycerols and mixed ethers (alkylated on both sides of polyethylene glycol ethers) and alkyl polyglucosides, sucrose esters, sorbitan esters, fatty acid glucamides and amine oxides.
- oxo alcohol ethoxylates are derived from oxoalcohols having 9 to 15 carbon atoms, to which preferably 3 to 15 moles of ethylene oxide are attached.
- a particularly preferred oxo alcohol ethoxylate in the context of the invention is C 3 -C 5 oxo alcohol, to which 7 moles of ethylene oxide are attached.
- a suitable commercial product is, for example, Lutensol® AO 7 from BASF.
- microcapsule dispersions described above are particularly advantageous in the preparation of liquid detergents or cleaners.
- a process according to the invention in which a liquid detergent or cleaning agent is mixed with a microcapsule dispersion as described above, preferably by stirring the microcapsule dispersion into the detergent or cleaning agent matrix or by continuous addition to a liquid detergent or conditioner and mixing via static mixing elements Therefore, a preferred embodiment of the invention.
- Another object of the invention is a textile washing process, using a washing or cleaning agent according to the invention (as described above), preferably in an automatic washing machine, wherein the washing temperature ⁇ 60 ° C, preferably ⁇ 40 ° C.
- Preferred washing or cleaning agents according to the invention are textile aftertreatment agents. These also contain the microcapsules used according to the invention as well as surfactants and / or builders. These are preferably fabric softeners, ie textile aftertreatment agents containing a cationic surfactant. Preferably contained cationic surfactants are esterquats. Esterquats are quaternary ammonium compounds having preferably two hydrophobic radicals, each containing an ester group as a so-called predetermined breaking point for easier biodegradation. The amount of cationic surfactant is preferably 2 to 80% by weight, advantageously 4 to 40% by weight, more preferably 6 to 20% by weight and in particular 8 to 15% by weight, in each case based on the total agent.
- polyquaternized polymers for example Luviquat® Care from BASF
- chitin-based cationic biopolymers and their derivatives for example the polymer available under the trade name Chitosan® (manufacturer: Cognis).
- Another object of the invention is a Textilkonditionierbacter using a textile aftertreatment agent according to the invention (as described above) in the rinse of an automatic washing machine.
- Another object of the invention is a textile drying process using a washing or cleaning agent according to the invention in an automatic clothes dryer.
- Another object of the invention is a textile conditioning process using a textile aftertreatment agent according to the invention in the form of a conditioning substrate in an automatic clothes dryer.
- Another object of the invention is the use of a textile aftertreatment agent according to the invention for conditioning textile fabrics.
- cleaning agents within the meaning of the invention are also cleaning agents, in particular cleaners for hard surfaces. These also contain the microcapsules used according to the invention and Surfactants and / or builders.
- cleaning detergents also include scent delivery systems comprising a container as well as particles for deodorizing and scenting the automatic dishwashing machine, these particles comprising scent-containing microcapsules.
- the cleaning agent according to the invention is selected from the group of hand dishwashing detergents, machine dishwashing detergents, toilet cleaners, pipe cleaners, universal cleaners, sanitary cleaners, oven cleaners or grill cleaners, metal cleansers, glass cleaners Window cleaner, the cleaning aids, the floor cleaning agent and the special cleaning agent, so is a preferred embodiment of the invention.
- Another object of the present invention is a particulate detergent or cleaning agent additive, comprising the microcapsules already described invention usable as well as surfactants and / or builders.
- Another object of the invention is the use of a washing or cleaning agent according to the invention in a washing or cleaning process for the deposition of microcapsules on the treated objects (surfaces) to enable the targeted release of preferably liquid active substances, such as in particular fragrances, on the objects by mechanical stimulus.
- Another object of the invention is the use of a washing or cleaning agent according to the invention in a washing or cleaning process for the deposition of microcapsules on the treated objects (surfaces) to enable the long-lasting release of preferably liquid active substances, in particular fragrances, on the objects by diffusion ,
- the aqueous solution is characterized by viscosity, solid content and pH.
- the viscosity is 540 mPas (measured at 20 rpm Brookfield), the solids content is 21% and the pH is 3.3.
- 3 g of copolymer are placed on a Petri dish and dried for 24 hours at 160 ° C in a drying oven. The weight is 0.69 g, which corresponds to a yield of 21, 6%.
- the template consists of 912 g of demineralised water, 240 g of AMPS and 7.5 g of poly (ethylene / propylene) glycol monomethacrylate (Bisomer PEM 63P HD ex Cognis, CAS No. 589-75-9).
- the mixture is placed under a protective gas atmosphere.
- the reaction mixture is heated to 75 ° C. with stirring (400 rpm). 1, 5 g of sodium peroxodisulfate are dissolved in 15 g of water and transferred with a syringe in the reactor.
