FR2598148A1 - STARCH-BASED FORMULATIONS. - Google Patents

Abstract

STARCH-BASED FORMULATIONS FOR PRESSURE APPLICATION, FORMING IN THE FORM OF PARTICLES AND FLOWING FREE AT ROOM TEMPERATURE, CHARACTERIZED IN THAT THEY CONTAIN: A. FROM CHEMICALLY MODIFIED STARCH, 72 TO 89 , 58 PARTIES; B. AT LEAST ONE RELEASE LUBRICANT, 0 TO 5 PARTS; C. AT LEAST ONE MELT FLOW ACCELERATOR, 0 TO 5 PARTS; D. A TEXTURING AGENT, 0.02 TO 1 PART; E. OF WATER, 10 TO 22 PARTS, AND IN THIS CASE, I. THE COMPONENTS B ETC SHALL ALWAYS ASSIST AT LEAST 0.4 PARTS AND AT LEAST 5 PARTS; AND II. THE SUM OF THE COMPONENTS A, B, C, D SUMMER IS ALWAYS EQUAL TO 100 PARTS.

Description

STARCH FORMULATIONS

  It is known to treat starch under the application of pressures and to form molded manufactured articles thereof under pressure, for example by injection molding. Preferably, these molded articles are manufactured to contain pharmaceuticals, edible products, chemicals and the like, particularly in the form of pharmaceutical cachets for the administration of specified doses of drugs. These containers generally consist of a container part and a closure part, the two parts adapting exactly to each other to

  the closed state and giving a tightly sealed container.

  The manufacture of these pressure vessels from natural starch is known from the application of

  European Patent No. 84 360 940.8 (Publication No. 118 240).

  In industrial manufacturing, it is necessary to manufacture these shaped articles under pressure, in particular the parts of pharmaceutical seals with very thin walls with the greatest precision and at high speed. In addition, it should

  appear during manufacturing a minimum of defective parts to minimize subsequent checks and interruptions of the machines to be filled.

  Controlling these manufacturing problems has been surprisingly difficult. With the manufacture of parts to

  very thin wall, whose wall thicknesses are for example less than 0.5 mm, these problems are even more intense.

  Very good flow behavior is particularly necessary both in terms of the powder used as raw material (starch mixture based on free flowing starch) and in terms of the entire molding process. by injection or from the angle of the liquid state. To avoid high pressures, the melt should flow as easily as possible and, for mixing with the additives and water, should have a distribution as homogeneous as possible over the entire temperature range at

which it is exposed.

  In addition, the injection molded parts should be easily removed from the mold, and should have good dimensional stability to avoid adhesion to the walls.

  of the tool or deformation during ejection.

  The problem can surprisingly be solved if 1. a starch-based starting mixture is used which is in the form of particles and flows freely at room temperature, which leads, under the conditions of treatment, to a molded article whose wall structure is practically amorphous, 2. the viscosity of the melt at a temperature of 90 20 to 240 C and in particular 140 to 190 C is between 2,500 and 50 Pa.s (= pascal x seconds), preferably 2,000 and 50 Pa.s, and in particular 1,500 and 50 Pa.s, and 3. the glass transition point of the mixture heated in a container closed at 140-1900C is at least equal at 251C, 25 preferably at least equal to 45 C, and in particular greater than 65 C. We manage to obtain these conditions with the

composition defined below.

  The composition specified below makes it possible to operate injection molding machines continuously for 24 hours a day, eliminating substantially all of the

  sources of error or disadvantages mentioned above.

  The present invention therefore relates to formulations basically based on starch, to be treated by application of pressure, which are in the form of fine particles and flow freely at ambient temperatures, characterized in that these formulations contain: Quantity (a) of chemically unmodified starch. 72 to 89, 58 parts (b) at least one lubricant / release agent ..................

  ....... 0 to 5 parts (c) at least one melt flow accelerator ...................... 0 to 5 parts (d) a texturing agent ............. 0.02 to 1 part (e) of water ............... ........ DTD: ..... 10 to 22 parts and in this case (i) the components (b) and (c) together always form at least 0.4 parts and at most 5 parts; and (ii) the sum of components (a), (b), (c), (d) and (e) .. DTD: is always equal to 100 parts.

