WO2013113086A1 - Film polymère d'agar hydrosoluble et son procédé d'obtention - Google Patents

Film polymère d'agar hydrosoluble et son procédé d'obtention Download PDF

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Publication number
WO2013113086A1
WO2013113086A1 PCT/BR2013/000043 BR2013000043W WO2013113086A1 WO 2013113086 A1 WO2013113086 A1 WO 2013113086A1 BR 2013000043 W BR2013000043 W BR 2013000043W WO 2013113086 A1 WO2013113086 A1 WO 2013113086A1
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agar
water
acid
film according
polymeric film
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PCT/BR2013/000043
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English (en)
Portuguese (pt)
Inventor
Ricardo YARA.
Cláudia SAMPAIO DE ANDRADE LIMA
Beate SAEGESSER SOS SANTOS
Júlio César BEZERRA PEREIRA
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Universidade Federal De Pernambuco
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Publication of WO2013113086A1 publication Critical patent/WO2013113086A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
    • C08B30/14—Cold water dispersible or pregelatinised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/12—Agar-agar; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B29K2001/08—Cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2005/00—Use of polysaccharides or derivatives as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/0062—Degradable water-soluble
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/12—Agar-agar; Derivatives thereof

Definitions

  • the present invention is applicable to the food industry and may also be applied to the pharmaceutical industry for the delivery of products for human or veterinary use.
  • the present invention relates to a fully water-soluble hot or cold polymeric film produced from Agar, a natural hydrocolloid polysaccharide widely used in the food industry.
  • the film produced will serve as support for the incorporation of natural, artificial and / or functional foods.
  • composition and technology of obtaining polymeric films for food applications is already widespread in the scientific literature. Specifically, such films are produced with a view to forming coating films to prevent the rapid deterioration of some perishable foods such as fruits, vegetables, meats and dairy products. These films are packaging that maintains mechanical integrity, improves appearance and promotes food maturation. Moreover, these biofilms are edible as they do not offer any harm to consumer health. Natural polymers, such as proteins and polysaccharides, form the basis of these films. All have the important feature of being completely biodegradable within a considerably short period of time.
  • An example of an edible packaging film is U.S. Patent Glucomannan / polyhydric Alcohol. Composition and Film Prepared Therefrom "(US Pat. No. 4,851,394, July 25, 1989), by Masao Kubodera, which describes glucomannan-based water resistant films, whether or not added to other polysaccharides, including agar.
  • Biofilm formation involves the addition of a plasticizer to the polymer.
  • the most commonly used substances in this function are polyalcohols, such as glycerol, triacetin, sorbitol, xylitol, maltitol and mannitol.
  • Plasticizers reduce intermolecular forces and increase the mobility of polymer chains, reducing possible discontinuities and brittle zones. They favor the transition of the material from a vitreous state to a rubbery or gummy state, with greater molecular mobility and, consequently, greater flexibility.
  • other technological aids may be incorporated into the biofilm composition, such as antimicrobials, antioxidants, emulsifiers, anti-humectants, flavors and dyes. These adjuvants allow the films to be adapted to the demand and industrial interests by maintaining and improving the physicochemical and microbiological qualities of foods.
  • Pululan biopolymer is the major filmogenic compound used in the production of commercial pharmaceutical films. The first
  • Listerine PocketPacks registered and marketed by Warner-Lambert Company, a Pfizer Inc. personal care branch.
  • Listerine PocketPaks are thin films, quickly solubilized by salivary secretion, used for 0 Carry active ingredients that eliminate the bacteria that causes bad breath and promote a feeling of freshness in the oral cavity.
  • the patent entitled "Fast dissolving orally consumable film” (US Patent No. 7,025,983, April 11, 2006) to Leung et al. Is the document on which this product is based.
  • Tobacco Compositions (WO Pat No. 2005/046363, May 26, 2005), US Smokeless Tobacco Company. "Water Soluble Film for Oral Administration with Instant Wettability" (US Pat. No. 6,709,671, Mar 23, 2004), by Horst Georg Zerbe et al., Discloses the invention of water soluble films for instant oral administration. wettability. These are compositions containing therapeutic agents and breath freshening agents produced by the coating technique. The invention relates to the use of water soluble polymeric agents as film formers, the water soluble cellulose-derived polysaccharides being described as ideal for the composition.
