JP2009155649A - Gel for dispensing active volatile material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new gel composition which is free of faults of conventional technology, easy in production and a self-support type product at room temperature, for example, a rubbery solid material. <P>SOLUTION: The gel composition contains (a) a 97.5-70% active volatile liquid component and (b) a 2.5-30% thermoplastic polyether-ester-amide elastomer expressed by formula (I), on the basis of the mass of the composition [in the formula, PA is a polyamide moiety; PE is a polyether moiety; and the coefficient n is an integer indicating a multiple of a repeat pattern]. The active volatile liquid component is a mixture of perfuming ingredients. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to the field of perfumery, and more particularly to gel compositions and consumer products associated with said gel compositions for distributing active volatile components to the surrounding space. The gel composition contains an active volatile liquid component and a thermoplastic polyether-ester-amide elastomer (PEEA).

  Active volatile material dispensers such as air fresheners are consumer products that are widely used in daily life, and several different types of active volatile material dispensers are known. However, many of the devices contain a limited amount of active volatile components, and thus the total weight of the carrier required to deliver the appropriate level of active volatile components, ie perfume, is relatively high. Examples of known products include hydrogel or wick type devices, which generally contain only up to 15% active volatile components relative to the total mass of the device.

  Thus, it is possible to carry a large amount of active volatiles and extend the active volatiles using a small amount of carrier, such as a resin, a support and / or packing of the resin. There is a need to develop devices that can deliver over time.

  Some solutions to the above problems have been proposed, but none are completely satisfactory.

  WO 00/24434 discloses solid gel compositions containing up to 90% perfume, functionalized polymers such as maleated polybutadiene or polyisoprene, and complementary functional crosslinkers such as polyoxyalkylene diamines. .

  However, the composition may have different flavoring ingredients, such as esters, aldehydes and alcohols, which can react with the functionalized polymer and / or cross-linking agent, thus changing the perfume fragrance and polymer release characteristics, etc. It has the disadvantage that some restrictions are imposed when blending fragrances. Furthermore, since the production and use of such gels is a method in which it is advantageous to associate the gel with a support, the amount of perfume relative to the amount of carrier is still limited.

  WO 97/26020 describes the possibility of having a composition containing up to 95% perfume with a polyether-ester-amide type polymer. However, in the method of preparation of the composition described in said patent, ie the “drageoir” or “masterbatch” method, one containing more than 55% perfume, despite the claims of the inventor's claim. It is impossible to obtain such a composition. In fact, when using the “Doradiol” method as disclosed in said patent application and a large amount (eg, greater than 60%) of perfume, the polyether-ester-amide polymer is not able to trap the entire perfume. It was therefore possible to confirm that the product obtained was a mixture of swelling resin soaked in excess of perfume. The other production method disclosed in the application, namely the “masterbatch” method (which is an extrusion method of the granules obtained by the “Doladiol” method) results in a lower perfume load. In other words, it is not possible for a person skilled in the art to produce a composition containing more than 55% fragrance from the content of WO 97/26020, despite the statement that the known composition has up to 95% fragrance. Actually impossible. In addition, the composition obtained according to the description of WO 97/26020 is not self-supporting unless it contains a small amount of perfume, thus requiring the use of special fillers, thus reducing the amount of carrier. The potential for reduction is limited.

  Thus, to limit the total weight of the volatile material dispenser, it is solid, self-supporting and has a large amount of active volatile while maintaining high fragrance delivery performance and extended fragrance diffusion into the surrounding space. There remains a need for compositions that can adequately confine minutes and that have minimal constraints on the choice of volatile components to be used.

WO00 / 24434 WO97 / 26020

  The object of the present invention was to provide a novel gel composition which does not have the disadvantages of the prior art, is easy to manufacture and is self-supporting at room temperature, for example a rubber-like solid.

  The present invention relates to a novel gel composition that is easy to manufacture and that is self-supporting at room temperature, such as a rubber-like solid. The gel composition can take in a large amount, ie up to 97.5% of the active volatile content of the total composition, and distribute it to the surroundings. “Active volatile content” as used herein refers to a component, substance or composition that can provide a benefit or effect to the surrounding environment, in particular a flavoring effect, insect repellent effect or insect attracting effect, insecticidal effect, antibacterial effect or bactericidal effect Means.

