WO2016005149A1

WO2016005149A1 - Low-odor polyurethane systems

Info

Publication number: WO2016005149A1
Application number: PCT/EP2015/063385
Authority: WO
Inventors: Jörg DIENDORF; Ruediger Landers; Eva Emmrich-Smolczyk
Original assignee: Evonik Degussa Gmbh
Priority date: 2014-07-09
Filing date: 2015-06-16
Publication date: 2016-01-14
Also published as: DE102014213290A1

Abstract

In order to provide low-odor polyurethane systems, in particular foams, an additive that is rich in odoriferous substances is used during synthesis of polyurethane systems, at least 5 wt% of the odiferous substances used having a ClogP value > 4 and a boiling point > 275°C.

Description

Low-odor polyurethane systems

The invention is in the field of polyurethanes and relates in particular to a perfume-containing additive for the production of polyurethane systems, a composition for the production of a polyurethane system, the use of perfume-containing additives in connection with polyurethane foams, a process for the preparation of a polyurethane system, a polyurethane system and the like Use.

Polyurethane systems in the context of this invention are, for. Polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or, in particular, polyurethane foams / foams.

Polyurethane foams are used in a wide variety of applications due to their excellent mechanical and physical properties. A particularly important market for various types of polyurethane foams, such as conventional ether and ester polyol based flexible foams, cold foams (often referred to as HR foams), viscoelastic foams, rigid foams, integral foams and microcellular foams, as well as foams whose properties lie between these classifications , such as B. semi-rigid systems, e.g. the automotive and furniture industries. B. rigid foams as a headliner, ester foams for interior lining of the doors and for punched sun visors, viscoelastic cold and soft foams used for seating systems, upholstered furniture and mattresses.

Because of their outstanding mechanical and physical properties, polyurethane foams are also extremely popular with end users and are in high demand, e.g. in connection with mattresses.

However, it is unfavorable that polyurethane foams or products containing them, such as e.g. Mattresses, usually with a smell can be afflicted. For example, consumers indicate that corresponding mattresses would smell more or less unpleasant at least in the first few days after unpacking, the odor being e.g. sometimes perceived as sweetish, sometimes as musty, sometimes as stinging. For some of these products, the perceived annoying odor is criticized by the consumer even after a month.

Although these odors pose no immediate health risk, they are still considered by consumers to be unacceptable harassment. Some consumers even have health concerns and, if possible, do not want to use the products because of the odor, although objectively no health concerns are justified, as demonstrated by pollutant measurements. For this reason, the foam manufacturers, in particular from the furniture industry and

Mattress industry, strives to take measures that meet the smell problem. Such measures include, for example, allowing the freshly made mattresses to be thoroughly air-dried at the factory before they are packaged and put into distribution. However, this is disadvantageous because it creates a delay in the production chain and, moreover, an increased storage capacity is necessary. Another measure is to mask the odor of the mattresses, which the consumer finds unpleasant, by means of a pleasant scent. For this perfume is used. This solution is basically only suboptimal and is usually vehemently rejected by the consumer, especially in the mattress area. The outgoing from the mattress, masking perfume smell is namely perceived very clearly by the consumer resting on it and also classified as a nuisance. In some cases it is even stated that the smell of perfume leads to headaches and to sleep problems. In addition, it is difficult to meet the different fragrance preferences of consumers.

Thus, there is still a desire from both the consumer and the industry side for as low-odor polyurethane foams.

The object of the present invention was therefore to provide as low-odor polyurethanes, in particular polyurethane foams. Surprisingly, it has now been found that perfume-containing additives, wherein at least 5 wt .-% of the fragrances contained therein, wt .-% based on the total amount of all fragrance contained in the additive, a ClogP value> 4 and a boiling point> 275 ° C have , the provision of low odor to odorless polyurethanes, especially polyurethane foams allow.

The present invention thus provides a fragrance-containing additive for the production of polyurethane systems, in particular a polyurethane foam, wherein at least 5 wt .-% of the fragrance contained in the additive, based on the total amount of all the fragrances contained in the additive, a ClogP value> 4 and a Boiling point> 275 ° C have.

This object solves the problem of the invention. Whenever the additive according to the invention is used in a process for the production of polyurethane systems, it is possible to provide polyurethanes, in particular polyurethane foams, which have a reduced odor, preferably down to odor neutrality.

The subject invention makes it possible that the emanating from polyurethane systems odor nuisance can be reliably minimized or advantageously even completely prevented. This allows e.g. as a result, the provision of such mattresses that smell significantly less or not at all on the first day after unpacking.

This is a very significant improvement over the previous proposals from the state The technique, because the additive of the invention thus allows for the first time the provision of polyurethane systems (in particular polyurethane foam), in which the odor problem is overcome. The intensity of the smell is reduced; the acceptance of the possibly remaining residual odor is increased, ie the odor of the conventional PU system, in particular foam is classified as unpleasant as the one in which the additive according to the invention with otherwise identical production method is used; the resulting PU system, in particular foam, is odorless; in the optimal case, even an odor extinction can take place. The term "fragrance" is well known to those skilled in the art. These are understood to mean chemical compounds with human-perceivable odor. Typical examples of fragrances include geraniol (floral odor), citral (smell of citrus), hex-3-en-1-ol (smell of grass and green leaves), thujone (herbaceous odor), (-) - carvone (mint Smell), santalol (woody odor). Fragrances preferred according to the invention are fragrances, ie fragrances with a pleasant odor effect for humans. The term "fragrances" is known to those skilled in the art Fragrances are used, for example, in alcoholic solution for the production of perfumes, in order to produce a lasting fragrance The opposite of fragrances are fragrances with kakosmophoren groups, such as 3-methyl-1 Butanthiol, which have a malodorous odor effect on humans.The "ClogP value" is also well known to those skilled in the art, in particular from the patent literature. It is due to the octanol / water partition coefficient. The octanol / water partition coefficient of a chemical compound, such as a fragrance, is the ratio between its equilibrium concentration in octanol and in water. Since these distribution coefficients often have high values, eg 1000 or higher, they are more conveniently given in the form of their base 10 logarithm, one speaks of the so-called log P value.

The experimental logP value of many fragrances is documented in the literature. However, logP values can most conveniently be calculated by the "CLOGP" program available from Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, California.

