Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/10—Packing paper
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
  • D21H17/24—Polysaccharides
  • D21H17/28—Starch
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
  • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents

Definitions

• the invention relates to the field of food packaging made of paper or cardboard resistant to fatty substances.
• Paper or cardboard packaging is much less suitable for storing food rich in water or fat, because they have a natural tendency to absorb water by chemical affinity, and because fat and gases can penetrate in paper or cardboard by migration or diffusion.
• the packaging is then physically damaged, risking being torn, so that the food risks being put in contact with oxygen and contaminants located outside the packaging, and degrading.
• the surface of cellulosic substrates such as paper or cardboard can be covered with one or more layers of organic and/or mineral materials in order to change the surface properties of said substrates.
• a material is spread on the surface of a cellulosic substrate to form a layer having low or even zero permeability to one or more liquid or gaseous compounds, said spread material is said to constitute a barrier coating layer, or more just a barrier layer.
• paper and cardboard can be covered either with a layer of plastic by laminating a plastic film on their surface, or with a layer comprising a fluoropolymer by coating.
• the plastic layer acts as a physical barrier, by complete occlusion of the pores of the paper or cardboard, preventing water, grease and gases, for example oxygen, from penetrating into the paper or cardboard.
• the fluoropolymer is generally dispersed in a small amount, generally 5 to 10% by weight, in a paper or board coating composition to form a generally non-occlusive barrier coating layer comprising said polymer distributed homogeneously throughout the layer .
• the layer comprising a fluorinated polymer acts as a chemical barrier, by developing a very low surface energy which creates a repulsion for any liquid, water or grease.
• Cargill patent EP3386745 teaches barrier coating compositions comprising starches with a weight average molecular weight ranging from 25,000 Da to 1,000,000 Da and having a glass transition temperature less than or equal to 120° C., to form a barrier layer to mineral oils and gases on a cellulosic substrate, in particular paper.
• This patent also discloses the possibility of adding a plasticizer, glycerol and sorbitol being preferred, in order to give flexibility to the barrier layer in use, without specifying the nature of this flexibility or its usefulness in the manufacture or the use of paper or cardboard, and a fortiori without disclosing the problem of grooving or folding the paper or cardboard.
• Patent application US2002/0142031 by Gilleland et al. discloses a composition for forming flexible grease and oxygen barrier films, one embodiment of said composition comprising a hydroxyethylated or hydroxypropylated starch and having a weight average molecular weight ranging from 100 kDa to 2000 kDa , and another embodiment of said composition comprising a waxy starch which may optionally have undergone a reduction in its molecular weight without disclosing a particular range of weight average molecular weight for these waxy starches.
• Example 18 shows papers coated with a flexible film made of hydroxyethylated thinned starch and fructose that can be folded in half while maintaining an excellent grease barrier.
• Patent US8017249 from Tate & Lyle discloses paper surfacing compositions forming a grease barrier on said paper, said barrier being tested with flat paper and with scored paper.
• the composition of this patent comprises a fluidized, non-crosslinked, hydrophobically modified starch, with octenylsuccinate waxy starch being preferred.
• Said non-crosslinked fluidized starch has between 0.1 and 10% by weight of hydrophobic substitute and has a viscosity of 1000 mPa.s at 35° C. for an adhesive with a dry matter content between 15 and 30% by weight.
• the composition is free of added low molecular weight proteins, sugars or polyols.
• the grooved surfaced papers have higher failure percentages in the “RP2” oil penetration test than the surfaced papers tested flat: the grooved papers therefore have a lower resistance to grease than the papers tested flat. The grooving therefore damaged the grease barrier. This patent therefore does not provide a grooving resistant grease barrier.
• paper or cardboard packaging intended to contain foods that release little or no water, but release fat, and being used for a period corresponding approximately to the duration of consumption of the food, generally Qualified as "disposable” or “single-use", paper or cardboard producers need their paper or cardboard to retain its ability to act as a barrier to fatty substances, i.e. to prevent fatty substances from passing through paper or cardboard, following its formatting and during its use. There is a need to form a layer of barrier coating on the paper or cardboard, which is flexible, even which is resistant to scoring and/or folding.
• the cellulosic substrates serving as a basis for the production of grease-resistant food packaging are thin materials, with a thickness less than or equal to 5 mm, particularly less than or equal to 1 mm, and flexible, which can be folded without tearing the paper at the fold.
• these substrates must undergo a "surfacing" operation aimed at forming on their surface a layer of a grease-resistant coating, that is to say having a grease permeability significantly lower than the virgin substrate, and as far as possible, being flexible.
• the flexibility of the assembly consisting of the cellulosic substrate and the barrier coating layer formed on the surface of said cellulosic substrate generally has the weak point of flexibility of said barrier coating layer.