  • the US patent "Fast dissolving films and coatings for controlled release of flavors, active pharmaceutical ingredients, food substances, and nicotine” (US Pat No. 2009/0253754 Al, Dec 04, 2008), by Francesca Selmin et al., Describes a film fast dissolving material to be used as a support for the release of materials into the oral cavity and the processes for producing it.
  • the film composition comprises a cellulose derivative film forming agent such as hydroxypropyl methyl cellulose (HPMC) preferably.
  • HPMC hydroxypropyl methyl cellulose
  • a plasticizer is also added; and a rapidly dissolving water-soluble compound, such as the synthetic polyethylene glycol-polyvinyl alcohol copolymer (Kollicoat IR) or sodium alginate.
  • the components are mixed in an emulsifying process without heating, forming the film by drying at room temperature.
  • Rapidly disintegrating sheet-like presentations of multiple dosage units (US Pat No. 5,629,003, 13 May 1997), to Michael Horstmann et al., Discloses a rapidly dissolving film in the form of slides in unit presentations. multi-dose.
  • the product is characterized by having a film former, specifically acetylated starch, in the proportion of 20-60% by mass, 2-40% of a gel former, 0.1-35% of active ingredients and above 40%.
  • % inert filler excipients further describes the use of 40% polar solvent and includes processing to form a homogeneous, spreadable extrudable mass.
  • the present invention utilizes as the base raw material in film production the polysaccharide known as agar, also simply called agar.
  • agar is a phycocolloid, a seaweed-based gel-forming substance that has the oldest and best-researched industrial application in the world, and was the first product to be used in the field.
  • food as a gelling agent.
  • the agar gel can be obtained in very dilute solutions containing a fraction of 0.5% to 1.0% of the raw material.
  • Agar in industry is a technological aid, with the following main functions: gelling, thickening, texturizing and stabilizing. Another popular application of agar is as the main solid culture medium used in microbiological studies and research.
  • agar The medicinal use of agar is also cited because of its classification as a soluble dietary fiber.
  • the definition of dietary fiber according to the report of the Board of Directors Committee of the American Association of Cereal Chemists (AACC Report. The Definition of Dietary Fiber. Cereal Foods World. Vol. 46, No. 3, Mar. 2001), Freely translated as: "Food fibers are the edible parts of vegetables or similar carbohydrates that are resistant to digestion and absorption in the human small intestine, having full or partial fermentation in the large intestine.
  • Dietary supplements include polysaccharides, oligosaccharides, lignin and associated plant substances. Dietary fibers promote beneficial biological effects, including laxation, and / or attenuation of plasma cholesterol and / or glucose levels.
  • Agar has the ability to increase volume and promote fecal bolus hydration, aiding in the regulation of intestinal transit, with mechanical and peristaltic reflex reflex excitation of the intestinal contractions When ingested, the agar has a digestibility of only 10% and a calorie content close to zero.These characteristics make it ideal as a raw material of food and drink for diabetics and people on diets. It is known that agar causes delayed gastric emptying, which may prolong the feeling of satiety after a meal. [8] The 2004 study by Maeda et al evaluated the effectiveness of a diet based on agar in combination with a conventional diet (traditional Japanese food) in obese patients with impaired glucose tolerance and c with type 2 diabetes.
  • Agar diet resulted in remarkable weight loss due to the maintenance of reduced calorie intake and promoted a significant improvement in the general conditions of the metabolic syndrome, with reduction in the values of the following physiological parameters: systolic and diastolic blood pressure; hemoglobin-bound glucose and plasma cholesterol.
  • the general characteristics of the agar are: non-toxic to most microorganisms and humans; melting point between 95 and 100 ° C and gelling at about 45 ° C; remain stable even under sterilization temperatures (120 ° C); It is physiologically inert since a small number of bacteria produce enzymes capable of promoting their hydrolysis.
  • Agar agar is a hydrocolloid embedded in the crystallized cellulose fibers of the cell walls of red agarophyte seaweed (Rhodophyceae family).
  • Agar basically consists of a heterogeneous mixture of two reserve polysaccharides: agarose and agaropectin.
  • Agarose is the gelling portion of agar and represents on average 70% of total matter.