  It has further been found that these formulations are suitable for use with pressure application processing, for example pressure molding, pressure injection, blow molding, extrusion, etc. These basic formulations may also contain

  other components, as will be described below. Parts 20 are always indicated as parts by weight.

  By chemically unmodified starch is meant a naturally occurring vegetable carbohydrate, consisting mainly of amylose and amylopectin. This starch is obtained, for example, from potatoes, rice, tapioca, mals, barley, oats, wheat and other plants. Likewise, the term "starch with a physically modified structure" means, for example, gelled or precooked starch and starch which is extremely soluble in water, for example starch whose average molar mass has 30 been reduced. This starch or a mixture of such starches can be processed into the specified composition under pressure and at elevated temperatures to form compact molded articles. Preferably, the proportion of physically altered starch relative to natural starch is not more than%, preferably not more than 20%. Natural starch is preferred. Starch (a) is present in the basic formulation, preferably in an amount of 72 to 89.58 parts, preferably from 85 parts and in particular approximately 79 to 83 parts per

  compared to 100 parts of this composition.

  The starch preferably has an amylose content of 0 to% and an amylopectin content of 100 to 30%. We prefer starch

potato.

  Suitable for example as lubricant / release agent (b) animal and vegetable fats, alone or in mixture, in particular hydrated fats,

  preferably those which are solid at room temperature.

  They preferably have a melting point above 500C. As a general rule, these fats are triglycerides whose acid proportions in C14, C16 and C18 are for example C18 (approximately 65%), C16 (approximately 30%) and

C14 (approximately 5%).

  The amount used is preferably between 0 and 5 parts, preferably 0 and 3 parts, in particular 0.6 and

  1.2 parts based on 100 parts of the base formulation.

  These lubricants / mold release agents act simultaneously as softening agents and viscosity lowering agents, so that the addition of special agents

  for this purpose is no longer necessary.

  As melt flow accelerator (c), solid monoet diglycerides are preferred, preferably long chain acids, preferably C14, C16, C18 fatty acids and phosphatides, in particular lecithin. . The amounts of additives which are preferred are between 0 and 5 parts, preferably 0.1 and 2 parts, in particular 0.2 and

  1 part, of these individual compounds or of a mixture of these compounds compared to 100 parts of the basic formulation.

  The sum of components (b) and (c) is always at least 0.4 parts, and it is preferably between 0.8 and 2.0 parts relative to 100 parts of the formulation

basic.

  The texturing agent (d) is titanium dioxide or silicon dioxide or a mixture of these compounds. It has been found that these compounds ensure a free flow of the starting material which is in powder form at room temperature and still prevent during the treatment that bridges are formed in the hopper and in the screw which could

  prevent the introduction of the raw material into the screw.

  Thanks to the addition of these components, the introduction is always done in an equal and constant manner and at the same speed from cycle to cycle.

  There is therefore no need to granulate or otherwise pretreat the starting material.

  The amount of texturing agent is preferably between 0.02 and 1 part relative to 100 parts of the base formulation. With regard to titanium dioxide, the optimum quantity to be added is approximately 0.4 parts, and with regard to silicon dioxide, it is approximately 0.1 parts, these two values being given relative to to 100 parts of the basic formulation. One can naturally add more titanium dioxide or silicon dioxide. This excess then acts as a load and can

  still negatively influence the properties of the product.

  The water is present in an amount of 10 to 22 parts, preferably from 10 to 20 parts, preferably from 15 to 19 parts per 100 parts relative to 100 parts of the basic formulation, the preferred intervals before, in particular , apply for

thin-walled objects.

  The process conditions depend mainly on the starch used, components (b) to (e) and

  additives mentioned in more detail below, which are present in the addition when necessary.

  The higher the water content, the lower the temperatures and pressures that can be chosen in the injection molding process. The lower the water content, the higher the pressures and temperatures to be chosen. Choosing the right pressures and temperatures is

  simple and any expert can do it easily.

  The molding pressures of thicker walled articles are between 300 x 105 N / m2 and 3000 x 105 N / m2, and for thinner walled articles, they are between 600 x 105 N / m2 and 3000 x 105 N / m2, preferably 900 x 105 N / m2 and 1,500 x 105 N / m2. For extrusion, pressures of a few bars can be used, for example less than 10 bars, this being a function of the water content. The working temperatures are especially between 80 and 240 ° C., preferably 130 and 210 ° C. and in particular 150 and 190 ° C. Devices can be used which are known per se, for

  example of injection molding machines or extruders.

