DE102015014581A1 - Prolamine-containing gels, process for their preparation and their use - Google Patents

Abstract

Gels containing at least one type of functionalized, non-functionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported prolamine macro- and / or micro- and / or nanoparticles of an average particle size d50 of 1 nm > 1000 μm and at least one type of gelling functional ingredient; Process for their preparation and their use.

Description

Field of the invention

The present invention relates to prolamins-containing gels.

Moreover, the present invention relates to a process for preparing the gels.

Furthermore, the present invention relates to the use of gels containing prolamins.

State of the art

The prior art cited in the present application is incorporated by reference into the present application.

Gels are omnipresent today and are used in almost every industry. They usually consist of silicone or other non-biodegradable substances.

• – Matratzen,
• – Schuhe,
• – Textilien,
• – Kühlpacks oder
• – Sportutensilien

genannt.As typical applications of gels are exemplary

• - mattresses,
• - Shoes,
• - textiles,
• - cooling packs or
• - Sporting utensils

called.

US Patent Application US 2015/040321 (A1) discloses the use of gel in body-supporting applications.

From the Chinese patent application CN 103980694 (A) is the processing of silica gel in mattresses out.

From the patent applications WO 2014/089952 (A1) and JP 2013/096030 (A) and the Chinese utility model CN 202436258 (U) The uses of gels in shoes are apparent.

The device for heat dissipation emerges from the American patent application US 2015/101786 (A1). Here, the body heat is cooled by gel and thus caused a cooling effect.

From the Korean patent KR 101476824 (B1) the use of gel and cooling is due to air circulation.

From the German patent application WO 2015/124219 (A1) The use of gel as a cooling layer in mattresses, toppers, protectors, bedspreads or pillowcases.

From the Taiwanese patent application TW 2015/18419 (A) further uses of silicone gels emerge.

Because many gels are silicone-containing and may contain other substances that adversely affect the body and the environment, it is necessary to find an alternative to the known gels, which may even be biodegradable and / or have a biocidal effect.

• – Akarizide gegen Milben,
• – Algizide gegen Algen,
• – Fungizide gegen Pilze,
• – Insektizide gegen Insekten,
• – mikrobiozide Ausrüstung gegen Keime,
• – Molluskizide gegen Schnecken,
• – Nematizide gegen Fadenwürmer und
• – Viruzide gegen Viren.

In order to prevent bacteria and thus pathogens from spreading, cleaning agents, disinfectants and personal care products are mixed with biocides. The following biocides are listed by way of example:

• - acaricides against mites,
• - algicides against algae,
• - fungicides against fungi,
• Insecticides against insects,
• - microbiocidal equipment against germs,
• - molluscicides against snails,
• - Nematicides against roundworms and
• - Viruzide against viruses.

Examples of known biocides are 10,10'-oxybisphenoxoarsine (OBPA), octylisothiazolinone (OIT), dichloroctylisothiazolinone (DCOIT), butylbenzisothiazolinone (BBIT), iodocarb (3-iodo-2-propynylbutylcabamate), zinc pyrithione (zinc salt of pyridine-2 thiol-1-oxide), trichlosan (polychlorinated phenoxyphenols), silver ions and silver, especially in the form of silver nanoparticles.

The known biocides have disadvantages such as a narrow range of applications, a relatively high toxicity, the tendency to cause resistance and Kreutzresistenzen and a still largely unexplained ecological long-term effect.

It is therefore the task of providing biocides that do not have these disadvantages.

Polyoxymetalates (POM) are inorganic polyacids with - in contrast to isopolyacids - at least two different central atoms. Heteropoly acids arise from weak, polybasic oxo acids of a metal (usually chromium, molybdenum, vanadium or tungsten) and a non-metal (usually arsenic, iodine, phosphorus, selenium, silicon or tellurium) as partial mixed anhydrides; Example: H ₃ [PM ₁₂ O ₄₀ ]: 12-molybdophosphoric acid (M = Mo) or 12-tungstophosphoric acid (M = W). The second central atom may also be actinide or lanthanide; The tungsten heteropolyacids are thermally much more stable than the analogous molybdenum compounds. Heteropolyacids of the general formula [(EO ₄ ) M ₁₂ O ₃₆ ] _n-8 with n = valence of the tetrahedrally coordinated element E (for example boron, silicon, zinc) have sometimes been referred to as Keggin acids. With octahedral coordinated heteroatom, the heterohexametallate type [(EO ₆ ) M ₆ O ₁₈ ] n _-12 (Anderson-Evans anions) is frequently found [cf. Römpp Online, Version 3.47 >> Heteropolyacids << ] .S

In your Article >> Fabrication and Characterization of Antibacterial-active Multilayer Films Based on Keggin Polyoxometalates and Methylene Blue <<, in Z. Naturforsch. 2010, 65b, pages 140 to 146, describe Dan Chen, Jun Peng, Haijun Pang, Pengpeg Zhang, Yuan Chen, Yan Shen, Chanyung Chen, and Huiyuan Ma , multilayer films based on the kegging polyoxymetalates alpha- [SiW ₁₂ O ₄₀ ] ^4- / alpha [PMo ₁₂ O ₄₀ ] ^3- , which show antibacterial activity against Escherichia coli.

