WO2018018112A1 - Method for obtaining crystallisation seeds, crystalisation seeds and use thereof - Google Patents

Method for obtaining crystallisation seeds, crystalisation seeds and use thereof Download PDF

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Publication number
WO2018018112A1
WO2018018112A1 PCT/BR2017/000084 BR2017000084W WO2018018112A1 WO 2018018112 A1 WO2018018112 A1 WO 2018018112A1 BR 2017000084 W BR2017000084 W BR 2017000084W WO 2018018112 A1 WO2018018112 A1 WO 2018018112A1
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Prior art keywords
crystallization
seeds
crystallization seeds
temperature
limonene
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PCT/BR2017/000084
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French (fr)
Portuguese (pt)
Inventor
Camila Aoyagui DOS SANTOS
Crystopher Stanley CARPENTER
Ana Paula Badan RIBEIRO
Priscilla Efraim
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Universidade Estadual De Campinas - Unicamp
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Publication of WO2018018112A1 publication Critical patent/WO2018018112A1/en

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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23DEDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/02Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23GCOCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
    • A23G1/00Cocoa; Cocoa products, e.g. chocolate; Substitutes therefor
    • A23G1/30Cocoa products, e.g. chocolate; Substitutes therefor
    • A23G1/32Cocoa products, e.g. chocolate; Substitutes therefor characterised by the composition containing organic or inorganic compounds
    • A23G1/36Cocoa products, e.g. chocolate; Substitutes therefor characterised by the composition containing organic or inorganic compounds characterised by the fats used
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/158Fatty acids; Fats; Products containing oils or fats
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115Fatty acids or derivatives thereof; Fats or oils
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/44Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof

Definitions

  • the present invention is in the food and beverage field and relates to a process for obtaining crystallization seeds using mixtures of ihardfat fully hydrogenated soybean oil), potential for accelerating and modifying crystallization of Fats such as crystallization seeds in polymorphic forms are most useful.
  • Cocoa butter is the major component in chocolates, characterizing the product's continuous phase as a dispersing matrix for solid cocoa, sugar and milk particles (LOISEL et al., 1998).
  • This fat can crystallize into 6 polymorphic forms, each with distinct thermodynamic stability and melting point, identified as X, II, III, IV, V and VI, or by Greek letters, y,, ⁇ 'and ⁇ . the most stable form VI (WILLE & LU TON, 1966).
  • the V or ⁇ form is the most desirable polymorph for chocolate (HINDLE, POVEY and SMITH, 2002).
  • the tempering process of chocolate is fundamentally a controlled crystallization in which, through heat and mechanical treatments, a specific percentage of crystals is produced in the most stable form of MC (HARTEL, 1991). Effective tempering can facilitate demolding, prevent fat-bloom from cooling and storage, and obtain a finished product with good gloss, texture (snap) and fusion characteristics.
  • TAGs active triglyceride nucleating agents
  • PPP tripalmitin
  • POP 1-palmityl-2-ooyoyl palmitin
  • SOS 1-stearyl-2-oleoylstearine
  • Lopes et al. (2015) developed spray cooling crystallization seeds employing soybean, cotton, palm and crambe hardfats, fully hydrogenated vegetable oils, which have a homogeneous high melting TAG composition.
  • Hardfats represent low cost industrial fats with great potential for modification and acceleration of cocoa butter crystallization (RIBEIRO et al. 2Q13).
  • Lipid microparticles (SLM) or soybean hardfat crystallization seeds obtained by Lopes et al. (2015) demonstrated the need for storage under controlled temperatures (between 25 and 45 ° C) for 1 to .139 days, aiming at the transition from unstable polymorphic forms ( ⁇ ) obtained after particle production to stable forces ( ⁇ ). Storage at 45 ° C for 24 hours allowed the transition to the ⁇ form.
  • high temperatures favored the agglomeration of SIM,
  • the present invention relates the use of the D-Lemonene polymorphic transition acceleration potential, verified in static crystallization of MC, for the production of stabilized crystallization seeds (form 3), which demonstrates the unprecedentedness. of the idea.
  • the idea is not just a simple application of D-limonene on a different lipid basis, but the production of stabilized microparticles by means of this monomer.
  • the present invention relates the use of the D-Limenon polymorphic transition acceleration potential, found in static crystallization of MC, to the production of stabilized crystallization seeds ( ⁇ form), which demonstrates the novelty of the idea.
  • the idea is not just a simple application of D-limonene on a different lipid basis, but the production of stabilized microparticles through this raonoterpene, aiming at application in chocolates and other industrial products or processes.
  • the chocolate therapy step is the formation of crystallization nuclei of the lipid phase of chocolate, with the formation of approximately 4% of stable beta-type crystals by a specific heat treatment. These crystals of triacylglycerol nature are responsible for structuring the crystal lattice in this stable form (beta), which characterizes the quality chocolate.
  • the present invention aims to propose a process for obtaining crystallization seeds under the stable ⁇ polymorphic habit, composed of mixtures between fully hydrogenated soybean hardfat oil and different concentrations of D-limonene or soybean oil. canola, obtained by spray cooling technique.
  • PMF medium palm fraction
  • FIG. IA shows the micrograph of pure soybean hardfat seeds performed at 25 ° C at 150x magnification, 500 bar;
  • FIG. 1B shows micrograph of soybean hardfat seeds with the addition of 5% D-limonene performed at 25 ° C in 150x magnification, 500u bar;
  • FIG. 1C shows micrograph of hardfat seeds with 7.5% canola oil addition performed at 25 ° C in 150x magnification, SOOpra bar;
  • FIG. 2A shows the XRD pattern (short spacing) of soybean hardfat microparticles, at times 0, 2, 7, 19 and 26 days at 25 ° C without addition of oils;
  • FIG. 2B shows the short spacing of the soybean hardfat microparticles at times 0, 4, 7, 19 and 26: days at 25 ° C with. addition of 7.5% canola oil;
  • FIG. 2C shows ⁇ diffractogram (short spacing) of the soybean hardfat microparticles at times 0, 2, 7, 1.9 and 26 days at 25 ° C with 5% D-limonene added.
  • FIG. 3 shows the tempering curve obtained for milk chocolate, with and without the addition of the microparticles of the invention: (a) conventional sealing, (b) tempering with addition of soybean hardfat + canola oil microparticles and (c) tempering with the addition of soybean hardfat art D-lirnonene microparticles,
  • the present invention relates to a process for obtaining crystallization seeds under the more stable polymorphic habit ⁇ ' , composed of mixtures between soybean hardfat and different concentrations of D-i.monene or canola oil comprising the following steps-- a) melt the hardfat. soybeans, for example in a bath, hot tanks or in a microwave oven, at a temperature ranging from 70 to 90 ° C, preferably from 75 to 80 ° C until complete melting of the fat crystals;
  • jacketed medium mixture for example in jacketed tank, under controlled temperature of L 70 to 90 C for 6 minutes;
  • atomizing the mixture was spray cooling system which may comprise a container maintained at -10 ° to 1.0 ° C, preferably between -2 and the 0 ° C using nozzle atora 0.2 to Zador 2 mm, preferably from 0.7 to 1 liter and compressed air pressures varying from 0.5 to 5 kgf / cm 2 , preferably from 1.0 to 2.0 kgf / cm 2 at room temperature;
  • g store in closed containers in a temperature controlled chamber of 10 to 30 ° C, preferably ⁇ 25 ° C.
  • Crystallization seeds were produced by the method described above using the spray cooiing technique initially with the addition of 1 to 15% d-limonene or cinnamon oil to the hardfat. soybeans, resulting in a relatively loose powder with no agglomeration.
  • Seed surfaces were evaluated by Scanning Electron Microscopy (ME). Water was used aluminum base (1.4 cm diameter by 0.6 thickness) with double sided copper tape and colloidal graphite layer. Then the seeds were pulverized and fixed in this structure, and the samples were analyzed under table type microscope with variable voltage acceleration of 10 kV, with 150 times increase.
  • ME Scanning Electron Microscopy
  • the crystallization seeds produced are visually presented as relatively loose powders without agglomeration. Scanning electron microscopy (MBV) showed its spherical shape and confirmed the absence of agglomeration. In addition, a smooth and homogeneous surface has been shown to prove the beneficial effect of D-limonene or canola oil on crystallization of hazdfat and on the formation of crystallization seeds.
  • MBV scanning electron microscopy
  • the mean diameter (D 5 a) of the microparticles was between 150 and 2,00pm, for comparison, the literature indicates a diameter of the microparticles range from 5 to 500 u for satisfactory application as crystallization seeds, Therefore, microparticles present this potential application.
