WO2018195625A1 - Composition for acting on a moisture barrier for a thermoplastic polymer, method for preparing the composition, method for preparing a polymer substrate, product and substrate - Google Patents
Composition for acting on a moisture barrier for a thermoplastic polymer, method for preparing the composition, method for preparing a polymer substrate, product and substrate Download PDFInfo
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- WO2018195625A1 WO2018195625A1 PCT/BR2018/050121 BR2018050121W WO2018195625A1 WO 2018195625 A1 WO2018195625 A1 WO 2018195625A1 BR 2018050121 W BR2018050121 W BR 2018050121W WO 2018195625 A1 WO2018195625 A1 WO 2018195625A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09D103/04—Starch derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Definitions
- the present invention generally concerns a composition which enhances the moisture barrier characteristic of thermoplastic polymers, for example for use in packaging.
- the invention further relates to processes for preparing a polymeric composition comprising such a composition, and substrates comprising such a barrier composition.
- Coatings and packaging containing polymers with varying capacities to prevent moisture passage are known in the industry.
- the present invention relates to various aspects of a moisture barrier acting composition which surprisingly improves the efficiency of such a barrier when used as an additive for polymers, particularly thermoplastic polymers, compared to nonadditive polymers.
- the invention relates, in a first aspect, to a moisture barrier acting composition for thermoplastic polymer, characterized in that it comprises:
- thermoplastic polymer embraces thermoplastic homo or copolymers, individually or in mixtures thereof, biodegradable or not, transparent or not, for example chosen from PVC (polyvinyl chloride), PLA (polylactic acid), PVOH (polyvinyl alcohol) ), PVA (polyvinyl acetate), one or more polyamides, one or more polyolefins, particularly polyethylene and polypropylene, ethylene vinyl acetate (EVA), ethylene acrylic acid (EEA), ethylene vinyl alcohol copolymers (EVOH).
- thermoplastic polymers are chosen from PVC, LDPE, PLA. More particularly, without imposing any limitation, homopolymer PVC is used.
- nanoargyl refers to natural or synthetic clay, modified or formulated, with particles of nanometric dimensions, particularly having a size of less than 100 ⁇ m. nanometers, for example montmorillonite, bentonide, vermiculite, smectica, kaolinite, muscovite, kanemite, revictite, grumantite, ilerite, taneolite, halloysite, rectorite, vermiculite, hectorite, hydrotalcite, stevensite, haloicite, medmontite, diitaite, nontrita saponite, keniaita, laponite, sauconite, saponite, magadite, soboquita, svindorlita, ledikita, pyrophyllite, volkonscoita, magadite, fluoromica and mixtures thereof. Particularly, without imposing any limitation, montmorillonite or he
- starch refers to natural starch from any source, for example native starch (corn, oats, rice, wheat, barley, rye, potato, cassava, etc.), chemically or enzymatically modified starch, or still their mixtures. Particularly, without imposing any limitation, acetylated starch is used.
- acidulant is an aid in exfoliating nanoargyl coverslips, aiding their dispersion in polymeric matrices.
- Any acidulants such as organic or inorganic acids compatible with the composition of the invention are suitable.
- carboxylic acids such as citric, acetic, maleic or adipic are suitable. More particularly citric acid is used.
- a polymeric crosslinking aid is an agent known to the person skilled in the art, that is, any agent or mixture of agents that assists cross-linking of polymers, typically providing modifications in mechanical properties, and / or also assisting in the reduction of porosity and consequent increase in the moisture barrier compared to a non additive thermoplastic polymer.
- unsaturated crosslinking auxiliaries e.g. containing double bonds
- cross-linked copolymers in the presence of peroxide initiators.
- Non-exhaustive examples of such crosslinking aids are unsaturated monomers of the allylic, vinyl or acrylic type, casein derivatives, carboxylic acid anhydrides (e.g., citric, acetic, maleic or adipic), oxidized sucrose.
- carboxylic acid anhydrides e.g., citric, acetic, maleic or adipic
- oxidized sucrose e.g., maleic anhydride is used.
- a free radical initiator suitable for the invention is, without excluding any others, a peroxide, chosen for example from benzoyl peroxide (BPO), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (DTBPH ), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3 (DTBHY), dicumyl peroxide (DCP), di (tert-butylperoxyisopropyl) benzene (DTBPIB.
- BPO benzoyl peroxide
- DTBPH 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
- DTBHY 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3
- DCP dicumyl peroxide
- DTBPIB di (tert-butylperoxyisopropyl) benzene
- thermoplastic polymer or multi-layer polymer substrates, optionally with other materials (paper, metal or metallised films, etc.), wherein at least one layer corresponds to the composition of the invention in question. addition to a thermoplastic polymer.
- films, films may be cited as products embodying the invention. isolated or internal extruded to multilayer substrates, and external coatings for porous substrates.
- each item of the composition of the invention (items 1 to 5) is mentioned in the table below, with reference to the nomenclature commonly used in general resin formulations: PCR or PHR ("parts per hundred parts resin” or “parts per hundred of resin”). Means the mass amount of additive incorporated into the compound formulation, relative to 100 mass units of resin.