In your Article >> Antibacterial activity of highly negatively charged polyoxoates, K27 (KAs4W40O140) and K18 (KSb9W21O86), and Keggin-structural polyoxotungstates against Helicobacter pylori <<, in Journal of Inorganic Biochemistry, 99 (2005), pages 1023 to 1031, describe Miyao Inoue, Keiko Segawa, Sae Matsunaga, Obuhiro Matsmoto, Mayumi Oda and Toshihiro Yamase the antibacterial activity of this polyoxymetalate (POM) based on determination of minimum inhibitory concentration (MIC) and fractional inhibitory concentration (FIK), time of death of bacteria, bacterial morphology and uptake of POM in bacterial cells.

From the American patent US 6,911,470 B1 POM are known to have antiretroviral activity.

From the American patents US 5,824,706 and US 6,020,369 are the prevention and treatment of respiratory viral infections known in which a POM-containing aerosol spray is applied to the lungs.

From the American patent application US 2008/0187601 A1 and the American patents US 6,723,349 B2 and US Pat. No. 7,097,858 B2 are topical POM-containing compositions are known by means of which pollutants, in particular warfare agents, are removed from the environment. Additionally, the topical compositions may still contain cerium, silver, gold, or platinum compounds. In particular, perfluoropolyethers (PFPE) can be used as the carrier. Thus, the warfare agent 2-chloroethylethyl sulfide (CEES) can be quantitatively oxidized to 2-chloroethylethyl sulfoxide (CEESO). These known topical compositions have the disadvantage that they can not be removed from the skin by water.

Zein is a prolamine found in the endosperm of corn kernels. It is thus part of a food. In addition, it is a waste product from bioethanol production and is used as animal feed and food additive. Other prolamins include gliadin from wheat, secalin from rye, avenin from oats, hordein from barley, oryzine from rice and kafirin from millet.

From the American patent US 2,185,123 discloses a process for the preparation of substantially nonaqueous, stable, alcoholic solutions of prolamins.

From the American patent US 3,370,054 For example, deamidated zein dispersions having a pH of at least 6.5 are known.

From the American patent US 6,410,048 (B1) Alcoholic polar lipid adducts are known which contain prolamins, in particular ceramides and polar lipids. The adducts can be used for the production of films or patches.

From the British patent GB 492,599 is a method for extracting zein from protein materials using aqueous alcoholic solutions known.

From the British patent GB 532,588 is a method for producing a stable solution of zein in alcohol known.

From the British patent GB 528,693 For example, a method of making a blend of zein with a bitumen wax is known.

From the European patent application EP 0 470 838 (A1) For example, a method is known in which sweeteners are coated with zein.

From the European patent EP 0 115 549 (B1) For example, bleeding pastes containing 30 to 60% by weight of prolamine are known.

In your Article >> Zein: the industrial protein from corn << in Industrial Crops and Products 13 2001, pages 171 to 192, Rishi Shukla and Munir Cheryan describe the substance Zein and its properties.

In his Article >> Zein: A History of Processing and Use << in Cereal Chem. 79, 2001, pages 1 to 18, John W. Lawton describes the substance zein , its properties and additionally names application areas.

In your Article >> Incorporation of food-grade anti-microbial compounds into biodegradable packing films << in J. Food Prot. 61, 1998, pages 1330 to 1335, describe Padgett, T., Han, IY and Dawson, P.L. the production of biodegradable packaging.

From the Chinese patent application CN 104387604 (A) It turns out that a highly moisture-resistant, biodegradable zein has been developed and made into a coating material.

From the American patent US Pat. No. 6,410,048 B1 Various plant prolamins have been used to test different manufacturing processes and to develop applications.

From the American patent US 5,397,834 , a biodegradable thermoplastic composition emerges based on starch and proteins.

From the Chinese patent application CN 102392334 (A) A zein-based fiber comes out which has a very high moisture permeability.

From the American patent US 4,224,219 For example, there is known a method by which zein can be rendered water-soluble. For this purpose, the zein is reacted with alkylene oxide and the derivative is isolated

Object of the present invention

The present invention was based on the object to replace conventional silicone and other substances and so to develop a new gel, so that the direct and / or indirect skin contact is not toxic and / or harmful. In addition, the new gel should be low in energy and carbon dioxide neutral. A biocide can be added to the gel without reducing or completely losing the beneficial properties of the gel. Furthermore, the gel should be versatile. Possible applications are in the textile industry, in medicine, in sports articles, sleeping articles and household goods, in the health industry, in the game industry, in surface technology, in hygiene articles, in pet supplies and for hobbyists. The gel should be recyclable and ensure a more environmentally friendly disposal.

Further tasks are evident from the description.

Inventive solution

Accordingly, a gel has been found which contains at least one prolamine and at least one gelling functional constituent, hereinafter referred to as "gel of the invention".

In addition, a process for the preparation of the gel according to the invention has been found in which at least one prolamine is mixed with at least one gelling functional constituent and which is referred to below as the "process according to the invention".

