WO2011020528A1 - Plasterboard panels and methods of making the same - Google Patents

Plasterboard panels and methods of making the same Download PDF

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Publication number
WO2011020528A1
WO2011020528A1 PCT/EP2010/004293 EP2010004293W WO2011020528A1 WO 2011020528 A1 WO2011020528 A1 WO 2011020528A1 EP 2010004293 W EP2010004293 W EP 2010004293W WO 2011020528 A1 WO2011020528 A1 WO 2011020528A1
Authority
WO
WIPO (PCT)
Prior art keywords
viscosity
starch
agent according
slurry
bonding agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2010/004293
Other languages
English (en)
French (fr)
Inventor
Stéphane BILTRESSE
Massimo Bregola
Andrea Forini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cargill Inc
Original Assignee
Cargill Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cargill Inc filed Critical Cargill Inc
Priority to RU2012110215/03A priority Critical patent/RU2509743C2/ru
Priority to US13/391,084 priority patent/US20120148873A1/en
Priority to PL10737768T priority patent/PL2467348T3/pl
Priority to EP10737768.1A priority patent/EP2467348B1/en
Priority to CN201080036812.1A priority patent/CN102498078B/zh
Priority to JP2012525055A priority patent/JP2013502360A/ja
Priority to DK10737768.1T priority patent/DK2467348T3/en
Priority to ES10737768T priority patent/ES2706904T3/es
Priority to BR112012003717A priority patent/BR112012003717A2/pt
Priority to HRP20190015TT priority patent/HRP20190015T1/hr
Priority to CA2771353A priority patent/CA2771353A1/en
Publication of WO2011020528A1 publication Critical patent/WO2011020528A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/38Polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/38Polysaccharides or derivatives thereof
    • C04B24/383Cellulose or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C04B2111/0062Gypsum-paper board like materials