- compositions of the invention may additionally contain other conventional additives such as filler, pigments, dyes, antioxidants, light and heat stabilizers, plasticizers, surfactants, oils, compatibilizing polymers (e.g. EVA, in nanoargyl-like contents) and other ingredients. known to the person skilled in the art.
- additives such as filler, pigments, dyes, antioxidants, light and heat stabilizers, plasticizers, surfactants, oils, compatibilizing polymers (e.g. EVA, in nanoargyl-like contents) and other ingredients. known to the person skilled in the art.
- Another aspect of the invention is a process for preparing the composition of the invention, comprising the following steps:
- a - disperse the nanoargyl in water (enough water to aid in the dispersion of nanoargyl and starch);
- composition thus obtained may be immediately used for the preparation of a polymeric substrate by the addition of a polymer according to the following steps:
- step H adding the polymer to the formulation obtained in step G, not dry, and mixing under stirring until complete dispersion;
- process in step J above refers to the type of operation with which the polymeric substrate of the invention is to be obtained, for example extrusion, calendering, blowing, injection, etc.
- the formulation of the invention may be stored for later use either as such or after drying. for removal of water.
- sufficient water is used to allow dispersion of the polymer.
- Still another aspect of the invention are polymeric substrates comprising between 2.5 and 20 w / w of the moisture barrier acting composition described above with respect to the weight of thermoplastic polymer.
- Still another aspect of the invention are products characterized in that they comprise polymeric compositions obtained by the process described above.
- Example 1 Preparation of a high moisture barrier polymer composition.
- M mean; IV - range of variation; CV - coefficient of variation.
Abstract
The present invention relates to a composition that improves the moisture barrier characteristic of thermoplastic polymers, said composition comprising nanoclay, starch, an acidifying agent, a polymer crosslinking aid and a free radical initiator. The invention also relates to methods for preparing said polymer composition and substrates comprising said barrier composition.
Description
COMPOSIÇÃO DE ATUAÇÃO SOBRE BARREIRA À UMIDADE PARA POLÍMERO TERMOPLÁSTICO, PROCESSO DE PREPARAÇÃO DE COMPOSIÇÃO, PROCESSO DE PREPARAÇÃO DE SUBSTRATO POLIMÉRICO, MOISTURE BARRIER COMPOSITION FOR THERMOPLASTIC POLYMER, COMPOSITION PREPARATION PROCESS, POLYMERIC SUBSTRATE PREPARATION PROCESS,
PRODUTO E SUBSTRATO PRODUCT AND SUBSTRATE
A presente invenção concerne, em sua generalidade, uma composição que aperfeiçoa a característica de barreira à umidade de polímeros termoplásticos, por exemplo, para uso em embalagens. A invenção refere-se ainda a processos para a preparação de uma composição polimérica que compreende tal composição, e substratos compreendendo tal composição de barreira. The present invention generally concerns a composition which enhances the moisture barrier characteristic of thermoplastic polymers, for example for use in packaging. The invention further relates to processes for preparing a polymeric composition comprising such a composition, and substrates comprising such a barrier composition.
Antecedentes da invenção Background of the invention
São conhecidas na indústria revestimentos e embalagens que contêm polímeros com capacidades variadas de impedir a passagem de umidade. Coatings and packaging containing polymers with varying capacities to prevent moisture passage are known in the industry.
Quando, entre as várias especificidades de um produto, surge a necessidade crítica de baixa permeabilidade a vapor d' água, as soluções comuns exigem a utilização de materiais mais nobres ou recursos elaborados, como o uso de laminados mais complexos. When, among the various specificities of a product, the critical need for low water vapor permeability arises, common solutions require the use of nobler materials or elaborate resources such as the use of more complex laminates.
Esse contexto da tecnologia atual mostra que o aperfeiçoamento da permeabilidade a vapor d' água de um polímero geralmente caminha associado a custos maiores, seja pelo material em si, seja pela maneira de prepará-lo. This context of current technology shows that improving the water vapor permeability of a polymer is often associated with higher costs, either by the material itself or by the way it is prepared.
De maneira surpreendente foi desenvolvida uma composição polimérica de alto desempenho quanto à barreira de umidade, e que permite a substituição vantajosa de materiais mais caros ou de fabricação mais complexa. Surprisingly, a high performance moisture barrier polymer composition has been developed which allows for the advantageous replacement of more expensive or more complex materials.
Descrição da invenção Description of the invention
A presente invenção refere-se a vários aspectos
de uma composição de atuação sobre barreira a umidade que, de forma surpreendente, aperfeiçoa a eficiência de tal barreira quando utilizada como aditivo de polímeros, particularmente polímeros termoplásticos, comparativamente a polímeros não aditivados. The present invention relates to various aspects of a moisture barrier acting composition which surprisingly improves the efficiency of such a barrier when used as an additive for polymers, particularly thermoplastic polymers, compared to nonadditive polymers.