Not least different uses of the gel according to the invention were found.

Advantages of the invention

In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention was based could be achieved with the aid of the gel according to the invention, the process according to the invention and the uses according to the invention.

In particular, it was surprising that the gel according to the invention had essentially a natural origin, with its main constituent, the prolamins, even finding use in foods and thus being edible.

In addition, it was surprising that the gels according to the invention exhibited, if at all, only a very low toxicity to humans, animals and plants, so that they were also ecologically harmless.

They do not decompose and / or segregate even during prolonged storage and / or your transport at changing temperatures and changing humidity.

Furthermore, it was surprising that the uses according to the invention, for example in medical technology, the game industry, the textile industry or for sports articles, for sleeping articles or household goods, in surface technology, in hygiene articles, in pet supplies and for hobbyists, were extremely broad. From this it became clear that in the uses according to the invention, significantly improved products were obtained which, above all, were significantly healthier than the known gels.

It was a very special additional advantage that the gels of the invention could be further processed by new methods. In addition, the use of the gels of the invention in plastic bags and alternatives to plastics has also been extremely useful.

Furthermore, it was surprising that for the application for thermal and / or cold packs, the gels according to the invention and also other gels could be cooled by means of Seebeck and / or Peltier elements. It was particularly surprising that, for example, an app could be integrated. In addition, using a feedback system, the temperature could be kept constant.

Detailed description of the invention

In the context of the present invention, the term >> nanoparticles << denotes a particle having an average particle size of 1 nm to <1000 nm.

Furthermore, the term >> microparticles << refers to particles having an average particle size of from 1 .mu.m to <1000 .mu.m. In addition, the term >> macroparticles << particles that are larger than 1000 microns.

The particle sizes can be measured by transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission microscopy (RTEM), atomic force microscopy (AFM), or scanning tunneling microscopy (TRM).

For the gels, applications and methods of the invention, prolamins in the form of macro- and / or micro- and / or nanoparticles are essential.

The prolamine particles can have a wide variety of morphologies and geometric shapes, so that they can be excellently adapted to the other constituents of the uses according to the invention.

Thus, they can be compact, and have at least one cavity and / or a core-shell structure. They may also have different geometric shapes, such as spheres, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, icosahedra, truncated icosahedra, dumbbells, tori, platelets, or needles with circular, oval, elliptical, square have triangular, quadrangular, pentagonal, hexagonal, heptagonal, octagonal, or star-shaped (tri-quad, quadrilateral, pentagonal, or polygonal) outline. If necessary, existing edges and corners can be rounded. It is also possible for two or more macro- and / or micro- and / or nanoparticles of different morphology and / or geometric form to be combined. For example, spherical zein macro and / or micro and / or nanoparticles may have pointed outgrowths in the form of cones. Furthermore, their surface may have depressions such that the zein macro and / or micro and / or nanoparticles have a strawberry or raspberry morphology. Last but not least, the dumbbell, tori, needles or plates can be bent in at least one direction of the room.

The diameter of the prolamine macro and / or micro- and / or nanoparticles, in particular the zein macro- and / or micro- and / or nanoparticles, in solution and / or suspension can vary very widely and therefore excellent be adapted to the respective intended use of the method according to the invention.

The gels of the invention to be used refer to the base materials. The main substance for this is zein, which, however, is also replaceable by other prolamins such as gliadin (wheat), secalin (rye), avenin (oats), hordein (barley) oryzine (rice) and kafirin (millet) and / or in combinations.

As gelling functional additives, for example, gum arabic, agar agar, pectin, polyhydroxyalkanoates, polyalkylene oxides, chitosan, chitin, collagen, gelatin, paper and paper-like materials and starch can be used.

The prolamine macro- and / or micro- and / or nanoparticles described above, in particular zein macro- and / or micro- and / or nanoparticles, in solution and / or suspension can be functionalized, not functionalized, aggregated, not aggregated, agglomerated, not agglomerated, supported and / or unsupported. For example, they may be functionalized, agglomerated and supported. But they can also not be functionalized and aggregated. The same applies to their polymer chains. These may also be functionalized, non-functionalized, aggregated, not aggregated, agglomerated, not agglomerated, supported and / or unsupported. For example, they may be functionalized, agglomerated and supported. But they can also not be functionalized and aggregated.

The prolamine macro and / or micro- and / or nanoparticles to be used according to the invention, in particular the zein macro- and / or micro- and / or nanoparticles, may be present in solution and / or suspension "nude". This means that their surface is not surrounded by a shell and / or is not functionalized.

In addition, the prolamine macro- and / or micro- and / or nanoparticles to be used according to the invention, in particular the zein macro- and / or micro- and / or nanoparticles, can be surrounded in solution and / or suspension by a shell and / or carry at least one functional group. The material of the shells may carry the functional groups or else the functional groups may be present directly on the surface of the prolamine macro- and / or micro- and / or nanoparticles.

The aggregates are loose aggregates of particles that are held together by cohesion and can not be distributed by conventional and known dispersion methods. Its inner surface is smaller than the sum of the surfaces of the primary particles.

