JPH07508688A - Polymer products and materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Title of invention: Polymer products and polymer materials technical field The present invention relates to polymer materials and products made from them, polymer products and polymer materials. It relates to methods and equipment for forming materials, especially those that can be easily disposed of when no longer needed. Regarding possible polymer products and polymer materials.

Conventional technology Polyvinyl acetate is a water-insoluble polymer obtained by polymerizing vinyl acetate. be. This polymer has acetyl groups removed by hydrolysis or alcoholysis. It is used in the production of polyvinyl alcohol (PVA). this Copolymers of vinyl alcohol and vinyl acetate are produced by partial removal of acetyl groups. It is also possible to obtain Vinyl alcohol is more common, but vinyl acetate may also be used. If such a copolymer is soluble in cold water, It is often referred to as ``hydrolyzed'' polyvinyl alcohol. residual vinyl acetate The content is usually about 11% by weight, corresponding to about 12% by mole. almost completely reversed As the reaction continues, crystallization of the polyvinyl alcohol increases and its dissolution in cold water increases. degree decreases significantly. This type of material is a well-hydrolyzed polyvinyl It is called alcohol. The content of residual vinyl acetate is usually 3 mol% or less.

wo92101556 (the disclosure content of which is included herein for reference) is particularly Describes certain degradable products that are in sheet form. Ru.

During use, the water-soluble PVA substrate is exposed to water on its surface due to the polymer composite structure. It is stated that contact with the person is to be avoided. However, such a structure Forming objects has been relatively difficult until now. In particular, as claimed in WO92101556 Special casting/molding and film blowing Coextrusion cannot produce satisfactory products. 1 thing is known.

The object of the invention is to improve the formation of polymeric materials as described in W092101556. It's about adding good.

The present invention uses polymeric materials of the type described in W092101556 to Formed by extrusion through a component die or by special multi-step forming methods , with significant unexpected benefits in terms of efficiency, speed and cost. This is based on our surprising discovery that Here we refer to "co-extrusion" "Molding" refers to the non-forming method described in WO92101556 above, as explained in detail below. The extrusion casting/molding process is completely different. It is noteworthy.

Sarajo of reward suction One aspect of the invention is to use water at a predetermined temperature (preferably low temperature), typically 20°C. A first organic polymer layer (partially hydrolyzed polyvinyl alcohol) soluble in etc.), which is adjacent to the first polymer and is more water soluble than the first polymer at the predetermined temperature. A second organic polymer layer that has significantly lower or is insoluble in water (fully hydrolyzed Polyvinyl alcohol, etc.), composite polymer products or polymers consisting of - Present methods for forming materials. This process consists of a composite polymer containing a polymer layer. Film blowing process or coextrusion where the material is extruded from a die assembly Molding process; alternatively, the polymer is extruded through a die hole as a separate polymer layer. , the polymer layers are then passed together between the nip means and the temperature and pressure of the nip means an extrusion/lamination process in which the polymer layers are laminated to form a composite polymeric material that includes polymer layers. ; alternatively, the first polymer layer is formed by extrusion or blow molding; The polymer layer of the tube 2 is then applied (e.g. by spraying, dipping, painting, rolling, etc.). It consists of a process in which it is applied as a covering layer.

When a product or material is made by film blow extrusion, the die is pressurized. a first suction port for receiving one side of the polymer and a pressurized port on the other side. Consisting of a second suction port for receiving the reamer and a pair of mandrel members, The first mandrel member is hollow along its length and the second mandrel member a first annular conduit is formed around the first mandrel; One of the organic polymers is transferred to the outer surface of a first mandrel member and A second annular conduit is formed on the outer periphery of the rail member, and the other organic polymer is The mandrel member is configured to be conveyed to the outer surface of the second mandrel member, and each suction The polymer is transported from the hole to each annular conduit around almost the entire circumference of each mandrel member. A polymer guide groove is provided in one or each of the annular conduits for guiding the annular conduit.

Such a die assembly for coextruding this material is a feature of the present invention. It constitutes the characteristic part. In a further aspect of the invention, the first and second Co-extrusion of composite polymer products or polymeric materials containing organic polymer layers A die assembly for receiving one of the pressurized polymer layers has a second die assembly for receiving one of the pressurized polymer layers. a second suction port for receiving the other of the pressurized polymer layers; elongated with an outlet downstream of the suction inlet for discharging the composite polymer material Consisting of a housing; and a pair of mandrel members housed in the housing. It will be done. The first mandrel member is hollow along its length and the second mandrel member is hollow along its length. a first annular conduit surrounding the first mandrel and formed on the outer circumference of the first mandrel; One organic polymer is transported from the outer surface of the first mandrel member to the outlet of the housing. a second annular conduit formed on the outer periphery of the second mandrel member; of organic polymer from the outer surface of the second mandrel member to the outlet of the housing. , the first and second annular conduits are made of a composite polymer material in which the two polymers include a polymer layer. The annular conductor is discharged from the discharge port of the housing and terminates therein. a polymer corresponding to one or each of the tubes, preferably wider than each annular conduit; The polymer guide groove guides the polymer from each suction port to each mandrel member. It is used to convey the annular conduit around almost the entire outer surface of the pipe.

Preferably, one guide groove is provided in each annular conduit; , it is best to provide two transport paths for the polymer entering through each inlet. preferable. That is, the first conveying path only moves the polymer in one direction around each mandrel. The second conveying path is for conveying the polymer to the other side. It is something. In this most preferred configuration, each path goes half way around the mandrel (suction (Seen from the entrance) They meet on the opposite side.

Preferably, the guide groove is cut into the outer surface of the mandrel. The width of the guide groove is Preferably, it tapers inward from the entrance, similar to the corresponding annular conduit. It is most preferable that the width be the same.