  For the same water content, potato starch can be more easily treated, that is to say under conditions of pressure and temperature lower than wheat starch. The degree of difficulty increases in the following order: potato starch, wheat starch, mals starch, rice starch. So we prefer potato starch and

  wheat starch, especially potato starch.

  In the starch formulations mentioned above, the starch can be replaced up to a maximum of%, but preferably not more than 20%, by a material or a mixture of other hydrophilic materials. These other hydrophilic materials are polymers, e.g. gelatin, vegetable proteins, e.g. sunflower protein, soy protein, cottonseed protein, peanut protein, rapeseed protein, blood protein, milk protein egg, acrylated proteins; water-soluble polysaccharides, for example: alginates, carrageenans, guar gum, agar-agar, gum arabic and related gums (ghatti gum, karay gum, gum tragacanth), pectin; water-soluble derivatives of cellulose: alkylcelluloses,

  hydroxyalkylcelluloses and hydroxyalkylalkylcelluloses, for example: methylcellulose, hydroxymethylcellulose, hydroxy35 ethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, cellulose esters and hydroxy- esters

  alkylcellulose such as, for example, cellulose acetylphthalate (CAP), hydroxypropylmethylcellulosephthalate (HPMCP); carboxyalkylcelluloses, carboxyalkylalkylcelluloses, carboxyalkylcellulose esters such as, for example: carboxymethyl5 cellulose and their alkali metal salts; water-soluble synthetic polymers such as, for example, polyacrylic acids and polyacrylic acid esters, polymethacrylic acids and esters of polymethacrylic acids, polyvinylacetates, polyvinylalcohols, polyvinylacetatephalates (PVAP), polyvinylpyrrolidone, polycrotonic acids; also suitable are phthalated gelatin, gelatin succinate, crosslinked gelatin, shellac, water-soluble chemical derivatives of starch, cationically modified acrylates and methacrylates having for example a tertiary or quaternary amino group, such as the diethylaminoethyl group, which can be quaternized if desired; and

other similar polymers.

  Preferably, the starch is not replaced by a

  more than about 3 to 10% of these compounds.

  To the basic formulation mentioned above, it is also possible to add softening agents, in an amount preferably between 0, 5 and 10 parts, in particular 0.5 and 5 parts, relative to the 100 parts specified. Alternatively, one can just as well mix the starting materials with liquid additives until they are completely absorbed and a tightly flowing mixture is formed. Excess or sticking of individually mixed particles between them should be avoided. These softening agents are, for example, polyalkylene oxides, such as, for example, polyethylene glycol, polypropylene glycol, polyethylenepropylene glycol; low molecular weight organic softening agents such as, for example, glycerin, glycerine mono-, di- and tri-acetate,

  propylene glycol, sorbitol, sodium diethylsulfosuccinate, triethyl citrate, tributyl citrate.

  The sum of the parts by weight of the water and the softening agent should preferably not exceed the maximum levels specified for the water. Preferably therefore, the sum of

  the water and the softening agent is equal to 10 to 22, preferably 10 to 20, and in particular 15 to 19 parts relative to 100 parts of the basic formulation.

  You can also dye the mixture. Dyes which are suitable are, for example, known azo dyes or organic or inorganic pigments, or dyes existing in their natural state. Preference is given to mineral pigments such as iron oxides or titanium oxides, which are known per se, in a concentration of 0.001 to 10%, preferably 0.5 to 5%,

  relative to the weight of all components.

  As mentioned above, the formulation according to the present invention can be used in all types of molding technique with application of pressures, such as for example pressure molding, injection molding, molding or extrusion. blowing, and it is possible to prepare items such as containers, bottles,

  sheets, bags, films, packaging materials, tubes, bars, pharmaceutical seals, in all of their various known variations.

  The invention will be explained in more detail using the

following examples.

