CA1049211A - Process for producing molded article composed of pullulan - Google Patents
Process for producing molded article composed of pullulanInfo
- Publication number
- CA1049211A CA1049211A CA219,180A CA219180A CA1049211A CA 1049211 A CA1049211 A CA 1049211A CA 219180 A CA219180 A CA 219180A CA 1049211 A CA1049211 A CA 1049211A
- Authority
- CA
- Canada
- Prior art keywords
- pullulan
- molded article
- screw
- process according
- water
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/12—Amylose; Amylopectin; Degradation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Dental Preparations (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A molded article composed of pullulan, is obtained by incorporating 1 to 50 weight % of water into the pullulan, and then subjecting the pullulan to extrusion- or injection-molding by use of a molding machine equipped with a plasticizing screw at a temperature in the range from 40° to 150°C. The thus obtained molded article is tough and transparent and has gas-barriering property and oil resistance. Furthermore, the molded article is hydrophylic and hence is spontaneously decomposable with ease in the air and in the ground.
A molded article composed of pullulan, is obtained by incorporating 1 to 50 weight % of water into the pullulan, and then subjecting the pullulan to extrusion- or injection-molding by use of a molding machine equipped with a plasticizing screw at a temperature in the range from 40° to 150°C. The thus obtained molded article is tough and transparent and has gas-barriering property and oil resistance. Furthermore, the molded article is hydrophylic and hence is spontaneously decomposable with ease in the air and in the ground.
Description
~049211 1 This invention relates to a process for pro-ducing a molded article from pullulan quickly and at a low cost.
Heretofore, a molded article of such thermo-plæstic resin as, for example, polyethylene, polyvinyl chloride, polystyrene, polypropylene or polyamide has been produced by melting the resin by means of an ex-truder or an injection molding machine, and then subjecting the resulting melt to extrusion- or injection-molding. When the above-mentioned procedure is adopted, however, the production of a molded article from such resin as pullulan is quite difficult since the pullulan, when used in the form of an anhydride, does not soften but decompose at above 200C.
The pullulan used in the present invention is a linear high polymer having repetition units, bonded through a-1,6-linkages, of maltotriose whlch is a trimer of glucose, and has a molecular structure represented by the formula, ~ .
_l _ o o~
O O ~
V-~
o o tq~ _ . . o o o~
'' ' V~L
o o o~
o o~
~o o7 ~v~L
o o o~
V ~L
o ~ o~
1 wherein n represents the polymerization degree, and is an integer of 20 to 10,000.
As is well known, pullulan is a glucan obtained by subjecting a pullulan-producing strain, e.g.
Pullularia ~ullulans, to submerged culture in a medium containing sucrose, starch syrup or glucose as a carbon source, and the molecular weight thereof is ordinarily in such a broad range as from 10,000 to 5,000,000 (refer to H. Bender, J. ~ehmann et al: Biochem. Biophys.
Acta, 36, 309 (1959); and Seinosuke Ueda: Kogyo Kagaku Zasshi (Journal of the Chemical Society of Japan Industrial Chemistry Section), 67, 757 (1962)). Being produced by the above-mentioned method, pullulan has such excellent characteristics that it is inexpensive and gives a molded article which is tough and trans-parent, has gas-barriering property and oil resistance, is hydrophilic, is spontaneously decomposable in the air and in the ground, and does not cause any public pol-lution due to combustion, i.e. does not generate harmful gas nor intense heat at the time of combustion.
For the production of a molded article from a composition containing pullulan as a main ingredient, there has hitherto been adopted only such flow film-forming process that an aqueous pullulan composition is defoamed, flowed on the surface of a smooth metal plate or the like, and then dried, and the resulting film is peeled off from the plate. However, the said process requires many operational steps and long drying time, so that much cost and time have been needed for produc-tion of the molded article. For the above reasons, it 1049Zl~
1 has entirely been :impossible to utilize molded articles in which the characteristics of pullulan have been displayed.
As the result of extensive studies on the above-mentioned points, the present inventors could easily mold pullulan by controlling the amount of` water to be incorporated into the pullulan and selecting the molding temperature and the molding machine employed, and discovered a process for producing at a high speed with low cost a molded article to which had been im-parted the aforesaid characteristics of pullulan.
Based on this discovery, the inventors have acçomplished the present invention.
An object of the present invention is to pro-vide a novel process for producing a molded article composed of pullulan.