Most preferably each guide groove continues into a corresponding annular conduit.

Additionally, each guide groove may be formed to run over a corresponding mandrel. preferable. Therefore, along the guide groove leading to the back of the mandrel (as seen from the suction port) The polymer that has already migrated and entered each annular conduit will be accessed via the associated inlet. The polymer enters the annular conduit relatively soon after entering the assembly, and the polymer enters the annular conduit relatively soon after entering the This means that they have moved essentially the same distance vertically.

The second mandrel is also advantageously hollow, allowing compressed air to blow through the center of the die. The film is inflated as it leaves the die.

Casting co-extrusion of separate sheets or casting extrusion and then When producing sheets by lamination, one (or more) one has a first suction port for receiving pressurized polymer; a second inlet for receiving the other polymer, and each sheet is extruded. consisting of individual elongated holes formed in the die.

The die assembly for coextrusion is also novel and constitutes a further feature of the invention. are doing. Composite polymer comprising first and second organic polymer layers adjacent to each other A die assembly for coextruding products or materials embodies aspects of the invention. These are shown below. This die assembly accepts one side of the pressurized polymer a first suction port for receiving the pressurized polymer; a second suction port for receiving the other pressurized polymer; a housing having an outlet downstream of the opening for discharging the composite polymer material; die means for forming the first elongated hole and the first suction port communicate with the first supplementary length; a first manifold channel stage provided to allow the and a die means provided for communicating the second suction port with the second slot. and a second manifold channel. Note that the first manifold The channel means extends in the direction of the slotted hole and extends the polymer from the slotted hole. It is configured to be pushed out. The second manifold channel also means a slotted hole. , and is configured to expand and push the polymer through the slotted hole. There is. and the first and second slots are formed of a composite polymer material including a polymer layer. The two polymers are terminated together so that they exit from the outlet of the housing. are doing.

into composite materials for cast extrusion and subsequent lamination of individual sheets. Depending on the desired number of calendars to be formed, the appropriate number of conventional die assemblies may be used. It may consist of a cast extrusion die with a suitable number of slotted holes and feed conduits.

Therefore, a single thermoplastic sheet, e.g. a rigid PVC sheet, can be cast In traditional extrusion processes, extrudable polymer composites are So-called ``coat hanger type'' or ``fitted'' with an entry channel. It is sent to a "Steer-type" die. Entry channel abruptly manifolds Spreads out into the channel and spreads the extrudable composite material into the mouth of a single slot die. I'm growing up. The manifold channel allows the composite material to spread to the tip of the die slot. The structure is designed to encourage growth. The width of the slot is determined by an adjustment screw that can be accessed from the outside. It can be adjusted appropriately by The extruded sheet material is pulled with appropriate tension. The material is then passed through conventional rollers and a finishing cutter.

Composite polymers are made by extrusion of individual layers and subsequent nip lamination. If the It is done at high temperature. Surface and/or electrostatic effects between polymers and/or All of the effects of air pressure appear to promote lamination. And the boundary surface No use of adhesives or fusing of layers is required.

For forming and coating processes to produce the desired composite polymer product or substance , the first (relatively water-soluble) polymer layer is formed by conventional extrusion or blowing. .

Formed by molding, a second (relatively water-soluble) polymer layer is formed by conventional methods. It is provided as a covering layer according to the method. Spraying of the second polymer liquid composite coated Special mention is made of processing.

Additionally, in a variation of this aspect of the invention, the second polymer layer is deposited at a predetermined temperature ( e.g. 20°C) than the first polymer (Not available) You can use the dried residue of the ink instead. This method (relatively soluble in water) For the production of easily degradable blow-molded rigid containers and bottles made of a first polymer, Particularly suitable. Such containers and bottles cannot contain non-aqueous substances such as oil or petroleum. used to contain and be relatively water-soluble to protect it from water-induced deterioration during use. The outside is coated with ink that will not stain.

The above-mentioned products and substances (materials) themselves are new, and their manufacturing processes are generally in accordance with the present invention. brings additional features.

In yet another aspect, the present invention provides a method for controlling the Providing polymer products or polymer materials made from water-soluble organic polymers. Ru. The surface of a product or substance is heated slowly, in whole or in part, at the same predetermined temperature. A waterproof protective coating coated with an ink that degrades quickly or does not degrade at all. is formed.

Similar to the composites described above, if the product or substance is only partially covered with ink, If the product is exposed to water during normal use, all surfaces expected to be exposed to water during normal use of the product are coated. be done.

Products or substances can be manufactured from polymers by conventional methods (extrusion, casting, blow molding, molding, etc.). A coating layer of liquid ink is then applied (spraying, dipping, etc.). by methods used in conventional film printing machines, such as dipping, coating or rolling), and dried.

A preferred soluble polymer is partially hydrolyzed polyvinyl alcohol .

The ink coating layer is an alcohol-based hydrocarbon-free liquid ink for flexographic printing. Preferably, it is a dry residue of the ink. This is a polyester for flexo printing. It is commercially available for use in olefin films. Coates Loli in Essex, UK The ink coating layer of the present invention can be obtained by using Lux Inc.'s ink "Orion" (trademark). Examples of suitable liquid inks include:

- In another embodiment of the invention, the product and the material are laminar. This form is A polymer film or sheet used in industrial manufacturing processes. present invention Other embodiment forms include pieces of such polymer sheets or films (pi eces). In particular, polymer or film fragments are It can be shaped into something with a curved part that is more than 100 degrees wide, such as a bottle.

The exposed surface of the polymer breaks down when it comes into contact with water, but the surface of the polymer is covered with a layer of ink. surface is protected. The ink acts as a barrier and is protected. protects the first polymer from decomposition even if the surface becomes wet.