EXAMPLE 1

  A composition consisting of 81 parts of natural potato starch, 1 part of hydrated triglyceride containing fatty acids C18 / C16C14 in a ratio of / 31/4% by weight, 0.7 part of lecithin, 0.3 part of titanium dioxide and 17 parts of water, is mixed in a powder mixer for 10 minutes. After that, a free flowing powder is obtained. This powder is loaded into the hopper of an injection molding machine and, at a temperature of 180 ° C. and a pressure of 1500 bars, it is injected into an injection molding tool intended for producing the body of the seal. and the closing part, the wall temperature of which is 40 C. After cooling and ejection from the mold, a body and a cover are obtained i ct i O 'L 0 ii Ol iiii O' ii 0 iii OI i 9'0 iiii O'Z I iii 0óL i Z'O I iiiii - iii ii i I 3 O'S iiii 5'0 iiii 6'0 ii I iii 5'1 ii ii _ i% I iiii aulq: 3 ap 81 P iI *. I 't I i II aI 6O i? 1 i <' 1 i a0Le: a6aA assela ii I. i 'L i {iii O'Z a ", ii" i 6'0 i si I ini - i (84ZI ii O0'ú ia, ii JoA L6ouoN 08 # ii RI iiii 06'Z ia it '! Ue asseJ6 ii - SO' Zi iiii 8'0 i *, ii i '. 0 ti si 2L9 i Z iii uAl'i i çZ <i} G [ep6, aA asseJI ii I ii 00'09 i 918 i1S iii I i aJelew I SZ <SL j aJJQt Op awUOd i 1it ii II i Sz <51 I JJQd ap PLWWOd i ú1L ii 96'úL i aJal Op Ouuod Zt iii I ii Z'SL i eDoldel i 1 iiiii II ii 5Z'08 I Za i 01t iii III 0'6L i zia I 6 i {i I i 1 0'8L i siew i8 1 I 0 '<L i Stew iziiii aLewlue ii Jatieew i '6i? La i 9 ii 0'S6 i sle q i5 1 {iii 0au L i wi ui 191Ui i 0 ii 9'86 i 9JJ Op S iiiiii 0O'8 i JJ9 9p Odi Z iii I i 9 9'89 i OJJQa ap adumod ú I iii I oj5 a iQew i 00 <e51 ajjoi op edwOd iii% I ad ^ '| ii I00 1 i NOUIWVi i {d3 ii Naw% d IoiN NO3) i NOO 1HVl Sc OE ta3 api aU Li Qdk.I i ad, (i%, (O INVSOdWOO iiiiii Si 01 odA, (q INVSOdW i I ne1a'aVL T nealqep al uolas saqueAins suoTr elnuio; sal quesTTTTn ua sanbolvue sieplnsga sap quaTqqo uo saqDrD ap satired sap sqnvjip ap 4Tnpga quaw - awmxlxa aiquiou un, nb aDoaqyp au uo, l qa auqDew el ap uot; dni -.aqu sues' VZ ans sainaq AUTqDew eI IaqiDew ATlle; quawalToDe nad uo 'abulgw aD DOaAv / rlduia V auTqDeu aun ans IaITe / u 4uawgsTP 7nad uo, I anb aiIauUOTSUaWTP 9gqTlTqes auuoq ap aMDPD ap S 8L86Sgz

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Claims (18)