• the flexibility of a grease barrier coating layer is its ability to withstand mechanical stresses while retaining its resistance to grease. There are two types of mechanical stress that food packaging paper or board undergoes: folding and creasing.
• Folding consists of folding the packaging back on itself along a generally straight direction, called a fold.
• the fold can be characterized by the angle traveled by the face of the paper folded on the opposite face, which can therefore range from 0°, that is to say no folding, to 180°, that is to say folding with physical contact between the two sides of the packaging.
• the fold can also be characterized by the application, or not, of a localized mechanical force at the level of the folding zone in order to form a physically well-marked fold, that is to say by forming an obtuse or acute angle. and not by forming a curve.
• Folding at an angle of 180° with the application of a mechanical force to form the fold is the most extreme folding condition, which makes it possible to test the maximum limit of the flexibility of paper or cardboard packaging, and which is a operation applying mechanical stresses on the packaging greater than the stresses applied by grooving.
• the grooving of paper or cardboard is a localized deformation of the surface of a paper or cardboard to produce a groove therein, that is to say a bendable zone. This consists of the application of a translational force in a direction perpendicular to the surface of the paper, over a certain length, using a convex profiled mechanical part, generally rounded in order to avoid cutting the paper.
• the paper or board is then moved down below the groove, creating a bulge on the side opposite the grooved side.
• the paper or cardboard does not see their resistance decrease, and the subsequent folding at 90° or 180° at the level of the groove must be possible without breaking said paper or cardboard.
• the ability to crease a paper or cardboard depends on both its weight and its thickness. Thus, it is generally possible to score paper or cardboard with a weight greater than or equal to 170 g/m2 and/or a thickness ranging from 0.17 mm to 0.6 mm.
• Flexibility means that the paper or cardboard covered with the barrier coating layer must have resistance to the penetration of fatty substances after grooving or folding that is as good as said paper or cardboard. before grooving or bending.
• a first object is a layer of barrier coating deposited on a cellulosic substrate comprising, preferably consisting of:
• non-crosslinked liquefied starch having a weight-average molecular mass greater than or equal to 3,000 kDa, preferably chosen from non-crosslinked liquefied waxy starches, white dextrins, white dextrins derived from waxy starch,
• a second object is a barrier coating composition comprising, preferably consisting of:
• non-crosslinked liquefied starch having a weight-average molecular mass greater than or equal to 3,000 kDa, preferably chosen from non-crosslinked liquefied waxy starches, white dextrins, white dextrins derived from waxy starch,
• a polyol chosen from sorbitol, xylitol, maltitol, or glycerol, preferentially from sorbitol, xylitol, maltitol, preferentially sorbitol,
• the mass of said polyol present in said barrier coating composition being equal to from 1 to 60% of the mass of said non-crosslinked fluidized starch, preferably from 3 to 30%, and more preferably from 5 to 13% .
• a third object is the use of a barrier coating layer according to the first object of the present application, on a paper or a cardboard, said barrier coating layer being flexible, preferably being resistant to grooving and/or folding.
• coating layer means a layer covering the surface of a cellulosic support or substrate, in other words located on the surface of said support or substrate, and not in said support or substrate.
• barrier to fatty substances or “barrier to grease”
• the applicant means the property of the barrier coating layer of being poorly permeable, or even of being impermeable, to solid or liquid fatty compounds, preferentially to liquid fatty compounds at temperatures greater than or equal to 20°C, the latter fatty compounds possibly being solid at temperatures below 20°C.
• These compounds can be organic and of natural origin, such as animal fat and vegetable oils, or organic and of synthetic origin such as mineral oils.
• the barrier coating layer is resistant to animal fats and to vegetable fats, preferentially to vegetable fats, and more preferentially to vegetable oils.
• This resistance is characterized by a breakthrough time of said greases according to the ASTM F119-82 test, greater than or equal to 15 minutes, preferably greater than or equal to 20 minutes, preferably greater than or equal to 25 minutes, preferably greater than or equal to 30 minutes, preferably greater than or equal to 35 minutes, and most preferably greater than or equal to 40 minutes.
• the barrier coating layer that is the subject of the present application is characterized by an oxygen transfer rate of less than or equal to 10 cubic centimeters per square meter per day under a pressure of 1 bar (denoted cm3 /m2.day.1bar), preferably less than or equal to 5 cm3/m2.day.1bar, more preferably less than or equal to 1 cm3/m2.day.1 bar, and most preferably less than or equal to 0.1 cm3/ m2.day.1bar.
• Oxygen transfer rate can be determined by ASTM-D3985-17.