The so-called "logP values" (= clogP values), which are the most reliable and widely used estimates for this physicochemical property, are used in this context

Invention therefore used in the selection of perfume ingredients. The "calculated logP values" are also documented in the literature or accessible via the "CLOGP" program of the Daylight Chemical Information Systems. If only experimental logP is available, it is possible to use the experimental logP value instead of the ClogP value. The "calculated logP" (this is the ClogP value) is determinable by the Harsch and Leo fragment approach (see A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Harsch, PG Sammens, JB Taylor and CA Ransden, Eds., P. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each of the Perfume ingredients and takes into account the numbers and types of atoms, the atomic bondability and chemical bonding.

The boiling points of many fragrances are e.g. in "Perfume and Flavor Chemicals" (Aroma Chemicals), S. Arctander, published by the author in 1969, incorporated herein by reference. Other boiling point values may be e.g. from various known chemical manuals and databases. If a boiling point is indicated only at a different pressure, typically a pressure lower than the normal pressure of 760 mm Hg, the boiling point at normal pressure can be determined approximately with the help of boiling point pressure nomographs such as those described in "The Chemist's Companion", AJ Gordon and RA Ford, John Wiley & Sons Publishers, 1972, pp. 30-36, are incorporated herein by reference.

According to the invention, it is necessary for the perfume-containing additive to have at least 5% by weight, based on the sum of the fragrances contained in the additive, of perfumes having a ClogP value> 4 and a boiling point> 275 ° C.

Compounds which can be used according to the invention, their preparation, the use of the compounds for producing the polyurethane system or foams and the polyurethane system or foams themselves are described in more detail below by means of exemplary embodiments, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the matters referred to, should form part of the disclosure content of the present invention. If the following information is given as a percentage, it is, unless stated otherwise, in% by weight. If mean values are given below, this is the number average, unless otherwise stated. Are below material properties such. As viscosities or the like, it is, unless otherwise stated, the material properties at 25 ° C. Be in the present

If the invention uses chemical (sum) formulas, the indicated indices may represent both absolute numbers and averages. In the case of polymeric compounds, the indices preferably represent average values. According to a preferred embodiment of the invention, at least 10% by weight, preferably at least 15% by weight, advantageously at least 20% by weight, more preferably at least 25% by weight and in particular at least 30 wt .-% of the odoriferous substances contained in the additive a ClogP value> 4 and a boiling point> 275 ° C, wherein a Upper limit, for example, at 70 wt .-%, 60 wt .-%, 50 wt .-% or 40 wt .-% may be, wt .-% in each case based on the sum of the fragrances contained in the additive.

Fragrances with a ClogP value> 4 and boiling point> 275 ° C are well known to the person skilled in the art, in particular according to a preferred embodiment of the invention they are selected from the group comprising ambrettolide, amyl cinnamic aldehyde, amyl cinnamaldehyde dimethyl acetal. isoamylsalicylate, aurantiol, benzylsalicylate, cardinen, cedrol, cedrylacetate, cinnamylcinnamate, cyclohexylsalicylate, ethylbrassylate, exaltolide, geranylanthranilate, hexadecanolide, hexylcinnamaldehyde, hexylsalicylate, methyldihydrojasmon, oxahexadecanolide-10, patchouli alcohol, phantolide, phenylethylbenzoate, thibetolide, gamma undecalactone and / or vetiveryl acetate. In principle, all fragrances with a ClogP value> 4 and boiling point> 275 ° C can be used. However, the aforesaid fragrances have proven to be particularly useful in accomplishing the objects of this invention and are particularly conducive to, for the purposes of this invention, e.g. reduce the intensity of the end product odor (e.g., a PU mattress), increase the acceptance of any residual odor, and render the resulting product more odorless overall.

The perfume-containing additive may in principle comprise, in addition to the perfume, other components, such as e.g. Solvents, emulsifiers and / or antioxidants. Other components may also be included in the perfume-containing additive, such as e.g. components typical of PU application, e.g. tertiary amines and / or silicone stabilizers.

As solvent, if present, in particular dipropylene glycol is used for the perfume-containing additive. Other solvents commonly used in perfumery, such as, in particular, dimethyl phthalate, diethyl phthalate, propanol and isopropyl alcohol, may e.g. also be used. Dipropylene glycol is odorless and not a fragrance in the sense of this invention. typical

Solvents such as, in particular, the said dimethyl phthalate, diethyl phthalate, propanol and isopropyl alcohol, and e.g. Ethanol, toluene, etc. are not fragrances in the sense of this invention.

Suitable antioxidants for the perfume-containing additive are e.g. Butylhydroxyanisole, tocopherol (e) and butylhydroxytoluene. Others, in particular in perfumery usual

Antioxidants can also be used.

Suitable emulsifiers for the perfume-containing additive are e.g. nonionic emulsifiers, ie surfactants which do not form ions in aqueous solution, e.g. Fatty alcohols (eg, lauryl, cetyl, stearyl or palmityl alcohol), partial fatty acid esters of polyhydric alcohols with saturated fatty acids (for example, glycerol monostearate, pentaerythritol monostearate, ethylene glycol monostearate, propylene glycol monostearate), partial fatty acid esters of polyhydric alcohols with unsaturated fatty acids (for example, glycerol monooleate, pentaerythritol monooleate); Polyoxyethylene esters of fatty acids (eg polyoxyethylene stearate), polymerization products of ethylene oxide and propylene oxide with fatty alcohols (fatty alcohol polyglycol ethers) or fatty acids

(Fatty acid). According to a preferred embodiment of the invention, the odoriferous additive according to the invention contains> 50% by weight, preferably> 60% by weight, in particular> 70% by weight, of fragrances, based on the total additive. According to a preferred embodiment of the invention, the additive according to the invention can advantageously contain up to 50% by weight, preferably up to 40% by weight, in particular up to 30% by weight of solvent, in particular dipropylene glycol. If desired, suitable antioxidants may be present in amounts <2% by weight, based on the total additive, with a lower limit of 0.001% by weight. If desired, suitable emulsifiers may be present in amounts of <2% by weight, based on the total additive, a lower limit being 0.001% by weight.

For example, an odiferous additive according to the invention may comprise 50-95% by weight of fragrances, 5-50% by weight of solvent, especially dipropylene glycol, optionally 0.001-2% by weight of antioxidant and optionally 0.001-2% by weight of emulsifier (s) , According to a further preferred embodiment of the invention, the fragrance-containing additive according to the invention may further comprise one or more, preferably tertiary amines, one or more silicone stabilizers.