  1.- Starch-based formulations to be treated by applying pressure, being in the form of particles and flowing freely at room temperature, characterized in that they contain: Quantity (a) of unmodified starch chemically. 72 A 89.58 parts (b) at least one lubricant / release agent ............................ 0 to 5 parts ( c) at least one melt flow accelerator ......   .......... 0 to 5 parts (d) a texturing agent ............. 0.02 to 1 part (e) of water ... ......................... 10 to 22 parts and in this case (i) the components (b) and (c) together always form at least 0.4 parts and not more than 5 parts; and (ii) the sum of components (a), (b), (c), (d) and (e). CLMF: is always equal to 100 parts.   2. Formulation according to claim 1, characterized in that the chemically unmodified starch consists of a carbohydrate existing in the natural state obtained from potato, rice, tapioca, mats, barley,   oats, wheat or other plants, gelled starch, precooked starch and / or starch which is extremely soluble in water. 3. Formulation according to any one of claims 1 or 2, characterized in that it contains starch in   concentration of 75 to 85 parts, and preferably 79 to 83 parts, compared to 100 parts of this formulation.   4.- Formulation according to any one of claims 1 to 3, characterized in that the starch consists   potato starch or wheat starch.   5. Formulation according to any one of Claims 1 to 4, characterized in that the component (b) is   present in concentration from 0 to 3 parts, preferably from 0.6 to 1.2 parts, relative to 100 parts of the formulation basic.   6. Formulation according to any one of Claims 1 to 5, characterized in that the component (b) is   consisting of an animal and / or vegetable fat, in particular these fats which are preferably solid at room temperature and whose melting point   is preferably greater than 50 C.   7.- Formulation according to claim 6, characterized in that these fats consist of a triglyceride containing proportions of acids C14-, C16- and   C18-, preferably for C18 (about 65%), for C16 (about 30%) and for C14 (about 5%).   8.- Formulation according to any one of claims 1 to 7, characterized in that the component (c) is   present at a concentration of 0.1 to 2 parts, preferably 0.2 to 1 part, relative to 100 parts of the formulation basic.   9. Formulation according to any one of Claims 1 to 8, characterized in that the component (c) is   consisting of a mono- and / or a di-glyceride, preferably long chain acids, preferably C14- fatty acids,   C16-, C18- and phosphatides, in particular lecithin.     o10.- Formulation according to any one of Claims 1 to 9, characterized in that the sum of the components (b) and (c) is at least equal to 0.8 to 2.0 parts per   compared to 100 parts of the basic formulation.   11.- Formulation according to any one of claims 1 to 10, characterized in that the texturing agent (d) consists of titanium dioxide and / or silicon dioxide. 12.- Formulation according to claim 11, characterized in that the titanium oxide is present in a concentration of about 0.4 part and the silicon oxide in concentration   about 0.1 parts relative to 100 parts of the formulation.   13.- Formulation according to any one of claims 1 to 12, characterized in that water is present in   concentration of 10 to 20 parts, preferably 15 to 19 parts, relative to 100 parts of the basic formulation.   14.- Formulation according to any one of claims 1 to 13, characterized in that the starch is replaced by   another hydrophilic material in quantities up to   %, preferably not exceeding 20%, and preferably between 3 and 10% (relative to starch).   15.- Formulation according to claim 14, characterized in that this hydrophilic material is chosen from, for example, gelatin, vegetable proteins, for example sunflower protein, soy proteins, cotton seed proteins, peanut proteins, proteins rapeseed, blood proteins, egg proteins, acrylated proteins; water-soluble polysaccharides, for example: alginates, carrageenans, guar gum, agar-agar, gum arabic and related gums (ghatti gum, karay gum, gum tragacanth), pectin; water-soluble derivatives of cellulose: alkylcelluloses, hydroxyalkylcelluloses and hydroxyalkylalkylcelluloses, for example: methylcellulose, hydroxymethyl15 cellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose such as cellulose esters and cellulose esters , celluloseacetylphthalate (CAP), hydroxypropylmethylcellulosephthalate 0 (HPMCP); carboxyalkylcelluloses, carboxyalkylalkylcelluloses, carboxyalkylcellulose esters such as, for example: carboxymethylcellulose and their alkali metal salts; water-soluble synthetic polymers such as, for example, polyacrylic acids and polyacrylic acid esters, polymethacrylic acids and esters of polymethacrylic acids, polyvinylacetates, polyvinylalcohols, polyvinylacetatephalates (PVAP), polyvinylpyrrolidone, polycrotonic acids; also suitable are phthalated gelatin, gelatin succinate, crosslinked gelatin, shellac, water-soluble chemical derivatives of starch, cationically modified acrylates and methacrylates having for example a tertiary or quaternary amino group, such as group   diethylamino4thyle, which can be quaternized if desired; and other similar polymers.   16.- Formulation according to any one of Claims 1 to 15, characterized in that this basic formulation   also contains softening agents in an amount of 0.5 to 10 parts, in particular 0.5 to 5 parts, relative to the 100 parts specified, preferably of polyalkylene oxides, of glycerin, of mono, di- and glycerin tri-acetate; propylene glycol, sorbitol, sodium diethyl sulfosuccinate, triethyl citrate, tributyl citrate.   17.- Formulation according to any one of claims 1 to 16, characterized in that the sum of the parts in   weight of water and softening agent does not exceed the maximum specified water content.   18.- Use of a formulation according to any one   of claims 1 to 17, intended for use in treatment by application of pressure.   19.- Use of a formulation according to any one   of claims 1 to 17 in pressure molding, injection molding, molding or extrusion blow molding.   20.- Articles made from such a formulation   as described in any one of claims 1 to 17,   manufactured with pressure application.   21. Pharmaceutical seals according to claim 20.