• the barrier coating layer which is the subject of the present application is characterized by a resistance to grease of at least 15 minutes according to the adapted ASTM F119-82 test and by a lower resistance to oxygen or equal to 10 cm3/m2.day.1 bar according to the ASTM-F1927 test.
• the barrier coating layer has a thickness of less than or equal to 7 microns, preferably less than or equal to 5 microns, more preferably less than or equal to 3 microns, and most preferably less than or equal to 1.5 microns. In addition, the barrier coating layer has a thickness greater than or equal to 0.5 micron, preferably greater than or equal to 1 micron.
• cellulosic support or cellulosic substrate is meant a flat material composed of virgin or recycled cellulose fibers glued together, for example by a glue based on cationic starch.
• This support can have a weight ranging from 10 g/m2 to 600 g/m2, preferentially from 15 g/m2 to 500 g/m2, preferentially from 20 g/m2 to 400 g/m2, preferentially from 25 g/m2 to 300 g/m2, and most preferably from 30 g/m2 to 200 g/m2. It can be a sheet of paper or cardboard.
• the cellulosic substrate can be kraft paper.
• the cellulosic support is a paper or a cardboard directly from the wet end of the paper or cardboard manufacturing process, or from the wet end and having undergone solely mechanical treatments in order to change its surface condition.
• the paper or cardboard according to this embodiment has not been treated by a surfacing or coating operation. Its surface condition can be described as “virgin”.
• the paper or cardboard has a Bendtsen porosity less than or equal to 700 mL/min, preferably less than or equal to 600 mL/min, preferably less than or equal to 500 mL/min, preferably less than or equal to 400 mL/min, preferably less than or equal to equal to 300 mL/min, preferably less than or equal to 200 mL/min, preferably less than or equal to 100 mL/min, and most preferably less than or equal to 50 mL/min.
• the cellulosic support is a virgin paper having:
• - a basis weight ranging from 10 to 120 g/m2, preferably from 15 g/m2 to 110 g/m2, preferably from 20 g/m2 to 100 g/m2, and most preferably from 25 g/m2 to 90 g/m2,
• the cellulosic support is a virgin cardboard having:
• - a weight ranging from 200 to 500 g/m2, preferably from 200 to 400 g/m2, preferably from 200 to 350 g/m2,
• Bendtsen porosity less than or equal to 200 mL/min, preferably less than or equal to 100 mL/min, less than or equal to 75 mL/min, and most preferably less than or equal to 50 mL/min.
• the barrier coating layer can be deposited on the cellulosic support by any known surfacing technique, such as the size-press (in English the "size-press”), the film press (in English the “film-press “), or the curtain coating (in English the “curtain coating”).
• the barrier coating layer deposited on the cellulosic support has an average surface weight less than or equal to 15 grams per square meter of said cellulosic substrate, noted g / m2, preferably less than or equal to 10 g / m2, more preferably less than or equal to 5 g/m2, even more preferably less than 5 g/m2.
• the barrier coating layer deposited on the cellulosic support has an average surface weight ranging from 0.5 to 5 grams per square meter of said cellulosic substrate, preferably from 1 to 4.5 g/m2 , more preferably from 2 to 4 g/m2, and most preferably from 2.5 to 3.5 g/m2.
• the Applicant means a barrier coating layer capable of withstanding the grooving operations, also called creasing, and/or bending operations required for shaping the cellulosic substrate, for example the folding of a cardboard box to make a box, or during its food use, or during the packaging of a foodstuff in paper by shaping by hand so that said paper is in contact with said commodity. That is to say which retains permeabilities to fatty substances and/or gases after the paper covered with the barrier coating layer has been grooved or folded, equal to, or close to, the permeabilities before grooved or folded.
• the barrier coating layer that is the subject of the present application is characterized by a resistance to grease after bending at 180° with marking of the fold, that is to say by a breakthrough time of said grease according to the ASTM F119-82 test. after folding at 180° with marking of the fold, greater than or equal to 15 minutes, preferably greater than or equal to 20 minutes, preferably greater than or equal to 25 minutes, preferably greater than or equal to 30 minutes, preferably greater than or equal to 35 minutes, and most preferably greater than or equal to 40 minutes.
• the resistance of the barrier coating layer to grooving can be evaluated by comparing the permeability to fatty substances and the Gurley or Bendtsen porosities before and after a grooving operation, for example on a "mini standard” device from "CreaseStream". , of a paper coated with a layer of barrier coating.
• the resistance of the barrier coating layer to folding can be evaluated by comparing the permeability to fatty substances before and after a folding operation, preferably a 180° folding operation with marking of the fold, in order to express the relative variation: 100 x [(breakthrough time after bending) - (breakthrough time before bending)] / (breakthrough time before bending).