The agglomerates are aggregates of primary particles and their aggregates, which are bridged over edges and corners. Their inner surface corresponds approximately to the sum of the surfaces of the primary particles.

The material of the sheath and / or the functional groups can be selected so that they have the physical and / or chemical properties of the prolamine macro- and / or micro- and / or Nanoparticles, in particular the zein macro and / or micro and / or nanoparticles, in solution and / or suspension in a desired manner modify or mask.

The sheaths and / or the functional groups can be attached to the surface of the prolaminic and / or micro- and / or nanoparticles via covalent and / or ionic bonds and / or electrostatic and / or van der Waals forces, in particular the zein macroscale and / or micro- and / or nanoparticles, be bound in solution and / or suspension.

The bond between the surface of the prolamine macro- and / or micro- and / or nanoparticles, in particular the zein macro and / or micro- and / or nanoparticles, in solution and / or suspension and the shell and / or or the functional group may be permanent or reversible, i. H. be solvable again.

The shells may be constructed of organic, inorganic and organometallic, polymeric, oligomeric and low molecular weight materials or combinations of at least two of these materials.

Examples of suitable functional groups and materials for the shells of the prolamine macro- and / or micro- and / or nanoparticles to be used according to the invention, in particular the zein macro- and / or micro- and / or nanoparticles in the following, are given below Solution and / or suspension listed. The person skilled in the art can select the functional groups and materials which are particularly suitable for the particular individual case on the basis of the properties profiles known to him.

Usual and known functional groups

Fluorine, chlorine, bromine and iodine atoms; Hydroxyl, thiol, ether, amino, peroxide, aldehyde, acetal, carboxyl, peroxycarboxyl, ester, amide and hydrazide groups; Nitrile, isonitrile, lactide, lactone, lactam, oxime, nitroso, nitro, azo, azoxy, hydrazine, hydrazone, sulfen, sulfenamide, sulfoxyid, sulfone, silane , Siloxane, phosphane, phosphoric acid and phosphate groups.

Common and known additives

Examples of suitable low-boiling organic solvents and high-boiling organic solvents are alcohols, water, ketones and esters.

Examples of suitable reinforcing fibers are nanocellulose, carbon nanotubes, carbon fibers, carbon nanofibers, glass fibers, quartz sand, wood wool, sisal fibers, aramid fibers, flax fibers, hemp fibers, jute fibers, kenaf fibers, wood flour and cellulose fibers.

Further examples of additives are dyes, colored pigments, white pigments, fluorescent pigments and phosphorescent pigments.

Furthermore, carbohydrates such as cellulose, modified cellulose, chitin, chitosan, carrageenan, collagen, starch, polystyrene, mycobond and glucose are good fillers. Further examples of additives are the following described materials.

monoalcohols

• Methanol, ethanol, propanol, isopropanol, butanol, isobutanol and their stereoisomers. Polyols such as glycerol.

polyhydroxycarboxylic

• Glycerol, citric, tartaric, threonine, ascorbic, gluconic, galacturonic, iduronic and lactobionic acids.

fatty acids

• Lauric, myristic, oleic, palmitic, linoleic, stearic, arachinic, behenic acid.

preservatives

• Sorbic acid, potassium sorbate, calcium sorbate, benzoic acid, sodium benzoate, potassium benzoate, calcium benzoate, 4-hydroxybenzoic acid ethyl ester, sodium 4-hydroxybenzoic acid ethyl ester, sodium sulfite, sodium bisulfite, sodium bisulfite, potassium bisulfite, calcium sulfite, calcium bisulfite, potassium bisulfite, potassium nitrite, sodium nitrite, sodium nitrate, potassium nitrate, acetic acid, potassium acetate, Sodium acetate, sodium diacetate, calcium acetate, lactic acid, propionic acid, sodium propionate, calcium propionate, potassium propionate, boric acid, sodium tetraborate, carbon dioxide, malic acid, fumaric acid and lysozyme