  • Polymorphic seed habit was determined by X-ray diffraction according to the AOCS Cj 2-95 method (AOCS, 2009). Was. used: a diffractometer using geometry. Bragg-Brentano ( ⁇ : 2 ⁇ ) with Cu- ⁇ radiation (k - 1.5418 ⁇ , 40KV voltage and 30mA current). Measurements were obtained with steps of 0.02 ° In 20 and acquisition time of 2s, with scans of 15 to 30 ° (2 ⁇ scale). The identification of the polymorphic form was determined from the values of the shorts spacings (distances between the parallel acyclic groups in the triacylglycerol) characteristic of the crystals.
  • FIG. 2A shows the diffractograms of the oil-free soybean harclfat sample and FIG. 2B of the sample with 7.5% canola oil added and FIG. 2C with addition of 5% D-1 imonene.
  • the crystallization seeds of the present invention under the most stable polymorphic habit B are composed of mixtures of soybean fully hydrogenated oil (kardfat) and different concentrations of D-limonene or canola oil obtained by Spray cooling technique features, the induction of crystals in the polyrriorphic form ⁇ , which is desirable in products such as chocolate due to the ability to accelerate or render unnecessary the expensive tempering or pre-crystallization stage.
  • crystallization seeds of the present invention may be applied to food, cosmetic, pharmaceutical and veterinary products to accelerate crystallization in fat crystallization and oil structuring processes.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
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Abstract

The present invention relates to a method for obtaining crystallisation seeds, with a great potential of use for accelerating and modifying the crystallisation of fats, as well as to crystallisation seeds with more stable polymorphic forms (β form).

Description

PROCESSO PARA A OBTENÇÃO DE SEMENTES DE CRISTALIZAÇÃO, SEMENTES DE CRISTALIZAÇÃO fi JSOS DAS MESMAS  PROCESS FOR OBTAINING CRYSTALIZATION SEEDS, CRYSTALIZATION SEEDS OF THE SAME
CAMPO DA INVENÇÃO FIELD OF INVENTION
[1] A presente invenção se insere na área de alimentos e bebidas e refere-se a um processo para a obtenção de sementes de cristalização utilizando-se de misturas do óleo totalmente hidrogenado de soja ihardfat) , potenciai na aceleração e modificação da cristalização de gorduras, como sementes de cristalização sob formas polimórficas mais está eis .  [1] The present invention is in the food and beverage field and relates to a process for obtaining crystallization seeds using mixtures of ihardfat fully hydrogenated soybean oil), potential for accelerating and modifying crystallization of Fats such as crystallization seeds in polymorphic forms are most useful.
FUNDAMENTOS DA INVENÇÃO  BACKGROUND OF THE INVENTION
[2] A manteiga de cacau (MC) é o principal componente em chocolates, caracterizando a fase continua do produto como matriz dispersante para as partículas sólidas de cacau, açúcar e leite (LOISEL et al. ,1998) . Essa gordura pode se cristalizar em 6 formas polimóríicas , cada uma com uma estabilidade termodinâmica e ponto de fusão distintos, identificadas como X, II, III, IV, V e VI, ou por letras gregas, y, , β' e β, sendo a forma VI a mais estável (WILLE & LU TON , 1966) . Por assegurar os atributos sensoriais adequados e microestrutura estável, a forma V ou βν é o polimorfo mais desejável para o chocolate (HINDLE, POVEY e SMITH, 2002). O processo de temperagem do chocolate é fundamentalmente uma cristalização controlada em que, por meio de tratamentos térmicos e mecânicos, se produz uma porcentagem específica de cristais na forma mais estável da MC (HARTEL, 1991) . A partir de uma temperagem eficiente, pode-se facilitar o desmolde, evitar a formação do fat-bloom no resfriamento e armazenamento e obter um produto final com boas características de brilho, textura (snap) e fusão. [2] Cocoa butter (MC) is the major component in chocolates, characterizing the product's continuous phase as a dispersing matrix for solid cocoa, sugar and milk particles (LOISEL et al., 1998). This fat can crystallize into 6 polymorphic forms, each with distinct thermodynamic stability and melting point, identified as X, II, III, IV, V and VI, or by Greek letters, y,, β 'and β. the most stable form VI (WILLE & LU TON, 1966). By ensuring adequate sensory attributes and stable microstructure, the V or βν form is the most desirable polymorph for chocolate (HINDLE, POVEY and SMITH, 2002). The tempering process of chocolate is fundamentally a controlled crystallization in which, through heat and mechanical treatments, a specific percentage of crystals is produced in the most stable form of MC (HARTEL, 1991). Effective tempering can facilitate demolding, prevent fat-bloom from cooling and storage, and obtain a finished product with good gloss, texture (snap) and fusion characteristics.
[3] ft produção de chocolate no Brasil somou 800 mil. toneladas em 2013, cora consumo de 790 mil toneladas acompanhando aproximadamente o volume produzido (ABIC&B, 2014) . Devido à significativa produção nacional de MC e chocolates, a substituição de seus processos de cristalização è um assunto estratégico do ponto de vista industrial. Isso se deve: uma vez que, em grande escala de produção, torna-se difícil o controle da temperatura nesta etapa, além de haver desvantagens com relação aos custos com energia e espaço (HACHIYA, KOYANO e SATO, 1989) .  [3] ft chocolate production in Brazil totaled 800 thousand. tons in 2013, with a consumption of 790 thousand tons, approximately following the volume produced (ABIC & B, 2014). Due to the significant national production of MC and chocolates, the replacement of their crystallization processes is a strategic matter from an industrial point of view. This is because, on a large scale of production, it is difficult to control temperature at this stage, and there are disadvantages with regard to energy and space costs (HACHIYA, KOYANO and SATO, 1989).
[41 Em busca de novos processos de pré- cristalização, uma nova técnica conhecida como semeadura ou seeding, tem sido progressivamente estudada para a substituição do: processo de temperagem. Nesta técnica, os agentes ativos de nucleação ou sementes de cristalização com. ponto de fusão acima de 34 °C seriam adicionados diretamente ao chocolate, após a etapa de ccnchage e antes da moldagem ou recobrimento (HACHIYA, KOYANO e SATO, 19891. Segundo Schenk e Peschar (2004) as sementes de cristalização devem conter a informação de empacotamento cristalino, induzindo à cristalização das gorduras em um polimorfo desejável. [41 In search of new pre-crystallization processes, a new technique known as sowing or seeding, have been progressively studied for the replacement of: tempering process. In this technique, nucleating active agents or crystallization seeds with. melting point above 34 ° C would be added directly to the chocolate after the cnchage step and prior to molding or coating (HACHIYA, KOYANO and SATO 19891. According to Schenk and Peschar (2004) crystallization seeds must contain the information of crystalline packaging, inducing fat crystallization into a desirable polymorph.
[5] Inúmeras vantagens são apontadas em função da aplicação de sementes de cristalização em chocolates: menor sensibilidade às variações de temperatura, rapidez, obtenção de produtos gordurosos com qualidade superior (LQNCHAMPT & MARTEL, 2004), a aceleração da cristalização, a cristalização eficaz entre misturas de gorduras vegetais e MC, a diminuição da incompatibilidade da MC com a gordura do leite {ZENG, BRAUN & WINDHAS, 2002) e o retardamento do fat- bloom (3VANBERG et al . 2013) . [5] Numerous advantages are pointed out due to the application of crystallization seeds in chocolates: lower sensitivity to temperature variations, speed, obtaining higher quality fatty products (LQNCHAMPT & MARTEL, 2004), acceleration of crystallization, effective crystallization. between blends of vegetable fats and MC, the decrease in MC incompatibility with milk fat (ZENG, BRAUN & WINDHAS, 2002) and fat retardation. bloom (3VANBERG et al. 2013).
[6] A maioria dos estudos e patentes envolvendo o desenvolvimento ou a aplicação de gérmens de cristalização emprega a MC como matéria-prima, aplicada já na fo ma polimórfica βν, desejável era chocolates { DESÇAMPS & KEGELAERS, 2009; FAGES, LETOURNEAU e GONUS, 2006; FICHTL , DIETRICH e SCHLIEHE-DIERKS, 2013; K.I T e HARTEL, 2Q1.0) - [6] Most studies and patents involving the development or application of crystallization germs employ MC as a raw material, already applied in the polymorphic form βν, desirable was chocolate {DESÇAMPS & KEGELAERS, 2009; FAGES, LETOURNEAU and GONUS, 2006; FICHTL, DIETRICH and SCHLIEHE-DIERKS, 2013; K.I T and HARTEL, 2Q1.0) -
[7] Existem: na li eratura diversos métodos de produção de sementes de cristalização, principalmente a partir da MC. Dentre eles destaca-se o emprego de fluido supercritico (FAGES, LETOORNE U e GONUS, 2006; FICHTL, DIETRICH e SCHLIEHE-DIERKS , 2013). [7] There are several methods of crystallization seed production in the literature, mainly from MC. Among them is the use of supercritical fluid (FAGES, LETOORNE U and GONUS, 2006; FICHTL, DIETRICH and SCHLIEHE-DIERKS, 2013).