• the grease-resistant barrier coating layer that is the subject of the application is characterized by a relative variation in the breakthrough time measured according to the ASTM F119-82 test greater than or equal to -30%, preferably greater than or equal to -25%, preferably greater than or equal to -20%, preferably greater than or equal to -15%, preferably greater than or equal to -10%, and most preferably greater than or equal to -5%.
• the barrier coating layer that is the subject of the present application is useful when it is formed on packaging paper or cardboard, preferably on paper or cardboard for primary food packaging, preferably on paper or cardboard for packaging food or prepared meals.
• These foods can be solid, liquid or pasty, preferably solid or pasty, and most preferably solid. Examples of solid foods are sandwiches, burgers, fries, baked or hash browns, vegetable salads, mixed salads, cookies, cakes, pastries, confectionery, breads, meats , charcuterie, pâtés, cured meats.
• Food wrapping papers are generally shaped by hand by the merchant to wrap the food in a shape that matches the shape of said food.
• Food packaging boxes are generally shaped beforehand during their production, in order to offer a volume greater than the volume of the food intended to be placed there.
• the food wrapping papers with a grease barrier coating layer can be papers for baking pastries (which corresponds to the English term "baking papers") in the form of a flat film or in the form of a mould, wrapping paper for pastries and confectionery, wrapping paper for meat, cold cuts and salted meats, interlayer papers for meat, cold cuts and salted meats, papers for sandwich or takeaway food packaging.
• the food packaging cartons with a grease barrier coating layer according to the subject of the present application can be shaped into boxes such as take-out meal boxes, sushi boxes, salad boxes, hamburger and fries boxes, pizza boxes, pastry boxes.
• barrier coating layer When the barrier coating layer is deposited on a food wrapping paper, for example hamburger wrapping paper or French fries wrapping paper, said barrier coating layer must persist, even when the The packaging is folded following its shaping and during its handling by the consumer. Ideally, this persistence should be at less equal to the duration of use by the consumer, for example the duration required to consume the food.
• the non-crosslinked liquefied starch useful for the barrier coating layer which is the subject of the present application can be obtained by liquefying a native starch chosen from cereal, legume or tuber starches.
• a native starch chosen from cereal, legume or tuber starches.
• the starch can be chosen from wheat, corn, potato, pea, tapioca and broad bean starches.
• the starch is a corn starch.
• starch chosen from varieties rich in amylopectin of said starches, also called “waxy starch”, from varieties naturally rich in amylopectin, or selected, hybridized, genetically modified to be rich in amylopectin.
• rich in amylopectin or “waxy”, is meant a starch containing at least 80% by weight of amylopectin, preferably at least 85%, more preferably at least 90%, more preferably at least 95%, and most preferably at least 99%.
• the starch is a corn starch rich in amylopectin.
• fluidified starch means a starch having undergone a hydrolysis operation, that is to say an operation aimed at reducing its average molecular weight, which allows a reduction in the viscosity of the adhesives prepared with said fluidized starch.
• the well-known techniques for preparing such liquefied starches are chemical treatments such as oxidation and acid treatments, enzymatic treatments, and hydrolytic dextrinification treatments and more generally pyroconversion treatments.
• non-crosslinked it is meant that the starch has not undergone crosslinking with any crosslinking agent whatsoever, that is to say that it has not undergone a reaction leading to an increase in its molecular weight.
• the thinned starch is a thinned starch by chemical treatment.
• Chemical treatments generally consist of subjecting a starch to the hydrolyzing action of a chemical agent at a temperature generally below 100°C.
• the chemical agent is an acid, oxidizing or peroxidizing compound, and can be implemented in liquid, solid and/or gaseous form.
• These chemical treatments can be carried out on a starch in suspension in water, in an aqueous solution of salts such as sodium sulphate or calcium sulphate, or in a hydroalcoholic solution, to limit the swelling or the bursting of the starch granules.
• Said suspension has a dry matter of less than or equal to 35-40% by weight, usually situated around 10 to 20% by weight.
• the chemical treatments can also be carried out on a dry starch having a humidity in practice of less than 25% by weight, often lying between 8 and 22% by weight.
• the thinned starch is a thinned starch by enzymatic treatment.
• Enzymatic treatments are carried out with enzymes, enzymatic cocktails or microorganisms on a starch in aqueous suspension, on a gelatinized starch or on a glue phase starch.
• the liquefied starch is a white dextrin obtained by hydrolytic dextrinification treatment on a native starch.
• Hydrolytic dextrinification treatments consist of the action of an acid compound on a starch in dry form and at high temperatures, generally between 120°C and 170°C, at very high, can exceed 180°C-200°C.
• the starch is often pre-acidified and pre-dried before being subjected to the treatment temperature, and has a humidity at most equal to 5% by weight during the treatment.