Such functionality has a wide range of applications. Generally, the products and materials of the invention are , can be used in the following cases: First, products that are wet or have the potential to get wet. First, the ink layer protects the soluble polymer, and later the soluble polymer Contact the unprotected side of the product with water. As a result, there is no degradation of the soluble polymer when desired. The ink prevents premature decomposition.

If the product consists of a polymer film, one or both sides of the film Suitably, it is coated with an insoluble ink. the required mechanical strength The polymer film has a sufficient thickness, e.g., about 5 μm to 1 mm, typically It should have a range of 10 μm to 200 μm, for example about 50 μm 2 .

The thickness of the ink layer ranges from about 1 μm to 7 μm, for example about 3 μm.

Non-film products are soluble products that are substantially or entirely coated with ink. It consists of a sexual “core.” Although such products are water resistant, Once the link layer is destroyed, water can break down the exposed core. Therefore, the entire product be understood.

In yet another aspect of the invention, an organic polymer is water-soluble at a predetermined temperature, typically 20'C. A method of making a polymeric product comprising a remer is provided. In this method, the product A coating of liquid ink is applied to the entire surface or part of the surface, and this coating dries. Forms a qualitatively water-resistant ink protective layer. This protective layer is Decomposes slowly or not at all.

If the product or substance consists of a polymer film, the liquid ink must be properly primed. The plank roller of a conventional film printing machine is first coated with a liquid ink filler. The lume is wrapped in a conventional manner onto a roll of polymer film.

Beautify the appearance of your products by using inks in the desired single color or combination of colors. It's okay. If desired, apply different colored inks sequentially to achieve the desired effect You can also do that.

As can be seen from the description of all aspects of the invention and the description of WO22101556, The rate at which the more rapidly soluble (first) polymer dissolves depends on polymer selection and processing. It can be changed by selecting the processing conditions. The time it takes for this polymer to dissolve is The duration can be selected depending on the expected use of the material, and ranges from approximately tens of seconds to several hours. Ru. The dissolution time of the soluble polymer is as follows. At least one side is exposed When a polymer sheet is placed in distilled water at 20"C, the sheet will degrade in less than 24 hours. Sufficiently dissolve and break up. This time is usually less than 8 hours, if possible For example, in the case of a 50 μm thick test sheet, it is preferably less than 10 seconds. Delicious.

In the case of the composite material described in WO22101556, a more soluble polymer; The weight ratio of less soluble polymer is at least 2:1, preferably less than 2:1. 3:1, more preferably at least 5:1, especially for thick products. In some cases, the ratio may be from 10:1 to 100:1.

Alternatively, a less soluble polymer may coat a more soluble polymer. Its normal thickness is preferably less than 20 μm, more preferably 10 μm. Also preferably less than 5 μm. The thickness may be 2 μm or less.

For composite film products, the total thickness of the film is generally between 5 μm and 1 mm. more generally from 10 μm to 200 μm.

Each polymer may be used in combination with other substances. For example, dyes and One or both of fillers and/or fillers may be used. These are traditionally done There is.

Products can take various forms. For example, a composite film contains 1 of each polymer. It is also possible to have only two layers each consisting of layers. In other cases, composite films have low solubility. A more soluble polymer may be sandwiched between two different polymers. of other materials You can add layers.

In the above process, the first (or only) water-soluble polymer is partially hydrolyzed. Polyvinyl alcohol is preferred. a second relatively water-insoluble Preferably the polymer is fully hydrolyzed polyvinyl alcohol . The extrudable and blow moldable precursor is a plasticized set of individual polymers. Preferably, it is a synthetic material.

In the case of extrusion, the plasticized composition of the first (water-soluble) polymer per 100 parts of plasticizer, about 1 to 60 parts, suitably about 5 to 35 parts (by weight) of plasticizer. or in quantity), more preferably about 10 to 20 parts; per 100 parts of polymer. of water up to about 30 parts, suitably 0 to 15 parts, more suitably 1 to 15 parts (by weight) more preferably about 3 to 15 parts, most preferably about 5 parts; Powdered silica as a slip agent (to promote material flow) per 100 parts of rimmer up to about 5 parts, suitably 0.01 to 5 parts (in fflfn or quantities), and so on. More preferably 0.01 to 3 parts, most preferably about 0.25 parts. like this The substances are novel and constitute a further aspect of the invention.

In the case of extrusion, the plasticized composition of the second polymer is of plasticizer in an amount of about 1 to 80 parts, suitably about 5 to 60 parts, preferably about 15 to 35 parts parts (by weight or quantity), more preferably about 25 parts; 100 parts of polymer. up to about 30 parts water, suitably 0 to 15 parts, more suitably 1 to 15 parts (by weight) more preferably about 3 to 15 parts, most preferably about 5 parts. up to about 3 parts of slip agent such as powdered silica per 100 parts of polymer; 0.01 to 3 parts (by weight or quantity), more preferably 0.01 to 3 parts, Most preferred is about 0.25 part. Such substances are new and the present invention Constitutes a further aspect.

The plasticizer can be selected from existing plasticizers for the polymer in question. polyvinyl aluminum In coal polymers, the plasticizer is glycerol, glycol, alkenediol (ethanediol, propanediol, butanediol, bentanediol or (hexanediol, etc.), alkenetriol (hexanetriol or triol) (limethylolpropane, etc.), fatty acid monoglycerol, or a mixture thereof It is.

The extrudable substances mentioned above are different from the water-soluble substances described in WO92101566. , usually predominant or granular. The substance of the present invention has a significant difference compared to known substances. It is particularly noteworthy that only a small amount of water is used. however, Other formation methods require large amounts of water. Such matters should be determined by a person skilled in the art. That is.

The components of the above substances are suitably mixed at high temperatures (e.g. about 110°C), but never It does not necessarily have to be this temperature. Mixing at low temperatures is also possible, but takes time. It will take a while.