  • Chemically, agarose is a neutral linear polymer made up of repeated agarobiose units, which in turn consists of a ⁇ -D-galactopyranose molecule bound 1 ⁇ 4 to an ⁇ -agarose molecule. 3,6-anhydro-L-galactose. These repeated units are linked 1 ⁇ 3 to form agarose.
  • Agaropectin a non-gelling fraction
  • a sulfated polysaccharide 3% to 10% sulfate
  • agarose varying percentages of sulfate ester, D-glucuronic acid and small amounts of pyruvic acid.
  • the agar is insoluble in cold water, but it expands considerably and absorbs about 20 times its own weight.
  • the average molecular weight of agar varies from 8,000 to over 100,000D. Dissolving in hot water is relatively rapid, promoting firm gel formation even at low concentrations.
  • This gel is thermo-reversible and is formed because agarose molecules have a double helix structure which aggregates to form a three-dimensional structure that holds water molecules in their interstices.
  • the strength of the gel is influenced by the following factors: concentration, time, pH and sugar content. The decrease in pH causes a noticeable reduction in gel strength. Agar solutions exposed to high temperatures for prolonged periods may degrade, resulting in decreased gel strength.
  • modified agar on the market that have the property of dissolving completely in water at a lower temperature and time than conventional. Examples include the following products:
  • QSA Quick Soluble Agar
  • “Takara Agaoligo” is a powder product, registered by the Japanese company Takara Shuzo Co., Ltd. The creators claim, based on various published scientific studies, that the product has pharmacological properties.
  • Agaoligo is formed from agar as a raw material for obtaining, by controlled partial acid hydrolysis, oligo polysaccharides called “agarooligosaccharides” (AOS).
  • AOS agarooligosaccharides
  • the hydrolysis can be performed using acid ion exchange resins as described in Tatsuji Enoki et al., "Agarobiose-containing composition” patent (US Pat. No.
  • OSA is composed mainly of agarobiose, agarotetraose, agaroexaose and agarooctaose, all containing anhydrogalactose at the reducing terminals.
  • Takara Agaoligo is a mixture of these AOS.
  • OSA has been shown to halt the production of Prostaglandin E2 and pro-inflammatory cytokines such as Tumor Necrosis Factor ⁇ (TNF- ⁇ ), which is considered the cause of rheumatism.
  • TNF- ⁇ Tumor Necrosis Factor ⁇
  • WANG et al. found that OSA exhibits antioxidant activity in eliminating hydroxyl free radicals and superoxide anion radicals and inhibiting peroxidation lipid.
  • the same researchers confirmed, in vivo and in vitro, the antitumor, antioxidative and immune enhancement activities of OSA produced by enzymatic hydrolysis.
  • CHEN et al. found that OSA has anti-angiogenic effects, which are associated with induction of endothelial cell apoptosis.
  • OSA has no effect. mutagenic or carcinogenic or any significant adverse effect.
  • the OSA LD50 has been shown to be greater than 2,000mg / kg.
  • starch which is of low cost and high availability in the market, has widespread application in the food industry.
  • starch-based films and derivatives as previously described in WO Pat. Nos. 2005039543, EP1417895 and EP 1738656, are quite unstable to changes in humidity and temperature due to the hydrophilic and semicrystalline nature of these biopolymers. Such characteristics make storage, technology for obtaining and short-term commercial application of starch films very difficult. In addition, the use of additional ingredients is necessary to preserve their characteristics under different storage conditions.
  • the pullulan polymer is also of natural origin, but it is a high cost material and difficult to obtain.
  • Cellulose-derived polymers are of semi-synthetic origin and need, in the vast majority of cases reported in the literature 5 (see US Pat No. 5,948,430 and US Pat No. 2009/0253754 Al), to be associated with other water-soluble materials. to obtain products with adequate characteristics of mechanical resistance and stability to environmental changes. All previously patented works utilize water-soluble polymers in the formation of fast dissolving films. However, none of them describe agar as an alternative raw material because it in its original form has low solubility in water at room temperature.
  • the aim of the present invention is to present a new product and manufacturing process for polymeric films using modified agar as the main component, and to solve the following problems presented in the state of the art: difficulty in handling, storage and portability of some food and pharmaceutical products. in the form of powders and granules; low solubility of agar in cold water; difficulty in obtaining some raw materials for the production of commercially available films, such as pullulan; the high energy value of starch based films and derivatives.
  • the technique described in the present invention promotes modification of the agar molecule using a low pH acid reaction medium (0 - 3).