[8] Em alguns poucos estudos foi testado o uso de agentes ativos de nucleação compostos por triacilgliceróis (TAG), como a tripalmitina (PPP) ou o uso de misturas de PPP e l-palmitil-2~oieoil-palmitina (POP) e entre triestearina ÍSSS) e l-esteariI'-2-oleoilestearina (SOS) (GWIE et al. 2006; PORE et al. 200.9) . São escassas as pesquisas que empreguem diferentes matérias—primas para a produção dos agentes de nucleação. Lopes et aí. (2015) desenvolveram sementes de cristalização por spray cooling empregando hardfats de soja, algodão, palma e crambe, óleos vegetais totalmente hidrogenados, -que apresentam uma composição homogénea de TAG de altos pontos de fusão.  [8] A few studies have tested the use of active triglyceride nucleating agents (TAGs) such as tripalmitin (PPP) or the use of mixtures of PPP and 1-palmityl-2-ooyoyl palmitin (POP) and between ISS (trystearine) and 1-stearyl-2-oleoylstearine (SOS) (GWIE et al. 2006; PORE et al. 200.9). There is little research employing different raw materials for the production of nucleating agents. Lopes et al. (2015) developed spray cooling crystallization seeds employing soybean, cotton, palm and crambe hardfats, fully hydrogenated vegetable oils, which have a homogeneous high melting TAG composition.
[9] Os hardfats representam gorduras de baixo custo industrial com grande potencial na modificação e na aceleração da cristalização de manteiga de cacau (RIBEIRO et ai. 2Q13) . As mi croparticulas lipidicas (SLM) ou sementes de cristalização à base de hardfat de soja obtidas por Lopes et al. (2015) demostraram a necessidade do armazenamento sob temperaturas controladas (entre 25 e 45°C) por 1 a .139 dias,, visando a transição de formas poiimórficas instáveis (α) , obtidas após a produção das partículas, para as for/nas estáveis (β) . 0 armazenamento à 45 °C por 24 horas possibilitou a transição para a forma β. Contudo, averiguou- se no mesmo estudo que altas temperaturas favoreceram a aglomeração das SIM, [9] Hardfats represent low cost industrial fats with great potential for modification and acceleration of cocoa butter crystallization (RIBEIRO et al. 2Q13). Lipid microparticles (SLM) or soybean hardfat crystallization seeds obtained by Lopes et al. (2015) demonstrated the need for storage under controlled temperatures (between 25 and 45 ° C) for 1 to .139 days, aiming at the transition from unstable polymorphic forms (α) obtained after particle production to stable forces (β). Storage at 45 ° C for 24 hours allowed the transition to the β form. However, it was found in the same study that high temperatures favored the agglomeration of SIM,
[10] Estudos anteriores já demonstraram. a possibilidade de acelerar a transição poiimórfica de hardfats com a adição de óleos. Ά adição de 20% de óleo de canola, por exemplo, aos hardfá ts de soja, co1 za e a1godáo foi capaz de promover a transição poiimór ica de α para β após cristalização a 0°C (DE MAN, DE MAN & BLACKMA , 1989) . Em outro estudo, a adição de 1,5% e 5% de D-li onenc, um óleo essencial, à manteiga de cacau e à gordura equivalente da manteiga de cacau (CBE) possibilito a transição poiimórfi ca da forma βν para a forma mais estável βνΐ durante cristalização ã 25°C (MIYASAK1 et al . 2015).  [10] Previous studies have already shown. the possibility of accelerating the poiimorphic transition of hardfats with the addition of oils. The addition of 20% canola oil to, for example, soybean, co1 za and aododon hardfaces was able to promote the polymorphic transition from α to β after crystallization at 0 ° C (DE MAN, MAN & BLACKMA, 1989). In another study, the addition of 1.5% and 5% D-liencenc, an essential oil, to cocoa butter and cocoa butter equivalent fat (CBE) enables the polymorphic transition from form βν to form more stable βνΐ during crystallization at 25 ° C (MIYASAK1 et al. 2015).
ESTADO DA TÉCHICA  State of Techica
[11] O documento intitulado ^Acceleration of poly orphic transitíon of cocoa battez and cocoa butter equivalem by addition of D-lim-onene" em nome de Miyasaki, E . et a.J.., refere-se à avaliação do polimorfismo das amostras cristalizadas da Manteiga de cacau (MC) macia (.Brasileira)' e de equivalente de Manteiga d cacau (CBE) , sem e com adição de 1,5% (m/m) e 5% (m/m) de D-limoneno. A invenção proposta difere de tal. documento principalmente pelo fato de se adicionar o D-limoneno em outra matéria- prima, hardfat de soja, co composição em ácidos graxos (AG) e em triacilgliceróis (TAG) substancialmente diferente da MC e de CBE mencionadas no documento. [11] The document entitled "Acceleration of poly orphic transition of cocoa battez and cocoa butter is equivalent to the addition of D-limonene" in the name of Miyasaki, E. et al., Refers to the evaluation of the polymorphism of crystallized samples from cocoa butter (MC) soft (.Brasileira) 'and d cocoa butter equivalents (CBE), without and with addition of 1.5% (w / w) and 5% (m / m) of d-limonene. The proposed invention differs from such a document mainly in that D-limonene is added in another raw material, soybean hardfat, fatty acid (AG) and triacylglycerol (TAG) composition substantially different from MC and CBE mentioned in the document.
[12] Vale ressaltar que no documento em nome de Míyasaki, é relatada uma cristalização na fase lipidica contínua da MC e de CBE com e sem adição de D-limoneno. à temperatura ambiente (25°C) , enquanto que a presente invenção não trata de uma simples cristalização estática e sim da produção de micropartículas (sementes) de arclfat de soja adicionadas de D-limoneno, cristalizadas peio processo de atomização por spray cooling.  [12] It is noteworthy that in the document on behalf of Míyasaki, a crystallization in the continuous lipid phase of MC and CBE with and without D-limonene addition is reported. at room temperature (25 ° C), whereas the present invention is not merely static crystallization but the production of D-limonene-added soybean arclfat microparticles crystallized by the spray cooling atomization process.
[13] Diferentemente de tal documento, a presente invenção relaciona o uso do potencial acelerador de transição polimórfica do D-Límoneno, verificado em cristalização estática de MC, para a produção de sementes de cristalização estabilizadas (forma 3), o que demonstra o ineditismo da ideia. Assim, a ideia não trata apenas de uma simples aplicação do D-limoneno em uma base lipidica diferente, mas da produção de micropartículas estabilizadas por meio desse monot erpeno .  [13] Unlike this document, the present invention relates the use of the D-Lemonene polymorphic transition acceleration potential, verified in static crystallization of MC, for the production of stabilized crystallization seeds (form 3), which demonstrates the unprecedentedness. of the idea. Thus, the idea is not just a simple application of D-limonene on a different lipid basis, but the production of stabilized microparticles by means of this monomer.
[141 O documento intitulado "The Effect of Lí onene on the Crystallízation of Cocca Butter" em. nome de Ray, J.et al. , refere-se à avaliação do comportamento de cristalização de MC após adição d 5% (m/m) de D-limoneno. Tal documento divulga uma c istalização estática da MC com e sem adição de D-limoneno: à temperatura de 2€-eC, De maneira diferente,: a presente invenção não trata de uma simples cristalização estática e sim. da produção de micropartículas (sementes) de hardfat de soja adicionadas de D-limoneno, cristalizadas pelo processo de atomização por spzây coolíng. Alé disso, a presente invenção também difere de tal documento pelo fato de se adicionar o D-limoneno era outra matéria-prima, hardfat de so a, com composição em ácidos cjraxos (A.G) e em triacilqliceróis (?AG) substancialmente diferente da MC. [141 The document entitled "The Effect of Linen on the Crystallization of Cocca Butter" in. Ray's name, J. et al. , refers to the evaluation of MC crystallization behavior after addition of 5% (w / w) D-limonene. Such a document discloses a static crystallization of MC with and without addition of D-limonene: at a temperature of 2 ° C and C. In a different way, the present invention is not just a simple static crystallization but. of the production of soybean hardfat microparticles added with D-limonene, crystallized by the spzây coolíng atomization process. Moreover, the present invention also differs from such document in that adding D-limonene was another raw material, hardfat. from so to, with a composition in fatty acids (AG) and triacylglycerols (ΔGA) substantially different from MC.