In particular, a perfume-containing additive according to the invention may contain silicone stabilizers, e.g. in an amount of> 1 wt .-%, advantageously> 30 wt .-%, preferably> 40 wt .-%, in particular> 50 wt .-%.

According to a further preferred embodiment of the invention, the odoriferous additive according to the invention comprises at least 5% by weight, preferably at least 10% by weight, in particular at least 15% by weight of fragrances having a CbgP value <3, an upper limit e.g. can be at 50 wt .-%, 40 wt .-%, 30 wt .-% or 20 wt .-%, wt .-% in each case based on the sum of the fragrances contained in the additive.

Fragrances with a ClogP value <3 are known in principle to the person skilled in the art, in particular the fragrances having a ClogP value <3 according to a further preferred embodiment of the

Invention selected from the group menthone, phenoxyethanol, Benzyldimethylcarbinolacetat. Piperonal, isobutyl salicylate, phenoxyethyl isobutyrate, anisaldehyde, fluoroacetate, rose oxide, Cyclal C. Fruten, ethyl 2-methyl butyrate. Benzyl alcohol, ethyl 2-methylpentanoate, benzyl acetate, phenylethyl alcohol, 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, tricyclodecenyl acetate, methylisobutenyltetrahydropyran, 4-methoxybenzaldehyde, 3,7, dimethyl-1,6-octadiene-3 ol 4-phenylbutan-2-o, phenytmethylethanoate, vanillin, coumarin and / or phenylacetaldehyde dimethyl acetal. In principle, all fragrances with a ClogP value <3 can be used. However, the above-mentioned fragrances have once again proven particularly useful to achieve the objectives of this invention and are particularly useful in the context of this invention, for example, to reduce the intensity of the end product odor (eg a PU mattress), the acceptance of possibly To increase remaining odor and make the resulting product odorless overall.

In the context of the invention, it has also proved to be advantageous if at least 5 different, preferably at least 10 different and in particular at least 15 different fragrances are contained in the additive according to the invention.

It has also proven to be advantageous for the purposes of the invention if the additive according to the invention contains fragrances having a boiling point <250 ° C, advantageously in amounts of 5 to 40 wt .-%, for example 5 to 30 wt .-% or 5 to 20 Wt .-% or 5 to 15 wt .-%, wt .-% in each case based on the sum of the odoriferous substances contained in the additive, in particular selected from the group comprising linalool, anisaldehyde, rose oxide, Cyclal C, ethyl 2-methyl butyrate, Allo ocimene, allyl heptanoate, cis-3-hexenyltiglate, citronellol, carvacrol, camphene, benzyl butyrate, trans-anethole, citronellyl acetate, citronellylnitrile, cyclohexylethyl acetate, decyl aldehyde, dihydromyrcenol, 3,5,5-trimethyl-1-hexanol, lymolene, beta-myrcene , Nonaldehyde, para-cymene, alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene. Basically, all fragrances with a boiling point <250 ° C can be used. The aforesaid fragrances, however, have proven to be particularly advantageous in achieving the objects of this invention and are particularly useful in the context of this invention e.g. reduce the intensity of the end product odor (e.g., a PU mattress), increase the acceptance of any residual odor, and render the resulting product more odorless overall.

According to a preferred embodiment, an additive according to the invention may advantageously comprise the following components

a) at least 10 wt .-%, preferably at least 15 wt .-%, advantageously at least

20 wt .-%, more preferably at least 25 wt .-% and in particular at least 30 wt .-% fragrances having a ClogP value> 4 and a boiling point> 275 ° C, wherein an upper limit, for. may be 70% by weight, 60% by weight, 50% by weight or 40% by weight,

b) at least 5 wt .-%, preferably at least 10 wt .-%, in particular at least 15

% By weight perfumes having a ClogP <3, with an upper limit e.g. may be 50% by weight, 40% by weight, 30% by weight or 20% by weight,

c) fragrances having a boiling point <250 ° C, advantageously in amounts of 5 to 40% by weight, wt .-% at a), b), c) each based on the sum of the fragrance contained in the additive include, wherein the inventive additive contains> 50 wt .-%, preferably> 60 wt .-%, in particular> 70 wt .-%, fragrances, based on the total additive, and wherein in the additive according to the invention at least 5 different, preferably at least 10 different and in particular at least 15 different fragrances are contained. It has also proven to be advantageous in the context of the invention to optionally use at least partially encapsulated fragrances.

For the purposes of the invention, encapsulated fragrances are preferably fragrances which are encapsulated in microcapsules. Microcapsules and their preparation are known to those skilled in the art. The microcapsules which can be used according to the invention may preferably be water-soluble and / or water-insoluble microcapsules. Preferably, however, they are water-insoluble microcapsules. The release of active substance from the microcapsule can take place during and / or after PU foam production.

In particular, it is preferred that the microcapsules usable according to the invention are water-insoluble microcapsules, the wall material of the microcapsules being polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and compounds containing NH groups may include. In particular, the water-insoluble microcapsules are drivable.

The term drittable microcapsules means such microcapsules, which can be opened or wrenched by mechanical rubbing or by pressure, as it arises, for example, when the human body is lying on a mattress, so that a content release results only as a result of mechanical action. Preferred microcapsules which can be used according to the invention have diameters in the range from 0.05 to 500 μm, preferably between 5 and 150 μm, in particular between 10 and 100 μm, for example. 10-80 [im. The core or (filled) cavity enclosing shell of the microcapsules has a thickness in the range between advantageously about 0.01 and 50 μιτι, preferably between about 0, 1 μιτι and about 30 μιτι, in particular between about 0.5 μΐΎΐ and about 8 pm. In particular, microcapsules, which have the aforementioned diameter and shell thickness, are drivable in the context of the invention.

The procedure in microcapsule preparation as such is well known to those skilled in the art. Suitable methods of microcapsule preparation are familiar to those skilled in the art and are e.g. in US 387052, in US Pat. No. 3,516,941, in US Pat. No. 3,415,758 or also in EP 0026914 A1. The latter describes, for example, the production of microcapsules by acid-induced condensation of melamine-formaldehyde precondensates and / or their C1-C4-alkyl ethers in water, in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid. For example, melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules, e.g. available from 3M Corporation or BASF. Suitable microcapsules are e.g. also described in WO 2001/049817 A2.