Examples of suitable POM are shown in the table. Table 1: Sum formulas of suitable POMs a) No Molecular formula family structure 1 [(NMP) ₂ H] ₃ PW ₁₂ O ₄₀ 2 [(DMA) ₂ H] ₃ PMo ₁₂ O ₄₀ 3 (NH ₄ ) ₁₇ Na [NaSb ₉ W ₂₁ O ₈₆ ] Inorganic crypt 4 alpha- (NH ₄ ) ₆ P ₂ W ₁₈ O ₆₂ Wells-Dawson structure 5 K ₁₀ Cu ₄ (H ₂ O) ₂ (PW ₉ O ₃₄ ) ₂ · 20H ₂ O Wells-Dawson structure 6 Na ₇ PW ₁₁ O ₃₉ Wells-Dawson structure 7 (NH ₄ ) ₁₄ (NaP ₅ W ₃₀ O ₁₁₀ ) Preyssler structure 8th (NH ₄ ) ₄ W ₁₀ O ₃₂ Preyssler structure 9 K ₁₀ (H ₂ W ₁₂ O ₄₂ ) Preyssler structure 10 Na ₁₂ P ₂ W ₁₅ O ₅₆ .18H ₂ O Lacunare (defective) structure 11 Na ₁₆ Ni ₄ (H ₂ O) ₂ (P ₂ W ₁₅ O ₅₆ ) ₂ · nH ₂ O Wells-Dawson sandwich structure 12 K ₁₂ Cu ₃ (PW ₆ O ₃₄ ) ₂ · nH ₂ O Kegging sandwich structure 13 K ₁₂ Zn ₃ (PN ₉ O ₃₄ ) ₂ · 15H ₂ O Kegging sandwich structure 14 [(CH ₃ ) ₄ N ⁺ ] ₄ SiW ₁₁ O ₃₉ O [SiCH ₂ CH ₂ C (O) OCH ₃ ] ₂ Organically modified structure 15 K ₅ Mn (II) PW ₁₁ O ₃₉ · nH ₂ O Transition-metal-substituted structure 16 K ₇ SiW ₉ Nb ₃ O ₄₀ · nH ₂ O Transition-metal-substituted structure 17 [(CH ₃ ) ₃ NH ⁺ ) ₇ SiW ₉ Nb ₃ O ₄₀ .nH ₂ O Substituted Keggin structure 18 K ₆ Nb ₃ PW ₉ O ₄₀ Peroxo Keggin structure a) cf. US 6,020,369 , Table 1, columns 3 to 10
n number, in particular integers, from 1 to 50

The functional groups and materials for the additives of the prolamine macro- and / or micro- and / or nanoparticles, in particular of the zein macro- and / or micro- and / or nanoparticles in solution and / or suspension, listed above are those listed above only by way of example and not exhaustively enumerated. The enumeration is therefore intended to illustrate the variety of possibilities, and the skilled person can readily specify other possibilities due to his general expertise.

The content of the prolamine macro- and / or micro- and / or nanoparticles to be used according to the invention can vary widely and depends on the respective intended use.

Another preferred constituent of the prolamine and / or micro- and / or nanoparticles to be used according to the invention is water. The water content can vary widely and also depends essentially on the intended use.

The prolamine and / or micro- and / or nanoparticles to be used according to the invention can be attached to or mixed with other micro- and / or nanoparticles. The prolamin and / or nanoparticles and the other micro- and / or nanoparticles can be bound to one another by covalent and / or ionic bonds, hydrogen bonds, electrostatic attraction and / or van der Waalskräfte.

The uses according to the invention are gels according to the invention for silicone alternatives. The present invention is versatile. Areas of application are the use in the textile industry, in medicine, in sports articles, sleeping articles, household goods, in the health industry, in the game industry, in surface treatment, in hygiene articles, in pet supplies and for hobbyists.

The following applications are examples of their categories:

textile industry

• Underwear market, such as bras and underpants, jackets, cushions (shoulder pads) and shoes;

medicine

• Gel pads for patients, gel patches for shoes;

sporting Goods

• Mouthguards, pads for rackets and / or paddles, bicycle saddles with and without cooling and heating function, bicycle accessories, such as handlebars with grips, which are also heatable and coolable, cuffs for the hands, which are connected to the handlebars of the bicycle and thus provides heat These functions can also be controlled via the app so that it warms up or cools down before driving;

sleeping Article

• Mattresses, pillows and toppers;

household goods

• Cookware;

Health industry

• Cooling packs, electric cooling packs, baby teething rings, dildos, plastic vaginas, breast implants with adjustable weights so that the vibration characteristics remain and the gel is filled with hollow bodies and optional materials and morphologies of different specific gravity;

game industry

• Toys that are padded, Glibberfiguren;

surface technology

• Coatings and 3D print materials;

Hygiene products

• POM-containing antibacterial sprays, liquid gel, glue, films and gel sticks;

Pet Supplies

• Cooling mats for animals, in particular dogs ;.

hobbyists

• Gels for crafting and gluing, for example as a structural gel.

The gels of the invention can be combined with apps and / or feedback systems to monitor and control functionality of the gels.

The applications listed above and areas of application are only exemplary and not exhaustive enumerated. The enumeration is therefore intended to illustrate the variety of possibilities, and the skilled person can readily specify other possibilities due to his general expertise.

For the purposes of the method according to the invention, the prolamine macro- and / or micro- and / or nanoparticles to be used according to the invention are preferably distributed homogeneously or inhomogeneously in the gel according to the invention.

Preferably, for the process according to the invention, liquid mixtures of the above-described prolamine macro- and / or micro- and / or nanoparticles to be used according to the invention are filled in plastic bags and / or alternatives to plastic.

For the preparation of the gels according to the invention, it is possible to use the customary and known mixing units, such as high-speed stirrers, Ultraturrax, inline dissolvers, homogenizing glands, static mixers or kneaders. In addition, hot plate, water baths and the like can also be used to prepare the liquid mixtures.

After preparation of the mixtures, they are preferably filled into plastic bags and / or alternatives to plastic. These can have different shapes and different strengths. You can have overflow system or have only a certain level. It could have any shape and size. This information depends on the respective application.