Trata a invenção, em um primeiro aspecto, de uma composição de atuação sobre barreira à umidade para polímero termoplástico, caracterizada por compreender: The invention relates, in a first aspect, to a moisture barrier acting composition for thermoplastic polymer, characterized in that it comprises:
- nanoargila; - nanoargyl;
- amido; - starch;
- acidificante; - acidifying;
- auxiliar de reticulação polimérico - polymeric crosslinking aid
- um iniciador de radicais livres. - a free radical initiator.
Conforme sentido aqui empregado "polímero termoplástico" engloba homo ou copolímeros termoplásticos, individualmente ou em misturas entre si, biodegradáveis ou não, transparentes ou não, por exemplo escolhidos dentre PVC (policloreto de vinila) , PLA (ácido polilático) , PVOH (polivinil álcool), PVA (acetato de polivinila) , uma ou mais poliamidas, uma ou mais poliolefinas particularmente polietileno e polipropileno, etileno-acetato de vinila (EVA) , etileno-ácido acrílico (EEA) , copolímeros de etileno e álcool vinílico (EVOH) . De forma particular os polímeros termoplásticos são escolhidos entre PVC, LDPE, PLA. De forma mais particular, sem impor qualquer limitação, utiliza-se PVC homopolímero . As used herein "thermoplastic polymer" embraces thermoplastic homo or copolymers, individually or in mixtures thereof, biodegradable or not, transparent or not, for example chosen from PVC (polyvinyl chloride), PLA (polylactic acid), PVOH (polyvinyl alcohol) ), PVA (polyvinyl acetate), one or more polyamides, one or more polyolefins, particularly polyethylene and polypropylene, ethylene vinyl acetate (EVA), ethylene acrylic acid (EEA), ethylene vinyl alcohol copolymers (EVOH). In particular thermoplastic polymers are chosen from PVC, LDPE, PLA. More particularly, without imposing any limitation, homopolymer PVC is used.
Conforme sentido aqui empregado, "nanoargila" refere-se a argila, natural ou sintética, modificada ou formulada, com partículas de dimensões nanométricas , particularmente tendo uma dimensão menor que 100
nanômetros, por exemplo montmorilonita, bentonida, vermiculita, smectica, caolinita, muscovita, kanemita, revdita, grumantita, ilerita, taneolita, halloysita, rectorita, vermiculita, hectorita, hidrotalcita, stevensita, haloicita, medmontita, diquita, nontronita, beidelita, volkonskoita, saponita, keniaita, laponita, sauconita, saponita, magadita, soboquita, svindorlita, ledikita, pirofilita, volkonscoita, magadita, fluoromica e misturas destas. De forma particular, sem impor qualquer limitação, utiliza-se montmorilonita ou hectorita. As used herein, "nanoargyl" refers to natural or synthetic clay, modified or formulated, with particles of nanometric dimensions, particularly having a size of less than 100 µm. nanometers, for example montmorillonite, bentonide, vermiculite, smectica, kaolinite, muscovite, kanemite, revictite, grumantite, ilerite, taneolite, halloysite, rectorite, vermiculite, hectorite, hydrotalcite, stevensite, haloicite, medmontite, diitaite, nontrita saponite, keniaita, laponite, sauconite, saponite, magadite, soboquita, svindorlita, ledikita, pyrophyllite, volkonscoita, magadite, fluoromica and mixtures thereof. Particularly, without imposing any limitation, montmorillonite or hectorite is used.
Conforme sentido aqui empregado, "amido" refere- se a amido natural de qualquer fonte, por exemplo, amido nativo (milho, aveia, arroz, trigo, cevada, centeio, batata, mandioca, etc), amido modificado química ou enzimaticamente, ou ainda suas misturas. De maneira particular, sem impor qualquer limitação, utiliza-se amido acetilado . As used herein, "starch" refers to natural starch from any source, for example native starch (corn, oats, rice, wheat, barley, rye, potato, cassava, etc.), chemically or enzymatically modified starch, or still their mixtures. Particularly, without imposing any limitation, acetylated starch is used.
Conforme sentido aqui empregado, acidulante é um auxiliar na esfoliação das lamelas da nanoargila, ajudando sua dispersão em matrizes poliméricas. São adequados quaisquer agentes acidulantes, tais como ácidos orgânicos ou inorgânicos compatíveis com a composição da invenção. De forma particular, sem impor qualquer limitação, são adequados ácidos carboxílicos como cítrico, acético, maleico ou adípico. De forma mais particular utiliza-se ácido cítrico. As used herein, acidulant is an aid in exfoliating nanoargyl coverslips, aiding their dispersion in polymeric matrices. Any acidulants such as organic or inorganic acids compatible with the composition of the invention are suitable. Particularly, without imposing any limitation, carboxylic acids such as citric, acetic, maleic or adipic are suitable. More particularly citric acid is used.