Definitions

  • the present invention relates to plasterboard panels, such as gypsum-based panels, and to methods of making such panels.
  • Plasterboard panels are used in the building industry for interior wall and ceiling construction. They are relatively cheap to produce and install compared to more traditional building materials and methods. Typically, they consist of a core material sandwiched between two sheets of liner material (e.g. paper) but may also be produced with only a single sheet of liner material or, indeed, none at all. Alternatively, a webbing may be incorporated directly into the core material. In any event, the composition of the core material will be instrumental in determining functional properties of the resulting panel (e.g. strength, water-resistance, sound and heat insulation, hardness, etc.).
  • Plasterboard panels are typically formed in a continuous process in which a slurry is provided by mixing dry ingredients with water.
  • the slurry (which will eventually form the core material of the plasterboard) is then deposited and sandwiched between two sheets of liner paper.
  • the resulting product is pressed to the required thickness by a forming plate and allowed to set.
  • the panel may then be cut to size and is dried to remove any excess water.
  • the dry ingredients of the slurry will normally include calcined gypsum, a bonding agent to ensure adhesion between the core material and the liner material, and one or more additives such as foaming agents, fire retardants, biocides, etc.
  • the bonding agent typically consists of starch which is added raw (uncooked) to the plaster slurry. During the manufacturing process, the starch is cooked (or "pasted"), resulting in an increase in viscosity and an increase in water holding capacity (also known as “water retention”). These effects together are detected as an improvement in the board's peeling force (i.e. in adhesion between core and liner materials). Unfortunately, a too great increase in viscosity will also affect migration ability and can, in turn, have a detrimental effect on adhesion.
  • a starch's water holding capacity plays a key role in the proper growth of gypsum crystals. This is most critical at the inter-phase between core material and liner material as the crystals interlock with the paper fibres to enhance adhesion. As such, a high peak viscosity which results in poor migration ability will also lead to reduced adhesion.
  • Acid-thinned starches have also been suggested as possible alternatives to native starches. Compared to native starches, acid-thinned starches exhibit a reduced peak viscosity during the pasting process and therefore better (faster) migration during gelatinisation. Acid-thinned starches are therefore more efficient than un-modified starches in this respect. However, because of their reduced viscosity, they also lead to lower water retention.
  • a bonding agent for use in the manufacture of plasterboard panels characterised in that it comprises a starch material having (i) a cold slurry viscosity of no more than 250 mPa.s, (ii) a peak viscosity of no more than 600 Brabender Units and (iii) a water retention value of no more than 90 g/m 2 .
  • a plasterboard panel comprising a core material and one or more sheets of strengthening material characterised in that the core material comprises a bonding agent as defined above.
  • a method of manufacturing a plasterboard panel comprising the steps of:
  • the bonding agent is a bonding agent as defined above.
  • the present invention provides a bonding agent for use in plasterboard production, and in particular for use in causing and/or improving the adhesion between the plasterboard's core materia! and its one or more liner sheets.
  • plasterboard refers to all types of building panels used in the construction industry. They may also be referred to, in the art, as drywall panels, wallboards, ceiling boards or ceiling linings, cement-boards and gypsum boards. They will be characterised by a core material and, optionally, one or more sheets of strengthening material.
  • the strengthening material will preferably be used to line the core material on one or both of its main surfaces but may also (or alternatively) be incorporated within the core material itself.
  • the strengthening material will preferably consist of a paper material, the thickness and quality of which will readily be determined by a person skilled in the art. Alternatively, a webbing material may be used, especially if it is intended for it to be incorporated within the core material. According to some embodiments, the strengthening material may also include foils, felts, plastics or other sheet materials.
  • the composition of the core material will vary from one manufacturer to another and depending on the intended end-use of the panel. Its main constituent will typically be calcined gypsum, also known as gypsum plaster. It may also include one or more additives such as fibres (typically paper and/or fibreglass), plasticizers, foaming agents, setting- accelerators (such as potash), chelating agents (such as EDTA or starch), mildew- and/or fire-retardants (such as fibreglass or vermiculite), water-proofing agents (such as wax emulsions for lower water absorption), and so on. A skilled person will be able to determine the necessary components of the core material based on his experience and on standard practice in the industry.