• Such treatments of pyroconversion give thinned starches called white dextrins or yellow dextrins (the latter being also called “British gums”) which are particularly dry, powdery and hygroscopic whose cold solubility is high, even total, in any case very significantly increased compared to to the cold solubility of the starting starch.
• the non-crosslinked liquefied starch is a white dextrin, more preferably a white dextrin of waxy starch, and most preferably a white dextrin of waxy maize starch.
• said non-crosslinked fluidized starch is also an alkylsuccinate modified starch, preferably an alkenylsuccinate modified starch, most preferably an octenylsuccinate modified starch.
• a starch is modified by a hydrophobic substituent attached to said starch in an amount ranging from 0.1% to 10% by weight relative to the weight of modified starch.
• Substitution by a hydrophobic substituent consists of the esterification of the free hydroxyls of starch with one or more hydrophobic molecules.
• the hydrophobic substituent can also be a molecule comprising a hydrophilic part and a hydrophobic part, the hydrophobicity of which is greater than the hydrophilicity.
• the hydrophobic substituent is an alkenylsuccinate, preferably an alkenylsuccinate having 2 to 12 carbon atoms, and more preferably an alkenylsuccinate having 6 to 10 carbon atoms, and most preferably an alkenylsuccinate having 8 carbon atoms. of carbons.
• the hydrophobic substituent is octenylsuccinate, which can be attached to the starch by esterification between the octenyl succinic anhydride and the hydroxyls of the starch, before or after the thinning, preferably after the thinning.
• the octenylsuccinate modified non-crosslinked fluidized starch comprises an amount of hydrophobic group ranging from 0.1 to 10% by weight, preferably from 1 to 4%, and most preferably from 1.5 to 3% by weight, relative to the weight of modified starch.
• the quantity of octenylsuccinate groups attached to the modified starch is determined by gas phase chromatography on a sample of modified starch derivatized in the methyl form and with internal calibration.
• the chromatography column is a DB1 capillary column from J&W Scientific or equivalent.
• the derivatization of the starch in the methyl form is carried out by transesterification with hydrochloric methanol then extraction with chloroform.
• the internal standard is methyl laurate.
• the amount of octenylsuccinate groups attached to the starch is then expressed as a percentage by weight relative to the gross mass of starch sample.
• the octenylsuccinate modified non-crosslinked fluidized starch is obtained by treatment of a waxy starch, even more preferentially by treatment of a waxy maize starch.
• the non-crosslinked fluidized starch useful for the barrier coating layer that is the subject of the present application has a weight-average molecular mass, denoted Mw, greater than or equal to 3000 kDa, preferably greater than or equal to 4000 kDa, plus preferably greater than or equal to 5000 kDa, even more preferably greater than or equal to 6000 kDa, and most preferably greater than or equal to 7000 kDa.
• the non-crosslinked fluidized starch also has a weight-average molecular mass less than or equal to 25,000 kDa, preferably less than or equal to 20,000 kDa, more preferably less than or equal to 15,000 kDa. , even more preferably less than or equal to 12,500 kDa, and most preferably less than or equal to 10,000 kDa.
• the non-crosslinked fluidized starch has a weight-average molecular mass ranging from 3,000 kDa to 25,000 kDa, preferentially from 4,000 kDa to 20,000 kDa, more preferentially from 5,000 kDa to 15,000 kDa, even more preferably from 6,000 kDa to 12,500 kDa, and most preferably from 7,000 kDa to 10,000 kDa.
• the barrier coating layer that is the subject of the present application combines grease resistance and resistance to folding and grooving thanks to the combination of a non-crosslinked fluidized starch of selected weight-average molecular weight and a polyol present at a mass content selected with respect to the mass of said uncrosslinked fluidized starch.
• the non-crosslinked fluidized starch have a weight-average molecular weight in a selected range defined by a lower bound and an upper bound.
• the lower limit of the weight-average molecular weight range of the non-crosslinked fluidized starch can range from 3,000 kDa to 7,000 kDa, preferably be equal to 3,000 kDa, more preferably to 4,000 kDa, more preferably at 5000 kDa, more preferably at 6000 kDa, and most preferably at 7000 kDa.
• This value of the lower limit seems to correspond to the weight-average molecular weight value below which the barrier coating composition has a sufficiently low viscosity to penetrate into the cellulosic substrate, paper or cardboard, and is thus dispersed therein so that a part of said composition cannot contribute to the formation of a barrier coating layer on the surface of the cellulosic substrate, and therefore that the remaining part of said composition which has not penetrated the cellulosic substrate, is not present in sufficient amount to form an effective barrier coating layer.