  • a low pH acid reaction medium (0 - 3)
  • partial hydrolysis of the agar chains occurs forming derivatives with various chain sizes.
  • the change increased the ability of the agar to dissolve in aqueous medium without affecting its film-forming property in the presence of a plasticizer.
  • the invention described herein demonstrates by simple technique and using low cost equipment and inputs, the transformation of agar into a highly water soluble compound at any temperature.
  • the product of this invention as it has a low metabolism index during digestion, can additionally be used as a vehicle for extemporaneous use in low calorie diets and as a vehicle for medicinal products for human or veterinary use, including diabetes patients.
  • agar films The use of fast dissolving agar films makes the preparation of food drinks much more practical, especially for children, the elderly, people with neurodegenerative diseases and people with physical and cognitive disabilities, as it facilitates their handling without causing waste for losses.
  • Each agar film will be presented as an individual slide containing a standardized amount of product, which will be packaged per unit or in multi-dose.
  • the preservation of the films, when kept in proper packaging, is superior to conventional commercial powders and granules.
  • the intrinsic characteristics of the agar predict that the films based on this material are less susceptible to microbiological and morphological changes due to ambient humidity and temperature elevation than powders and granules in general, making the product of this invention even safer in terms. preservation of the products conveyed by this film.
  • the invention relates to the production of agar-based polymeric films having the following characteristics: short-term dissolution (up to 3 minutes) in water at any temperature; good mechanical properties of strength and flexibility; pleasant organoleptic aspects after dissolution in water, with adequate palatability and which do not add to the possible products conveyed no significant change in appearance; wide stability to the ambient variations of temperature and humidity, conserving in the long term its intrinsic characteristics; economically viable production chain with low environmental impact.
  • the simplest biofilm production technique applied on a laboratory scale, is called "casting". This is the technique used in forming the agar biofilms described herein, in which a filmogenic solution with water is prepared and then applied to an inert support and dried for solvent evaporation. It is an inexpensive technique because it demands less equipment and resources compared to other production techniques. The film may be made or cut to the size, shape or thickness desired for its intended purpose.
  • Agar also has the advantages of being a 100% natural product, free of toxicity and practically unabsorbed by the gastrointestinal system. Both agar and other components of this formulation are readily available from the market without the risk of supply problems.
  • the agar-based film is a great business opportunity in view of its technological and commercial appeal, as it is a differentiated product. Rapidly dissolving films are part of a still growing market worldwide and are little explored in Brazil. Research by Technology Catalysts predicts that the estimated $ 500 million soluble film pharmaceutical market in 2007 could reach $ 2 billion in 2012. [9] Based on the growth trend of the last decade, this market can reach revenues of up to $ 13 billion by 2015.
  • Agar film may also serve as a support for the delivery of pharmacological active ingredients.
  • the thin films of Rapid dissolution is therefore a modern and innovative pharmaceutical form for drug delivery.
  • Pharmaceutical use of agar films may be direct or indirect. Direct use refers to the administration of medicines through mucous tissues of the human body, such as buccal, ocular, vaginal, urethral and rectal mucosa. With the advantage over traditional forms (tablets, capsules, gels, eye drops, suppositories and eggs) of more practical and intuitive administration, they can be used more easily in pediatric, geriatric, physically and / or cognitively disabled patients and patients. with neurodegenerative disorders (parkinsonism, Alzheimer's syndrome and schizophrenia, for example).
  • the biofilms can be placed directly in the buccal region, over or below the tongue, so that salivary secretion can promptly promote its dissolution, without requiring the obligatory consumption of water.
  • This form of administration facilitates use by people with impaired swallowing (dysphagia).
  • Administration of the films through these routes allows the absorption of the drug directly into the bloodstream, without affecting the digestive enzymes or first pass effect on the liver.
  • films are faster, safer, and more effective forms than traditional pharmaceutical forms because, in comparison, they reduce the dose required for the effect of the drug.
  • Another advantage of oral application of agar films is that, due to its virtually absent enzymatic digestion by bacteria, it can be considered a non-cariogenic product, reinforcing its applicability as a pediatric product.
  • fast dissolving films represent an association of the efficiency of a liquid pharmaceutical form with the practicality of a solid form.