It has been found that the water-insoluble microcapsules which can be used according to the invention, in particular the aminoplast capsules for example, can be incorporated particularly well and homogeneously into the resulting body, for example a mattress, in the foaming process. After the production of the body, for example the mattress, these capsules then usually have a certain brittleness, so that a targeted release of fragrance from the capsule can take place by the action of mechanical force. In this way, even after prolonged storage under the influence of mechanical force targeted a fragrance can be caused. If the additive according to the invention contains skin care ingredients such as almond oil, green tea extract or aloe vera preparations, D-panthenol, plankton extract, vitamin C, urea and / or glycine, in particular in microencapsulated form (preferably water-insoluble Microcapsules), so there is also a preferred embodiment of the invention. For example, (preferably water-insoluble) microcapsules can be used which contain both fragrances and ingredients for the care of the skin. Preferably used skin-care active substances are preferably also essential oils, such as Angelica fine - Angelica archangelica, rosewood - Aniba rosae odora. Sage - Salvia officinalis.

In this way, a targeted equipment of PU systems, such as. PU foam, for example with skin care capsule systems. For example, a mattress can be provided in this way, which gives off skin-care substances during use.

According to a further preferred embodiment of the invention, the additive according to the invention contains fragrance precursor.

The optional use of perfume precursors in the additives according to the invention is likewise very advantageous, preferably if these are present in the (preferably water-insoluble) microcapsule which can be used according to the invention. A fragrance precursor is a compound which releases a desired odor and / or perfume molecule by the breaking of a chemical bond, for example by hydrolysis. Typically, to form a perfume precursor, a desired perfume raw material is chemically combined with a carrier, preferably a slightly volatile or moderately volatile carrier. The combination results in a less volatile and more hydrophobic perfume precursor with improved attachment to fabrics. The fragrance is then released by disrupting the binding between the perfume raw material and the carrier, for example, by a change in pH (eg, by perspiration), humidity, heat, and / or sunlight. The perfume raw material for use in perfume precursors are typically saturated or unsaturated volatile compounds containing an alcohol, an aldehyde and / or a ketone group. Fragrance raw materials useful herein include any fragrant substances or mixtures of substances.

Particularly advantageous, usable according to the invention fragrance precursor obey the following formula

in which R is hydrogen, linear C 1 -C 8 -alkyl, branched C 3 -C 20 -alkyl, cyclic C 3 -C 20 -alkyl, branched cyclic C 6 -C 20 -alkyl, linear C 6 -C 20 -alkenyl, branched C 6 -C 20 -alkenyl, cyclic C6 -C 20 alkenyl, branched cyclic C 6 -C 20 alkenyl, substituted or unsubstituted C 6 -C 20 aryl, and mixtures thereof; R, R ² and R ^{3 are} independently linear, branched or substituted C ¹ -C 20 alkyl; linear, branched or substituted C 2 -C 20 alkenyl; substituted or unsubstituted C3-C20 cyclic alkyl; substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 40 alkyleneoxy; substituted or unsubstituted C3-C40 alkyleneoxyalkyl; substituted or unsubstituted C6-C40 alkylenearyl; substituted or unsubstituted C6-C32 aryloxy; substituted or unsubstituted C6-C40 alkyleneoxyaryl; C6-C40 oxyalkylene-enaryl and mixtures thereof. The use of such substances, in particular in the invention (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention. A preferred embodiment is when the fragrance precursor usable according to the invention releases compounds, obeying the following formula o

R - C - OR ¹ in which R is hydrogen, methyl, ethyl, phenyl and mixtures thereof; R is selected from the group consisting of 4- (1-methylethyl) cyclohexanemethyl, 2,4-dimethyl-3-cyclohexen-1-ylmethyl, 2,4-dimethylcyclo-hex-1-ylmethyl, 2,4,6- Trimethyl 3-cyclohexen-1-ylmethyl, 2-phenylethyl, 1- (4-isopropylcyclohexyl) ethyl, 2,2-dimethyl-3- (3-methylphenyl) propan-1-yl, 3-phenyl-2-propene 1-yl, 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) -2-buten-1-yl, 3-methyl-5-phenyl-pentan-1-yl, 3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -4-penten-2-yl, 2-methyl-4-phenylpentan-1-yl, cis-3-hexene 1-yl, 3.7-dimethyl-6-octen-1-yl, 3,7-dimethyl-2,6-octadien-1-yl, 7-methoxy-3-y-dimethyloctan-2-yl, 6,8-dimethylnonane 2-yl, cis-6-nonen-1-yl, 2,6-nonadien-1-yl, 4-methyl-3-decen-5-yl, benzyl, 2-methoxy-4- (1-propenyl) phenyl.2-methoxy-4- (2-propenyl) phenyl and mixtures thereof. The use of such substances, in particular in the invention (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention. Further particularly advantageous fragrance precursors which can be used according to the invention are acetals or ketals, preferably obeying the following formula

in which R is linear C1-C20-alkyl, branched C3-C20-alcyl, cyclic C6-C20-alkyl, branched cyclic C6-C20-alkyl, linear C2-C20-alkenyl, branched C3-C20-alkenyl, cyclic C6-C20 - Alkenyl. branched cyclic C6-C20 alkenyl, substituted or unsubstituted C6-C20 aryl, and mixtures thereof; R ^{1 is} hydrogen or R; R ² and R ^{3 are} each independently selected from the group consisting of linear C 1 -C 20 -alkyl, branched C ³ -C 20 -alkyl, cyclic C ³ -C 20 -alkyl, branched cyclic C 6 -C 20 -alkyl, linear C 6 -alkyl C20-alkenyl. branched C6-C20 alkenyl, cyclic C6-C20 alkenyl, branched cyclic C6-C20-AI-kenyl. C6-C20 aryl, substituted C7-C20 aryl, and mixtures thereof. The use of such substances, in particular in the invention (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention.

Further particularly advantageous, inventively used bare fragrance precursor obey the following formula

in which R ¹ , R ² , R ³ and R ⁴ independently of one another are linear, branched or substituted C 1 -C 20 -alkyl; linear, branched or substituted C2-C20 alkenyl; substituted or unsubstituted cyclic C5-C20-alkyl; substituted or unsubstituted C 6 -C 20 aryl, substituted or unsubstituted C 2 -C 40 alkyleneoxy; substituted or unsubstituted C3-C40 alkyleneoxyalkyl; substituted or unsubstituted C6-C40 alkylenearyl; substituted or unsubstituted C6-C32 aryloxy; substituted or unsubstituted C6-C40 alkylene-oxyaryl; C 6 -C 40 oxyalkylene aryl; and mixtures thereof. The use of such substances, in particular in the invention (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention.