[ 153 Adicionalmente, de maneira distinta como ocorre no documento em nome de Ray, J.et aí.,, a presente invenção relaciona o uso do potencial acelerador de transição polirnórfiea do D-Lím.oneno, verificado em cristalização estática de MC, para a produção de sementes de cristalização estabilizadas (forma β) , o qu demonstra o ineditismo da ideia. Assim, a ideia não trata apenas de uma simples aplicação do D-limoneno em uma base lipídica diferente, mias da produção de microparticulas estabilizadas por meio desse raonoterpeno, visando aplicação em chocolates e em outros produtos ou processos industriais.  [153] In addition, unlike Ray, J. et al., The present invention relates the use of the D-Limenon polymorphic transition acceleration potential, found in static crystallization of MC, to the production of stabilized crystallization seeds (β form), which demonstrates the novelty of the idea. Thus, the idea is not just a simple application of D-limonene on a different lipid basis, but the production of stabilized microparticles through this raonoterpene, aiming at application in chocolates and other industrial products or processes.
[16] O documento intitulado "Impact of Limonene. on the Physical Pxoperties of educed Fat Chocolate", em nome de Do, T. A. L et al., refere-se aos efeitos na textura (dureza) e na viscosidade do chocolate com a adição direta do D-limoneno (3% m/m em relação à massa do chocolate) . Além disso, o interesse no D-limoneno, presente em tal documento, consiste na sua possível substituição parcial da MC no chocolate, visando a produção- de chocolates com reduzido teor de gordura. Percebe-se que o D-límoneno foi aplicado diretamente no chocolate, visando principalmente os seus efeitos nas propriedades físicas e mecânicas e não na aceleração da sua cristalização. Já na presente invenção, de forma totalmente diferente, o D-limoneno é carreado pelas sementes de cristalização, sendo futuramente aplicado em chocolates sob esta forma, visando a aceleração ou eliminação dei etapa de emperagem,  [16] The document entitled "Impact of Limonene. On the Physical Pxoperties of Educated Fat Chocolate" in the name of Do, TA L et al., Refers to the effects on the texture (hardness) and viscosity of chocolate with the addition of D-limonene (3% w / w relative to chocolate mass). Moreover, the interest in D-limonene present in this document is its possible partial substitution of MC in chocolate, aiming at the production of low fat chocolates. It is noticed that D-limonene was applied directly to chocolate, mainly aiming at its effects on the physical and mechanical properties and not on the acceleration of its crystallization. Already in the present invention, in a totally different way, D-limonene is carried by the crystallization seeds, being later applied in chocolates in this form, aiming at the acceleration or elimination of the emperage step,
[17 J O documento US200625B1 refere-se à produção de chocolate com reduzido/baixo teor de gordura através da adição de até 5% {m/m) de D-limoneno antes, durante, e após a etapa de conchagem. A presente invenção, era contrapartida, difere de tal documento principalmente pelo - D-limoneno ser carreado pelas sementes de cristalização, e ser futuramente aplicado em chocolates sob esta forma e não sob a forma continua, visando a aceleração ou eliminação da etapa de teraperagem. Cabe ressaltar ainda que no documento US2G0625B1, 0 D-limoneno foi aplicado direta ente na etapa anterior à temperagem, demonstrando as diferenças nos ob etivos de sua adição ao produto. [17 OJ US200625B1 refers to the production of reduced / low fat chocolate by adding up to 5% (w / w) D-limonene before, during, and after the milking step. The present invention, in contrast, differs from such a document principally in that D-limonene is carried by the crystallization seeds, and is applied in the future to chocolates in this form and not in continuous form, aiming at acceleration or elimination of the therapy step. It is also noteworthy that in US2G0625B1, D-limonene was applied directly in the pre-tempering step, demonstrating the differences in the objectives of its addition to the product.
[18] Assim, como pode ser observado, o efeito do D- limoneno- sobre a aceleração das transições poliinórficas e estabilização cristalina da manteiga de cacau (MC) é bastante conhecido e documentado no estado da técnica. Entretanto, tal uso mostra-se restrito a esta atéria-prima co o fase lipidica continua, não sendo direcionado para fabricação de chocolates, em especial, para acelerar ou tornar desnecessária a etapa de teraperagem, objetivo da presente invenção. Ά etapa de teraperagem de chocolates tem como função a formação de núcleos de cristalização da fase lipidica do chocolate, com a formação de aproximadamente 4% de cristais estáveis do tipo beta, através de um tratamento térmico especifico. São estes cristais, de natureza triacilglicerólica, os responsáveis pela estruturação da rede cristalina nesta forma estável (beta), que caracteriza o chocolate de qualidade.  [18] Thus, as can be seen, the effect of D-limonene- on the acceleration of polynorphic transitions and crystalline stabilization of cocoa butter (MC) is well known and documented in the state of the art. However, such use is restricted to this raw material as the continuous lipid phase is not directed to the manufacture of chocolates, in particular to accelerate or render unnecessary the therapeutic stage, object of the present invention. The chocolate therapy step is the formation of crystallization nuclei of the lipid phase of chocolate, with the formation of approximately 4% of stable beta-type crystals by a specific heat treatment. These crystals of triacylglycerol nature are responsible for structuring the crystal lattice in this stable form (beta), which characterizes the quality chocolate.
[19] Ά adição direta de D-limoneno a massa do chocolate não cumpre a função tecnológica da teraperagem., pois este composto não configura cristais de triacilgliceróis . É o uso do hardfat de óleo soja, composto de moléculas triacilglicerólicas na forma de micropar icalas , que tem a função de prover estes cristais beta estáveis, em teores correspondentes aos utilizados na temperagem, visaindo a. sua substituição como processo tecnológico. O ϋ-límoneno incorporado à microparticuia do hardfat de óleo de soja demonstra a capacidade de acelerar a transição polimórfica e estabilizar a .microparticuia lipídica, para que possa ser aplicada como tal; uma vez que esta transição mostra-se bastante lenta e requer tratamento térmico especifico para estabilização. [19] direta Direct addition of D-limonene to the chocolate mass does not fulfill the technological function of therapy. triglycerides. It is the use of soybean oil hardfat, composed of triacylglycerol molecules in the form of microparicas, which has the function of providing these stable beta crystals, in contents corresponding to those used in tempering, aiming at. its replacement as a technological process. The β-limonene incorporated into the soybean oil hardfat microparticles demonstrates the ability to accelerate the polymorphic transition and stabilize lipid microparticles so that it can be applied as such; since this transition is very slow and requires specific heat treatment for stabilization.
[20] Assim, a partir da presente invenção, percebe se que para que o processo de temperagem possa ser substituído pela adição de microparticulas ( seeding) , estas precisam ter natureza lipídica equivalente à manteiga de cacau ou sucedâneos, isto é, composição triací iglícerólica adequada, para que possam direcionar as transições e estabilização polimôrficas características destes componentes. O D-limoneno, portanto, tem atuação como um aditivo para a microparticuia composta de hardfat de óleo de soj a . [20] Thus, from the present invention realizes that for which the process of tempering may be substituted by the addition of microparticles (seeding), they need to have lipid nature equivalent to cocoa butter or substitutes, i.e. triací composition suitable for the polymorphic transitions and stabilization characteristic of these components. D-limonene therefore acts as an additive for the microparticle composed of soybean oil hardfat.
OBJECTIVOS DA INVENÇÃO  OBJECTIVES OF THE INVENTION
[21] A presente invenção tem por objetivo propor um processo para a obtenção de sementes de cristalização sob o hábito polimôrfico ma s estável β, compostas por misturas entre óleo totalmente hidrogenado (hardfat} de soja e diferentes concentrações de D-limoneno ou óleo de canola, obtidas pela técnica spray cooling.  [21] The present invention aims to propose a process for obtaining crystallization seeds under the stable β polymorphic habit, composed of mixtures between fully hydrogenated soybean hardfat oil and different concentrations of D-limonene or soybean oil. canola, obtained by spray cooling technique.
{22} Adicionalmente, é u objetivo da presente invenção as sementes de cristalização com superfície lisa e homogénea, em formato esférico e com ausência de aglomeração co o um produto a ser aplicado em chocolates ô outras bases lipidicas para acelerar ou direcionar a cristalização. {22} In addition, it is an object of the present invention to have smooth surface crystallization seeds and homogeneous, spherical in shape and with no agglomeration as a product to be applied to chocolates or other lipid bases to accelerate or direct crystallization.