Extrusion is carried out under pressure and at high temperatures. The exact pressure and temperature conditions used Set by the skilled person based on polymer melting and decomposition conditions.

If necessary, processing aids such as antifoam agents and lubricants can be used.

The features of these conventional processes, which are within the ordinary knowledge of those skilled in the art, can be incorporated into the method of the present invention. The detailed explanation will be omitted here.

Particularly novel and preferred features of the method of the invention are described below.

First, in the case of polyvinyl alcohol, an extrusion die between 190°C and 240'C is used. ) temperature (e.g. about 215°C) has been found to give good results.

Additionally, each polymer composition was added to a short screw with a drip feeder to prevent clogging. - It is suitable to feed the die by an extruder. Fairly short time at desired compression state Avoid applying excessive shearing force to the composition when conveying the composition to the die suction port. The extruder must be configured to allow As a result, the polymer deteriorates significantly (approximately 4 minutes under normal extrusion conditions for PVA compositions).

These requirements can be met using the following screw extruders for individual compositions: I realized that I can be satisfied by doing this. That is, the screw extruder is , the extrusion tank has two or more compression zones, and the steam is released between these zones. The extrusion vessel is kept at a constant temperature or a series of temperatures along its length. Temperature is well controlled. After the last compression zone, the composition reaches the die inlet do. If necessary, the temperature of the composition can be adjusted by feeding it through a temperature-regulated adapter. Adjust the temperature to

Accordingly, another aspect of the invention provides a process for making a composite polymer article or part. In , an extrudable plasticized composition of an organic polymer is made of a composite polymer. Provided is a device for feeding a product or substance into an extrusion die in a process for manufacturing it.

This device has two or more compression zones in the extrusion tank, and some of these zones A vented screw extruder and temperature control means. and °. The extrusion tank has one or a series of maintained at temperature.

The extrusion die can be a coextrusion die that accepts both polymers, or it can accept both polymers individually. openings for extruding the polymers individually and for laminating the polymer layers after extrusion. and a nip means downstream of the die opening. These and conveying each polymer through its respective screw extruder as described above. is preferred. However, the die uses a relatively water-soluble polymer for later coating. It may be a single die for extruding only.

The location of the compression zone along the extrusion tank is selected to suit the specific location being conveyed. Ru. The first compression zone is located far downstream from the extrusion tank and reaches the compression zone. The composition should gain considerable momentum before being removed, making it easier to transport and preventing clogging. is preferred (i.e., avoids clogging in the compression area, reduces shear of the composition, The compression of the composition increases properly and gradually until reaching the compression zone). Composition The last compression region before reaching the die is constructed as before and the composition is gradually The compression zone is reached while being compressed (i.e. less shear, Furthermore, the assembly from the aperture in a region of substantially zero compression just before the final compression region. This prevents the product from flowing backwards. ).

The compression ratio of the screw extruder, the diameter of the screw barrel and the screw speed are Set to suit the particular material being transported. Thus, for example, plasticized Insoluble PVA compositions are suitably delivered with compression ratios ranging from 1.1:1 to 5.6:1. (more preferably 2.15:1). On the other hand, plasticized soluble PVA The composition is suitably conveyed with a compression ratio in the range of 1.5:1 to 6:1 (more preferably is approximately 3=1). Compared to plasticized soluble PVA compositions, plasticized non-soluble PVA compositions Soluble PVA compositions require relatively high screw speeds and small diameter screw barrels. Preferably, the coextrusion die is conveyed to the coextrusion die. More preferably, plasticized The insoluble PVA composition was passed through an 18 mm diameter screw at a screw speed of about 7 Orpm. Conveyed via Lew barrel. On the other hand, the plasticized soluble PVA composition Conveyed through a 25 mm diameter screw barrel at a screw speed of approximately 5 Orpm. It is more preferable that the

As previously mentioned, temperature is controlled along the screw barrel. screw barrel The temperature of each part increases and becomes approximately constant or decreases toward the die. plasticized For the screw conveying the insoluble PVA composition, the screw barrel The temperature at each successive 1/3 position towards the die is suitably 180±30'C. , 230±30'C, and 250±30'C. It has been found. Furthermore, a screw conveying the plasticized soluble PVA composition -, is the temperature at each successive 1/3 position constant toward the die? , it is preferable that the temperature is slightly lowered, i.e. 203±30'C, 202± It has been found that steps of 30°C and 199±30°C are preferred.

Local chestnut yo Ω and village field Particular uses of the layered products produced by means of the invention include disposable packaging materials, and sanitary products such as diapers and toilet bowl liners. In these , one side is required to be moisture resistant. Using a film that implements the present invention After use, the product along with its contents is dumped into the toilet bowl and decomposes. stop You can flow the whole thing. The benefits of convenience are obvious, but there are also From an environmental conservation perspective, PVA only decomposes into harmless carbon dioxide and water. non-toxic, non-toxic, and non-hazardous prior to chemical decomposition.

A further field of application is water-decomposable containers, for example rigid containers for oil.

These are made by blow-molding a first water-soluble polymer into the shape of a container using a conventional method, and then a water-soluble second polymer or a water-insoluble ink skin (e.g. (for example, by spraying).

Ku saliva Ω Kai single desire dehu Embodiments of the invention will now be described with reference to the accompanying drawings, in which: FIG.

FIG. 1 is a longitudinal cross-sectional view of a coextrusion die assembly.

FIG. 2 is a top view of the die assembly of FIG. 1.

FIG. 3(a) is a plan view of the lower housing block portion of the die assembly of FIG. , and (b) is a longitudinal sectional view thereof.

FIG. 4(a) is a bottom view of the first mandrel portion of the assembly of FIG. b) is a front view.