［式中、ＰＡはポリアミド部分を表し、ＰＥはポリエーテル部分を表し、係数ｎは繰り返しパターンの倍数を示す整数を表す］
の熱可塑性ポリエーテル−エステル−アミドエラストマー（ＰＥＥＡ）
を含むゲル組成物であり；この場合前記ゲル組成物はその損失弾性率よりも高い貯蔵弾性率を有しており、即ちゴム様固形物の様に振る舞う。 Accordingly, the first subject of the present invention is:
a) 97.5% to 70% active volatile liquid component based on the weight of the gel composition, and b) 2.5% to 30% based on the weight of the gel composition.

[Wherein, PA represents a polyamide portion, PE represents a polyether portion, and a coefficient n represents an integer indicating a multiple of the repeating pattern.]
Thermoplastic polyether-ester-amide elastomer (PEEA)
The gel composition has a storage modulus higher than its loss modulus, i.e. behaves like a rubbery solid.

  Storage modulus is the energy storage capacity of a material and is related to the stiffness of the material. Loss modulus represents the energy dissipated by the material and reflects the damping properties of the material.

  The gel according to the present invention may optionally contain at least one component selected from the group consisting of an antioxidant, a UV-inhibitor, an oil-soluble dye, a solvent and a bitter agent.

  The active volatile liquid component of the gel of the present invention is intended to be dispersed by the composition of the present invention into ambient air or an enclosed space such as a room, cupboard, drawer, etc. The active volatile liquid component consists essentially of one or more active volatile materials, but may contain one or more suitable solvents, such as those conventionally used in functional perfumes.

  In order to promote the formation of the gels of the invention, the active volatile liquid component is advantageously limited in total amount of hydroxy derivatives, ie compounds having at least one hydroxy group (examples are alcohols or glycols) ).

  The maximum amount of hydroxy derivative that can be present in the active volatile liquid component depends on the exact nature of the derivative, the number of the derivative, and also the total amount of active volatile liquid component used in the gel of the invention. Dependent. Those skilled in the art will be able to define such maximum amounts using their general knowledge and a limited number of routine experiments. However, by way of non-limiting example, active volatility that may contain up to 80% tertiary alcohol or up to 40% primary alcohol when used at a level of 90% relative to the total mass of the gel of the present invention. Mention may be made of liquid components.

  As active volatile materials, for example, fragrances or flavoring ingredients can be used, in which case the consumer product may be of the air freshener type. Other suitable active volatile materials are deodorants or disinfectants, or any other volatile material that can impart a significant and positive effect on air quality when it is diffused into the air It may be.

  As a fragrance | flavor or a fragrance | flavoring component, normally all the components or a mixture of components conventionally used in fragrance | flavors can be used. These may be manufactured from careful chemicals. Often, however, these may be some complex mixtures of natural or synthetic derived volatile components. The nature of these ingredients can be found in fragrance specialist books such as S. Arctander (Perfume and Flavor Chemicals, Montclair NJ, USA 1969) and similar references, a more detailed description of which is given here. Absent.

  With respect to the perfuming effect that can be exerted by the compositions of the present invention, the same principles apply to the manufacture of similar compositions for diffusing deodorizing or disinfecting steam, although specifically mentioned in the above description. In this case, the perfume has been replaced by a deodorant composition, fungicide, insecticide, insect repellent or insect attractant. The term “disinfecting vapor” is not only a vapor of a substance that can increase the tolerance of the ambient air of the observer, but can also attract or repel certain species of insects, for example houseflies or mosquitoes, or It may relate to a substance that may have bactericidal activity or bacteriostatic activity. Of course, mixtures of these agents can also be used.

  As described above, the active volatile liquid component may contain a suitable solvent. The presence of a solvent can be advantageous to have a single phase liquid or to adjust the evaporation rate of volatiles to ambient air. The solvent may belong to the system of isoparaffin, paraffin, hydrocarbon, glycol ether, glycol ether ester, ester or ketone.