Ainda é um objetivo da presente invenção propor o uso das referidas sementes de cristalização na semeadura na produção industrial de. chocolates, acelerando ou tornando desnecessária a etapa de. temperagem; co o controle microbiológico e ainda em aplicações em óleo de Palma ou em estearina ou era fração média da Palma (PMF) como agentes de nucleação, para a indução da cristalização n forma polim.órfica β, colaborando para o desen olvimento de sucedâneos da manteiga de cacau, visando a- aplicação em chocolates .  It is still an object of the present invention to propose the use of said crystallization seeds in sowing in industrial production of. Chocolates, speeding up or making the step of. temperament; microbiological control and also in palm oil or stearin or medium palm fraction (PMF) applications as nucleation agents, for the induction of crystallization in polymorphic form β, contributing to the development of butter substitutes cocoa beans for application in chocolates.
BREVE DESCRIÇÃO DAS FX6US&S  BRIEF DESCRIPTION OF FX6US & S
[23] Ã FIG. IA mostra a micrografia das sementes de hardfat de soja puro realizada a 25 °C em aumento de I50x, barra de 500 ;  [23] FIG. IA shows the micrograph of pure soybean hardfat seeds performed at 25 ° C at 150x magnification, 500 bar;
[24] A FIG. 1B mostra a micrografia das sementes de hardfat de soja comi adição de 5% de D-limoneno realizada a 25 °C em aumento de 150x, barra de SOOu ;  [24] FIG. 1B shows micrograph of soybean hardfat seeds with the addition of 5% D-limonene performed at 25 ° C in 150x magnification, 500u bar;
[25] A FIG. 1C mostra a micrografia das sementes de hardfat de so a com adição de 7,5% de óleo de canola realizada a 25°C em aumento de 150x, barra de SOOpra;  [25] FIG. 1C shows micrograph of hardfat seeds with 7.5% canola oil addition performed at 25 ° C in 150x magnification, SOOpra bar;
[26] A FIG. 2A mostra o difratograma (short spacing) das micropartícuias de hardfat de soja, nos tempos 0, 2, 7, 19 e 26 dias a 25°C sem adição de óleos; [26] FIG. 2A shows the XRD pattern (short spacing) of soybean hardfat microparticles, at times 0, 2, 7, 19 and 26 days at 25 ° C without addition of oils;
[27] Ά FIG. 2B mostra o difratograma [short spacing) das micropartleu1as de hardfat de soja, nos tempos 0, 4, 7, 19 e 26: dias a 25°C com. adição de 7,5% de óleo de canola; e  [27] Ά FIG. 2B shows the short spacing of the soybean hardfat microparticles at times 0, 4, 7, 19 and 26: days at 25 ° C with. addition of 7.5% canola oil; and
[28] A FIG. 2C mostra σ difratograma (short spacing) das micropartículas de hardfat de soja, nos tempos 0, 2, 7, 1.9 e 26 dias a 25 °C com adição de 5% de D-límoneno. [28] FIG. 2C shows σ diffractogram (short spacing) of the soybean hardfat microparticles at times 0, 2, 7, 1.9 and 26 days at 25 ° C with 5% D-limonene added.
[29] A FIG. 3 mostra a curva de temperagem obtida para o chocolate ao leite, com e sem a adição das micropartículas da invenção: (a) emperagem convencional, (b) temperagem com adição das micropartículas de hardfat de soja + óleo de canola e (c) temperagem com adição das micropartículas de hardfat cie soja ÷ D-lirnoneno,  [29] FIG. 3 shows the tempering curve obtained for milk chocolate, with and without the addition of the microparticles of the invention: (a) conventional sealing, (b) tempering with addition of soybean hardfat + canola oil microparticles and (c) tempering with the addition of soybean hardfat art D-lirnonene microparticles,
[30} Cabe destacar que houve redução de 90% no tempo total de retenção na temperatura de cristalização.  [30} It should be noted that there was a 90% reduction in the total retention time in the crystallization temperature.
DESCRIÇÃO DETALHADA DA IHVENÇÃO  DETAILED DESCRIPTION OF THE IHVENTION
[31] A presente invenção refere-se a um processo para a obtenção de sementes de cristalização sob o hábito polímórfico mais estável β', compostas por misturas entre óleo totalmente hidrogenado {hardfat) de soja e diferentes concentrações de D-Íi.moneno ou óleo de canola compreendendo as seguintes etapas-- a) fundir o hardfat. de soja, por exemplo em banho- ma ia, tanques encaraisados ou em forno de micro-ondas,· em uma temperatura variável de 70 a 90°C, preferencialmente de 75 a 80°C até completa fusão dos cristais de gordura; [31] The present invention relates to a process for obtaining crystallization seeds under the more stable polymorphic habit β ' , composed of mixtures between soybean hardfat and different concentrations of D-i.monene or canola oil comprising the following steps-- a) melt the hardfat. soybeans, for example in a bath, hot tanks or in a microwave oven, at a temperature ranging from 70 to 90 ° C, preferably from 75 to 80 ° C until complete melting of the fat crystals;
b) adicionar de 1 até 15%, preferencialmente de 5 a 7,5% m/m, de D-limoneno ou de 1 a 15% de óleo de canola, preferencialmente de 5 a 10% m/m;  b) adding from 1 to 15%, preferably from 5 to 7.5% w / w, of D-limonene or from 1 to 15% canola oil, preferably from 5 to 10% w / w;
c) aquecer a mistura sob agitação na faixa entre 70 e 90*O, preferencialmente de 75 a 8Q°C através de placa de aquecimento de 2 a 5 minutos para completa solubilí zação dos óleos adicionados;  c) heating the stirred mixture in the range of 70 to 90 ° C, preferably 75 to 80 ° C through a 2 to 5 minute heating plate to complete solubilization of the added oils;
d) estabilizar a mistura meio encamisado, por exemplo em tanque encamisado, sob temperatura controlada de 70 a 90GC durante 6 minutos; d) stabilize the jacketed medium mixture, for example in jacketed tank, under controlled temperature of L 70 to 90 C for 6 minutes;
e) atomizar a mistura era sistema de spray coolíng, o qual pode ser constituído por um recipiente mantido em temperatura entre -10° a 1.0 °C, preferencialmente entre -2 o e 0°C, utilizando bico atora zador de 0,2 a 2 mm, preferencialmente de 0,7 a liam e pressões de ar comprimido variáveis entre 0,5 a 5 kgf/cm2, preferencialmente entre 1,0 e 2,0 kgf/cm2 à temperatura ambiente; e) atomizing the mixture was spray cooling system which may comprise a container maintained at -10 ° to 1.0 ° C, preferably between -2 and the 0 ° C using nozzle atora 0.2 to Zador 2 mm, preferably from 0.7 to 1 liter and compressed air pressures varying from 0.5 to 5 kgf / cm 2 , preferably from 1.0 to 2.0 kgf / cm 2 at room temperature;
f) acondicionar as sementes dé cristalização obtidas: em embalagens do tipo Pouch, metalizadas e com zip ou em outro sistema de embalagem que seja barreira a vapor de água, luz e gases; e  (f) packaging the obtained crystallization seeds: in Pouch-type packaging, metallized and zipped or in another packaging system that is a vapor barrier for water, light and gases; and
g) armazenar em recipientes fechados em câmara com temperatura controlada de 10 a 30 °C, preferencialmente < 25°C.  g) store in closed containers in a temperature controlled chamber of 10 to 30 ° C, preferably <25 ° C.
[32] As sementes de cristalização foram produzidas pelo método acima descrito com uso da técnica de spray cooiing inicialmente com a adição de 1 até 15% d D-limoneno ou óleo de canela ao hardfat de. soja, resultando em um pó relativamente solto e com ausência de aglomeração.  [32] Crystallization seeds were produced by the method described above using the spray cooiing technique initially with the addition of 1 to 15% d-limonene or cinnamon oil to the hardfat. soybeans, resulting in a relatively loose powder with no agglomeration.
Caracter zação das Sementes  Seed Characterization
Morfologia  Morphology
[33] As análises da morfologia e da microestrutura das sementes de cristalização foram realizadas nas amostras logo após a sua produção e após 7, 15 e 30 dias de armazenamento em câmara com temperatura controlada a 25 °C, para averiguação de possíveis alterações visuais ocorridas nas sement.es duran e estocagem..  [33] Crystallization seed morphology and microstructure analyzes were performed on the samples immediately after production and after 7, 15 and 30 days of storage in a temperature controlled chamber at 25 ° C to investigate possible visual changes. in sement.es duran and stocking ..