It is particularly preferred if the fragrances used comprise silicic acid ester mixtures which are silicic acid esters of the formulas (I) and (II) immediately following

(II)

contain, wherein all R are independently selected from the group containing H, the straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C1-6 hydrocarbon radicals and the perfume alcohol residues and / or Bizidalkoholreste, and m values from the range 1 to 20 and n takes values from the range 2 to 100. Preferably, the silicic acid esters of formulas (I) and (II) each contain at least one Riechstoffalkoholrest and / or Bizidalkoholrest. The silicic acid ester mixtures can be used in particular in the invention (preferably water-insoluble) microcapsules used. It has surprisingly been found that the presence of the silicic acid ester mixtures results in that the purpose of the invention can be further improved.

Particularly suitable perfume precursors are reaction products of compounds comprising at least one primary and / or secondary amine group, for example an amino-functional polymer, especially an amino-functional silicone, and a perfume ingredient selected from ketone, aldehyde and mixtures thereof. The use of such substances, in particular in the invention (preferably water-insoluble) microcapsules, corresponds to a preferred embodiment of the invention. The additive according to the invention is used, as described, for the preparation of polyurethane systems. The preparation of the polyurethane systems using the additive according to the invention can advantageously be carried out in the usual way.

Another object of the present invention is a process for the preparation of a polyurethane system by reacting one or more polyol components with one or more isocyanate components in the presence of one or more catalysts, the Reactions are cyanate isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, wherein a fragrance-containing additive according to the invention, as described above, is used. In carrying out the process according to the invention for the preparation of the polyurethane systems, it may be advantageous if, in addition, water, physical blowing agents, flame retardants and / or further additives are added.

The polyurethane system may in particular be polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or in particular polyurethane foams / foams.

Another object of the present invention is a polyurethane system, in particular polyurethane foam / foam, prepared using an additive according to the invention as described above, in particular comprising 0.00001 to 5 wt .-% of the additive. The Polyurethanschau m / foam is in particular polyurethane hard foam m, flexible polyurethane foam, viscoelastic foam, HR foam, semi-rigid polyurethane foam, thermoformable polyurethane foam or integral foam.

As the isocyanate component, all isocyanates, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se, can be used in the process according to the invention. Suitable isocyanates in the sense of this invention are preferably all polyfunctional organic isocyanates, such as ^{4,4'-diphenylmethane} diisocyanate (MDI) and its isomers, toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Particularly suitable is the mixture known as "polymeric MDI"("crudeMDI") of MDI and higher condensed analogues having an average functionality of 2 to 4, and the various isomers of TDI in pure form or as a mixture of isomers. Particularly preferred isocyanates are mixtures of TDI and MDI.

As polyol suitable polyols in the context of this invention are preferably all organic substances having a plurality of isocyanate-reactive groups, and their preparations can be used. Preferred polyols are all polyether polyols and polyester polyols customarily used for the preparation of polyurethane systems, in particular polyurethane foams.

Polyether polyols may, for. B. be obtained by reaction of polyhydric alcohols or amines with alkylene oxides. Polyester polyols are preferably based on esters of polybasic carboxylic acids (which may be either aliphatic, for example adipic acid or aromatic, for example phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols). In addition, natural oils based on natural oils (natural oil based polyols, NOPs) can be used. These polyols are derived from natural oils such as soy or palm oil and can be used unmodified or modified. Another class of polyols are those obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of 100: 1 to 5: 1, preferably 50: 1 to 10: 1. Such prepolymers are preferably used dissolved in polyol, wherein the polyol preferably corresponds to the polyol used to prepare the prepolymers.

Yet another class of preferably usable polyols are the so-called Füllkörperpolyole (polymer polyols). These are characterized by the fact that they contain solid organic fillers to a solids content of 40 wt .-% or more in disperse distribution. One can e.g. use among others:

SAN polyols: These are highly reactive polyols containing a copolymer based on styrene / acrylonitrile (SAN) dispersed.

PHD polyols: These are highly reactive polyols which also contain polyurea in dispersed form.

PIPA Polyols: These are highly reactive polyols which contain a polyurethane in dispersed form, for example, by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol. The solids content, which depending on the application may preferably be between 5 and 40% by weight, based on the polyol, is responsible for an improved cell opening, so that the polyol is particularly foamable controlled with TDI and no shrinkage of the foams occurs. The solid acts as an essential process aid. Another function is to control the hardness via the solids content, because higher solids contribute to a higher hardness of the foam.

The formulations containing solids-containing polyols are significantly less intrinsically stable and therefore, in addition to the chemical stabilization by the crosslinking reaction, rather require physical stabilization as well.

Depending on the solids content of the polyols, these may be e.g. alone or e.g. be used in admixture with the above unfilled polyols.

A ratio of isocyanate component to polyol component, expressed as an index, in the context of this invention is in the range from 10 to 1000, preferably 40 to 350. This index describes the ratio of actually used isocyanate to isocyanate (calculated for a stoichiometric reaction with polyol). An index of 100 stands for a molar ratio of the reactive groups of 1 to 1. Suitable catalysts which can be used in the process according to the invention are preferably substances which contain the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-polyol). Water) or catalyze the di- or trimerization of the isocyanate. Typical examples are amines such as triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1, 2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol and bis (dimethylaminoethyl) ethers, tin salts of organic carboxylic acids, tin compounds such as dibutyltin dilaurate, and potassium salts such as potassium acetate. The use of reactive amines, such as dimethylaminoethoxyethanol, which are chemically bonded in the polyurethane system, in particular foam, corresponds to a preferred embodiment of the invention.

Suitable amounts of these catalysts in the process of the invention depend on the type of catalyst and are usually in the range of 0.01 to 5 pphp (= parts by weight based on 100 parts by weight of polyol) and 0, 1 to 10 pphp for potassium salts. Suitable water contents in the process according to the invention depend on whether or not physical blowing agents are used in addition to the water. In the case of pure water-driven foams, the values are typically preferably 1 to 20 pphp, if other blowing agents are used in addition, the amount of use is reduced to usually e.g. 0 or e.g. 0, 1 to 5 pphp. In order to obtain a high mah weight, preferably neither water nor other propellants are used.

Suitable physical blowing agents for the purposes of this invention are gases, for example liquefied C0 ₂ , and volatile liquids, for example hydrocarbons having 4 or 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1, 2-dichloroethane. Furthermore, ketones (eg acetone) or aldehydes (eg methylal) are suitable as blowing agents. As stabilizers, the substances mentioned in the prior art can be used.