  • core materials used in accordance with the present invention will include a specific bonding agent.
  • the bonding agent will comprise a starch material characterised in that it has (i) a cold slurry viscosity of no more than 250 mPa.s, preferably of no more than 200 mPa.s, more preferably of no more than 150 mPa.s and most preferably of no more than 100 mPa.s; (ii) a peak viscosity of no more than 600 Brabender Units (BUs), preferably of no more than 400 BUs, more preferably of no more than 200 BUs, and most preferably of no more than 100 BUs; and (iii) a water retention value of no more than 90 g/m 2 , preferably of no more than 80 g/m 2 , more preferably of no more than 70 g/m 2 .
  • BUs Brabender Units
  • the starch material will have a cold slurry viscosity of between 100 and 150 mPa.s (especially of about 125 mPa.s), a peak viscosity of between 100 and 200 BUs (especially of about 160 BUs), and a water retention value of between 60 and 80 g/m 2 (especially of about 70 g/m 2 ).
  • a cold slurry viscosity of between 100 and 150 mPa.s (especially of about 125 mPa.s)
  • a peak viscosity of between 100 and 200 BUs especially of about 160 BUs
  • a water retention value of between 60 and 80 g/m 2 (especially of about 70 g/m 2 ).
  • starch material may refer to any native or modified starch or starch derivative from any source.
  • the starch material may be (or may be derived from) a native or modified maize starch, waxy maize starch, wheat starch, tapioca starch, potato starch, rice starch, sago starch or a mixture of two or more thereof.
  • the starch material will be a modified starch or a mixture of two or more modified starches.
  • Starch modifications may include physical modification (e.g. by heat treatment), chemical modifications (e.g. etherification, esterification, cationisation or cross-linking) and/or enzymatic modifications.
  • the starch material of the present invention will be a thermally modified starch, advantageously obtained by dry or semi-dry modification.
  • the core material will typically comprise up to 5% of the bonding agent.
  • it will comprise between 0.1% and 5%, in particular between 0.1 and 1%, by weight (based on total dry weight) of the bonding agent.
  • the bonding agent in turn, will preferably comprise the starch material in an amount of at least 50% by weight on a dry weight basis. More preferably, it will comprise at least 70% by weight of the starch material. According to certain embodiments, it may contain at least 80% by weight of the starch material.
  • the bonding agent may contain the starch material in an amount, by weight, of 85% or more, 90% or more, 95% or more, or even 99% or more.
  • the bonding agent will consist of the starch material.
  • the bonding agent of the present invention will not comprise any acid-thinned or enzymatically degraded starches.
  • the bonding agent may comprise one or more additives.
  • a flowing agent such as silica-based products or phosphate salts.
  • these flowing agents need only be added in an amount of 0.1% or less by weight (based on the total bonding agent dry weight).
  • the bonding agents of the present invention will preferably contain 0.1% or less by weight flowing agent, more preferably 0.05% or less, even more preferably 0.01 % or less.
  • It may also comprise one or more hydrocolloids such as xanthan gum, guar gum, pectin and/or carrageenan.
  • the one or more hydrocolloids will be included in the bonding agent in an amount (based on total dry weight) of 5-10%.
  • the bonding agent of the present invention will be mixed with the other so-called dry ingredients of the core material (e.g. calcined gypsum + optional additives) and a slurry will be formed by adding water.
  • the slurry will then be shaped to a desired thickness.
  • One or more sheets of strengthening material may be incorporated within the slurry and/or used to line it on one or more of its surfaces.
  • the slurry, thus shaped, will then be allowed to dry. If necessary, once fully or partially dried, the boards may be finished (e.g. cut to size, coated, treated, etc.). Each of these steps may, advantageously, be performed in a continuous production process. This method is also a part of the present invention.
  • the slurry will be spread out, in a uniform manner, over a sheet of strengthening material (paper, for instance).
  • a second sheet of strengthening material is then applied to the remaining, exposed surface of the slurry, effectively resulting in an enclosed envelope of slurry.
  • the drying step may be carried out in several phases. Thus, for example, it will be preferred to allow the shaped slurry first to set. This can be performed, on the production line, on a series of setting belts.
  • the slurry Once the slurry has set (hardened), it can be cut into panels of a desired length and the drying step can then be completed, in a kiln, drying chamber or multilevel dryer for instance. The dried panels can then be finished (e.g. trimmed) and used.
  • additional steps - such as printing or forming joints - may also be incorporated into the above process.