[34.] A superfície das sementes foi avaliada por Microscopi Eletrônica de Varredura (ME ) . Utilizou-se u a base de alumínio (1,4 cm de diâmetro por 0,6 de espessura) com fita dupla face de cobre e camada de grafite coloidal . Em seguida as sementes forma pulverizadas e fixadas nesta estrutura, sendo as amostras analisadas em microscópio do tipo mesa com aceleração de voltagem variável de 10 kV, com aumento de 150 vezes. [34.] Seed surfaces were evaluated by Scanning Electron Microscopy (ME). Water was used aluminum base (1.4 cm diameter by 0.6 thickness) with double sided copper tape and colloidal graphite layer. Then the seeds were pulverized and fixed in this structure, and the samples were analyzed under table type microscope with variable voltage acceleration of 10 kV, with 150 times increase.
[35] As sementes de cristalização produzidas se apresentam visualmente na forma de pós relativamente soltos e com ausência de .aglomeração. A microscopia eletrônica de varredura (MBV) evidenciou o seu fo mato esférico e comprovou a ausência da aglomeração. Além disso, mostraram-se cora uma superfície lisa e homogénea, comprovando- se o efeito benéfico do D-limoneno ou do óleo de canola na cristalização cio hazdfat e na formação das sementes de cristalização.  [35] The crystallization seeds produced are visually presented as relatively loose powders without agglomeration. Scanning electron microscopy (MBV) showed its spherical shape and confirmed the absence of agglomeration. In addition, a smooth and homogeneous surface has been shown to prove the beneficial effect of D-limonene or canola oil on crystallization of hazdfat and on the formation of crystallization seeds.
.5iârcetro médio e distribuiçâo de tamanho das partículas . 5i average diameter and particle size distribution
[36] O diâmetro volumétrico médio e a distribuição de tamanho das micropart ículas foram determinados em. analisador de distribuição de tamanho de partículas com sistema de difração de raios laser. As amostras foram dispersas em solução aquosa contendo 0,5% Cm/m} do emulsificante Tween® 20 e então adicionadas à unidade de dispersão do equipamento, que foi preenchidl- com água destilada. A análise foi conduzida à temperatura ambiente (25°C) e o diâmetro médio [36] Mean volumetric diameter and size distribution of microparticles were determined in. particle size distribution analyzer with laser diffraction system. The samples were dispersed in an aqueous solution containing 0.5% Cm / m 2 of Tween® 20 emulsifier and then added to the equipment dispersion unit, which was filled with distilled water. The analysis was conducted at room temperature (25 ° C) and the average diameter
(D50) foi calculado a partir de sete replicatas e considerando o diâmetro médio de uma esfera de mesmo volume(D50) was calculated from seven replicates and considering the average diameter of a sphere of the same volume
(D[4,.3]]. A polídispersídade foi avaliada peio índice span, calculado por (D?o ~ Dio) /D¾or correspondente aos diâmetros de 10, 50 e 90% da distribuição. 0 índice de poiidíspersidade indicou a. variação do tamanho das partículas. [37] Esta análise foi conduzida nas amostras logo após a sua produção e após 7, 15 e 30 dias de armazenamento em câmara de temperatura controlada a 25°C, para averiguação do aparecimento de possível aglomeração durante estocagera, (D [4, .3]]. Polydispersity was evaluated by the span index, calculated by (D? -Dio) / D¾o r corresponding to the diameters of 10, 50 and 90% of the distribution. variation in particle size. [37] This analysis was conducted on the samples immediately after production and after 7, 15 and 30 days of storage in a 25 ° C controlled temperature chamber to ascertain the possible agglomeration during storage,
[38] O diâmetro médio (D5o) das micropartícuias ficou entre 150 e 2,00pm, À título de comparação, a literatura aponta, uma faixa de diâmetro das micropartícuias de 5 a 500 u para uma satisfatória aplicação como sementes de cristalização, sendo assim, as micropartícuias apresentam esse potencial de aplicação. [38] The mean diameter (D 5 a) of the microparticles was between 150 and 2,00pm, for comparison, the literature indicates a diameter of the microparticles range from 5 to 500 u for satisfactory application as crystallization seeds, Therefore, microparticles present this potential application.
Hábito polimórfico  Polymorphic habit
[39] 0 hábito polimórfico das sementes foi determinado por difraçáo de raios-X, segundo o método AOCS Cj 2-95 (AOCS, 2009) . Foi. utilizado: um Difratôraetro utilizando geometria. Bragg-Brentano (Θ:2Θ) com radiação Cu- Κα (k - 1.5418 Â, tensão de 40KV e corrente de 30mA) . As medidas foram obtidas com passos de 0,02° Em 20 e tempo de aquisição de 2s, com varreduras de 15 a 30° (escala 2Θ) . A identificação da forma polimórfi a foi determinada a partir dos valores dos shorts spacings (distâncias entre os grupos acíia paralelos no tríacíIglícerol ) característicos dos cristais .  [39] Polymorphic seed habit was determined by X-ray diffraction according to the AOCS Cj 2-95 method (AOCS, 2009). Was. used: a diffractometer using geometry. Bragg-Brentano (Θ: 2Θ) with Cu- Κα radiation (k - 1.5418 Â, 40KV voltage and 30mA current). Measurements were obtained with steps of 0.02 ° In 20 and acquisition time of 2s, with scans of 15 to 30 ° (2Θ scale). The identification of the polymorphic form was determined from the values of the shorts spacings (distances between the parallel acyclic groups in the triacylglycerol) characteristic of the crystals.
[40] As sementes foram analisadas quanto ao hábito polimórfico após 1, 2, 7, 19 e 26 dias em armazenamento a 25° C, sendo que t - 1 correspondeu a 18 horas após a produção. A FIG. 2A mostra os difratogramas da amostra de harclfat de soja sem adição de óleos e a FIG. 2B da amostra com adição de 7,5% de óleo de canola e FIG. 2C com adição de 5% de D- 1 imoneno.  [40] Seeds were analyzed for polymorphic habit after 1, 2, 7, 19 and 26 days of storage at 25 ° C, with t - 1 corresponding to 18 hours after production. FIG. 2A shows the diffractograms of the oil-free soybean harclfat sample and FIG. 2B of the sample with 7.5% canola oil added and FIG. 2C with addition of 5% D-1 imonene.
[41] Verificou-se que a amostra de hárdfat de soja sem adição cie óleos (Figura 2A) cristalizou-se sob a forma poiimórfica menos estável , observada pelo pico característico em 4,14 Â. Mesmo durante o armazenamento da amostra por 26 dias a 25°C, não foi observada qualquer transição poiimórfica.. Diferentemente, a amostra adicionada de óleo de canola demonstrou apresentar uma transição poiimórfica completa da forma para a forma β em apenas 4 dias de armazenamento a 25°C (Figura 2B) , através da definição dos picos relacionados aos short spacings característicos da forma β: 4,60 3,84 Â e 3,69 Ã a partir de t :::: 4. [41] It was found that the soy hardfat sample without addition of oils (Figure 2A) it crystallized into the less stable polymorphic form, observed by the characteristic peak at 4.14 Â °. Even during storage of the sample for 26 days at 25 ° C, no polymorphic transition was observed. In contrast, the added sample of canola oil was shown to have a complete polymorphic transition from form to β form in just 4 days of storage at 25 ° C (Figure 2B) by defining the peaks related to the characteristic short spacings of the form β: 4.60 3.84 Â and 3.69 Ã from t :::: 4.
[42] Como pôde ser observado no dífr tograraa da Figura 20, picos bem definidos referentes à forma (3> são visualizados para os short spacings 4,60 A, 3,88 Ã e 3,73 Ã para a. amostra com adição de D-limoneno ao hardfat de soja desde o tempo t ~ 1 (18 horas após a produção das micropartícuias ) , o que demonstrou a rápida transição poiimórfica dos cristais de gordura. Apesar do D-limoneno representar um terpeno, cuja estrutura é bem diferente de u a molécula de tríacíigiícerol, esse óleo essencial foi capaz de afetar o comportamento de cristalização dos triacilgliceróis (TAG) do hardfat de soja, acelerando a transição poiimórfica muito mais eficientemente que a adição do óleo de canola, que apresenta TAG cora AG de tamanho de cadeia muito próximos aos existentes no haxdfat, apesar de predominantemente insaturados. [42] As can be seen from the diffraction of Figure 20, well-defined peaks concerning the shape (3> are displayed for the short spacings 4.60 A, 3.88 Ã and 3.73 Ã… for the sample with the addition of D-limonene to soybean hardfat since time t ~ 1 (18 hours after microparticles production), which demonstrated the rapid polymorphic transition of fat crystals, although D-limonene represents a terpene whose structure is quite different from In a triacylglycerol molecule, this essential oil was able to affect the triacilglycerol (TAG) crystallization behavior of soybean hardfat, accelerating the polymorphic transition much more efficiently than the addition of canola oil, which has TAG with chain size AG very close to those in haxdfat, although predominantly unsaturated.