  • Biofilms can serve as a support for principle active delivery, which would require prior dissolution in hot or cold water, in order to promote the reconstitution of the oral drug in solution or suspension forms for extemporaneous use.
  • Agar films are more stable, better conservable and faster dissolving than reconstituting powders and granules conventional. They are also products capable of delivering precise doses of one drug per slide unit, when production uniformity is guaranteed.
  • Agar films would allow information and images to be printed on their surface using edible inks. Such information may be, for example: company logo, quantity or dose per unit, net weight, composition, warnings and warnings, various symbols and drawings.
  • films for food products can be for direct, oral or indirect consumption, being pre-solubilized in cold or hot water or placed on food, and may even go through any process. cooking.
  • the films can be applied and used for decorative purposes, according to the creative process of the user.
  • the novelty of the present invention is the use of the modified agar as a fast dissolving polymeric film based raw material and the process for its production.
  • Agar modification by acid ensures the production of flexible and resistant films that are easily soluble in water at any temperature.
  • agar is described by the scientific community as a product that can undergo a hydrolysis reaction resulting in a decrease in its molecular weight and hence its gelatinizing power.
  • Partial and controlled agar hydrolysis may be performed by the following methodologies or combinations thereof: (1) acid hydrolysis, (2) alkaline hydrolysis and (3) enzymatic hydrolysis.
  • the acid hydrolysis production process uses steps already established in the literature [1, 2, 3].
  • modified acid partial hydrolysis agar films the inventors generally proceeded as follows:
  • phase A In an inert, high temperature resistant container, the agar was dispersed in a ratio of 0.5 to 2g per 100 ml of water under constant agitation. It was then heated to boiling for total solubilization of the material, with a reduction of 50 to 70% of the initial volume. The gel formed was named phase A. 2) In another inert, high-temperature-resistant container, the acid was stirred and heated in the same proportion as phase A. Hot acid can be named phase B. The technique allows variation of the amount of the amount of phase A in the ratio of 3 parts to each part of acid (phase B).
  • phase A The hot (phase A) gel was slowly dripped into the acid (phase B). The obtained mixture was continuously stirred and evaporated to 50 to 90% reduction of the total volume. Throughout the hydrolysis process, the reaction medium was kept in a pH range between 0 and 3.
  • isopropyl alcohol was added in a ratio of 0.7 to 0.9 volumes for each volume of the solution described in item 4, or alternatively, ethyl alcohol in the ratio of two to four volumes for each volume of the solution described in item 4.
  • the mixture was cooled to a temperature between -30 ° C and + 8 ° C until total precipitation of the material.
  • the precipitated material is a dense, slightly yellowish white solid, which was isolated by centrifugation between 380 and 10,000 g (Rcf) for a period of 5 to 30 minutes, depending on the amount. The supernatant was gently discarded to avoid product loss. Alcohol was added for resuspension of the material which was centrifuged again as often as necessary until elimination of residual acid.
  • modified agar may be dried to reserve for later use or a glycerol solution may be added thereto, in the ratio of 0.05g to 0.20g for each gram ( g) modified agar or even another plasticizing agent for obtaining the film.
  • the mixture was brought to the circulating and renewed oven at a constant temperature of 38 to 45 ° C for a period of 16 to 24 hours.
  • Drying time may vary from 1 hour upwards or downwards.
  • Some polymer hydrolysis processes and film formation processes are cited and recognized in the literature, such as: use of wet heat from pressurized water vapor (autoclaving); microwave heating; condensation reflux system; heating by immersion technique (water bath); acid catalysis by cationic ion exchange resins, fibers or membranes; application or association of hydrolysis in alkaline medium; application or association of hydrolysis by enzymatic action; application of ultrasonic vibration (ultrasound); application of electromagnetic waves; application of unbalanced plasma; electrochemical processes; simple or complex coacervation; roller, drum or spray-dryer extrusion and processing system.
  • the present invention applies the direct heating process in acid reaction medium to promote partial agar hydrolysis and the casting technique to induce film formation. These are the most economical processes and technologies that are most easily adaptable to industry.
  • the state of the art of this invention dictates that the agar, to be subjected to the partial acid hydrolysis process, must be fully solubilized in the aqueous medium and without any color change upon heating. These factors are preponderant to the proper progress of the process.