FIG. 5 is a side view of the mandrel portion of FIG. 4(b) when viewed from the left side. Figure 6 (a) is a bottom view of the second mandrel section of the assembly of FIG. 1; (b) is a bottom view of the second mandrel section of the assembly of FIG. It is a front view.

FIG. 7 is a side view of the mandrel portion of FIG. 6(b) seen from the right side.

FIG. 8(a) is a plan view of the upper housing block of the assembly of FIG. , (b) are longitudinal cross-sectional views (details are shown enlarged).

9 is a longitudinal cross-sectional view of the die push portion of the assembly of FIG. 1. FIG.

FIG. 10(a) is a plan view of the bottle part of the assembly in FIG. 1, and FIG. 10(b) is a front view. It is a diagram.

FIG. 11(a) is a plan view of the clamp ring portion of the assembly of FIG. b) is a longitudinal sectional view.

FIG. 12 is a semi-schematic cross-sectional view of a cast coextrusion die assembly.

FIG. 13 is a diagram of the die assembly of FIG. 12, seen along line AA in the direction of the arrow. .

FIG. 14 is a schematic diagram of the first coextrusion molding apparatus.

FIG. 15 is a schematic diagram of a second coextrusion molding apparatus.

FIG. 16 shows a part of the extruder screw used in the apparatus of FIG. 14 or 15. FIG.

FIG. 17 is a cross-sectional view of a film whose negative side is protected by an ink protection layer.

FIG. 18 is a cross-sectional view of a film protected on both sides with an ink protection layer.

Actual example Momijiri Hanryo In the examples below, the insoluble and soluble layers consist of PVA. PV used A is "rMowiol" (registered trademark) manufactured by Hoechst AG. The soluble layer is , Mowiol 26-88 was used. Average molecule of partially hydrolyzed PVA The amount is 103000, the degree of hydrolysis is 88 mol%, measured as a 4% aqueous solution. The viscosity is 20 mPa, s''.The insoluble layer is Mowiol 56/98. It was prepared by mixing MOwiol 28/99 at a ratio of 50:50. Furthermore, these is fully hydrolyzed and the viscosity and degree of hydrolysis are as per these specifications as above. The figures are substantially the same as those listed in the book.

The plasticized Mowiol 26-88 had the following composition (the ratio is Mowiol 26-88). parts by weight per 100 parts of wiol 26-88).

Mowiol 26-88 (100) Glycerin (plasticizer) 15 Distilled water 5 Powdered silica R9720,25 Powdered silica R972 was manufactured by Aerosil and was used as a slip agent.

First, all these ingredients were mixed in a Car Perkins high-speed mixer in a pan preheated to 110°C. (manufactured by Baker Birkins). Next, turn the mixer to about 600 rpm. After about 6 minutes of rotation, these ingredients started to bulge up on the sides of the mixer. that Place the composition in a cooler for about 15 minutes or until the temperature drops below 40°C. I placed it.

In the mixing process, the glycerin plasticizer and silica slip agent coat the Mowiol microparticles. The distilled water is absorbed by the Mowiol microparticles. During this process, the temperature increases .

Plasticized 50: 50 Mowiol 56-98 and Mowio128- 99 consists of the following composition (proportions are by weight based on 100 parts of Mowio 1 mixture) quantity).

Mowiol 56-98 (50) Mowiol 28-99 (50) Glycerin (plasticizer) 25 Water 5 Powdered silica R9720,25 These raw materials were first heated to 110'C in a Kerr Perkins high speed mixer. I put it in. Rotate the mixer at about 60 rpm for 30 seconds, then at 1000-120 rpm. Rotate at 0 rpm for about 15-17 minutes, and the ingredients will bulge on the sides of the mixer. I started. Then, place the ingredients in a cooler for about 15 minutes or until the temperature reaches 40°C. I left it until it was lower.

The liquid ink used was alcohol-based for printing polyolefin films. This is a flexo printing ink that does not contain hydrocarbons, and the product name is "Orion" (UK). Essex Cora Lorillux: Coates (manufactured by Lorilleux) Met. Such inks have low odor and have low solvent retention. n) is small and when applied to the surface of the polymer, it dries relatively quickly and leaves a good surface bond. It adheres well, is resistant to freezing temperatures, and has moderate anti-static and anti-slip properties. There is.

If necessary, mix existing additives, diluents, colorants, or solvents with the liquid ink. It's okay to have it.

Bagiho Naoda Distortion A coextrusion die assembly is shown in FIGS. 1-11. This assembly The lower housing is surrounded by electric heating jacket 2 (approximately 600W, 240V). the first (outer) mandrel part 3 and the inner part of the first mandrel part 3; A second (inner) mandrel part 4 provided in the hollow part and an upper housing part 5. , the die push part 6, the bin 7 provided in the die push part 6, and the upper clamp. It is composed of a bling section 8.

The metal housing block 1 has a cylindrical shape, and a pair of metal housing blocks 1 are arranged at a positional relationship of about 120°. It has the suction port 9.10 near the base. There are 6 screw holes on the top of the block. 11 is formed to receive the bolt 12 and connect the upper block 5 to the lower block 1. Fixed. The same number of holes are formed on the bottom of block 1 to receive bolts 14. and fixes the base 15 of the inner mandrel 4.

Each suction port 9.10 is provided with an adapter piece 16.17, which can be fitted with a large diameter screw. - An extruder (described below with reference to Figures 12 and 13) is connected to the suction port. adapter tape The base is made of metal and is equipped with an electric heating jacket 18 whose temperature can be adjusted. ing. Most commonly the temperature maintained by electric heating jackets 2 and 18 are nearly identical, and adapters 16 and 17 accept temperature controllers for polymeric materials. functions as

As described below, the first (outer) mandrel 3 is typically cylindrical and is attached to the housing. The mandrel 4 fits snugly into the mandrel block 1 and receives the mandrel 4 (inside the second hole). It has a central channel 19 for transmitting.