Redução do te po de temperagem  Tempering Time Reduction
[43] O tempo de temperagem foi avaliado na aplicação enr chocolate ao leite. Avaliou-se o processo de temperagem convencional e o processo (seeding) quando as: micropartícuias da presente invenção foram adicionadas. [44] A Figura 3 demonstra o comportamento das curvas da temperagem convencional e com a adição das microparticulas (seeding) . [43] Tempering time was evaluated in the application of chocolate milk. The conventional tempering process and the seeding process were evaluated when the microparticles of the present invention were added. [44] Figure 3 demonstrates the behavior of conventional tempering curves and the addition of microparticles (seeding).
[45] De acordo com os resultados obtidos, foi possível obter 90% de redução no tempo de retenção na temperatura de cristalização e 26% de redução do tempo total de temperagem.  [45] According to the results obtained it was possible to obtain 90% reduction in retention time at crystallization temperature and 26% reduction in total tempering time.
[46] Adicionalmente, os chocolates obtidos a partir deste estudo apresentaram brilho, facilidade de desmolde e as microparticulas não puderam ser percebidas durante a degustação e fusão do chocolate na boca.  [46] In addition, the chocolates obtained from this study showed brilliance, ease of demolding and microparticles could not be perceived during tasting and melting of chocolate in the mouth.
[47] Com os resultados obtidos por meio da aplicação das microparticulas em chocolates dos tipos amargo e ao leite, é possível verificar uma redução de até 90% do tempo de retenção na temperatura de cristalização, o que demonstra, em nível industrial, a necessidade apenas do resfriamento do. chocolate para se atingir a temperatura de cristalização da manteiga de cacau (MC) , com possibilidade de eliminação ou substituição de um equipamento de processo (temperadeira) .  [47] With the results obtained from the application of microparticles in bitter and milk chocolates, it is possible to observe a reduction of up to 90% of the retention time in the crystallization temperature, which demonstrates, at an industrial level, the need for cooling only. chocolate to reach the crystallization temperature of cocoa butter (MC), with the possibility of eliminating or replacing a process equipment (tempering).
APLICAÇÕES DA RESSMTS INVENÇÃO  RESSMTS APPLICATIONS INVENTION
[48] Dentre as inúmeras aplicações que as sementes de cristalização da presente invenção, sob o hábito polimórfico mais estável B, compostas por misturas entre óleo totalmente hidrogenado (kardfat) de soja e diferentes concentrações de D-limoneno ou óleo de canola, obtidas pela técnica spray cooling apresentam, destaca-se a indução da dos cristais na forma polirriórfíca β, desejável em produtos como o chocolate pela capacidade de acelerar ou tornar desnecessária a dispendiosa etapa de temperagem ou pré-cristalização.  [48] Among the numerous applications that the crystallization seeds of the present invention under the most stable polymorphic habit B, are composed of mixtures of soybean fully hydrogenated oil (kardfat) and different concentrations of D-limonene or canola oil obtained by Spray cooling technique features, the induction of crystals in the polyrriorphic form β, which is desirable in products such as chocolate due to the ability to accelerate or render unnecessary the expensive tempering or pre-crystallization stage.
[49] Outras aplicações tecnológicas das sementes de cristalização obtidas sob a forma polimórfics β incluem a aplicação em óleo de Palma ou na fração média da Palma (PMF) ou em estearina como agentes de nueleação, para. a indução da cristalização na forma polimórfica β, colaborando para o desenvolvimento de sucedâneos da manteiga de cacau. [49] Other technological applications of seed of Crystallization obtained in the form of polymorphics β include application in palm oil or in the medium fraction of palm (PMF) or stearin as thinning agents for. the induction of crystallization in the polymorphic form β, contributing to the development of cocoa butter substitutes.
[50] Adicionalmente, as sementes de cristalização da presente invenção, podem ser aplicadas em produtos alimentícios, cosméticos, farmacêuticos e veterinários, visando a aceleração da cristalização em processos de cristalização de gorduras e estruturação de óleos.  [50] In addition, the crystallization seeds of the present invention may be applied to food, cosmetic, pharmaceutical and veterinary products to accelerate crystallization in fat crystallization and oil structuring processes.
[51] No que se refere à aplicação das sementes de cristalização em processos de produção de produtos alimentícios, as aplicações são na produção de chocolates, recheios para confeitaria, recheios de biscoito, balas que contenham gordura, margarinas, manteigas, spreads (pastas) de chocolate e similares, coberturas, óleo de palma e suas frações, gorduras iáuricas e suas f ações.  [51] As regards the application of crystallization seeds in food production processes, applications are in the production of chocolates, confectionery fillings, cookie fillings, fat-containing candies, margarines, butters, spreads. of chocolate and the like, toppings, palm oil and its fractions, lauric fats and their fractions.
[52] No que se refere à aplicação das sementes de cristalização em processos de produção de cosméticos, as aplicações são em produtos de base lipidica, por exemplo manteigas corporais, hidratantes e batons.  [52] As regards the application of crystallization seeds in cosmetic production processes, applications are in lipid based products, for example body butters, moisturizers and lipsticks.
[53] Na aplicação das sementes de cristalização na produção de produtos farmacêuticos, as aplicações são em excipientes fa macêuticos, ácidos graxos ou triacilgliceróis purificados e. misturas de ácidos graxos ou triacilgliceróis.  [53] In the application of crystallization seeds in the production of pharmaceutical products, applications are in pharmaceutical excipients, purified fatty acids or triglycerides and. mixtures of fatty acids or triglycerides.
[54] Por fim, no que se refere à aplicação das sementes de cristalização em. produtos veterinários, as aplicações são em medicamen os e alimentos contendo excipient.es de base lipidica.  [54] Finally, as regards the application of crystallization seeds in. Veterinary products, the applications are in medicines and foods containing lipid-based excipients.
[55] Salientasse que os exemplos citados acima não restringem o escopo de aplicação da invenção, apenas exemplificam suas possibilidades. [55] Points are that the above examples do not restrict the scope of application of the invention, only exemplify its possibilities.

Claims

REIVINDICAÇÕES
1. Processo para a obtenção de sementes de cristalização, caracterizado pelo fato de compreender as seguintes etapas:  1. Process for obtaining crystallization seeds, characterized in that it comprises the following steps:
a) fusão do hardfat de soja em u a temperatura variável de 70 a 90eC, preferencialmente de 75 a 8-0*C ; a) melting the soybean in water hardfat temperature ranging from 70 to 90 C and preferably from 75 to 8-0 ° C;
b) adição de 1 até 15%, preferencialmente de 5 a 7,5% m/m, de D-limoneno;  b) adding 1 to 15%, preferably 5 to 7.5% w / w, of D-limonene;
c) aquecimento a mistura sob agitação na faixa entre 70 e 90 °C, preferencialmente de 75 a 80°C, de 2 a 5 minutos até completa homogeneização dos óleos adicionados;  c) heating the stirred mixture in the range from 70 to 90 ° C, preferably from 75 to 80 ° C, from 2 to 5 minutes until complete homogenization of the added oils;
d) estabilização a mistura em meio encamisado sob temperatura controlada entre 70 e 90 °C durante 6 min;  d) stabilizing the mixture in jacketed medium under controlled temperature between 70 and 90 ° C for 6 min;
e) atomização a mistura em um recipiente resfriado entre -10° a 10°C, preferencialmente entre -2° a 0°C, utilizando bico atomizador de 0,2 a 2,0 mm, preferencialmente de 0,7 a 1 mm e pressão de ar comprimido variável entre 0,5 e 5,0, preferencialmente entre 1,0 e 2,0 kgf/cm2 â temperatura arnbiente; e) atomizing the mixture in a cooled container at -10 ° to 10 ° C, preferably at -2 ° to 0 ° C, using 0.2 to 2.0 mm atomiser nozzle, preferably 0.7 to 1 mm and compressed air pressure ranging from 0.5 to 5.0, preferably from 1.0 to 2.0 kgf / cm 2 at ambient temperature;
f) acondicionamento das sementes de cristalização em embalagens com barreira ao vapor d água, luz e gases; e g) armazenamento era câmara com temperatura controlada de. 10 a 30 °C, pref rencialmente ≤ a 25 °C.  (f) conditioning of crystallization seeds in vapor, light and gas vapor barrier packaging; and g) storage in a temperature controlled chamber of. 10 to 30 ° C, preferably ≤ 25 ° C.