Advantageously, the compositions of the invention may contain one or more stabilizers. These are, in particular, carbon atoms containing silicon compounds, preferably selected from the polysiloxanes, polydimethylsiloxanes, organomodified polysiloxanes, polyether-modified polysiloxanes and polyether-polysiloxane copolymers.

As one or more carbon atoms having silicon compounds, the substances mentioned in the prior art can be used. Preferably, those Si compounds are used which are particularly suitable for the particular type of foam. Suitable siloxanes are described, for example, in the following documents: EP 0839852, EP 1544235, DE

102004001408, WO 2005/1 18668, US 2007/0072951, DE 2533074, EP 1537159, EP 533202, US Pat 3933695, EP 0780414, DE 4239054, DE 4229402, EP 0867465. The preparation of the Si compounds can be carried out as described in the prior art. Suitable examples are for. In US 4147847, EP 0493836 and US 4855379. In particular, organically modified Si compounds can be used. Particularly preferred, usable organically modified Si compounds are, for example, those according to the following formula (IV)

k D _m D ' _n T ₀ Q _p (IV)

With

M = [R ² R ₂ SiO _1/2 ]

D = [RR Si0 _2/2 ]

D '= [R ³ R Si0 _2/2 ]

T = [R Si0 _3/2 ]

Q = [Si0 _4/2 ]

k = 0 to 22, preferably 2 to 10, more preferably 2

m = 0 to 400, preferably 0 to 200, particularly preferably 2 to 100

n = 0 to 50, preferably 0.5 to 20, particularly preferably 0.7 to 9

o = 0 to 10, preferably 0 to 5, particularly preferably 0

p = 0 to 10, preferably 0 to 5, particularly preferably 0

R ² = R or R ³

R = independently of one another alkyl or aryl radicals or H, preferably methyl, ethyl, propyl or phenyl, preferably methyl or phenyl

R ³ = organic modifications, for example polyethers or a monovalent radical having 1 to 30 C atoms with at least one heteroatom selected from the group N. S, O, P, F, Cl, Br

R ³ in formula (IV) are preferably radicals from the group

-CH ₂ CH ₂ CH ₂ O [CH ₂ CH ₂ O] _a [CH ₂ CH (CH ₃ ) O] _b [CHR ⁴ CHR ⁴ O] _c R ⁵

-CH ₂ CH ₂ CH ₂ CN

-CH ₂ CH ₂ CF ₃

-CH ₂ CH ₂ CH ₂ Cl

With

R ⁵ = alkyl, aryl, urethane, carboxyl, silyl or H, preferably H, -Me, or -C (0) Me

R ⁴ = alkyl, aryl, which may optionally be interrupted by oxygen, particularly preferably H, Me,

Et or Ph,

a = 0 to 100, preferably 0.5 to 70, particularly preferably 1 to 40

b = 0 to 100, preferably 0.5 to 70, particularly preferably 0 to 40

c = 0 to 50, preferably 0 to 15, particularly preferably 0

a + b + c> 3.

In particular, unmodified Si compounds can be used.

Particularly preferred, usable unmodified Si compounds are, for example, those of the following formula (V) M _q D _r (V)

With

M, D as defined in the previous formula (IV), and

q = 2

r = 0 to 50, preferably 1 to 40, particularly preferably 2 to 30.

Particularly preferably, the abovementioned Si compounds, in particular of the formula (IV) and / or (V), can be used individually or in combination with one another. In the case of mixtures, a compatibilizer may additionally be used. This may be selected from the group of aliphatic or aromatic hydrocarbons, particularly preferably aliphatic polyethers or polyesters.

It may be advantageous if in the siloxane compounds of the formula (IV) at least 10 equivalents (and at most 50 equivalents) of the radicals R ^{2 are} alkyl groups having 8 to 22 carbon atoms (based on the total number of radicals R ² in the siloxane).

Preferably, from 0.05 to 10 parts by mass of silicon compounds can be used per 100 parts by mass of polyol components.

In particular, the use of the abovementioned silicon compounds in combination with the additives to be used according to the invention makes it possible to achieve very good results with regard to the polyurethanes aimed for according to the invention.

In addition to or instead of water and optionally physical blowing agents, other chemical blowing agents which react with isocyanates to evolve gas, such as formic acid or carbonates may be present in the additive composition according to the invention.

Suitable optional flame retardants in the context of the present invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethylmethanephosphonate (DMMP),

Dimethylpropane phosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids such as expanded graphite and melamine are suitable as flame retardants. By the method according to the invention polyurethane systems, in particular polyurethane foams can be prepared, which are particularly odorless.

The term polyurethane is to be understood in the context of the invention in particular as a generic term for a polymer prepared from di- or polyisocyanates and other isocyanate-reactive species, such as amines, the urethane bond does not have to be exclusive or predominant type of bond. Also, polyisocyanurates and polyureas are expressly included. The preparation according to the invention of polyurethane systems, in particular polyurethane foams or the preparation of the polyurethane systems / polyurethane foams can be carried out by all methods familiar to the person skilled in the art, for example by hand mixing or preferably by means of high pressure or low pressure foaming machines. The process according to the invention can be carried out continuously or batchwise. A discontinuous implementation of the method is preferred in the production of molded foams, refrigerators or panels. Continuous process control is preferred in the manufacture of insulation boards, metal composite elements, blocks or spraying processes.

In the process according to the invention, the perfume-containing additives used according to the invention can preferably be added directly before or else only during the reaction (to form the urethane bonds). Preferably, the combination / addition of the compound takes place in a mixing head, as well as in a batch process for finished polyol systems. A subsequent addition of the additive to the otherwise finished product is also included in the invention.

The polyurethane systems according to the invention may preferably contain from 0.0001 to 10% by weight, advantageously from 0.005 to 5% by weight, in particular from 0.01 to 3% by weight, based on the total composition of the polyurethane system, of the additive according to the invention.

The polyurethane systems of the invention may preferably be a polyurethane foam, in particular z. For example, a polyurethane hardshell m, a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semi-rigid polyurethane foam, a thermoverform ble

Polyurethane foam or an integral foam, preferably a polyurethane HR foam.