Another object of the invention is to provide a process in which a molded article composed of pullulan can be produced at a high speed with low cost.
A further object of the invention is to provide a molded article composed of pullulan which is tough and transparent, has gas-barriering property and oil resistance, and is spontaneously decomposable in the air and in the ground.
Other objects and advantages of the invention will become apparent from the explanation given below.
In accordance with the present invention, there is provided a process for producing a molded article composed of pullulan, characterized in that pullulan is incorporated with 1 to 50 weight % of water, 1~49Zll 1 and then subjected to extrusion- or injection-molding by use of a molding machine equipped with a plasticizing screw at a temperature in the range from 40 to 150C.
~he molecular weight of the pullulan used in the present invention is preferably from 50,000 to 1,000,000 in view of the moldability thereof and the mechanical strength of the resulting molded article.
~he amount of water to be incorporated into the pullulan in the present process is 1 to 50 weight ~, preferably 5 to 30 weight ~0. If the amount of water is less than 1 weight %, the pullulan can be plasticized with quitc difficulty, while if the amount thereof is more than 50 weight %, the pullulan can be easily plasticized, but is undesirably increased in adherence to metal to make the handling thereof extremely difficult. At the time of molding, the pullulan may be in any form of powders, flakes or pellets. According to the present invention, pullulan may be incorporated with water in any manner. For example, pullulan may be moistened by allowing it to stand in a high humidity atmosphere, or pullulan in the form of powders, flakes or pellets may be uniformly sprayed with water to absorb the water therein. Further, pullulan may be incorporated with, in addition to water, a polyhydric alcohol such as glycerin, ethylene glycol, polyethylene glycol, sorbitol, propylene glycol, polypropylene glycol or maltitol, dimethyl sulfoxide, plasticized PVA, high molecular weigh~ amylose or gelatin as a plasticizer or softener.
Even when pullulan is additionally incorporated with one or more of pigments, dyes and fillers, a molded 1`
-- S
10492~1 article can successfully be obtained without any injury during the molding operation.
In the present invention, the molding temperature is in the range of 40 to 150C., preferably 60 to 120C. If the molding temperature is below 40C., the pullulan composition is plasticized with relative difficulty and requires a great ~ driving power, and, in some cases, the molding machine is damaged.
4 If the molding temperature is in the range of 60C. to 120C., an extremely favorable molded article is obtained with less screw-driving power and with less foam in the molded article. Even if the molding temperature is 100 to lS0 C., no foam due to evap-oration of water is formed at all in the molded article, though the reasons therefor has not been elucidated yet.
The molding machine equipped with a plasticing screw which is used in the present invention may be any of mono- or _ ' multi-axial screw extruders, or screw preplasticating or screw - inline type injection molding machines which are ordinarily used for the molding of general thermoplastic synthetic resins by those skilled in the art.
Molded articles produced according to the process of the present invention include films, sheets and pipes which are obtained by use of extruders equipped at the tips with dies having slits or annular slits; filaments, rods and profile produced by use of dies having nozzles of various shapes; molded articles such as vessels obtained by subjecting plasticized pullulan to injection-molding by use of injection molding machines 1049Zll 1 equipped with metal molds of various shapes; and hollow articles obtained by use of blow molding machines.
The present invention has such advantages that for the production of molded articles from pullulan, conventional molding machines for general thermoplastic resins can be utilized as they are; not only pullulan is inexpensive but also the cost required for the molding thereof is markedly low; and pullulan is spontaneously decomposable in the air and in the ground, and does not cause any public pollution even when burned. According-ly, when such excellent characteristics inherent to pullulan as high mechanical strength, gas barriering property, transparency, oil resistance, moisture absorptivity and water solubility are imparted to molded articles, it is evident that the application scope of the molded articles is immeasurable.
The present invention is illustrated in detail below with reference to examples, but the examples are for illustration, and the invention is not limited to the examples.
Example 1 Powdery pullulan having a molecular weight of 150,000 was uniformly sprayed with water so as to in-corporate 30 weight ~0 of water into the powder. The thus treated pullulan powder was fed to a screw extruder ; (screw diameter 30 mm.; ~/D = 20) equipped at the tip with a T-die having a slit of 1 mm. in aperture and 300 mm. in width, and molded into a sheet at a resin temperature of 100C. with a screw rotation number of ~049Zll 1 30 r.p.m. This sheet was tough and transparent, and no formation of foams was observed at all in the sheet.