2. Processo para a obtenção de sementes de cristalização, caracterizado pelo fato de compreender as seguintes etapas:  2. Process for obtaining crystallization seeds, characterized in that it comprises the following steps:
a) fusão do hardfat de soja em. uma temperatura variável de 70 a. 90 °C, pref rencialmente de 75 a 80 °C;  (a) fusion of soybean hardfat into. a variable temperature of 70 a. 90 ° C, preferably 75 to 80 ° C;
b) adição de 1 a 15% de óleo de canola, preferencialmente de 5 a 10% m/m; c) aquecimento da mistura sob agitação na faixa entre 70 e 90°C, preferencialmente de 75 a 80-°C, de 2 a 5 minutos até completa homogeneização dos óleos adicionados; b) adding 1 to 15% canola oil, preferably 5 to 10% w / w; c) heating the mixture under stirring in the range from 70 to 90 ° C, preferably from 75 to 80 ° C, from 2 to 5 minutes until complete homogenization of the added oils;
d) estabilização1 da mistura em meio encara sado sob temperatura controlada entre 70 e 90°C durante 6 min; d) stabilization 1 of the mixture in medium at controlled temperature between 70 and 90 ° C for 6 min;
e) atomização da mistura em um recipiente resfriado entre -10° a 10°C, pref rencialmente entre -2o a 0°C, utilizando bico ato izador de 0,2 a 2, 0 mm, preferencialmente de D, a 1 mm e pressão de ar comprimido variável entre 0,5 e 5,0, preferencialmente entre 1,0 e 2,0 kgf/cm2 à temperatura ambiente ; e) spraying the mixture into a cold container from -10 ° to 10 ° C, pref the rencialmente between -2 to 0 ° C using basic scavenger act from 0.2 to 2, 0 mm, preferably D, 1 mm and compressed air pressure ranging from 0.5 to 5.0, preferably from 1.0 to 2.0 kgf / cm 2 at room temperature;
f ) acondicionamento das sementes de cristalização êm embalagens com barreira ao vapor de água, luz e gases; e g) armazenamento em câmara com temperatura controlada de 10 a 30°C, pref rencialmente ≤ a 25 °C.  (f) packaging of crystallization seeds in packagings with a vapor barrier of water, light and gas; and g) storage in a temperature controlled chamber of 10 to 30 ° C, preferably ≤ 25 ° C.
3. Processo, de acordo com as reivindicações 1 e 2, caracterizado pelo fato de utilizar a técnica de spra cooling.  Process according to Claims 1 and 2, characterized in that the spra cooling technique is used.
4- Sementes de cristalização caracterizadas pelo fato de serem obtidas pelo processo das reivindicações 1,2 e 3 e estarem sob o hábito polimórfico mais estável β.  Crystallization seeds characterized in that they are obtained by the process of claims 1,2 and 3 and are under the most stable polymorphic habit β.
5. Sementes de cristalização, de acordo com a reivindicação 4, caracterizadas pelo fato de apresentarem formato esférico, superfície lisa e homogénea e ausência de aglomeração .  Crystallization seeds according to claim 4, characterized in that they have a spherical shape, smooth and homogeneous surface and no agglomeration.
6. Sementes de cristalização, de acordo com a reivindicação 4, caracterizadas pelo fato de apresentarem diâmetro médio Dso entre 150 e 200 pm.  Crystallization seeds according to claim 4, characterized in that they have an average diameter Dso of between 150 and 200 pm.
7. Sementes de cristalização, de acordo com a reivindicação 4, caracterizadas pelo fato de apresentarem picos referentes ao hábito polimórfico β para short spacings 4,60 Â; 3/86 Â ou 3,84 Â e 3,73 Â ou 3,69 Â. Crystallization seeds according to claim 4, characterized in that they contain peaks related to polymorphic habit β for short spacings 4.60 Â; 3/86 Â or 3.84 Â and 3.73 Â or 3.69 Â.
8.: Sementes de cristalização caracterizadas por compreenderem até .1 a 15% de D-limoneno ou 5 a 10% de óleo de oanola em sua composição, estarem sob o hábito polimórfico mais estável β, apresentar picos referentes à forma β para short spacings 4,60 Ã, 3,88 A ou 3,8 Â e 3,73: Â ou 3,69 Â, formato esférico, com superfície lisa e homogénea, com ausência de aglomeração e diâmetro médio Dso entre 150 e 200μιτι.  8. Crystallization seeds, characterized in that they comprise up to .1 to 15% D-limonene or 5 to 10% oanola oil in their composition, are under the most stable polymorphic habit β, and present peaks of the form β for short spacings. 4.60 Ã, 3.88 A or 3.8 Â and 3.73: Â or 3.69 Â, spherical shape, smooth and homogeneous surface, with no agglomeration and mean diameter Dso between 150 and 200μιτι.
9. Uso das sementes de cristalização conforme definido nas reivindicações de 4 a 7 ou 8, caracterizado pelo fato de ser para processos de cristalização de gorduras e estruturação de óleos, em que as referidas sementes atuam na aceleração da cristalização.  Use of crystallization seeds as defined in claims 4 to 7 or 8, characterized in that they are for fat crystallization and oil structuring processes, wherein said seeds act to accelerate crystallization.
10. Uso das sementes de cristalização conforme definidas nas reivindicações de 4 a 7 ou 8, caracterizado pelo fato de ser para orientação do polimorfismo.  Use of crystallization seeds as defined in claims 4 to 7 or 8, characterized in that they are for orientation of the polymorphism.
11. Uso das sementes de cristalização de acordo com a reivindicação 10, caracterizado pelo fato da orientação do polimorfismo ser para forma de maior estabilidade 0.  Use of crystallization seeds according to claim 10, characterized in that the orientation of the polymorphism is for the highest stability form.
12. Uso das sementes de c istalização conforme definidas nas reivindicações de 4 a 7 o 8 caracterizado pel fato de ser na preparação de produtos alimentícios, cosméticos, farmacêuticos e veterinários.  Use of the catalyst seeds as defined in claims 4 to 7, characterized in that they are in the preparation of food, cosmetic, pharmaceutical and veterinary products.
13. Uso das sementes de cristalização, de acordo com. a rei indicação 12, caracterizado pelo fato de o produto alimentício ser selecionado do grupo compreendido por chocolates; recheios para confeitaria; recheios de biscoito; balas que contenham gordura; margarinas; manteigas; spreads (pastas) de chocolate e similares; coberturas; óleo de palma e suas frações; gorduras láuricas e suas frações. 13. Use of crystallization seeds according to. King Indication 12, characterized in that the foodstuff is selected from the group of chocolates; confectionery fillings; cookie fillings; bullets containing fat; margarines; butters; spreads chocolate pastes and the like; coverings; palm oil and its fractions; lauric fats and their fractions.
14. Uso das sementes de cristalização, de acordo cora a reivindicação 13, caracterizado pelo fato de reduzir o tempo» de retenção na temperatura de cristalização era até 901 e reduzir o tempo total da etapa de temperagem era pelo menos 26%, quando aplicadas em produção de chocolates.  Use of the crystallization seeds according to claim 13, characterized in that reducing the retention time at the crystallization temperature was up to 901 and reducing the total tempering step time by at least 26% when applied to chocolate production.
15. Uso das sementes de cristalização, de acordo com a reivindicação 12, caracterizado pelo fato de o produto cosmético ser selecionado do grupo compreendido por produtos de base lipidica, por exemplo manteigas corporais, hidratant.es, batons, excipientes, ácidos graxas ou triacilgliceróis purificados e misturas de ácidos graxos ou triacilgliceróis .  Use of crystallization seeds according to claim 12, characterized in that the cosmetic product is selected from the group consisting of lipid-based products, for example body butters, moisturizers, lipsticks, excipients, fatty acids or triglycerides. and mixtures of fatty acids or triglycerides.
16. Uso das sementes de cristalização, de acordo com a reivindicação 12, caracterizado pelo fato de o produto farmacêutico ser selecionado do grupo compreendido por excipientes farmacêuticos, ácidos graxos ou triacilgliceróis purificados e misturas de ácidos graxos ou triacilgliceróis.  Use of crystallization seeds according to claim 12, characterized in that the pharmaceutical product is selected from the group consisting of pharmaceutical excipients, purified fatty acids or triglycerides and mixtures of fatty acids or triglycerides.
17. Uso das sementes de cristalização, de acordo com a reivindicação 12, caracterizado pelo fato de o produto veterinário ser selecionado do grupo compreendido por medicamentos e alimentos; contendo excipientes de base lipidica . 17. Use of crystallization seeds, according to claim 12, characterized in that the veterinarian product is selected from the group comprised of medicines and foods; containing lipid based excipients.
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