The polyurethane systems of the invention, preferably polyurethane foams, z. As a refrigerator insulation, insulation board, sandwich panel, pipe insulation, spray foam, 1- & 1, 5-component foam foam (1 1, 5-component foam foam is a foam that is produced by destroying a container in the can), wood imitation, model foam , Foam packaging, mattress, furniture upholstery, automotive seat cushion, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, caulk, sealant and adhesive, or used to make such products.

Another object of the invention is a composition for producing polyurethane foam comprising at least one urethane and / or isocyanurate catalyst, at least one blowing agent, at least one isocyanate component and an inventive additive. The term composition in this sense also encompasses multicomponent compositions in which two or more components are to be mixed to produce a chemical reaction which results in the production of polyurethane foam. The term composition in this sense comprises in particular the mixture (mixture) of at least one urethane and / or isocyanurate catalyst, at least one blowing agent, at least one isocyanate component and at least one polyol component and an additive according to the invention.

A preferred composition of the invention for producing polyurethane foam may include polyol e.g. in amounts of from 25 to 75% by weight, water e.g. in amounts of 1 to 7% by weight, catalyst e.g. in amounts of 0.05 to 3% by weight, physical blowing agent e.g. in amounts of 0 to 25% by weight (for example 0.1 to 25% by weight), stabilizers (such as, for example, Si-containing and non-Si-containing, in particular Si-containing, and non-Si-containing organic stabilizers and surfactants) eg in amounts of 0.3 to 5% by weight, isocyanate e.g. in amounts of from 20 to 50% by weight and the additive to be used according to the invention, e.g. in amounts of from 0.00001 to 5% by weight (preferably 0.00005 to 2.5% by weight).

With regard to preferred embodiments of these aforementioned compositions, reference is made to the preceding description, in particular with regard to the additive to be used.

Another object of the invention is the use of the additives according to the invention to improve the odor of polyurethane foams and / or to provide odorless polyurethane foams. The addition of the additives according to the invention can, as described above, to the polyurethane system (in particular polyurethane foam), preferably in an amount of 0.00001 to 10 wt .-%, advantageously 0.005 to 5 wt .-%, in particular 0.01 to 3 % By weight, based on the total weight of the polyurethane system (in particular polyurethane foam), wherein the addition may be effected before, during or after the preparation of the polyurethane system (in particular the polyurethane foam). Another object of the invention is a polyurethane system (in particular

Polyurethane foam) containing additives as described above, in an amount of preferably 0.001 to 10 wt .-%, advantageously 0.005 to 5 wt .-%, in particular 0, 10 to 3 wt .-% based on the total weight of the polyurethane system (in particular Polyurethane foam), in particular obtainable by adding the additives before, during or after the preparation of the polyurethane system, in particular polyurethane foam.

If desired, in the context of the present invention, it is additionally possible to make use of the optional use of odor absorbers known per se. These include, on the one hand, silicates, such as, preferably, phyllosilicates, e.g. Montmorillonite, kaolinite, bentonite and talc. Further optional supplementary odor absorbers are, for example, zeolites,

Zinc ricinoleate, cyclodextrins and chlorophyll. It has become within the scope of the invention especially the complementary, but purely optional use of Zinkricinoleat and / or cyclodextrins proven. Based on the weight of the resulting PU system, in particular foam, the aforementioned optionally usable known odor absorbers can, if desired, be used in amounts of up to 5% by weight, for example if desired in amounts of from 0.001 to 3% by weight.

Another object of the invention is the use of the polyurethane systems according to the invention, in particular foams, as refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1, 5-component can foam, wood imitation, model foam, packaging foam, mattress, furniture upholstery, material in Automotive interiors, automotive seat cushion, headrest, instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet back foam, filter foam, sealing foam, sealant and adhesive or for the production of corresponding products, in particular as a material in motor vehicle interiors.

In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

Examples

To evaluate the removal of bad odors, a perfume-containing additive according to the invention was foamed in a flexible polyurethane foam (A).

The perfume-containing additive according to the invention sufficed in its constituents of the following general formula:

25-30% by weight odoriferous substances with a ClogP value> 4 and a boiling point> 275 ° C,

10-15% by weight odoriferous substances having a ClogP value <3,

30-45% by weight of solvent (DPG)

10-25% by weight of other fragrances

0, 1-2 wt .-% emulsifier, antioxidant

For comparison, instead of the additive according to the invention, the fragrance limonene (boiling point 177.6 ° C., clogP 4.35) was foamed in otherwise identical manner in a flexible polyurethane foam (B).

The proportion of each case used fragrances was in each case 0, 1 parts by weight based on the specified recipe. The two foams so mixed with fragrances were each compared with a foam (C) to which no fragrance was added at all.

The foams were produced according to the following specifications at 22 ° C. and 753 mm Hg air pressure in a wooden box mold with polyethylene film as release agent:

0.07 part by weight of Kosmos® 29 (stannous 2-ethylhexanoate)

30 parts by weight of polyol CP 3322 (commercially available polyol from DOW)

70 parts by weight of polyol CP 755 (commercially available polyol from DOW)

7 parts by weight of polyol CP 1421 (commercially available polyol from DOW)

- 1, 95 parts by weight of water

0.2 part by weight of Tegoamin® BDE (bis (dimethylaminoethyl) ether solution)

0.3 parts by weight of Tegoamin® 33 (triethylenediamine solution)

0.2 part by weight of Tegoamin® DMEA (dimethylethanolamine solution)

- 0.3 parts by weight of Ortegol® 76 (cell opener additive)

- 0.9 parts by weight Tegostab® BF 2470 (silicone foam stabilizer)

- 40.3 parts by weight of tolylene diisocyanate (TDI 80) (corresponding to an index of 85).

and 0, 1 parts by weight of fragrances (via scent-containing additive in foam A, via limonene in foam B, without fragrance in foam C). In a paper cup, the tin catalyst becomes tin (II) 2-ethylhexanoate, the three polyols, the

Water and the three amine catalysts submitted and for 60 s with a disk stirrer at 1000 Mixed rpm. For this purpose, the fragrance-containing additive (for foam A) or limonene (for foam B) is added. Subsequently, the isocyanate is added and incorporated with the same stirrer for 7s at 1500 U / min. The mixture begins to foam in the cup. Therefore, it is poured directly after the end of stirring in a Verschäumungsbox. This has a floor area of 17 x 17 cm and a height of 30 cm. To the outside, a 5 cm thick PU foam insulation prevents over-cooling. Inside, the box is designed with a plastic film to subsequently remove the hardened foam. The foam rises after pouring into the foaming box. The finished foam was then kept airtight in odorless plastic bags. For the odor evaluation of the foam, cubes of the size 10-10 cm ^{3 were} cut out and transferred into glasses with a volume of 1 L, from which the samples were smelled. The jars were closed with a screw cap. The odor test was carried out after 24 hours of storage of the glasses at 22 ° C.