- AMPS AMPS with 83 g of PEM 63P HD are metered over a period of one hour by means of a peristaltic pump. This is followed by a half-hour post-reaction. The mixture is then cooled to room temperature and treated with 1, 5 g preservative.
- the aqueous solution is characterized by viscosity, solid content and pH.
- the viscosity is 1 10 mPas (measured at 20 rpm Brookfield), the solids content is 23% and the pH is 3.1. 3 g of copolymer are placed on a Petri dish and dried for 24 hours at 160 ° C in a drying oven. The weight is 0.68 g, which corresponds to a yield of 21, 6%.
- Example I.2 resorcinol capsule
- the capsules produced are formaldehyde-free and can be prepared as stable core / shell microcapsules from the aqueous slurry without problems to a dry
- the loading of the capsules can be carried out instead of Butylphenylacetat with other gaseous, liquid or solid hydrophobic materials and classes of substances, in particular fragrances or perfume oils.
- Example I.3 hydroxycitronellal-containing resorcinol microcapsules
- Example 1.4 Helional-containing resorcinol microcapsules
- Example I.5 citral-containing resorcinol microcapsules
- Example I.6 Bourgeon-containing resorcinol microcapsules
- Example I.7 Triplal-containing resorcinol microcapsules
- Example 1.8 Ligustral-containing resorcinol microcapsules
- Example 1.9 Vertocitral-containing resorcinol microcapsules
- Example 1.10 Florhydral-containing resorcinol microcapsules
- Example 1.1 Citronellal-containing resorcinol microcapsules
- Example 1.12 Citronellyloxyacetaldehyde-containing resorcinol microcapsules. In another example series phloroglucin microcapsules were prepared. Analogously to the method according to Example I.2. The 5.5 g of resorcinol used there were completely replaced by 6.3 g of pho- roglucinol. In this way you got:
- Example 14 hydroxycitronellal-containing phloroglucin microcapsules
- Example 15 helional-containing phloroglucin microcapsules
- Example 16 Citral-containing phloroglucin microcapsules
- Example 17 Bourgeon-containing phloroglucin microcapsules
- Example .18 Triplal-containing phloroglucin microcapsules
- Example 19 Ligustral-containing phloroglucin microcapsules
- Example 20 Vertocitral-containing phloroglucin microcapsules
- Example 22 citronellal-containing phloroglucin microcapsules
- nonwovens made of cellulose (area: 24.5 cm ⁇ 39 cm) were impregnated with 20 g of the liquid conditioner according to Example 11.1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL11752566T PL2614134T3 (en) | 2010-09-10 | 2011-09-09 | Microcapsule containing detergent or cleaning agent |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE201010040564 DE102010040564A1 (en) | 2010-09-10 | 2010-09-10 | Microcapsule-containing washing or cleaning agent |
PCT/EP2011/065618 WO2012032145A1 (en) | 2010-09-10 | 2011-09-09 | Microcapsule containing detergent or cleaning agent |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2614134A1 true EP2614134A1 (en) | 2013-07-17 |
EP2614134B1 EP2614134B1 (en) | 2017-11-08 |
Family
ID=44583076
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11752566.7A Not-in-force EP2614134B1 (en) | 2010-09-10 | 2011-09-09 | Microcapsule containing detergent or cleaning agent |
Country Status (8)
Country | Link |
---|---|
US (1) | US8901064B2 (en) |
EP (1) | EP2614134B1 (en) |
KR (1) | KR101778830B1 (en) |
DE (1) | DE102010040564A1 (en) |
ES (1) | ES2656533T3 (en) |
HU (1) | HUE038132T2 (en) |
PL (1) | PL2614134T3 (en) |
WO (1) | WO2012032145A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2708593A1 (en) * | 2012-09-14 | 2014-03-19 | The Procter & Gamble Company | Fabric care composition |
CN104094923B (en) * | 2013-04-09 | 2016-06-15 | 民政部一零一研究所 | A kind of antiseptic preserving fluid for corpse, tissue and dissection and using method thereof |
CA2918844A1 (en) * | 2013-08-28 | 2015-03-05 | The Procter & Gamble Company | Microcapsule-containing detergent or cleaning agent |