Example 2 Powdery pullulan having a molecular weight of 70,000 was allowed to stand for 24 hours in an atmosphere kept at a temperature of 25C~ and a relative humidity of lOO~o SO as to incorporate 10 weight % of water into the powder. The thus treated pullulan powder was fed to a screw extruder (screw diameter 30 mm;
~/D = 20) equipped at the tip with a die having a hole of 2.5 mm. in diameter, and extruded to the form of a strand. This strand was transparent, and no formation of foams was observed in the strand. The strand was cut into pellets of 4 mm. in length which were then fed to a screw inline type injection molding machine (injec-tion capacity 3 oz.) equipped with a cup-molding metal mold, and molded at a resin temperature of 120C. to ; obtain a tough and transparent cup.
Comparative Example 1 The extrusion molding of Example 1 was re-peated, except that the screw was rotated so that the resin temperature became 30C. As the result, the resin was not plasticized but merely filled in the extruder, and hence could not be extruded to the form of a sheet.
When the resin was extruded at a resin temperature of above 150C., the formation of fo~ was observed in the resulting sheet.
Comparative Example 2 Powdery pullulan having a molecular weight of 150,000 was vacuum-dried at 130C. for 24 hours to an absolutely dried j powder, which was then fed to a screw extruder. As a result, the resin could not be extruded at any temperature.
' ~, .
. ~
Heretofore, a molded article of such thermo-plæstic resin as, for example, polyethylene, polyvinyl chloride, polystyrene, polypropylene or polyamide has been produced by melting the resin by means of an ex-truder or an injection molding machine, and then subjecting the resulting melt to extrusion- or injection-molding. When the above-mentioned procedure is adopted, however, the production of a molded article from such resin as pullulan is quite difficult since the pullulan, when used in the form of an anhydride, does not soften but decompose at above 200C.
The pullulan used in the present invention is a linear high polymer having repetition units, bonded through a-1,6-linkages, of maltotriose whlch is a trimer of glucose, and has a molecular structure represented by the formula, ~ .
_l _ o o~
O O ~
V-~
o o tq~ _ . . o o o~
'' ' V~L
o o o~
o o~
~o o7 ~v~L
o o o~
V ~L
o ~ o~
1 wherein n represents the polymerization degree, and is an integer of 20 to 10,000.
As is well known, pullulan is a glucan obtained by subjecting a pullulan-producing strain, e.g.
Pullularia ~ullulans, to submerged culture in a medium containing sucrose, starch syrup or glucose as a carbon source, and the molecular weight thereof is ordinarily in such a broad range as from 10,000 to 5,000,000 (refer to H. Bender, J. ~ehmann et al: Biochem. Biophys.
Acta, 36, 309 (1959); and Seinosuke Ueda: Kogyo Kagaku Zasshi (Journal of the Chemical Society of Japan Industrial Chemistry Section), 67, 757 (1962)). Being produced by the above-mentioned method, pullulan has such excellent characteristics that it is inexpensive and gives a molded article which is tough and trans-parent, has gas-barriering property and oil resistance, is hydrophilic, is spontaneously decomposable in the air and in the ground, and does not cause any public pol-lution due to combustion, i.e. does not generate harmful gas nor intense heat at the time of combustion.
For the production of a molded article from a composition containing pullulan as a main ingredient, there has hitherto been adopted only such flow film-forming process that an aqueous pullulan composition is defoamed, flowed on the surface of a smooth metal plate or the like, and then dried, and the resulting film is peeled off from the plate. However, the said process requires many operational steps and long drying time, so that much cost and time have been needed for produc-tion of the molded article. For the above reasons, it 1049Zl~
1 has entirely been :impossible to utilize molded articles in which the characteristics of pullulan have been displayed.
As the result of extensive studies on the above-mentioned points, the present inventors could easily mold pullulan by controlling the amount of` water to be incorporated into the pullulan and selecting the molding temperature and the molding machine employed, and discovered a process for producing at a high speed with low cost a molded article to which had been im-parted the aforesaid characteristics of pullulan.
Based on this discovery, the inventors have acçomplished the present invention.
An object of the present invention is to pro-vide a novel process for producing a molded article composed of pullulan.
Another object of the invention is to provide a process in which a molded article composed of pullulan can be produced at a high speed with low cost.