• the upper limit of the weight-average molecular weight range of the non-crosslinked fluidized starch can range from 25,000 kDa to 10,000 kDa, and preferably be equal to 25,000 kDa, more preferably to 20,000 kDa, more preferably at 15,000 kDa, more preferably at 12,500 kDa. This limit seems to correspond to the weight-average molecular weight value above which the non-crosslinked fluidized starch forms a brittle barrier coating layer, that is to say non-flexible, or at least insufficiently flexible to resist bending and grooving.
• the cross-linked fluidized starch associated with a polyol in a content according to the subject of the application, allows the formation of a flexible barrier coating layer, which resists folding. , in particular to 180° folding with marking of the fold, and to grooving.
• the barrier coating layer comprises a polyol at a content in the range from 5% to 13% by weight relative to the weight of non-crosslinked fluidized starch:
• a barrier coating layer formed on a closed paper with a deposit of 2.5 g/m2 +/- 0.25 g/m2, presents breakthrough times greater than 20 minutes, even reaching 48 minutes. These breakthrough times are almost unchanged following the 180° bend with marking of the fold.
• This layer of The barrier coating is therefore flexible, and sufficiently resistant to grease to be able to be used in food packaging papers or cardboards.
• a sufficiently high and flexible grease barrier coating layer can be formed on laboratory equipment as demonstrated in the examples at a deposit of 2.5 gsm +/-0.25gsm; however, the implementation of a barrier coating composition with such starch and such polyol contents is not possible on an industrial size machine, for at least one of the following two reasons.
• a first reason is that the viscosity of said composition is too high to be correctly applied to the paper by any surfacing technique.
• a second reason is an excessively high water content in said composition, due to the dilution of said composition to reach a viscosity suitable for the industrial machine, then exceeding the water evaporation capacities generally available.
• the weight-average molecular mass of the non-crosslinked fluidized starch is determined using steric exclusion chromatography of the HPSEC-MALLS type (High Performance Size Exclusion Chromatography coupled online with Multiple Angle Laser Light Scattering) . It is expressed in kilodaltons, noted kDa.
• This mass can be measured by steric exclusion chromatography, according to the following protocol:
• HPLC high performance liquid chromatography
• - 3rd column (column connected to the detector): GPC/SEC Suprema 8x300 mm column, particle size 3 pm, porosity 1,000 A, molar mass 100 - 1,000,000 Da, and whose elution solvent is for example a aqueous solution of 0.1 M sodium nitrate, containing 0.02% by mass of sodium azide;
• the weight-average molecular masses can be determined from the spectra obtained, for example by reprocessing the 1st order exponential spectra, using the ASTRA v.8 type analysis software
• the polyol useful for the purpose of the present invention is chosen from sorbitol, xylitol, maltitol, or glycerol, preferentially from sorbitol, xylitol, or maltitol, and more preferentially is sorbitol.
• the mass of polyol present in the barrier coating layer is equal to from 1 to 60% of the mass of non-crosslinked fluidized starch present in said barrier coating layer, preferentially from 3 to 30%, preferentially from 4 to 20%, more preferably from 5 to 13%.
• the barrier coating layer that is the subject of the present application combines grease resistance and resistance to folding and grooving thanks to the combination of a non-crosslinked fluidized starch of selected weight-average molecular weight and a polyol present at a mass content selected with respect to the mass of said uncrosslinked fluidized starch.
• the lower limit of this range can range from 1 to 5% polyol by weight relative to the weight of non-crosslinked fluidized starch, preferably be 3%, more preferably be equal to 4%, and most preferably 5 %. This lower limit seems to correspond to the minimum polyol content required for the latter to provide a plasticizing effect to the barrier coating layer, and thus give it sufficient flexibility to resist bending and grooving.
• the upper limit of the range of polyol content in the coating layer can range from 13 to 30% polyol by weight relative to the weight of non-crosslinked fluidized starch, preferably be equal to 20%, and any preferably at 13%.
• This upper limit seems to correspond to the maximum content of polyol that the barrier coating layer can comprise beyond which the balance between the non-crosslinked fluidized starch and the polyol is broken. Beyond this limit, it seems that the barrier coating layer can no longer be formed correctly on the surface of the paper or cardboard because a non-negligible part of the barrier coating composition penetrates into the cellulosic substrate and is then dispersed therein, which decreases the amount of barrier coating composition effectively available to form an effective barrier coating layer on the surface of said cellulosic substrate.