  Examples of commercially available solvents useful in the present invention are Isopar® H, J, K, L, M, P or V (isoparaffin; manufacturer: Exxon Chemical), Norpar® 12 or 15 (paraffin; Manufacturer: Exxon Chemical), Exxsol® D 155/170, D 40, D 180/200, D 60, D 70, D 80, D 100, D 110 or D 120 (dearomatized hydrocarbons; manufacturer: Exxon Chemical), Dowanol (registered trademark) PM, DPM, TPM, PnB, DPnB, TPnB, PnP or DPnP (glycol ether; manufacturer: Dow Chemical Company), Eastman (registered trademark) EP, EB, EEH, DM, DE, DP or DB (glycol ether; manufacturer: Eastman Chemical Company) Dowanol® PMA or PGDA (glycol ether ester; manufacturer: Dow Chemical Company) or Eastman® EB acetate, Eastman® DE acetate, Eastman (Registered trademark) DB acetate, Eastman (registered trademark) EEP (all glycols) Chromatography ether esters; all origin: those known under the trademark Eastman Chemical Company). Other examples of solvents useful in the present invention are dipropylene glycol, propylene glycol, ethylene glycol ethyl ether acetate, ethylene glycol diacetate, isopropyl myristate, diethyl phthalate, 2-ethylhexyl acetate, methyl n-amyl ketone or di-isobutyl. It is a ketone.

  The amount of solvent present in the active volatile liquid component may vary over a wide range, and as a non-limiting example, 0% to 40%, preferably 0% to 30%, based on the weight of the active volatile liquid component. The amount consisting of can be mentioned.

  Those skilled in the art of producing volatile liquid components are completely capable of selecting the components and their concentrations necessary for the production of active volatile liquid components that provide the desired benefits while at the same time allowing the formation of the gels of the invention. is there.

  The composition of the present invention may contain volatile liquid components in an amount consisting of 70% to 97.5% (percentages are relative to the total mass of the composition). In a preferred embodiment of the invention, the volatile liquid component is present in an amount comprised between 80% and 96%, more preferably in an amount comprised between 87% and 95%.

  The second component of the gel composition of the present invention is an elastomer. This polymer is actually a component that provides the mechanical properties of the gel component of the present invention.

［式中、ＰＡはポリアミド部分を表し、ＰＥは直鎖又は分枝鎖ポリオキシアルキレングリコール部分を表し、この場合アルキレン基は少なくとも２個の炭素原子を有し、係数ｎは繰り返しパターンの倍数を示す整数を表す］
の熱可塑性ポリエーテル−エステル−アミドエラストマー（ＰＥＥＡ）である。 The elastomer is a formula

[Wherein PA represents a polyamide moiety, PE represents a linear or branched polyoxyalkylene glycol moiety, wherein the alkylene group has at least two carbon atoms, and the coefficient n is a multiple of the repeating pattern. Represents an integer
Thermoplastic polyether-ester-amide elastomer (PEEA).

The PEEA polymer comprises a dicarboxylic acid polyamide moiety having a terminal carboxyl functionality of 300-15000 average molecular weight and a linear or branched aliphatic polyoxyalkylene glycol having a terminal hydroxyl functionality and an average molecular weight of 200-6000. As a result of copolymerization in the melt phase. The reaction is carried out under a substantially reduced pressure at a temperature comprised between 100 ° C. and 400 ° C., with the general formula Ti (OR) _{4 wherein} R is a C ₁ -C ₂₄ linear or branched aliphatic hydrocarbon group. Wherein the mass proportion of the reaction mixture is comprised between 0.01% and 5%] in the presence of a catalyst comprising a tetraalkylorthotitanate. Alternatively, the PEEA polymer may be the result of copolymerization of a polyamide having a terminal diamino functional group and a polyoxyalkylene glycol having a terminal dicarboxyl functional group under conditions similar to those described above.

  Said thermoplastic polyether-ester-amide elastomers are best known under the trade name PEBAX® (manufacturer: ATOFINA, France), some of which are US Pat. No. 4,331,786, US Pat. No. 4,864,014, GB 2063279, EP 281461 or It is described in related patent literature.

  For the purposes of the present invention, all types of PEBAX® can be used, which can contain a perfume that is at least 2.3 times its own weight, preferably more than 5 times its own weight. it can.

  Preferred elastomers are those having a melting point comprised between 170 ° C. and 100 ° C. measured according to standard ASTM D789 and a Shore A hardness comprised between 60A and 92A measured according to standard ASTM D1484. is there. Examples of such PEBAX® are grades 4033, 3533 or 2533.