A further object of the invention is to provide a molded article composed of pullulan which is tough and transparent, has gas-barriering property and oil resistance, and is spontaneously decomposable in the air and in the ground.
Other objects and advantages of the invention will become apparent from the explanation given below.
In accordance with the present invention, there is provided a process for producing a molded article composed of pullulan, characterized in that pullulan is incorporated with 1 to 50 weight % of water, 1~49Zll 1 and then subjected to extrusion- or injection-molding by use of a molding machine equipped with a plasticizing screw at a temperature in the range from 40 to 150C.
~he molecular weight of the pullulan used in the present invention is preferably from 50,000 to 1,000,000 in view of the moldability thereof and the mechanical strength of the resulting molded article.
~he amount of water to be incorporated into the pullulan in the present process is 1 to 50 weight ~, preferably 5 to 30 weight ~0. If the amount of water is less than 1 weight %, the pullulan can be plasticized with quitc difficulty, while if the amount thereof is more than 50 weight %, the pullulan can be easily plasticized, but is undesirably increased in adherence to metal to make the handling thereof extremely difficult. At the time of molding, the pullulan may be in any form of powders, flakes or pellets. According to the present invention, pullulan may be incorporated with water in any manner. For example, pullulan may be moistened by allowing it to stand in a high humidity atmosphere, or pullulan in the form of powders, flakes or pellets may be uniformly sprayed with water to absorb the water therein. Further, pullulan may be incorporated with, in addition to water, a polyhydric alcohol such as glycerin, ethylene glycol, polyethylene glycol, sorbitol, propylene glycol, polypropylene glycol or maltitol, dimethyl sulfoxide, plasticized PVA, high molecular weigh~ amylose or gelatin as a plasticizer or softener.
Even when pullulan is additionally incorporated with one or more of pigments, dyes and fillers, a molded 1`
-- S
10492~1 article can successfully be obtained without any injury during the molding operation.
In the present invention, the molding temperature is in the range of 40 to 150C., preferably 60 to 120C. If the molding temperature is below 40C., the pullulan composition is plasticized with relative difficulty and requires a great ~ driving power, and, in some cases, the molding machine is damaged.
4 If the molding temperature is in the range of 60C. to 120C., an extremely favorable molded article is obtained with less screw-driving power and with less foam in the molded article. Even if the molding temperature is 100 to lS0 C., no foam due to evap-oration of water is formed at all in the molded article, though the reasons therefor has not been elucidated yet.
The molding machine equipped with a plasticing screw which is used in the present invention may be any of mono- or _ ' multi-axial screw extruders, or screw preplasticating or screw - inline type injection molding machines which are ordinarily used for the molding of general thermoplastic synthetic resins by those skilled in the art.
Molded articles produced according to the process of the present invention include films, sheets and pipes which are obtained by use of extruders equipped at the tips with dies having slits or annular slits; filaments, rods and profile produced by use of dies having nozzles of various shapes; molded articles such as vessels obtained by subjecting plasticized pullulan to injection-molding by use of injection molding machines 1049Zll 1 equipped with metal molds of various shapes; and hollow articles obtained by use of blow molding machines.
The present invention has such advantages that for the production of molded articles from pullulan, conventional molding machines for general thermoplastic resins can be utilized as they are; not only pullulan is inexpensive but also the cost required for the molding thereof is markedly low; and pullulan is spontaneously decomposable in the air and in the ground, and does not cause any public pollution even when burned. According-ly, when such excellent characteristics inherent to pullulan as high mechanical strength, gas barriering property, transparency, oil resistance, moisture absorptivity and water solubility are imparted to molded articles, it is evident that the application scope of the molded articles is immeasurable.
The present invention is illustrated in detail below with reference to examples, but the examples are for illustration, and the invention is not limited to the examples.
Example 1 Powdery pullulan having a molecular weight of 150,000 was uniformly sprayed with water so as to in-corporate 30 weight ~0 of water into the powder. The thus treated pullulan powder was fed to a screw extruder ; (screw diameter 30 mm.; ~/D = 20) equipped at the tip with a T-die having a slit of 1 mm. in aperture and 300 mm. in width, and molded into a sheet at a resin temperature of 100C. with a screw rotation number of ~049Zll 1 30 r.p.m. This sheet was tough and transparent, and no formation of foams was observed at all in the sheet.