The type of plastic can vary. The list below is the exemplary plastics for use.

plastics

Thermoplastics:

• Acrylonitrile butadiene styrene (ABS), polyamides (PA), polylactate (PLA), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyetheretherketone (PEEK) and polyvinyl chloride (PVC).

elastomers:

• Natural rubber (NR), acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR) and ethylene-propylene-diene rubber (EPDM).

Bio-plastics

Strength and strength blends:

Corn, wheat, potatoes in Europe, tapioca, water-repellent, biodegradable polymers such as polyesters, polyester amides, polyurethanes or polyvinyl alcohol.

Cellulose products:

• Cellulose acetate (CA), celluloid, cellophane, vulcanized fiber, cellulose nitrate, cellulose propionate and cellulose acetobutyrate.

Polylactic acid (PLA)

polyhydroxyalkanoates:

• Polyhydroxybutyrate (PHB)

The plastics listed above are only given by way of example and not exhaustively. The enumeration is therefore intended to illustrate the variety of possibilities, and the skilled person can readily specify other possibilities due to his general expertise.

In the method according to the invention, the gel according to the invention is mixed with the prolamine macro- and / or micro- and / or nanoparticles used in accordance with the invention, in particular the zein macro- and / or micro- and / or nanoparticles, in solution and / or suspension bottled in sachets. It is advantageous if this happens under a protected atmosphere, so that no oxygen reaches the gel according to the invention.

After the gel has been manufactured and filled in protective atmosphere in plastic bags and / or alternative to plastic, it can be integrated into the intended applications. The surface may be antibacterial and / or hydrophobic and / or hydrophilic.

It is understood that the features mentioned above and explained in more detail below can be used not only in the specified combinations and configurations, but also in other combinations and configurations or in isolation, without departing from the scope of the present invention.

Examples

Here, examples are described which are not limiting for the substance according to the invention, the application according to the invention and the process according to the invention.

Example 1 with comparative experiment: The preparation of a gel with use as a cooling pack

A gel was made with zein and gelatin which was filled into plastic bags or other alternatives to plastic and sealed with vacuum (Series 1).

Forms of execution could be individually anatomically shaped: for eyes, forehead, head, neck, chest, shoulder, arm, hand, elbow, back, spinal canal, hip, thigh, lower leg, knee, ankle and ankle. Here different shapes and sizes could vary, depending on the application.

In parallel, a gel pad was produced which did not contain zein micro- and / or nanoparticles (comparative series 1).

The two gel pads were placed in a freezer at -18 ° C for several hours. Then they were taken out and tested. It was found that the gel pad with the zein macro- and / or micro- and / or nanoparticles was significantly less frozen than that of the comparative series 1.

Example 2: The preparation of a gel with use for electronic cooling packs / heat packs

A gel was made with zein and gelatin or silicone, which was filled in plastic bags and sealed with vacuum.

The temperature was regulated by a Seebeck element and the cooling pack was cooled. The cold was transferred to the skin through the gel pad. The Seebeck element is operated with battery and / or PV and / or battery and / or mains connection and thereby obtained the necessary power supply. The Seebeck element was electrically isolated.

Pre-cooling accelerated the cooling effect. An amplification of the Seebeck effect could be achieved by means of a fan. Examples were the pope fan and / or cooling fins. Of Furthermore, a protection system against electric shocks and burns can be attached to the fans and / or cooling fins.

Forms of execution could be individually anatomically shaped: for eyes, forehead, head, neck, chest, shoulder, arm, hand, elbow, back, spinal canal, hip, thigh, lower leg, knee, ankle and ankle. Here different shapes and sizes could vary, depending on the application.

The control took place via integrated sensors and sensors. There were programmable curves of cooling programs and / or timers / timers, indicating when the cooling phase came to an end and when it should be restarted; also cycles could be set.

There were also programs that could be entered manually and / or preprogrammed programs. These programs could also be controlled via an app on the smartphone and / or tablet and / or smart home system.

On hot days, the gel pads described above were able to provide cooling, and on cold days, the Seebeck element could work in the opposite direction, warming up the gel pad. This could be available as an alternative, or used in combination.

Another option was a multifunctional use. Here, a gel pad was attached to each side of the Seebeck element. The gel pad became cold on one side and warm on the other side at the same time.

The surface of the gel pads was antibacterial. Due to a lotus effect, the surface was easily wiped off. For example, suction nipples, bandages, straps and / or hook and loop fasteners and / or eyelet closures could be used for attachment to the body.

The Seebeck elements could also be flexible and also combined with massage systems. Furthermore, a compartmentalization could be incorporated in the gel pads. These could be moved fixed and / or freely movable therein. For example, the walls of the compartments could be isotropic and / or have a honeycomb structure. The walls of the compartments were isolated.

Another possibility was to have a freely selectable number of Seebeck elements and thus to produce different temperature zones.

Example 3: The preparation of a gel with use for saddles

A gel was made with zein and gelatin which was filled in plastic bags and sealed with vacuum.

There was an alternative to the conventional gels and also a new structure for the saddles.

In a series simply the conventional filling was replaced.

In another series, the gel was processed in professional bike saddles, so that a higher comfort was created and the pressure could distribute better. Here, the gel could be sprayed directly in a designated saddle and / or even be dimensionally stable or it could be present in a plastic bag.