The outer mandrel 3 is made of metal, and the outer surface of the mandrel is cut with a full-nose cutter. A reamer guide groove 20 is formed. Note that this guide groove is located at the base of the mandrel. It creeps up in both left and right directions, and the width becomes narrower as it goes up, forming a mandrel. terminates on the opposite side of the cable.

In use, polymeric substances entering through the suction port 9 are directed to a relatively wide section of the guide groove 20. We reach minute 21, at which point we split and go in both directions.

When a large amount of polymer enters the suction port, the polymer flows from the guide groove to the relatively large diameter of the mandrel. It overflows from the small upper part 22 of. The upper part 22 of the mandrel is connected to the adjacent housing block. It is somewhat forward of the upper part 23 within the lock 1 and forms a first annular conduit 24. Ru. This conduit 24 receives the polymer from the guide groove 20 and the suction port 9 and receives the polymer from the mandrel. Transfer the polymer onto the tube 3.

The guide groove 20 facilitates even distribution of the polymer around the mandrel 3.

The mandrel 3 has a hole 25 radially formed in the wall near its base and a second The suction port 10 and the second (inner) mandrel 4 are communicated with each other. More details later do. Furthermore, there are six holes 26 at the base of the outer mandrel 3, and the inner mandrel 3 has six holes 26 at its base. Receives bolts to hold the base 15 of the rail 4 in place.

The second (inner) mandrel 4 is also generally cylindrical, but more so than the first mandrel 3. is small and fits snugly within the central channel 19 of the first mandrel. ing. The second mandrel 4 also has a central channel 27, but this As mentioned above, this is for feeding compressed air in the extrusion blowing process.

The inner mandrel 4 generally has a similar shape and function to the outer mandrel 3, and It has polymer guide grooves 28 similar to those cut into the mandrel 4. This poly The guide groove 28 extends from the second housing suction port 10 and the hole 25 of the mandrel 3. The upper part 30 of the inner wall of the first mandrel 3 and the second mandrel pass through the outer peripheral surface of the mandrel 4. The polymer is fed into a second annular conduit 29 formed by the upper part 31 of the core. It's crowded. The upper part 31 of the second mandrel has a somewhat smaller diameter, so that It is spaced apart from the upper part 30 of the inner wall. The guide groove 28 increases as it moves away from the suction port 10. As the width increases, the width becomes narrower, and like the guide groove 20 of the mandrel 3, the upper part of the mandrel 4 is It is formed so that it creeps up in one direction.

At the base 15 of the inner mandrel 4, the mandrel 4 is fixed to the housing block 1. Six outer holes 31 are formed for receiving the bolts 14 that are attached to the bolts 14. At the base 15 furthermore has an inner hole 32 for bolting the mandrel 4 to the outer mandrel 3. are doing.

At the upper end of each ° conduit 24.29 there is a constriction 33.34 into which the film is glued. Each polymer is flattened and its thickness adjusted before it is assembled into the desired two-layer film.

In the case of the first conduit 24, the constriction 33 is in the cylindrical upper block 5 of the assembly. It is formed by a protrusion 35 in the section. Block 5 tapers towards the top The extruded polymer passes through the constriction 33 in the radial direction. the other port coming from the second conduit through the constriction 34. Combine with Rimmer.

Block 5 is bolted to the top of housing block 1 through six holes 37. has been done. Also, six small holes 38 smaller than the holes 37 are also located at the upper edge of the block 5. The clamp ring 8 is fixed to the block 5 with bolts.

This will be explained in detail later.

Furthermore, there are four holes 39a on the upper side of the block 5, and the hollow inside of the block 5 has four holes 39a. The bolt 39b for fixing the die push 6 is received in the section. This will also be detailed later explain.

The die push 6 is a hollow cylindrical structure with an inner surface that expands outward as it goes up. , forming a chamber 40 for accommodating the bottles 7. Bottle 7 is hollow and passes through the bottle. downwards until it reaches the wide upper part of the central channel 27 of the inner mandrel 4; Secure the bottle. The center channel 27 and the center channel of the hollow bolt Creates an air passage through the center of the assembly to allow compressed air to flow through the die assembly. vinegar. The outer surface of the bin 7 becomes thicker as it goes up, which makes the die housing The composite polymer film is guided through the discharge port 41 and onto the assembly. lum blowing area.

An annular rib 42 is formed around the base of the bottle 7, and this The constriction in the aforementioned second conduit 29 when located near the top 30 of the inner wall of the drell 3 34 is formed.

The upper clamp ring 8 covers the upper block 5 and the shoulder 43 of the die pusher 6. The die push 6 is fixed to the upper block 5 and attached to the clamp ring 8. It is bolted to the upper block 5 through six holes 44 (for clarity). Only one such hole is shown in FIG. 11(b) for purposes of illustration).

The upper block 5 is then suitably surrounded by an electrical heating jacket 45.

12 and 13 show a shared press-a die assembly with two slots. It is. This die assembly consists of two parts including conventional heating means (not shown). housing block parts 50a, 50b, a regulator and a supply means (described later). an upper slot die 51 with a regulator and a lower slot die 51 with a regulator and supply means as well; 52.

Slot dies 51 and 52 are each spaced apart from a fixed central double-sided lip 55. defined by a variable upper lip 53 and a variable lower lip 54, each variable lip The lip can be moved closer or further away from the fixed lip, making it possible to 1! ! Screws 56,57 vary the width of the individual slots.

FIG. 13 (Schematic diagram of a conduit for passing extrudable material through the upper die 51) As shown in detail in FIG. First, the composition first enters the housing via the inlet 58. The suction port 58 is horizontal. It expands in the direction to form a manifold channel 59. manifold channel The channel 59 directs the composition laterally and also opens the manifold channel. and into the mouth of an elongated and relatively narrow slotted conduit 60 that comprises.