  • the above process can be performed at higher speeds when using a bonding agent in accordance with the present invention. Without wishing to be bound by theory, it is believed that this is thanks to better modulation of water retention.
  • the resulting plasterboard panels have been found to have improved peel- resistance compared to panels produced with standard bonding agents at the same dosage rates (due to the improved mobility of the present starch materials during the drying step and their superior water holding capacity).
  • this means that the bonding agent of the present invention is able to reduce or prevent peeling off and separation of strengthening materials from the core material of the plasterboard panel.
  • Preferred embodiments of the present invention have been described by way of illustration only. Modifications of these and further embodiments will be apparent to a person skilled in the art upon reading of this disclosure and will therefore be considered within the scope of the present invention. Further embodiments of the present invention will now be described in the following, non-limiting examples.
  • Method 1 Cold Slurry Viscosity (CSV) Principle: a 44% dry basis slurry of the starch material to be tested is made at 25°C. When fully dispersed, a Brookfield viscosity measurement is made.
  • CSV Cold Slurry Viscosity
  • Viscosity is measured in mPa.s with a number 2 spindle at 100 rpm (note: if the viscosity is above the scale maximum (400 mPa.s) the test can be repeated using a no. 3 spindle at 100 rpm).
  • Method 2 Peak Viscosity Principle: the starch material is dispersed in water and subjected to the Brabender Viscosity test, using a Viscograph E (Brabender) apparatus and following the manufacturer's instructions.
  • starch slurry for each starch material to be tested, 480 mg of starch slurry is prepared with 15% by weight of the starch material.
  • the samples are prepared in 600 ml low-form glass or plastic beakers using demineralised water and mixed with a plastic rod or spoon. When homogeneity is achieved, the slurry is poured into the cup of the prepared Brabender viscometer, and the measuring head and sensor are inserted. A 350 cmg cartridge and a revolution speed of 75 rpm are used. The sample is heated from 50 0 C (starting temperature SO) to 95°C (nominal temperature S1 ) at a heating rate of 1.5°C/min. The sample is then held at S1 for 30 min.
  • Viscosity is measured in Brabender Units (BU). Four viscosities can be reported, namely:
  • Hot paste viscosity viscosity after precisely 30 min at 95 0 C
  • water released by a composition during the application of pressure is absorbed by a filter paper.
  • the increase in weight of the filter paper is then used to determine the quantity of water released by the composition and, therefore, its water holding capacity (or "water retention value").
  • the starch material to be tested is batch cooked at 20% dry solids for 30 min at 96°C. 12 parts of the cooked starch (at 20% dry solids) are then added to 100 parts gypsum (such as Kemwhite gypsum - at 66% dry solids) together with water to form a slurry with a final dry solid content of 53% by weight.
  • gypsum such as Kemwhite gypsum - at 66% dry solids
  • the method uses an AA-GWR Gravimetric Water Retention Meter (Model 250), following the manufacturer's instructions.
  • a Blue Ribbon filter paper is weighed (weight 1 : before test).
  • the filter is then placed on the sample plate and covered with a Millipore filter (5 ⁇ m pore size), glossy side up.
  • the cylinder is then placed on the plate with the sealing face upwards.
  • sample D is the most suitable material for use in accordance with the present invention, i.e. with (1) low slurry solubility, (2) a low peak viscosity and (3) high water retention simultaneously.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
PCT/EP2010/004293 2009-08-19 2010-07-14 Plasterboard panels and methods of making the same Ceased WO2011020528A1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
RU2012110215/03A RU2509743C2 (ru) 2009-08-19 2010-07-14 Гипсокартонные панели и способы их изготовления
US13/391,084 US20120148873A1 (en) 2009-08-19 2010-07-14 Plasterboard panels and methods of making the same
PL10737768T PL2467348T3 (pl) 2009-08-19 2010-07-14 Płyty gipsowe i sposoby ich wytwarzania
EP10737768.1A EP2467348B1 (en) 2009-08-19 2010-07-14 Plasterboard panels and methods of making the same
CN201080036812.1A CN102498078B (zh) 2009-08-19 2010-07-14 灰泥板材及其制备方法
JP2012525055A JP2013502360A (ja) 2009-08-19 2010-07-14 プラスターボードパネル及びその製造方法
DK10737768.1T DK2467348T3 (en) 2009-08-19 2010-07-14 PLASTIC PANELS AND METHODS OF PRODUCING THEREOF
ES10737768T ES2706904T3 (es) 2009-08-19 2010-07-14 Paneles de placas de yeso y métodos de fabricación de los mismos
BR112012003717A BR112012003717A2 (pt) 2009-08-19 2010-07-14 painéis de chapa de gesso e métodos de produção dos mesmos
HRP20190015TT HRP20190015T1 (hr) 2009-08-19 2010-07-14 Paneli od žbuke i postupci njihove proizvodnje
CA2771353A CA2771353A1 (en) 2009-08-19 2010-07-14 Plasterboard panels and methods of making the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09010662.6 2009-08-19
EP09010662 2009-08-19