Example 4: The preparation of a gel with use for textiles, in particular bras

A gel was made with zein and gelatin which was filled into plastic bags and alternatives for plastic and sealed with vacuum.

The gel was incorporated in five different variants for bras.

The first variant is the gel pad. It is to be used as an insert in the conventional bra. It gives the breast more support and makes it look bigger and / or shapely.

The above-described gel pad could be placed in the bra and also be fixed by a Velcro fastener. The gel pad could not move in the bra anymore.

The gel pad could also be fully integrated into the bra.

Another BH model consisted of hollow fibers that acted as an exoskeleton. The gel described above was filled into this exoskeleton. The tissue was now light and thin, but at the same time very stable and formative.

An inventive sports bra had a so-called chamber system. He had two chambers A and B. These were connected to each other. The chambers contained the gel described above, which could move from chamber A to chamber B and vice versa. In addition, a chip could be incorporated, which could measure, inter alia, the running speed, and pulse and oxygen content. This could be coupled with an app, so you could monitor all important functions with the help of his smartphone and / or tablet.

Furthermore, the bra can also be self-adhesive or consist only of cups.

Example 5: Shoulder Pads:

There are shoulder pads in various jackets. These could also be replaced by a gel pad. For this purpose, as described above, the gel pads are made and then covered with textiles. They could then be fastened in clothing in any way.

Example 6: Gel as hygiene article

A gel was made with zein and gelatin, which was filled in plastic bags and alternatives for plastic. These are added preservatives, POMs and other additives to achieve an antibacterial effect.

The gel could be filled into spray bottles and then sprayed on surfaces. These were then disinfected and new bacteria could no longer form. Here could also form a film that was antibacterial.

Another option was a gel for hand disinfection. Here, the gel could be put directly on the hands, and thus the bacteria on the hands were killed.

Furthermore, the gel could be produced in the form of a gel stick. Here, the consumer is possible to apply the gel on any surface.

The options listed above are only exemplary and not exhaustive enumerated. The enumeration is therefore intended to illustrate the variety of possibilities, and the skilled person can readily specify other possibilities due to his general expertise.

Example 7

In the following, in this example, the invention is based on the 1 to 4 be explained further. The 1 to 4 should illustrate in a simplified, not true to scale representation of the principle of operation. Show it

1 the cross section through a device 1 comprising a gel pad 2 and a Seebeck element 3 ;

2 the cross section through a device 1 comprising a gel pad 2 , which is designed as a massage surface, and a Seebeck element 3 ;

3 the cross section through a device 1 comprising a Seebeck element 3 , on the cold and the warm side, each with a gel pad 2 connected is;

4 the cross section through a device 1 comprising a series of coplanar Seebeck elements 3 , their cold and warm sides in total with a gel pad 2 are connected.

In the 1 to 4 the reference signs have the following meaning:

LIST OF REFERENCE NUMBERS

1

Device comprising at least one gel pad 2 and at least one Seebeck element 3

2, 2a, 2b

Gelpad

2.1, 2.1a,

2.1b

Plastic containers

2.2, 2.2a,

2.2b

gel

3, 3, 3b, 3c

Seebeck element

4

heat sink

5

electrical connections

6, 6a, 6b

thermally conductive adhesive layer

7

functional device

8th

electrical insulation and sealing

9a, 9b, 9c

electrically insulating, heat-conducting container

10a, 10b

electrical connection between two Seebeck elements

Example 7.1

The 1 shows the cross section through a device 1 comprising a gel pad 2 and a Seebeck element 3 ,

Seebeck elements were used 3 detailed in the American patent US 5,610,366 , the American patent application US 2010/022911 A1, the international patent application WO 97/44993 A1 , the German patent application DE 101 12 383 A1 or the company font of Hi-Z Technology Inc., "Use, Application and Testing of Hi-Z Termoelectric Modules", authors: FA Levitt, NB Elsner and JC Bass , to be discribed.

Preferably thermoelectric modules in "egggrate" configuration (egg-box configuration) were used, as for example in the international patent application WO 97/44993 , Page 2, last paragraph, to page 15, last paragraph, in conjunction with the 1A to 14 and 27 to be discribed.

The gelpad 2 consisted of a sturdy, flexible plastic container 2.1 with a square plan, with a zein gel 2.2 in which a liquid polyalkylene oxide was used as the gelling ingredient was filled.

The gelpad 2 was by means of a thermally conductive adhesive layer 6 of the aluminum nitride particles containing the hot side of the Seebeck element 3 firmly bonded.

The cold side of the Seebeck element 3 was connected to a heat sink. As heat sinks cooling fins or water-carrying cooling hoses were used.

The Seebeck element 3 was over the electrical connections 5 with a functional device 7 electrically connected. Using the functional device 7 could the physical properties of the device 1 be adjusted and / or controlled.

As functional devices 7 These include temperature controllers, cable connectors, batteries and / or batteries, sensors and / or sensors, as well as PCs, laptops, smartphones and other electronic devices with chips that use programs or apps to monitor the temperature of the zein gel, for example 2.2 and thus its viscosity over the Seebeck element 3 controlled.