  In a further advantageous embodiment of the invention, the elastomer has a Shore A hardness of 70A to 85A or a Shore D hardness of 35D to 20D, for example PEBAX® 3533 or 2533.

  As indicated above, the compositions of the present invention are characterized by the fact that the polymer is present in an amount consisting of 2.5% to 30% (percentages are relative to the total mass of the composition). In a preferred embodiment of the invention, the polymer is present in an amount comprised between 4% and 20% relative to the weight of the gel composition.

  As mentioned above, it is possible to add to the gel composition according to the invention several optional ingredients which act, for example, as antioxidants, UV-inhibitors, dyes, solvents or even bitter agents.

  Non-limiting examples of useful antioxidant components include sterically hindered amines, ie, derivatives of 2,2,6,6-tetramethyl-piperidine, such as Uvinul® (manufactured by BASF AG) or Tinuvin ( (Registered trademark) (manufacturer: Ciba Specialty Chemicals), as well as alkylated hydroxyarene derivatives such as butylated hydroxytoluene (BHT).

  The antioxidant component may be blended in the composition according to the invention in an amount consisting of 0% to 3% (percentages are relative to the total mass of the composition). Advantageously, the antioxidant component is present in an amount comprised between 0.1% and 2%.

  Non-limiting examples of useful UV-inhibitors include benzophenone, diphenyl acrylate or cinnamate, such as those available under the trademark Uvinul® (manufacturer: BASF AG).

  The UV-inhibitor component may be formulated in the composition according to the invention in an amount comprised between 0% and 0.5% (percentages are relative to the total mass of the composition). Advantageously, the UV-inhibitor component is present in an amount comprised between 0.01% and 0.4%.

  Another optional component of the composition of the present invention is a dye. Suitable dyes are oil soluble. Non-limiting examples of suitable dyes are anthraquinone derivatives, methine, azo, triarylmethane, triphenylmethane, azine, aminoketone, spiroaxine, thioxanthane, phthalocyanine, perylene, benzopyran or perinone. Examples of such dyes that are commercially available are Sandoplast® Violet RSB, Violet FBL, Green GSB Blue 2B or Savinyl® Blue RS (all anthraquinone derivatives, manufacturer: Clariant Huningue SA), Oilsol (Registered trademark) Blue DB (anthraquinone; manufacturer: Morton International Ltd.), Sandoplast (registered trademark) Yellow 3G (methine, manufacturer: Clariant Huningue SA), Savinyl (registered trademark) Scarlet RLS (azo metal complex manufacturer: Clariant Huningue SA ), Oilsol (R) Yellow SEG (monoazo; manufacturer: Morton International Ltd.), Fat Orange (R) R (monoazo; manufacturer: Hoechst AG), Fat Red (R) 5B (diazo; manufacturer: Hoechst AG ), Neozapon® Blue 807 (phthalocyanine; manufacturer: BASF AG), and Fluorol® Green Golden (perylene; manufacturer: BASF AG).

  The dye component may be incorporated in the composition according to the invention in an amount consisting of 0% to 1% (percentages are relative to the total mass of the composition). Advantageously, the dye component is present in an amount comprised between 0.005% and 0.5%.

  The presence of a bitter agent is desirable to make the product taste unpleasant and in particular makes the composition less likely to be consumed by infants. Non-limiting examples include isopropyl alcohol, methyl ethyl ketone, methyl n-butyl ketone or even a denatonium salt, such as denatonium benzoate, also known under the trademark Bitrex® (manufacturer: Mac Farlan Smith Ltd.).

  The bitter agent component may be blended in the composition according to the invention in an amount consisting of 0% to 6% (percentages are relative to the total mass of the composition). In the case of Bitrex®, the maximum amount may be reduced to 0.1% of the total mass of the composition.

  Advantageously, the bitter agent component is present in an amount comprised between 0.5% and 5%. In the case of Bitrex®, this amount may consist of 0.001% to 0.05% of the total mass of the composition.