The odor control was rated by a trained panel of 1 1 people. Here two parameters were requested:

• intensity of the smell = extent of the smell

Acceptance of the odor = extent of the discomfort The foam samples (A), (B) were each compared against (C).

Comparison: Untreated foam (C) and foam with additive (A) according to the invention

As the table shows, the additive was able to reduce the intensity of the odor compared to the comparison sample. In addition, the smell of the control sample was perceived as more unpleasant. In this case, a clear majority of the subjects classified the sample according to the invention as odorless.

The odor test was repeated twice by the subjects, the above results being confirmed in exactly the same way.

Comparison: Untreated foam (C) and foam limonene (B)

As the table shows, could not be reduced by the added fragrance, the intensity of the odor compared to the reference sample. The majority of respondents felt that the perfumed sample smelled even more. The smell of the control was perceived as more unpleasant. The overwhelming majority of the subjects rated the lime scented sample as not odorless.

Also this odor test was repeated twice by the test persons, whereby the above-mentioned results were confirmed in exactly the same way. From the results it can be seen that the subjects have judged a foam, which was treated with an additive according to the invention, as less intense smelling, with the remaining residual odor found greater acceptance than the smell of the untreated object. In addition, they predominantly judged that the sample does not smell like covered with perfume, but rather is classified as odorless, which is to be regarded as an indication of a bad odor extinction.

By contrast, when using the non-inventive fragrance, no reduction of the odor intensity was observed in the majority. The treated sample smelled rather like covered with perfume. Evidence of a bad odor extinction could not be found.

Claims

claims:

1. fragrance-containing additive for the production of polyurethane systems, in particular a polyurethane foam, wherein at least 5 wt .-% of the fragrances contained, based on the total amount of all the fragrances contained in the additive, a ClogP value> 4 and a boiling point> 275 ° C.

2. Additive according to claim 1, characterized in that at least 10 wt .-%, preferably at least 15 wt .-%, advantageously at least 20 wt .-%, more preferably at least 25 wt .-% and in particular at least 30 wt. -% of the odoriferous substances contained, based on the total amount of all the fragrances contained in the additive, have a ClogP value> 4 and a boiling point> 275 ° C.

3. Additive according to claim 1 or 2, characterized in that the fragrances with ClogP value> 4 and boiling point> 275 ° C are selected from the group Ambrettolid, Amylzimtaldehyd,

Amylzimtaldehyddimethylacetal, iso-amyl salicylate, aurantiol, benzyl salicylate, cardinene, cedrol, cedryl acetate, cinnamyl cinnamate, cyclohexyl salicylate, Ethylbrassylat, exaltolide, Geranylanthranilat, hexadecanolide, hexyl cinnamic aldehyde, hexyl salicylate, Methyldihydrojasmon, oxahexadecanolide-10, patchouli alcohol, Phantolide, phenylethyl benzoate, Thibetolid, gamma-undecalactone and / or vetiveryl acetate.

4. Additive according to one of claims 1 to 3, characterized in that at least 5 wt .-%, preferably at least 10 wt .-%, in particular at least 15 wt .-% of the fragrances contained, based on the total amount of all fragrances contained in the additive , have a ClogP value <3.

5. An additive according to claim 4, characterized in that the fragrances with a ClogP value <3 are selected from menthone, phenoxyethanol, Benzyldimethylcarbinolacetat, piperonal, isobutyl, phenoxyethyl, butanaldehyde, Floracetat, Rosenoxid, Cyclal C, Fruten, ethyl 2- methyl butyrate, benzyl alcohol, ethyl 2-methyl pentanoate, benzyl acetate, phenylethyl alcohol, 2,4-

Dimethyl-3-cyclohexene-1-carbaldehyde, tricyclodecenyl acetate, methylisobutenyltetrahydropyran, 4-methoxybenzaldehyde, 3.7, dimethyl-1, 6-octadien-3-ol 4-phenylbutan-2-one, phenytomethylethanoate, vanillin, coumarin and / or phenylacetaldehyde dimethyl acetal.

6. Additive according to one of claims 1 to 5, characterized in that it comprises at least 5 different, preferably at least 10 different and in particular at least 15 different fragrances.

7. Additive according to one of claims 1 to 6, characterized in that the fragrances contained are at least partially micro-encapsulated.

8. Additive according to one of claims 1 to 7, characterized in that fragrance precursors are included.

9. Additive according to one of claims 1 to 8, characterized in that solvent, antioxidants, (preferably tertiary) amines, silicone stabilizers and / or emulsifiers are included.

10. A composition for the preparation of a polyurethane system, in particular a polyurethane foam, characterized in that it comprises an additive according to any one of claims 1 to 9 and one or more organic isocyanates having two or more isocyanate functions, one or more polyols having two or more isocyanate reactive groups, catalyst (s) for the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, water, optionally physical blowing agent, optionally flame retardant and optionally further additives.

1 1. Use of additives according to any one of claims 1 to 9 for the improvement of the odor of polyurethane foams.

12. Use of additives according to any one of claims 1 to 9 for the provision of odorless polyurethane foams.

13. Use of additives according to any one of claims 1 1 or 12, wherein the additives are added before, during or after the preparation of the polyurethane foams.

14. A process for the preparation of a polyurethane system by reacting one or more polyol components with one or more isocyanate components in the presence of one or more catalysts which catalyze the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, characterized in that an additive according to any one of claims 1 to 9 is used.

15. A polyurethane system prepared using an additive composition according to any one of claims 1 to 9, in particular comprising 0.00001 to 5 wt .-% of the additive according to any one of claims 1 to 9.

16. Use of polyurethane systems according to claim 15 as a refrigerator insulation, insulation board, sandwich element, pipe insulation, spray foam, 1- & 1, 5-component foam foam, imitation wood, model foam, packaging foam, mattress, furniture upholstery, material in motor vehicle interiors, automotive seat cushion, headrest, Instrument panel, automotive interior trim, automotive headliner, sound absorbing material, steering wheel, shoe sole, carpet backside foam, filter foam, sealing foam, sealant and adhesive or for the production of such products, especially as a material in motor vehicle interiors.