• the barrier coating layer comprises a hydrophobic modified, preferably octenylsuccinate modified, non-crosslinked fluidized starch having a weight-average molecular mass ranging from 3,000 kDa to 25,000 kDa:
• Such a barrier coating layer can have a sufficiently significant resistance to grease to consider food use under conditions where it would never be folded or grooved, called “flat”, that is to say that it can present a breakthrough time greater than or equal to 10 minutes, or greater than or equal to 30 minutes, according to our adapted ASTM F119-82 test. But when such a layer of barrier coating undergoes bending or grooving, its resistance to grease can be greatly degraded, with a reduction in the breakthrough time which can be at least 30%, and then being less than or equal 20 minutes or even 10 minutes.
• the "flat" grease resistance to the adapted ASTM F119-82 test is always good , or even slightly better, for example with increased breakthrough times of 2 to 7 minutes compared to 1% polyol, and secondly, the resistance to grease is maintained or slightly reduced following a 180° bend with marking of the fold , for example with breakthrough times reduced from 0% to 6%: these polyol contents, associated with a crosslinked fluidified starch of molecular weight according to the subject of the invention, in the barrier coating layer gives the latter a improved flexibility, and sufficient for use in food packaging.
• the grease resistance of said barrier coating layer deteriorates, with breakthrough times falling below 20 minutes, or even 10 minutes. Without being bound by theory, the applicant believes that this decrease in grease resistance is due to the formation of the barrier coating layer in the paper, partly or totally, and not on the paper.
• the barrier coating composition according to the second object of the present application is an aqueous solution, or an aqueous suspension, which, once applied to the surface of the cellulosic support, forms the barrier coating layer according to the first object of the this request.
• the barrier coating composition comprises, preferably consists of:
• sorbitol xylitol, maltitol, or glycerol
• preferentially from sorbitol, xylitol, or maltitol, and more preferentially is sorbitol
• the mass of said polyol present in said barrier coating composition being equal to 1 to 60% of the mass of said non-crosslinked fluidized starch, preferably 3 to 30%, and more preferably 5 to 13%.
• said barrier coating composition comprises at least one additive chosen from synthetic polymers or dyes.
• This barrier coating composition can be a composition to be applied by a so-called cellulosic substrate surfacing technique.
• a barrier surfacing composition is an aqueous solution of non-crosslinked fluidized starch, in other words a glue, which does not contain any solid mineral particles such as pigments, and in which the polyol has been dissolved.
• the purpose of applying this composition is to fill the porosity of the cellulosic substrate, and to reduce the roughness of the surface of said substrate, and to form a barrier coating layer.
• the barrier surfacing composition is applied to a virgin cellulosic substrate.
• the mass percentage of non-crosslinked fluidized starch in the barrier coating composition ranges from 1 to 50% by weight of said composition, preferably from 5 to 30%, more preferably from 10 to 25%.
• the barrier coating composition that is the subject of the present application has a Brookfield viscosity at 20° C. of less than or equal to 300 mPa.s, preferably comprised in a range extending from 100 to 300 mPa.s.
• a third object of the present application is the use of a barrier coating layer according to the first object of the present application on a paper or a cardboard, to form a food packaging, said barrier coating layer being flexible, preferably being resistant to scoring and/or folding.
• the use is made by depositing the barrier coating layer on a virgin paper or cardboard, and more preferably by depositing the barrier coating layer on a virgin paper or cardboard by an operation of surfacing said paper or cardboard with a barrier coating composition according to the second object of the present application.
• the barrier coating layer can thus be "deposited”, that is to say “formed by deposition”, on one side or on both sides of a cellulosic substrate, in order to obtain a resistant cellulosic substrate. to grease and gas on one side only or on both sides.
• Example 1 Characterization of “closed” base paper and “open” base paper
• the base paper used in Examples 1, 2 and 3 is a flexible packaging paper based on virgin fibers which has the characteristics and performance in the ASTM F119-82 grease permeability test of Table 1.
• Example 2 measurement of resistance to grease for a deposit of 1.25 q/m2 +/-0.25 q/m2
• - Stabilys® BA 23 waxy starch modified octenylsuccinate with 1.8-2.2% by weight of octenylsuccinate relative to the total mass of starch, and thinned with hydrochloric acid until reaching a Mw of approximately 3900 kDa, marketed by the applicant,
• - Stabilys® BA 25 waxy starch modified octenylsuccinate with 1.8-2.2% by weight of octenylsuccinate relative to the total mass of starch, and fluidized with acid hydrochloric acid to reach a Mw of approximately 11,000 kDa, marketed by the applicant,
• AOS native waxy starch modified octenylsuccinate up to 1.8-2.5% by weight of octenylsuccinate relative to the total mass of starch, then transformed into a glue at approximately 10% DM, and then hydrolyzed with 0.001% to 0.03% by weight alpha-amylase based on the weight of starch.