Example 7.2

The 2 shows a cross section through another device 1 comprising a gel pad 2 and a Seebeck element 3 ,

The construction and functionality correspond to the device 1 Example 7.2 of the device of Example 7.1, except that the the Seebeck element 3 opposite surface of the gel pad 2 had a studded profile that was used as a massaging surface. Using the Seebeck element 3 and functional devices 7 could the temperature and thus the viscosity of the gel pad 2.2 be adjusted so that massages were possible under different conditions.

Example 7.3

The 3 shows a cross section through another device 1 comprising two gel pads 2a and 2 B and a Seebeck element 3 ,

The gelpads 2a and 2 B each consisted of a stable, flexible plastic container 2.1a and 2.1b that with zein gels 2.2a and 2.2b in which a liquid polyalkylene oxide was used as the gelling ingredient were filled. Both gelpads 2a and 2 B had a square floor plan.

The gelpad 2a was by means of a thermally conductive adhesive layer 6a containing aluminum nitride particles with the hot side of the Seebeck element 3 firmly bonded. The gelpad 2 B was by means of a thermally conductive adhesive layer 6b , which also contained aluminum nitride particles, with the cold side of the Seebeck element 3 firmly bonded.

To the outside application of the device 1 were the pages of the Seebeck element 3 using electrical insulation and sealing 8th protected. The electrical connections 5 were in a suitable place by the seal 8th and at least one of the functional devices listed above 7 connected.

It was a peculiarity of the device 1 Example 3 that a warm gel pad 2a with a cooled gel pad 2 B could be combined, which opened up numerous applications.

Example 7.4

The 4 shows a cross section through another device 1 comprising two gel pads 2a and 2 B and a Seebeck element 3 ,

The device 1 of the 4 corresponded in its structure, its function and its potential applications of the device 1 of the 3 , The difference was that in the device 1 of the 4 instead of a Seebeck element 3 flush to each other, and via the electrical connections 10a and 10b electrically interconnected and mechanically connected Seebeck elements 3a . 3b and 3c were used. Every Seebeck element 3a . 3b and 3c was in an electrically insulating, heat-conducting, gas and fluid-tight encapsulation 9a . 9b and 9c embedded.

The device 1 of Example 4 was especially suitable for outdoor use.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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• WO 2014/089952 (A1) [0009]
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• WO 2015/124219 (A1) [0012]
• TW 2015/18419 A [0013]
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Cited non-patent literature

• Römpp Online, Version 3.47 >> Heteropolyacids << [0019]
• Article >> Fabrication and Characterization of Antibacterial-active Multilayer Films Based on Keggin Polyoxometalates and Methylene Blue <<, in Z. Naturforsch. 2010, 65b, pages 140-146, describe Dan Chen, Jun Peng, Haijun Pang, Pengpeg Zhang, Yuan Chen, Yan Shen, Chanyung Chen, and Huiyuan Ma. [0020]
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Claims (10)

Gels containing at least one type of functionalized, unfunctionalized, aggregated, non-aggregated, agglomerated, non-agglomerated, supported and / or unsupported prolamine macro and / or micro and / or nanoparticles of median particle size d ₅₀ of FIG nm to> 1000 microns and at least one type of gelling functional ingredient. Gels according to claim 1, characterized in that the prolamins are selected from the group consisting of gliadin, secalin, avensin, hordein, zein, oryzine and kafirin. Gels according to claim 1 or 2, characterized in that the prolamine is zein. Gels according to any one of claims 1 to 3, characterized in that the gelling functional ingredients are selected from the group consisting of gum arabic, agar-agar, pectin, polyhydroxyalkanoates, polyalkylene oxides, chitosan, chitin, collagen, gelatin, paper and paper-like materials and starch , are selected. Gels according to one of claims 1 to 4, characterized in that they are combined with at least one Seebeck element and / or at least one Peltier element. A process for preparing gels according to any one of claims 1 to 5, characterized in that at least one type of prolamine macro- and / or micro- and / or nanoparticles is mixed with at least one gelling functional ingredient, after which the mixture is homogenized , Use of the gels according to one of claims 1 to 5 and / or the gels prepared according to the method according to claim 6 as silicone alternatives. Use according to claim 7, characterized in that the gels are used in the textile industry, in medicine, in sports articles, sleeping articles, household goods, in the health industry, games industry, surface technology, in hygiene articles, pet supplies and for hobbyists. Use according to claim 7 or 8, characterized in that the gels in underwear market for bras and pants, jackets, upholstery, shoulder pads and shoes; as gel pads for patients; as a gel plaster for shoes; as a mouthguard, padding for rackets and / or paddles and bicycle saddles; as mattresses, pillows and toppers; as cookware; as cool packs, electric cool packs, baby teethers and dildos; as toys, which are padded, as well as Glibberfiguren; as coatings and 3D print; Materials; POM-containing antibacterial sprays, liquid gels, adhesives, films and gel sticks; as cooling mats for animals; and as gels for crafting and gluing and as a structure gel. Use according to any one of claims 7 to 9, characterized in that the gels are combined with apps and / or feedback systems to monitor and control the functionality of the gels.

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