Um auxiliar de reticulação polimérica é um agente conhecido do técnico no assunto, ou seja, qualquer agente ou mistura de agentes que auxilie na reticulação ( "crosslink" ) de polímeros, tipicamente propiciando
modificações em propriedades mecânicas, e/ou também auxiliando na diminuição da porosidade e consequente aumento na barreira à umidade, em comparação com um polímero termoplástico não aditivado. Sem estar vinculado a explicações científicas, agentes auxiliares de reticulação insaturados (por exemplo, contendo duplas ligações) são propensos a formar copolímeros reticulados em presença de iniciadores de peróxido. Exemplos não exaustivos de tais auxiliares de reticulação são monômeros insaturados, do tipo alílico, vinílico ou acrílico, derivados de caseína, anidridos de ácidos carboxílicos (por exemplo, cítrico, acético, maleico ou adípico) , sacarose oxidada. De forma particular utiliza-se anidrido maleico. A polymeric crosslinking aid is an agent known to the person skilled in the art, that is, any agent or mixture of agents that assists cross-linking of polymers, typically providing modifications in mechanical properties, and / or also assisting in the reduction of porosity and consequent increase in the moisture barrier compared to a non additive thermoplastic polymer. Without being bound by scientific explanations, unsaturated crosslinking auxiliaries (e.g. containing double bonds) are prone to forming cross-linked copolymers in the presence of peroxide initiators. Non-exhaustive examples of such crosslinking aids are unsaturated monomers of the allylic, vinyl or acrylic type, casein derivatives, carboxylic acid anhydrides (e.g., citric, acetic, maleic or adipic), oxidized sucrose. In particular maleic anhydride is used.
Um iniciador de radicais livres adequado à invenção é, sem excluir quaisquer outros, um peróxido, escolhido, por exemplo, dentre peróxido de benzoila (BPO) , 2 , 5-dimetil-2 , 5-di ( terc-butilperoxi ) hexano (DTBPH) , 2,5- dimetil-2 , 5-di ( terc-butilperoxi ) hexina-3 (DTBHY) , peróxido de dicumila (DCP) , di- ( terc-butilperoxiisopropil ) benzeno (DTBPIB. De forma particular utiliza-se peróxido de benzoila . A free radical initiator suitable for the invention is, without excluding any others, a peroxide, chosen for example from benzoyl peroxide (BPO), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (DTBPH ), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3 (DTBHY), dicumyl peroxide (DCP), di (tert-butylperoxyisopropyl) benzene (DTBPIB. In particular peroxide is used of benzoyl.
Estão incluídas no escopo da invenção realizações que compreendem substratos em camada única de polímero termoplástico ou em multicamadas de polímeros, opcionalmente com outros materiais (papel, filmes metálicos ou metalizados, etc), em que ao menos uma das camadas corresponde à composição da invenção em adição a um polímero termoplástico. Included within the scope of the invention are embodiments comprising single-layer thermoplastic polymer or multi-layer polymer substrates, optionally with other materials (paper, metal or metallised films, etc.), wherein at least one layer corresponds to the composition of the invention in question. addition to a thermoplastic polymer.
Apenas a título de exemplo, podem ser citados como produtos que concretizam a invenção garrafas, filmes
extrusados isolados ou internos a substratos multicamadas , e revestimentos externos para substratos porosos. By way of example only, films, films may be cited as products embodying the invention. isolated or internal extruded to multilayer substrates, and external coatings for porous substrates.
De maneira particular, sem excluir qualquer outra, o teor individual de cada item da composição da invenção (itens 1 a 5) é mencionado na tabela abaixo, fazendo-se referência à nomenclatura usualmente utilizada quando das formulações com resinas em geral: PCR ou PHR ("partes por cem partes de resina" ou "parts per hundred of resin") . Significa a quantidade em massa de aditivo incorporada na formulação do composto, em relação a 100 unidades de massa da resina. Particularly, without excluding any other, the individual content of each item of the composition of the invention (items 1 to 5) is mentioned in the table below, with reference to the nomenclature commonly used in general resin formulations: PCR or PHR ("parts per hundred parts resin" or "parts per hundred of resin"). Means the mass amount of additive incorporated into the compound formulation, relative to 100 mass units of resin.
O polímero mencionado na tabela acima The polymer mentioned in the table above
(particularmente em pó ou peletizado) é aquele a ser aditivado com a formulação da invenção, com vista a aumentar sua característica de barreira à umidade. (particularly powdered or pelleted) is one to be added to the formulation of the invention in order to increase its moisture barrier feature.
As composições da invenção podem adicionalmente conter outros aditivos convencionais como carga, pigmentos, corantes, antioxidantes, estabilizantes à luz e ao calor, plastificantes, surfactantes , óleos, polímeros compatibilizantes (por exemplo, EVA, em teores semelhantes à da nanoargila) e outros ingredientes conhecidos do técnico no assunto.