Publications (1)

Publication Number Publication Date
WO2011020528A1 true WO2011020528A1 (en) 2011-02-24

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ID=41664916

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Application Number Title Priority Date Filing Date
PCT/EP2010/004293 Ceased WO2011020528A1 (en) 2009-08-19 2010-07-14 Plasterboard panels and methods of making the same

Country Status (12)

Country Link
US (1) US20120148873A1 (enExample)
EP (1) EP2467348B1 (enExample)
JP (1) JP2013502360A (enExample)
CN (1) CN102498078B (enExample)
BR (1) BR112012003717A2 (enExample)
CA (1) CA2771353A1 (enExample)
DK (1) DK2467348T3 (enExample)
ES (1) ES2706904T3 (enExample)
HR (1) HRP20190015T1 (enExample)
PL (1) PL2467348T3 (enExample)
RU (1) RU2509743C2 (enExample)
WO (1) WO2011020528A1 (enExample)

Cited By (7)

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CN103011701A (zh) * 2011-09-28 2013-04-03 比亚迪股份有限公司 一种玻化微珠保温砂浆及其制备方法
WO2017109459A1 (en) * 2015-12-22 2017-06-29 Saint-Gobain Placo Sas Method for the production of gypsum-based boards and stucco slurry comprising non-pregelatinized migratory starch for use therewith
WO2019018478A1 (en) * 2017-07-18 2019-01-24 United States Gypsum Company PLASTER COMPOSITION COMPRISING AN UNCELLED STARCH HAVING AVERAGE VISCOSITY, AND METHODS AND PRODUCTS THEREOF
US10399899B2 (en) 2012-10-23 2019-09-03 United States Gypsum Company Pregelatinized starch with mid-range viscosity, and product, slurry and methods related thereto
US10464847B2 (en) 2012-10-23 2019-11-05 United States Gypsum Company Pregelatinized starch with mid-range viscosity, and product, slurry and methods related thereto
US10875935B2 (en) 2012-10-23 2020-12-29 United States Gypsum Company Method of preparing pregelatinized, partially hydrolyzed starch and related methods and products
US10919808B2 (en) 2017-07-18 2021-02-16 United States Gypsum Company Gypsum composition comprising uncooked starch having mid-range viscosity, and methods and products related thereto

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GB201309058D0 (en) * 2013-05-20 2013-07-03 Bpb United Kingdom Ltd Composite construction panel having improved substrate board and method for the manufacture thereof
RU2645000C1 (ru) * 2017-01-10 2018-02-15 федеральное государственное бюджетное образовательное учреждение высшего образования "Белгородский государственный технологический университет им. В.Г. Шухова" Сердечник гипсокартонного листа на основе модифицированного гипсового вяжущего

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US2044401A (en) * 1929-08-15 1936-06-16 United States Gypsum Co Core composition and method of manufacturing same
US4667654A (en) * 1985-07-10 1987-05-26 National Starch And Chemical Corporation Pulse combustion process for the preparation of pregelatinized starches
WO1996022311A1 (en) * 1995-01-18 1996-07-25 National Starch And Chemical Investment Holding Corporation Thermally-inhibited pregelatinized granular starches and flours and process for their production
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JP2013502360A (ja) 2013-01-24
EP2467348A1 (en) 2012-06-27
EP2467348B1 (en) 2018-12-19
ES2706904T3 (es) 2019-04-01
RU2012110215A (ru) 2013-09-27
CA2771353A1 (en) 2011-02-24
CN102498078A (zh) 2012-06-13
DK2467348T3 (en) 2019-02-11
BR112012003717A2 (pt) 2016-04-05
CN102498078B (zh) 2015-01-28
RU2509743C2 (ru) 2014-03-20
HRP20190015T1 (hr) 2019-03-08
US20120148873A1 (en) 2012-06-14

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