FR3025211B1 (en) * | 2014-08-29 | 2016-08-26 | Ipc | STABLE DISINFECTANT COMPOSITION INCLUDING MICROCAPSULES |
DE102015205802A1 (en) * | 2015-03-31 | 2016-10-06 | Henkel Ag & Co. Kgaa | Detergent composition with bleach catalyst and perfume capsules |
DE102017111445A1 (en) | 2017-05-24 | 2018-11-29 | Henkel Ag & Co. Kgaa | Microcapsule system for polysensory scent effects |
DE102017111444A1 (en) | 2017-05-24 | 2018-11-29 | Henkel Ag & Co. Kgaa | Microcapsule system for polysensory scent effects |
WO2020114571A1 (en) * | 2018-12-03 | 2020-06-11 | Symrise Ag | Microcapsules |
FR3091878B1 (en) | 2019-01-22 | 2023-06-16 | Calyxia | CLEANING PRODUCT COMPOSITIONS WITH ENHANCED OLFACTIVE PROPERTIES |
FR3091877B1 (en) | 2019-01-22 | 2023-06-16 | Calyxia | DETERGENCE COMPOSITIONS WITH ENHANCED OLFACTIVE PROPERTIES |
US11970627B2 (en) * | 2020-01-21 | 2024-04-30 | Heraeus Deutschland GmbH & Co. KG | Formulation for application onto glass, porcelain, tiles, metals and plastic foil |
KR102445205B1 (en) * | 2022-08-01 | 2022-09-20 | 주식회사 케이컴퍼니 | Textile coating composition for preventing crease, crease resistant textile and method for fabricating the same |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3726803A (en) * | 1970-02-16 | 1973-04-10 | Ncr | Capsule wall treating process utilizing condensation polymerization and capsule product |
US3755190A (en) | 1971-11-09 | 1973-08-28 | Ncr | Capsule manufacture |
AT330930B (en) | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES |
JPS63269146A (en) | 1987-04-28 | 1988-11-07 | Fuji Photo Film Co Ltd | Photosensitive microcapsule and photosensitive material |
US4918317A (en) | 1987-07-02 | 1990-04-17 | The Mead Corporation | Radiation dosimeter |
DE3723873A1 (en) | 1987-07-18 | 1989-01-26 | Henkel Kgaa | USE OF HYDROXYALKYLPOLYETHYLENE GLYCOLETHERS IN RINSE AID FOR MACHINE CLEANING |
CA1329035C (en) | 1987-12-03 | 1994-05-03 | Joseph Gerald O'connor | Method for producing amine-formaldehyde microcapsules and photosensitive microcapsules produced thereby |
JP2587696B2 (en) | 1989-02-17 | 1997-03-05 | 富士写真フイルム株式会社 | Photosensitive material |
DE3929052A1 (en) | 1989-09-01 | 1991-03-07 | Basf Ag | METHOD FOR PRODUCING SPHERICAL, HARD MONO- OR OLIGODISPERSE PARTICLES MELAMINE RESIN |
DE19833347A1 (en) | 1998-07-24 | 2000-01-27 | Basf Ag | Low-formaldehyde dispersion of microcapsules made from melamine-formaldehyde resins |
DE10000223A1 (en) * | 2000-01-05 | 2001-07-12 | Basf Ag | Microcapsules which are useful in, e.g. detergent or skin care compositions, can release a fragrance from a hydrophobic core when the polymer coating of the capsule is broken down |
DE10000621A1 (en) | 2000-01-10 | 2001-07-12 | Basf Ag | Low-viscosity, formaldehyde-reduced dispersions of microcapsules made from melamine-formaldehyde resins |
GB0802489D0 (en) * | 2008-02-11 | 2008-03-19 | Givaudan Sa | Product |
-
2010
- 2010-09-10 DE DE201010040564 patent/DE102010040564A1/en not_active Ceased
-
2011
- 2011-09-09 PL PL11752566T patent/PL2614134T3/en unknown
- 2011-09-09 HU HUE11752566A patent/HUE038132T2/en unknown
- 2011-09-09 ES ES11752566.7T patent/ES2656533T3/en active Active
- 2011-09-09 KR KR1020137009038A patent/KR101778830B1/en active IP Right Grant
- 2011-09-09 WO PCT/EP2011/065618 patent/WO2012032145A1/en active Application Filing
- 2011-09-09 EP EP11752566.7A patent/EP2614134B1/en not_active Not-in-force
-
2013
- 2013-03-08 US US13/789,778 patent/US8901064B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2012032145A1 * |
Also Published As
Publication number | Publication date |
---|---|
ES2656533T3 (en) | 2018-02-27 |
KR101778830B1 (en) | 2017-09-14 |
DE102010040564A1 (en) | 2012-03-15 |
US8901064B2 (en) | 2014-12-02 |
KR20130140662A (en) | 2013-12-24 |
US20130203642A1 (en) | 2013-08-08 |
PL2614134T3 (en) | 2018-04-30 |
HUE038132T2 (en) | 2018-09-28 |
EP2614134B1 (en) | 2017-11-08 |
WO2012032145A1 (en) | 2012-03-15 |
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