Outro aspecto da invenção é um processo de preparação da composição da invenção, caracterizado por compreender as seguintes etapas: The compositions of the invention may additionally contain other conventional additives such as filler, pigments, dyes, antioxidants, light and heat stabilizers, plasticizers, surfactants, oils, compatibilizing polymers (e.g. EVA, in nanoargyl-like contents) and other ingredients. known to the person skilled in the art. Another aspect of the invention is a process for preparing the composition of the invention, comprising the following steps:
A - dispersar a nanoargila em água (quantidade de água suficiente para auxiliar na dispersão da nanoargila e do amido) ; A - disperse the nanoargyl in water (enough water to aid in the dispersion of nanoargyl and starch);
B - adicionar o amido; B - add starch;
C - adicionar o acidulante; C - add the acidulant;
D - agitar constantemente até homogeneização do meio; D - stir constantly until homogenization of the medium;
E - aquecer a mistura até atingir a temperatura abaixo 100°C mantendo a agitação; E - heating the mixture to a temperature below 100 ° C while stirring;
F - Atingida a temperatura cessar o aquecimento e manter a agitação até que a mistura atinja a temperatura ambiente; F - Once the temperature has ceased to heat and keep stirring until the mixture reaches room temperature;
G - adicionar o auxiliar de reticulação e o iniciador de radicais livres, sob agitação, até dispersão completa. G - Add the crosslinking aid and free radical initiator under stirring until complete dispersion.
Dentro de outro aspecto da invenção, a composição assim obtida pode ser imediatamente utilizada para a preparação de um substrato polimérico, pela aditivação de um polímero, conforme as etapas mencionadas a seguir: Within another aspect of the invention, the composition thus obtained may be immediately used for the preparation of a polymeric substrate by the addition of a polymer according to the following steps:
H - adicionar o polímero à formulação obtida na etapa G, não seca, e misturar, sob agitação, até dispersão completa;H - adding the polymer to the formulation obtained in step G, not dry, and mixing under stirring until complete dispersion;
I - Secar a mistura até remoção da umidade. I - Dry the mixture until moisture is removed.
J - Processar a mistura. J - Process the mixture.
A palavra "processar" na etapa J acima refere-se ao tipo de operação com a qual se deseja obter o substrato polimérico da invenção, por exemplo: extrusão, calandragem, sopro, injeção, etc. The word "process" in step J above refers to the type of operation with which the polymeric substrate of the invention is to be obtained, for example extrusion, calendering, blowing, injection, etc.
Alternativamente, após o item G acima, a formulação da invenção pode ser estocada para uso posterior, seja como tal, seja após ser submetida a secagem
para retirada da água. Neste último caso, após a estocagem da formulação e antes ou concomitantemente à etapa H, utiliza-se quantidade suficiente de água para permitir a dispersão do polímero. Alternatively, after item G above, the formulation of the invention may be stored for later use either as such or after drying. for removal of water. In the latter case, after storage of the formulation and prior to or concurrently with step H, sufficient water is used to allow dispersion of the polymer.
Verifique-se que a água utilizada no processo da invenção (seja na etapa A, seja na etapa H) serve de meio de processamento e é mais tarde removida. Sua quantidade, portanto, não é um aspecto essencial da invenção. Verify that the water used in the process of the invention (either in step A or in step H) serves as the processing medium and is later removed. Its quantity, therefore, is not an essential aspect of the invention.
Ainda outro aspecto da invenção são substratos poliméricos caracterizados por compreender entre 2,5 e 20 p/p da composição de atuação sobre barreira à umidade descrita mais atrás, em relação ao peso de polímero termoplástico . Still another aspect of the invention are polymeric substrates comprising between 2.5 and 20 w / w of the moisture barrier acting composition described above with respect to the weight of thermoplastic polymer.
Ainda outro aspecto da invenção são produtos caracterizados por compreender composições poliméricas obtidas pelo processo descrito mais atrás. Still another aspect of the invention are products characterized in that they comprise polymeric compositions obtained by the process described above.
EXEMPLOS : EXAMPLES:
São dados a seguir exemplos meramente ilustrativos de realização da presente invenção, sem impor qualquer limite à extensão da invenção, definida nas reivindicações anexas. The following are merely illustrative examples of the embodiment of the present invention without imposing any limit to the scope of the invention as defined in the appended claims.
Exemplo 1 - preparação de uma composição polimérica de alta barreira de umidade. Example 1 - Preparation of a high moisture barrier polymer composition.
Foi preparado um filme extrusado com uma composição polimérica de acordo com a invenção, tal como descrito abaixo. An extruded film with a polymeric composition according to the invention was prepared as described below.
A - Em um aparelho Turrax a 18.000 rpm, durante 60 minutos, foram dispersados 10 g de montmorilonita em 400 g de água; B - Em seguida, foram adicionados 100 g de amido acetilado; C - Em seguida, foram adicionados 1 g de ácido cítrico;
D - Agitou-se constantemente até a completa incorporação do amido ; A - In a Turrax apparatus at 18,000 rpm for 60 minutes, 10 g of montmorillonite was dispersed in 400 g of water; B - Then 100 g of acetylated starch were added; C - Then 1 g of citric acid was added; D - Stirred constantly until complete starch incorporation;
E - Aqueceu-se a mistura até atingir 90°C, mantendo a agitação ; E. The mixture was heated to 90 ° C while stirring;
F - Atingida a temperatura, interrompeu-se o aquecimento, mantendo a agitação; F - Once the temperature was reached, the heating was interrupted, keeping the stirring;
G - Adicionaram-se 40 g de anidrido maleico e 0,02g de peróxido de benzoila; G - 40 g of maleic anhydride and 0.02g of benzoyl peroxide were added;
H - adicionou-se 1000 g de PVC homopolimero à massa obtida na etapa G, sob agitação; H - 1000 g of homopolymer PVC was added to the mass obtained in step G under stirring;
I - A mistura foi seca em estufa a 90°C até remoção da umidade ; I - The mixture was oven dried at 90 ° C until moisture was removed;
J - A mistura foi processada em extrusora para obtenção de um filme transparente com 250μάθ espessura. J - The mixture was processed by extruder to obtain a transparent film with 250μάθ thickness.