• a surfacing composition was prepared comprising a starch chosen from the 4 starches of the previous paragraph and sorbitol according to the protocol for preparing a surfacing composition described in the "methods" section of the present application,
• the surfacing composition was deposited in an amount of 1.25 g/m2 to +/- 0.25 g/m2 according to the paper surfacing protocol described in the “methods” section of the present application.
• the barrier coating layer formed by depositing approximately 1.25 g/m2 of a starch and sorbitol composition has breakthrough times of approximately 5 minutes regardless of the combination of weight average molecular weight of starch and sorbitol content. Such a breakthrough time is indicative of an insufficient grease barrier to allow food use, even temporary.
• the increase in the sorbitol content leads to a “moderate” increase in the breakthrough time up to a sorbitol content of 13%, then to a subsequent reduction in the breakthrough time.
• the folding caused a reduction in the breakthrough times, but in much smaller proportions than for a deposit of 1.25 g/m2.
• the barrier coating layers formed with Stabilys® BA 23 and BA 25 and with sorbitol in the amount of 5 to 13% by weight of starch deposited in the amount of 2.5 g/m2 according to table 7, have breakthrough times ranging from 15 minutes to 48 minutes.
• the breakthrough times after bending are almost equal to the breakthrough times before bending.
• the breakthrough times of the barrier coating layers formed with a starch of Mw 19,000 kDa decreased by ⁇ 5% to ⁇ 53% following folding, regardless of the value of the sorbitol content in said layer.
• the barrier coating layers formed by depositing approximately 5 g/m2 on the closed paper all have breakthrough times greater than or equal to equal to 120 minutes, regardless of the combination of starch and sorbitol content. On the closed paper, the deposit of 5 g/m2 therefore gives extremely grease-resistant barrier coating layers. This amount of deposit even makes it possible to form layers of barrier coating having a breakthrough time greater than 0 minutes on the open paper, although these breakthrough times (5-10 minutes) remain quite insufficient for use in food packaging.
• this folding has caused a strong degradation of the barrier coating layers which then have breakthrough times reduced by 32% to 83% depending on the combinations of Mw of starch and of sorbitol content. These degradations are high regardless of the sorbitol content: the presence of sorbitol did not prevent or moderate these degradations.
• the surfacing compositions are prepared with a “dry starch” content ranging from 5 to 20% so that the Brookfield viscosity at 50° C. is comprised in a range ranging from 100 to 300 mPa.s.
• the surfacing composition is finally passed through an ultrasonic tank to eliminate the air bubbles.
• This device allows the spreading of the surfacing composition on the surface of the paper at an adjustable height, speed and pressure independently and reproducible.
• the spreading speed is set at 8 m/min.
• the pressure is regulated by a system of 6 counterweights each weighing 190 grams.
• This device is equipped with a heating plate with regulated temperature set at 80° C., and an infrared drying device used with a power of 1000 watts.
• the protocol is as follows:
• the spreading is triggered at a speed of 8 m/min with a bar chosen from among bars n°0, 8, 12, 25, and 35, which correspond to application thicknesses ranging from 0 mm to 0.050 mm ( bar 35) and equipped with 4 to 8 counterweights of 190 g,
• infrared drying is set to the power of 1000 watts
• the paper is then conditioned for at least 48 hours in a regulated room at a temperature of 23°C and a relative humidity of 50% +/-2%
• the folding implemented in the present application consists in folding a sheet of paper or cardboard on itself under the action of a 10 kg brass roller with dimensions length 270 mm x diameter 75 mm.
• the sheet of paper or cardboard is folded on itself, so that the fold is parallel to the direction of the paper machine, that is to say the direction of movement of the paper in the industrial machine or the direction of movement of the cylinder in the case of laboratory equipment.
• This fold is made manually by applying light hand pressure along the length of the area to be bent.
• the 10 kg roll is then applied to the area to be bent by rolling it back and forth.
• the bending is carried out in the room regulated in temperature and relative humidity (23°C and 50% RH).
• the grease barrier is evaluated according to the ASTM F119-82 test protocol "standard test method for rate of grease penetration of flexible barrier materials (rapid method)" modified according to the following points:
• the oil which is an "ISIO4" vegetable oil from the Lesieur brand, consisting of 62% rapeseed oil, 21% OIéisol (sunflower oil with a high oleic acid content), 12% sunflower oil and 5% linseed oil,
• the breakthrough control frequency is adapted according to the time required to achieve breakthrough: every 5 minutes for a duration of 0 to 30 min, every 10 minutes for a duration of 30 to 60 min, every 15 minutes for a duration of 60 to 120 minutes. Beyond a duration of 120 minutes, the test is stopped.
• the result of this test is the time in minutes when a first trace of the oil piercing through the paper is observed, called the breakthrough time. If the breakthrough time is less than or equal to 1 minute, then the value of 0 is assigned to the breakthrough time.

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