  • the acid required for the hydrolysis reaction should be selected from those that have application in the food or medicine industry, for example: hydrochloric acid; sulfuric acid; nitric acid; phosphoric acid; Acetic Acid; trifluoroacetic acid; Citric acid; fumaric acid; malic acid; acid formic; Tartaric acid; lactic acid; Ascorbic acid.
  • the acids may be used at any concentration to obtain an initial reactive solution with a pH between 0 and 3, preferably less than 1. To obtain the product developed in this invention, the best result was obtained when using glacial acetic acid PA
  • solvents may be used but the technique is not limited to them: ethyl alcohol, acetone and isopropyl alcohol. The latter being the most suitable for the process.
  • the solvent precipitates the modified agar and extracts the acid from the reaction medium after its application in successive washes of the material.
  • the solvent used may be recovered and reused for the same purpose.
  • the modified and purified agar can be oven temperature controlled drying with air circulation and renewal of 38 ° C to 45 ° C for 8 to 12 hours as a step optional process. It can then be crushed (pulverized) using appropriate instruments and stored in a moisture free environment protected from light and high temperatures. The stored powder will serve as raw material for subsequent resolubilization in water and addition of the plasticizing agent.
  • the agar used as the base raw material for film production can be obtained from species recognized as biopolymer producers, mainly from the botanical genera Gelidium and Gracilaria, according to the traditional techniques of industrial or master production, observed in the literature [4 ].
  • one or more water-soluble or water-dispersible polymers in any proportion may be included in the modified agar film composition in order to promote adjustments in their physicochemical characteristics.
  • polymers suitable for this purpose but not limited to: starches and derivatives (modified and pregelatinized; dextrins; celluloses and derivatives (e.g.
  • hydroxypropyl methyl cellulose hydropropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose
  • pectin proteins and derivatives (eg gelatin, casein, collagen, zein); polyvinyl pyrrolidone; polyvinyl alcohol; alginic acid and derivatives; natural gums (e.g., guar gum, xanthan gum); polyethylene glycol; polyethylene oxide; carrageenan; glucomannan; chitosan; pullulan; fucoidan.
  • One or more agar film forming agents may optionally be added, preferably from those in the class of polyhydric alcohols and derivatives, which include: glycerol; sorbitol; mannitol; propylene glycol; xylitol, maltitol; galactitol; isomaltate; glycerol triacetate; glycerol tricaprylate; monoacetin; diacetin; triacetin.
  • polyhydric alcohols and derivatives which include: glycerol; sorbitol; mannitol; propylene glycol; xylitol, maltitol; galactitol; isomaltate; glycerol triacetate; glycerol tricaprylate; monoacetin; diacetin; triacetin.
  • emulsifying agents surfactants, surfactants, disintegrants
  • flavoring agents coloring agents (dyes); sweeteners; anti bacteria nos; antifungal agents; antioxidants; fillers; antiumectants; sensory stimulating agent.
  • coloring agents dyes
  • sweeteners anti bacteria nos
  • antifungal agents antifungal agents
  • antioxidants fillers
  • antiumectants sensory stimulating agent. 5
  • formulations containing agar as a filmogenic agent were produced in triplicate (ANNEX 1, 2 and 3), varying glycerol concentrations and reaction time. The physical and sensory aspects of the films produced were visually evaluated.
  • GLYCEROL 0 50pL 100 pL 150 pL 200 pL
  • HYDROLIE ANNEX 1 The Negative Pattern (no glycerol added) has formed translucent and brittle films that are difficult to remove from the plastic container. Formula IA was the only one that made films, but they were also brittle. The other films (1B, 1C and 1D) formed a viscous gel difficult to extract from the container. Standard and Al films were fully solubilized in hot water in less than 1 minute, but were not fully solubilized in ice water. The film completely disintegrated within 4 minutes on average, but there was still residual, fibrous, unsubstituted appearance. ANNEX 2: The films of the Negative Standard formulas 2A and 2B were translucent and brittle.