Example 2 Powdery pullulan having a molecular weight of 70,000 was allowed to stand for 24 hours in an atmosphere kept at a temperature of 25C~ and a relative humidity of lOO~o SO as to incorporate 10 weight % of water into the powder. The thus treated pullulan powder was fed to a screw extruder (screw diameter 30 mm;
~/D = 20) equipped at the tip with a die having a hole of 2.5 mm. in diameter, and extruded to the form of a strand. This strand was transparent, and no formation of foams was observed in the strand. The strand was cut into pellets of 4 mm. in length which were then fed to a screw inline type injection molding machine (injec-tion capacity 3 oz.) equipped with a cup-molding metal mold, and molded at a resin temperature of 120C. to ; obtain a tough and transparent cup.
Comparative Example 1 The extrusion molding of Example 1 was re-peated, except that the screw was rotated so that the resin temperature became 30C. As the result, the resin was not plasticized but merely filled in the extruder, and hence could not be extruded to the form of a sheet.
When the resin was extruded at a resin temperature of above 150C., the formation of fo~ was observed in the resulting sheet.
Comparative Example 2 Powdery pullulan having a molecular weight of 150,000 was vacuum-dried at 130C. for 24 hours to an absolutely dried j powder, which was then fed to a screw extruder. As a result, the resin could not be extruded at any temperature.
' ~, .
. ~
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a molded article from pullu-lan, characterized in that pullulan is incorporated with 1 to 50 weight % of water and is then extruded or injection-molded by means of a molding machine equipped with a plasticizing screw at a temperature in the range of 40° to 150°C.
2. A process according to Claim 1, wherein the molecular weight of the pullulan is 50,000 to 1,000,000.
3. A process according to Claim 1, wherein the pullulan includes a plasticizer or softener.
4. A process according to Claim 3, wherein the plasti-cizer or softener is glycerin, ethylene glycol, polyethylene glycol, sorbitol, propylene glycol, polypropylene glycol, maltitol, dimethyl sulfoxide, plasticized PVA, high molecular weight amy-lose or gelatin.
5. A process according to Claim 1, 2 or 3 wherein the pullulan is additionally incorporated with a pigment, a dye and/
or a filler.
or a filler.
6. A process according to Claim 1, 2 or 3 wherein the pullulan extruded or injection-molded by means of a mono- or multi-axial screw extruder, or a screw preplasticating or screw inline tupe injection molding machine.
7. A process as claimed in Claim 1, 2 or 3 in which the water is incorporated in an amount of 5 to 30 weight %.
8. A process as claimed in Claim 1, 2 or 3 in which the temperature is from 60°C to 120°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1382874A JPS5318071B2 (en) | 1974-02-01 | 1974-02-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049211A true CA1049211A (en) | 1979-02-27 |
Family
ID=11844122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA219,180A Expired CA1049211A (en) | 1974-02-01 | 1975-01-31 | Process for producing molded article composed of pullulan |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5318071B2 (en) |
| CA (1) | CA1049211A (en) |
| FR (1) | FR2259684B1 (en) |
| GB (1) | GB1493411A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2556985T3 (en) | 2011-01-11 | 2016-01-21 | Capsugel Belgium Nv | New hard capsules comprising pululane |
| CA3059527A1 (en) | 2017-04-14 | 2018-10-18 | Capsugel Belgium Nv | Pullulan capsules |
| BR112019021396A2 (en) | 2017-04-14 | 2020-04-28 | Capsugel Belgium Nv | pullulan manufacturing process |
-
1974
- 1974-02-01 JP JP1382874A patent/JPS5318071B2/ja not_active Expired
-
1975
- 1975-01-27 GB GB3516/75A patent/GB1493411A/en not_active Expired
- 1975-01-31 CA CA219,180A patent/CA1049211A/en not_active Expired
- 1975-01-31 FR FR7503055A patent/FR2259684B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2504116B2 (en) | 1977-06-30 |
| JPS50108357A (en) | 1975-08-26 |
| FR2259684A1 (en) | 1975-08-29 |
| JPS5318071B2 (en) | 1978-06-13 |
| GB1493411A (en) | 1977-11-30 |
| DE2504116A1 (en) | 1975-08-14 |
| FR2259684B1 (en) | 1977-04-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |
Effective date: 19960227 |
|
| MKEX | Expiry |
Effective date: 19960227 |