The manifold channel 59 has a diameter that tapers inward and a tip end. (in the direction of flow of the extrudable material) 13, the dotted ellipses indicate the changing contours of the manifold channels), Slot conduits 60 thereby formed in the housing blocks 50a, 50b. The composition is spread at the mouth of the upstream part of. When viewed from above as shown in Figure 13, The upstream end of this conduit is arcuate, as shown by line 61, so that The composition that has passed outward from side to side along the manifold channels in response to The distance traveled through the conduit 60 to reach the pre-entry region 62 is short. It becomes. A bendable limit bar 63 (with screws 64) is provided in the inlet front area 62. (adjustable) and, if necessary, reduce the width of this area to improve the flow of the composition. Adjust.

The straight line indicated by the dotted line in FIG. 13 represents the width of the conduit 60 and the entrance frontal region 62. (As shown, the width is constant and somewhat narrower than the manifold channel, but 53, 54, and the final die exits at 54 and 55).

From the entrance frontal region 62, the composition enters each slot at lips 53 and 54 and 54 and 55. The stack of coextruded sheets passes through the upstream mouth of the die and exits the die. A coextruded part in the form of a layer is formed and then rolled or cut in conventional manner. It is processed through a processor and a take-out device.

Jingwarinuki forming equipment 14 and 15 schematically show a coextrusion molding apparatus, and the apparatus of FIG. is a die assembly 70 having the shape shown in FIGS. 1 to 11, and the apparatus of FIG. 15. includes a die assembly 71 having the shape shown in FIGS. 12 and 13.

The first suction port of the die assembly 70 contains the above-mentioned soluble polyvinyl alcohol. A plasticized composition is connected between the first heating supply chamber 73 and the adapter piece 16. The first aperture is It is supplied via the adapter piece 16.

The second suction port of the die assembly 7o is filled with the above-mentioned insoluble polyvinyl alcohol. The plasticized composition of the plastic material is in contact between the second heating supply chamber 75 and the adapter piece 17. A low compression extrusion screw 74 with a barrel diameter of 18 mm is connected to the second It is supplied via the adapter piece 17.

The upper suction port of the die assembly 71 contains the above-mentioned soluble polyvinyl alcohol. between the first heating supply chamber 73 and the adapter piece 80. By means of a connected intermediate compression extrusion screw 72 with a barrel diameter of 25 mm, the first 1 adapter piece 80.

The lower suction port of the die assembly 71 is filled with the above-mentioned insoluble polyvinyl alcohol. The plasticized composition is placed between the second heating supply chamber 75 and the adapter piece 81. The second adapter is connected by a low compression extrusion screw 74 with a barrel diameter of 18 mm. It is supplied via the adapter piece 81.

As shown in detail in FIG. 16, the extrusion screw 72 is The length/diameter ratio (L/D”) is 25:1 and the compression ratio is 3:1. Ta. The screw has 72 compression zones 76 and 77, which are separated by zone 78. They are separated by In region 78, the polymer composition is not compressed and the barrel Steam is released from the ventilation lower 9 on the wall. The screw is 53-54 rpm operated at a speed of

The extrusion screw 74 has the same structure as the normal screw 72, but the L/D ratio is 1. 8:1, the compression ratio is 2.15:1, and the screw rotation speed is 71.4 ppm. there were.

For the blown film extrusion of Figure 14, approximately 0.75 to 1 meter above the die. A pair of nip rollers 83 are provided at the station, and the produced film is collected at a collection point. (not shown). In the case of injection molding in Figure 15, the extruded film The process is carried out by conventional removal equipment, rollers and finishing cutters (not shown). taken out.

Screw flights run the entire length of the extruder, but are In Figure 16, only the first and last screw flights are shown to .

The process is the process The Mowio 1 composition was prepared as described above and placed in the hopper of extruder feed chamber 73.75. I put it in 90.91. A drip feeder is installed to prevent clogging at the hopper outlet. used.

The composition is removed at the first screw portion in region 92 and passes into the barrel of the extruder. nothing. For soluble polymers, the barrel temperature is maintained at approximately 203 ± 30°C in this region. and, for insoluble polymers, maintained at about 180±30°C.

The diameter of the screw valley slightly below the extruder is towards the barrel wall (area 93). The length of the taber section is parallel to the wall of the barrel. be. In this region (region 93) the material is compressed. Here, in the soluble polymer The barrel temperature is maintained at approximately 202 ± 30 °C, and for insoluble polymers, the temperature of the barrel is maintained at approximately 202 ± 30 °C; 30±3060.

After that, the diameter of the screw valley becomes significantly smaller and the compression is released (area 9 5). Steam is released through the open lower part 9 of the barrel.

Compression is repeated in region 96 of the extruder before reaching the adapter piece and die. . In region 98, for soluble polymers, the barrel temperature is approximately 199±30"C. For insoluble polymers, the barrel temperature is maintained at approximately 250 ± 30 °C. It will be done.

Temperature control is provided by a conventional electrical jacket.

In either case, the dia 0.71 is heated to 214'C and the heated PvA The composition is added by means of individual screws in a ratio of e.g. 5:1 (soluble/insoluble). supplied to the die. In the case of blown film extrusion (Fig. 14), warm air is simultaneously It is blown out from the hole in the center of A0. No bubbles in the blown film It is generated on the upper side of A. In this case, a thin insoluble PVA layer is placed on the inside (or optionally depending on which polymer is fed to which inlet of the die).

Cold air is blown outside of the bubbles on the die, again in a conventional manner.

The blown air quickly dries the bubbles to a non-stick state. the result , the air bubbles are flattened between nip rollers 83, collected, folded flat, and then Then, it is cut into a single sheet.