The gel composition of the present invention has the following production steps:
a) heating a mixture of active volatile liquid component, elastomer and optional compound in a container at a temperature comprised between 90 ° C. and 150 ° C. b) sufficiently dissolving the polymer, Obtained by a production method comprising the steps of cooling to a temperature comprised between 60 ° C. and 100 ° C., and c) injecting the solution obtained in b) into a mold or container having a suitable shape to obtain the composition of the present invention. be able to.

  In order to avoid the loss of volatile constituents, the treatment is preferably carried out in a closed or pressurized container, which is separately provided with a cooler.

  The heating step is an essential step because we only obtain a sufficiently homogeneous mixture of the components when the active volatile liquid component and the polymer are simply mixed at room temperature or similarly processed. Therefore, it was found that the gel composition according to the present invention, that is, the rubber-like solid composition, could not be obtained.

  Another advantage of the above manufacturing method is that by injecting a homogeneous mixture of volatile liquid and resin into a suitable mold or container, the composition of the appropriate shape can be obtained without additional powerful heating steps, such as extrusion steps. You can get things directly.

  As mentioned above, the gel composition according to the invention is particularly suitable for the manufacture of consumer products for dispersing volatile materials in the surrounding space. Accordingly, consumer products containing or related to the gel composition according to the invention are also an object of the invention.

  Such consumer products may be used in flavoring or sterilizing devices, such as solid or gel type air fresheners, diaper buckets, depending on the nature of the volatile liquid component used in the manufacture of the gel composition. It may be a freshener, an automotive freshener, a closet freshener, a cat toilet freshener, a shoe freshener or a garbage bucket freshener, an insecticidal device or an insect repellent device.

  The consumer product of the present invention is merely the gel composition of the present invention formed into an appropriate shape as opposed to the consumer product of the prior application, that is, the gel support is unnecessary. is there. The gel composition of the present invention may have any suitable shape.

  It is understood that the gel of the present invention may be accompanied by a container containing the composition. In such cases, various types of containers can be used. By way of non-limiting example, at least one material that is made of a material that does not transmit any vapor of the volatile liquid component and through which the vapor of the volatile liquid component can be diffused into the air surrounding the consumer product. A container having an opening can be mentioned. The container may also entirely enclose the gel, and at least a portion of the container is made of a material that allows vapors of volatile liquid components to escape into the air surrounding the consumer product.

  To prevent the volatile liquid vapor from diffusing to the surroundings during storage, whether or not the consumer product includes a container, the consumer product or one of the containers through which the volatile liquid vapor can permeate. The part may be sealed by any known method, for example with a plastic film that is impermeable to volatile liquid phase vapors. The consumer easily activates the consumer product by simply removing the seal, after which the volatile liquid phase begins to diffuse into the ambient air.

  The invention will now be described in further detail using the following examples.

Example 1
Manufacture of a perfumed gel composition according to the invention 61.38 g of perfume base (Tropical 438872, manufacturer: Firmenich SA) was added to a polymer (Pebax® 2533) in a 100 ml 2-neck round bottom flask equipped with a 200 mm Leibig cooler and a thermometer. SA 01 granules, manufacturer: Atofina) 6.82 g. The flask was placed in an electronic stirrer / heating mantle and the contents were heated to 120-135 ° C. with continuous stirring, after which the polymer granules were dissolved in the perfume base. Stirring was continued for another 5 minutes to ensure complete dissolution of the polymer. The resulting mixture was cooled to about 90 ° C. and five shallow glass containers (having a surface area of about 18 cm ² ) were each filled with 6.50 g. After cooling to room temperature, the composition formed a clear, self-supporting rubbery gel that contained 90% by weight of a perfume base.

  The initial mass of the samples was recorded and then placed in a temperature / humidity controlled test room. Thereafter, the mass of each sample was recorded at regular intervals until 30 days after the start of the test. In 30 days, 70% of the original mass of the perfume base had evaporated from the gel.

Example 2
Preparation of a perfumed gel composition according to the present invention A fragrance-based composition was prepared by mixing the following ingredients:

65.79 g of perfume base was added to 7.31 g of Pebax® 2533 SA 01 granules (manufacturer: Atofina) in a 100 ml 2-neck round bottom flask equipped with a 200 mm Leibig condenser and thermometer. The flask was placed in an electronic stirrer / heating mantle and the contents were heated to 120-135 ° C. with continuous stirring, after which the Pebax® granules were dissolved in the perfume base. Stirring was continued for an additional 5 minutes to ensure complete dissolution of Pebax®. The resulting mixture was cooled to about 90 ° C. and five shallow glass containers (having a surface area of about 18 cm ² ) were each filled with 6.50 g. After cooling to room temperature, the composition formed a clear rubber-like gel that contained 90% by weight of a perfume base.