EXEMPLO 2 - Dois filmes, um de acordo com a invenção, obtido conforme o exemplo 1 acima (Fórmula 1), e outro (Fórmula 2) de PVC do estado da técnica, ou seja, sem a composição da invenção, foram comparados quanto à permeabilidade ao vapor d' água (TVPA), a 38°C, em 90% de umidade, conforme o padrão ASTM F1249, utilizando o equipamento Permatran-W® modelo 3/34 da empresa norte- americana MOCON. EXAMPLE 2 Two films, one according to the invention, obtained as per example 1 above (Formula 1), and another (Formula 2) of prior art PVC, ie without the composition of the invention, were compared for water vapor permeability (TVPA) at 38 ° C at 90% humidity according to ASTM F1249 standard using Permatran-W® Model 3/34 equipment from the US company MOCON.
Os resultados obtidos foram: The results obtained were:
Tabela 1. Taxas de permeabilidade ao vapor d' água (TPVA) a 38≡C/90%UR - Método Permatran. Table 1. Water vapor permeability rates (TPVA) at 38≡C / 90% RH - Permatran Method.
TPVA (g água .m 2. dia x) TPVA (g water .m 2 .day x )
Amostra Sample
M Leituras individuais (IV) CV (%) M Individual Readings (IV) CV (%)
1, 44 (257, 0 μπι)/1, 26 (254, 9 μπι) 1.44 (257.0 μπι) / 1.26 (254.9 μπι)
Fórmula 1 1, 63 8,1 Formula 1 1.63 8.1
1, 67 (262, 1 μπι) /2, 13 (258, 7 μπι) 1.67 (262.1 μπι) / 2.13 (258.7 μπι)
Fórmula 2 4, 53 5, 06 (263, 5 μπι)/4, 60 (262, 3 μπι) 8, 8
4, 16 (263, 4 μη)/4,31 (261,0 μπι) Formula 2 4, 53.56 (263.5 μπι) / 4.60 (262.3 μπι) 8,8 4.16 (263.4 μη) / 4.31 (261.0 μπι)
Valores referentes a quatro determinações Values for four determinations
M - média; IV - intervalo de variação; CV - coeficiente de variação . M - mean; IV - range of variation; CV - coefficient of variation.
A comparação acima demonstra que um substrato polimérico que contém a composição da invenção apresenta uma permeabilidade à umidade muito inferior em relação ao polímero do estado da técnica, que não contém a composição da invenção . The above comparison demonstrates that a polymeric substrate containing the composition of the invention has a much lower moisture permeability than the prior art polymer which does not contain the composition of the invention.
Sabe-se que um técnico no assunto, com base nas informações contidas neste documento pode fazer realizações particulares da invenção não expressamente descritas, mas que desempenham funções iguais ou semelhantes, para atingir resultado de mesma natureza. Tais realizações equivalentes estão englobadas pelas reivindicações anexas.
It is known that one skilled in the art, based on the information contained herein, may make particular embodiments of the invention not expressly described but performing the same or similar functions to achieve the same result. Such equivalent embodiments are encompassed by the appended claims.
Claims
1. Composição de atuação sobre barreira à umidade para polímero termoplástico caracterizada por compreender nanoargila, amido, acidificante, auxiliar de reticulação polimérico e iniciador de radicais livres. 1. Moisture barrier acting composition for thermoplastic polymer comprising nanoargyl, starch, acidifier, polymeric crosslinking aid and free radical initiator.
2. Composição de acordo com a reivindicação 1 caracterizada pelo fato do mencionado polímero termoplástico ser um ou mais dentre PVC (policloreto de vinila) , PLA (ácido polilático) , PVOH (polivinil álcool), PVA (acetato de polivinila) , uma ou mais poliamidas, uma ou mais poliolefinas , etileno-acetato de vinila (EVA) , etileno-ácido acrílico (EEA) , copolímeros de etileno e álcool vinílico (EVOH) . Composition according to Claim 1, characterized in that said thermoplastic polymer is one or more of PVC (polyvinyl chloride), PLA (polylactic acid), PVOH (polyvinyl alcohol), PVA (polyvinyl acetate), one or more. polyamides, one or more polyolefins, ethylene vinyl acetate (EVA), ethylene acrylic acid (EEA), ethylene vinyl alcohol copolymers (EVOH).
3. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado polímero termoplástico é um ou mais dentre PVC, LDPE e PLA. Composition according to Claim 1, characterized in that said thermoplastic polymer is one or more of PVC, LDPE and PLA.
4. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado polímero termoplástico é PVC homopolímero . Composition according to Claim 1, characterized in that said thermoplastic polymer is homopolymer PVC.
5. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que são utilizados os teores de 0,1 e 3,5 PCR de nanoargila; 1,5 e 15 PCR de amido; entre 1 e 10% de acidulante em relação ao peso da nanoargila; 1 e 6 PCR de auxiliar de reticulação; 0,03 e 0,5% de iniciador em relação ao peso do auxiliar de reticulação. Composition according to Claim 1, characterized in that the nanoargyl 0.1 and 3.5 PCR contents are used; 1.5 and 15 starch PCR; between 1 and 10% acidulant in relation to the weight of nanoargyl; 1 and 6 crosslinking aid PCR; 0.03 and 0.5% initiator in relation to the weight of the crosslinking aid.
6. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que a mencionada nanoargila é selecionada dentre uma ou mais de montmorilonita, bentonida, vermiculita, smectica, caolinita, muscovita, kanemita, revdita, grumantita, ilerita, taneolita,
halloysita, rectorita, vermiculita, hectorita, hidrotalcita, stevensita, haloicita, medmontita, diquita, nontronita, beidelita, volkonskoita, saponita, keniaita, laponita, sauconita, saponita, magadita, soboquita, svindorlita, ledikita, pirofilita, volkonscoita, magadita, fluoromica e misturas destas. Composition according to Claim 1, characterized in that said nanoargyl is selected from one or more of montmorillonite, bentonide, vermiculite, smectica, kaolinite, muscovite, kanemite, revdit, grumantite, ilerite, taneolite, halloysite, rectorite, vermiculite, hectorite, hydrotalcite, stevensite, haloicite, medmontite, dichita, nontronite, beidelite, volkonskoita, saponite, keniaita, laponite, sauconite, saponite, magadite, sobocyte, svindorlite, ledikite, pyrophyllite, pyrophyllite, pyrophyllite mixtures of these.
7. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que a mencionada nanoargila é montmorilonita ou hectorita. Composition according to Claim 1, characterized in that said nanoargyl is montmorillonite or hectorite.
8. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado amido é um ou mais dentre amido natural, amido química ou enzimaticamente modificado, e suas misturas. Composition according to Claim 1, characterized in that said starch is one or more of natural starch, chemically or enzymatically modified starch, and mixtures thereof.
9. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado amido é amido acetilado . Composition according to Claim 1, characterized in that said starch is acetylated starch.
10. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado acidulante é um ou mais dentre os ácidos cítrico, acético, maleico ou adípico. Composition according to Claim 1, characterized in that said acidulant is one or more of the citric, acetic, maleic or adipic acids.
11. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado auxiliar de reticulação polimérica é um ou mais dentre monômeros insaturados do tipo alílico, vinílico ou acrílico, derivados de caseína, anidridos dos ácidos carboxílicos cítrico, acético, maleico ou adípico, e sacarose oxidada. Composition according to Claim 1, characterized in that said polymeric crosslinking aid is one or more of allyl, vinyl or acrylic type unsaturated monomers, casein derivatives, citric, acetic, maleic or adipic carboxylic acid anhydrides. , and oxidized sucrose.
12. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado auxiliar de reticulação polimérica é anidrido maleico. Composition according to Claim 1, characterized in that said polymeric crosslinking aid is maleic anhydride.
13. Composição de acordo com a reivindicação 1
caracterizada pelo fato de que o mencionado iniciador de radicais livres é um ou mais dentre os peróxidos um peróxido, escolhido por exemplo dentre peróxido de benzoila (BPO) , 2, 5-dimetil-2, 5-di (terc-butilperoxi) hexano (DTBPH) , 2 , 5-dimetil-2 , 5-di ( terc-butilperoxi ) hexina-3 (DTBHY) , peróxido de dicumila (DCP) , di- (terc- butilperoxiisopropil ) benzeno (DTBPIB) . Composition according to claim 1 characterized in that said free radical initiator is one or more of the peroxides a peroxide, chosen for example from benzoyl peroxide (BPO), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane ( DTBPH), 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3 (DTBHY), dicumyl peroxide (DCP), di (tert-butylperoxyisopropyl) benzene (DTBPIB).
14. Composição de acordo com a reivindicação 1 caracterizada pelo fato de que o mencionado iniciador de radicais livres é peróxido de benzoila. Composition according to Claim 1, characterized in that said free radical initiator is benzoyl peroxide.
15. Composição de acordo com a reivindicação 1 caracterizada pelo fato de conter adicionalmente um ou mais aditivos selecionados dentre carga, pigmentos, corantes, antioxidantes, estabilizantes à luz e ao calor, plastificantes, surfactantes , óleos, polímeros compatibilizantes . Composition according to Claim 1, characterized in that it additionally contains one or more additives selected from filler, pigments, dyes, antioxidants, light and heat stabilizers, plasticizers, surfactants, oils, compatibilizing polymers.