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  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Manufacturing & Machinery (AREA)
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  • Mechanical Engineering (AREA)
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  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un film polymère entièrement hydrosoluble, à chaud ou à froid, produit à partir d'agar, un polysaccharide hydrocolloïdal naturel largement utilisé dans l'industrie alimentaire. L'agar a été modifié par réaction à chaud en milieu acide. Le changement a augmenté la capacité de dissolution de l'agar en milieu aqueux sans altérer sa capacité filmogène en présence d'un agent plastifiant. En effet, sous sa forme initiale, l'agar présente une faible solubilité dans l'eau à température ambiante et aucun autre film ne présente une dissolution rapide en vue d'une utilisation comme système véhicule pour produits alimentaires. Le film ainsi produit sert de support pour l'incorporation d'aliments naturels, artificiels et/ou fonctionnels. Il peut en outre être utilisé dans l'industrie pharmaceutique, comme véhicule pour principes actifs. Parmi les avantages de l'utilisation de ce film, on citera notamment sa non-toxicité et sa rapidité d'élimination sans métabolisation par l'organisme, outre la simplicité de sa technique d'obtention.
PCT/BR2013/000043 2012-02-02 2013-02-08 Film polymère d'agar hydrosoluble et son procédé d'obtention WO2013113086A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151629A (zh) * 2014-07-25 2014-11-19 福建农林大学 可食性小笼包垫膜及其制备方法
US20210308914A1 (en) * 2020-04-07 2021-10-07 Yi Hsuan Sung Artificial Botanicals and Methods of Making Same
WO2024167940A1 (fr) * 2023-02-06 2024-08-15 Sway Innovation Co. Films minces flexibles à base d'algues et systèmes et procédés de coulée en solution associés

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5867168A (ja) * 1981-10-20 1983-04-21 Toyo Seikan Kaisha Ltd 流動食品内蔵粒状カプセル体の製造方法
US4851394A (en) * 1986-12-30 1989-07-25 Uni Colloid Kabushiki Kaisha Glucomannan/polyhydric alcohol composition and film prepared therefrom
JPH01228444A (ja) * 1988-03-08 1989-09-12 Osaka Kagaku Gokin Kk 熱水難溶性可食膜状製品及びその製造法
US5681601A (en) * 1989-01-25 1997-10-28 Cultor Ltd. Low calorie fat substitute
CN1245650A (zh) * 1999-08-17 2000-03-01 刘志国 一种由琼脂制成的食品表面覆膜及方法
US6322814B1 (en) * 1994-03-04 2001-11-27 Ian James Miller Manufacture of and uses for low molecular weight agars and agaroids
US7217817B1 (en) * 1999-05-14 2007-05-15 Takara Bio Inc. Agarobiose-containing composition
JP4543887B2 (ja) * 2003-11-10 2010-09-15 東レ株式会社 多糖類含有組成物および涙液層安定化点眼剤

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5867168A (ja) * 1981-10-20 1983-04-21 Toyo Seikan Kaisha Ltd 流動食品内蔵粒状カプセル体の製造方法
US4851394A (en) * 1986-12-30 1989-07-25 Uni Colloid Kabushiki Kaisha Glucomannan/polyhydric alcohol composition and film prepared therefrom
JPH01228444A (ja) * 1988-03-08 1989-09-12 Osaka Kagaku Gokin Kk 熱水難溶性可食膜状製品及びその製造法
US5681601A (en) * 1989-01-25 1997-10-28 Cultor Ltd. Low calorie fat substitute
US6322814B1 (en) * 1994-03-04 2001-11-27 Ian James Miller Manufacture of and uses for low molecular weight agars and agaroids
US7217817B1 (en) * 1999-05-14 2007-05-15 Takara Bio Inc. Agarobiose-containing composition
CN1245650A (zh) * 1999-08-17 2000-03-01 刘志国 一种由琼脂制成的食品表面覆膜及方法
JP4543887B2 (ja) * 2003-11-10 2010-09-15 東レ株式会社 多糖類含有組成物および涙液層安定化点眼剤

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151629A (zh) * 2014-07-25 2014-11-19 福建农林大学 可食性小笼包垫膜及其制备方法
CN104151629B (zh) * 2014-07-25 2016-04-06 福建农林大学 可食性小笼包垫膜及其制备方法
US20210308914A1 (en) * 2020-04-07 2021-10-07 Yi Hsuan Sung Artificial Botanicals and Methods of Making Same
US11872727B2 (en) * 2020-04-07 2024-01-16 Yi Hsuan Sung Artificial botanicals and methods of making same
WO2024167940A1 (fr) * 2023-02-06 2024-08-15 Sway Innovation Co. Films minces flexibles à base d'algues et systèmes et procédés de coulée en solution associés

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