  The fact that the perfume is 90% loaded means that in order to absorb the same amount of perfume, the composition according to the invention is compared to a composition comprising up to 55% perfume as disclosed in WO 97/26020. Means that only less than a quarter of the resin is required, thus representing a drastic reduction of the support resin.

Example 3
Production and mechanical characterization of a perfumed gel composition according to the invention Four perfume bases:
・ Tropical 438872 (Manufacturer: Firmenich SA)
・ Spring Blossom 150531 BG (Manufacturer: Firmenich SA)
・ Citrowood 150783 (Manufacturer: Firmenich SA)
・ Cantina 150685 F (Manufacturer: Firmenich SA)
Was used to make a perfume gel according to the method described in Example 1.

Dynamic mechanical analysis was used to determine the mechanical properties of the perfume gel. Compression mode measurements were performed using a parallel plate dynamic mechanical analyzer (DMA 2980, manufacturer: TA Instruments) equipped with a temperature controller. Storage elastic modulus (M ′), loss elastic modulus (M ″) and tan δ were measured under the conditions shown in Table 1.

  Storage modulus (M ') is the energy storage capacity of a material and is related to the stiffness of the material. Loss modulus (M ″) represents the energy dissipated by the material and reflects the damping properties of the material.

  Sample M 'and M "values are shown in Table 2, with quoted ranges for the three experiments tested for each sample.

  Under the conditions tested, the storage modulus for the gel is higher than the loss modulus. As a result, the deformation is reversible and the gel behaves like a rubbery sample. Furthermore, the gel was self-supporting.

Example 4
Production of perfume gel composition according to the present invention having various perfume concentrations A perfume gel was produced using the apparatus and method described in Example 1. As an active volatile liquid component, a fragrance, namely Spring Blossom 150531 BG (manufacturer: Firmenich SA) was used. Additional perfume gels containing lower levels of Pebax® 2533 SA 01 as described in Table 3 were made using the same perfume.

  As shown in Table 3, a gel according to the present invention having a resin content of 2.5% of the total mass of the composition can be obtained. This means that with the production method according to the invention, Pebax® resin can contain up to 40 times its perfume.

Claims (10)

In the gel composition:
a) 97.5% to 70% active volatile liquid component based on the weight of the gel composition, and b) 2.5% to 30% based on the weight of the gel composition.

[Wherein, PA represents a polyamide portion, PE represents a polyether portion, and a coefficient n represents an integer indicating a multiple of the repeating pattern.]
A gel composition characterized in that the active volatile liquid component is a mixture of perfuming ingredients.   The gel composition according to claim 1, further comprising a solvent selected from the group consisting of isoparaffin, paraffin, hydrocarbon, glycol ether, glycol ether ester, ester and ketone.   The gel composition of claim 1 wherein the volatile liquid component is present in an amount comprised between 80% and 96%, wherein the percentage is relative to the total weight of the composition.   The gel composition according to claim 1, wherein the elastomer is present in an amount of 4 to 20% based on the weight of the gel composition.   The gel composition of claim 1 further comprising an antioxidant compound that is a sterically hindered amine or alkylated hydroxyarene derivative.   The gel composition according to claim 1, further comprising a dye which is an anthraquinone, methine, azo, triarylmethane, triphenylmethane, azine, aminoketone, spirooaxin, thioxanthane, phthalocyanine, perylene, benzopyran, or a perinone derivative. .   Furthermore, the gel composition of Claim 1 containing the bitter agent which is isopropyl alcohol, methyl ethyl ketone, methyl n-butyl ketone, or a denatonium salt.   Consumer product containing or related to the gel composition according to any one of claims 1-7.   9. A consumer product according to claim 8, in the form of a perfume device or a disinfection device.   9. A consumer product according to claim 8, in the form of an air freshener, a diaper bucket freshener, an automotive freshener, a closet freshener, a cat toilet freshener, a shoe freshener or a garbage bucket freshener.