16. Processo de preparação de composição conforme uma qualquer das reivindicações 1 a 15, caracterizado por compreender as seguintes etapas: Process for preparing a composition according to any one of claims 1 to 15, characterized in that it comprises the following steps:
A - dispersar a nanoargila em água; A - disperse nanoargyl in water;
B - adicionar o amido; B - add starch;
C - adicionar o acidulante; C - add the acidulant;
D - agitar até homogeneização do meio; D - shake until homogenization of the medium;
E - aquecer a mistura até atingir temperatura abaixo de 100°C mantendo a agitação; E - heating the mixture to a temperature below 100 ° C while stirring;
F - atingida a temperatura cessar o aquecimento até que a mistura atinja a temperatura ambiente; F - when the temperature is reached, the heating ceases until the mixture reaches room temperature;
G - adicionar o auxiliar de reticulação e o iniciador de radicais livres, sob agitação, até dispersão completa. G - Add the crosslinking aid and free radical initiator under stirring until complete dispersion.
17. Processo de acordo com a reivindicação 16
caracterizado pelo fato de compreender uma etapa adicional de secagem da massa obtida na etapa G até remoção da água. Process according to claim 16 characterized in that it comprises an additional step of drying the dough obtained in step G to removal of water.
18. Processo de preparação de substrato polimérico caracterizado por compreender, posterior e adicionalmente às etapas da reivindicação 16 ou da reivindicação 17, as etapas de: A polymeric substrate preparation process further comprising, in addition to the steps of claim 16 or claim 17, the steps of:
H - adicionar polímero à formulação obtida na etapa G, não seca, e misturar, sob agitação, até dispersão completa; H - adding polymer to the formulation obtained in step G, not dry, and mixing under stirring until complete dispersion;
I - Secar a mistura até remoção da umidade; I - Dry the mixture until moisture is removed;
J - Processar a mistura. J - Process the mixture.
19. Processo de acordo com a reivindicação 18 caracterizado pelo fato da etapa J ser uma ou mais dentre extrusão, calandragem, sopro, injeção. Process according to Claim 18, characterized in that step J is one or more of extrusion, calendering, blowing, injection.
20. Produto caracterizado por ser compreender composição conforme uma qualquer das reivindicações 1 a 15. Product characterized in that it comprises a composition according to any one of claims 1 to 15.
21. Produto de acordo com a reivindicação 20 caracterizado pelo fato de ser compreender um substrato polimérico obtido conforme uma das reivindicações 18 e 19. Product according to claim 20, characterized in that it comprises a polymeric substrate obtained according to one of claims 18 and 19.
22. Produto de acordo com uma qualquer das reivindicações 20 ou 21 caracterizado por compreender substratos em camada única de polímero termoplástico ou em multicamadas de polímeros, opcionalmente com outros materiais, em que ao menos uma das camadas corresponde a um substrato contendo uma composição de acordo com uma das reivindicações 1 a 15. Product according to either of Claims 20 and 21, characterized in that it comprises thermoplastic polymer or multilayer polymer single layer substrates, optionally with other materials, wherein at least one of the layers corresponds to a substrate containing a composition according to the invention. one of claims 1 to 15.
23. Substrato caracterizado por compreender entre 2,5 e 20% p/p da composição conforme uma qualquer das reivindicações 1 a 15, em relação ao peso de polímero termoplástico .
Substrate comprising from 2.5 to 20% w / w of the composition according to any one of claims 1 to 15, based on the weight of thermoplastic polymer.
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| BRBR1020170088510 | 2017-04-27 | ||
| BR102017008851-0A BR102017008851B1 (en) | 2017-04-27 | COMPOSITION OF ACTION ON MOISTURE BARRIER FOR THERMOPLASTIC POLYMER, COMPOSITION PREPARATION PROCESS, POLYMERIC SUBSTRATE PREPARATION PROCESS, PRODUCT AND SUBSTRATE |
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| US6279736B1 (en) * | 1995-04-19 | 2001-08-28 | Capitol Specialty Plastics, Inc. | Barrier pack having an absorbing agent applied to the interior of the pack |
| WO2010065750A1 (en) * | 2008-12-03 | 2010-06-10 | Ecosynthetix Inc. | Process for producing biopolymer nanoparticle biolatex compositions having enhanced performance and compositions based thereon |
| US20110293957A1 (en) * | 2008-12-30 | 2011-12-01 | Caisa Johansson | barrier material and method for making the same |
| WO2015157823A1 (en) * | 2014-04-16 | 2015-10-22 | Plantic Technologies Ltd | Starch compositions and use thereof |
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2018
- 2018-04-23 WO PCT/BR2018/050121 patent/WO2018195625A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6279736B1 (en) * | 1995-04-19 | 2001-08-28 | Capitol Specialty Plastics, Inc. | Barrier pack having an absorbing agent applied to the interior of the pack |
| WO2010065750A1 (en) * | 2008-12-03 | 2010-06-10 | Ecosynthetix Inc. | Process for producing biopolymer nanoparticle biolatex compositions having enhanced performance and compositions based thereon |
| US20110293957A1 (en) * | 2008-12-30 | 2011-12-01 | Caisa Johansson | barrier material and method for making the same |
| WO2015157823A1 (en) * | 2014-04-16 | 2015-10-22 | Plantic Technologies Ltd | Starch compositions and use thereof |
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