In particular, FIG. 17 shows a partially hydrolyzed ( A flexible polymeric film consisting of a substrate layer 101 of PVA (soluble) is shown. ing. As previously mentioned, the covering layer 102 is a dry, insoluble layer of "Orion" ink. It is a residue. FIG. 18 shows a modification of the film of FIG. 17, in which the ink coating Layer 102 is applied to both sides of substrate layer 101. In both cases, the covering layer 102 is , applied as a liquid by conventional ink printing methods and then dried in air.

Ink coatings can be applied to all types of polymeric products, but include thin-walled and enclosed products. This method is particularly effective in the case of products or thin film products. At the end of the product's useful life, If the protective ink coating is simply broken or scratched, the polymer will be degraded by water and It is further broken down by the natural activities of living things. Ink in much smaller quantities than polymers The coating layer naturally diffuses as the polymer decomposes. The ink coating layer itself is This is because it does not have the mechanical strength of

,,,-1,Muichi,,-N-PCT/GO93100854 Front page continuation tree (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE) , 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN.

TD, TG), AT, AU, BB, BG, BR, CA.

CH, CZ, DE, DE, DK, ES, FI, GB, HU, JP, KP, KR, KZ, LK, LU, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU.

SD, SE, SK, UA, US, VN (72) Inventor Goninan Kevin Mark UK B522 0RY Unis Ton-Super-Mare Wall Silverberry Road 49

Claims (40)

[Claims] 1. a first organic polymer layer that dissolves in water at a predetermined temperature; and the first organic polymer. adjacent to the polymer, and has significantly lower water solubility than the first polymer at the predetermined temperature. A composite polymer product consisting of squid or a second polymer layer that is water-insoluble. or a method of forming a polymeric material, comprising: a composite polymer comprising said polymer layer; – A film blowing process or co-extrusion process where the material is extruded from a die assembly. Extrusion process; alternatively, the polymer is extruded through a die hole as a separate polymer layer. The polymer layers are then passed together between nip means to increase the temperature of said nip means. Pressures that are laminated together under pressure and pressure to form a composite polymeric material that includes polymer layers. extrusion/lamination step; alternatively, extrusion or blow molding of the first polymer layer; the second polymer layer is then applied as a covering layer. Forming a composite polymer product or polymer material characterized by comprising a coating process how to. 2. 2. The method of claim 1, wherein the film blowing die blows a pressurized polymer. a first inlet for receiving one of the pressurized polymers and the other for receiving the pressurized polymer. It consists of a second suction port for inserting the air, a pair of mandrel members, and a first mandrel member. The rel member is hollow along its length and surrounds the second mandrel and further A first annular conduit is formed on the outer periphery of the first mandrel, and a first annular conduit is formed on the outer periphery of the first mandrel. one of the reamers is conveyed to the outer surface of the first mandrel member and A second annular conduit is formed on the outer periphery of the plastic member, and a second annular conduit is formed on the outer periphery of the second organic polymer. configured to convey to an outer surface of the second mandrel member; Polymer is applied from the suction port to each of the annular conduits around almost the entire outer circumference of each of the mandrel members. A polymer guide groove for conveying the polymer is provided in one or each of the annular conduits. Composite polymer products are produced by film blow extrusion, which is characterized by Rui is the process of making polymer materials. 3. Claim 2, wherein each conduit of the die assembly is provided with one guide groove. the method of. 4. Each said guide groove provides two conveyances for the polymer entering through each suction port. The first conveying path is for polymer only in one direction around each mandrel. The second conveyance path is designed to convey the polymer in the other direction. 4. The method according to claim 2 or 3, wherein: 5. 5. The method according to claim 2, wherein each of said guide grooves is cut into an outer surface of said mandrel. Method described in one of the following. 6. The width of each guide groove tapers inwardly as it moves away from the suction port. The method described in Section 5. 7. By co-extruding polymer layers or by extruding separate polymer layers. After forming polymers, by laminating them, you can create composite polymer products or polymer materials. 2. The method of claim 1, wherein the casting die is configured to form a pressurized polymer. a first suction port for receiving one of the pressurized polymers, and the other for receiving the pressurized polymer. a second suction inlet for extrusion and an elongated slot through which each polymer layer is extruded. A method characterized by: 8. At least one of the suction ports communicates with the entry channel. , the entry channel widens to become a manifold channel, and the polymer 8. The method according to claim 7, wherein the material is expanded at the mouth of a slot die. 9. Composite polymers can be made by extrusion forming separate polymer layers and then laminating them. Any one of all previous claims forming a product or polymeric material A method according to claim 1, characterized in that the lamination is carried out between nip rollers. 10. After forming the first polymer layer by extrusion molding or blow molding, the first polymer layer is formed by extrusion molding or blow molding. 2 polymer layers are formed as the covering material to form a composite polymer product or polymer material. 2. The method according to claim 1, wherein the coating layer is applied by spraying. A method characterized by: 11. After extrusion molding or blow molding the first polymer layer, forming the covering layer. Claim 1, wherein a composite polymer product or polymer material is formed by A variation of the method described above, in which the second polymeric coating layer is applied at a predetermined temperature to the second polymeric coating layer. A liquid ink that dissolves more slowly than the first polymer (or not at all) A method characterized in that it is replaced by a dry residue. 12. The ink is alcohol-based, hydrocarbon-free for flexographic printing. 12. The method of claim 11, wherein the ink is a liquid ink. 13. The first polymer contains about 1 to 60 parts of plasticizer per 100 parts of polymer. and up to about 30 parts of water and up to about 5 parts of a slip agent. A method as claimed in any one of the preceding claims in which the molding is performed. 14. The second polymer contains about 1 to 80 parts of plasticizer per 100 parts of polymer. , from a plasticized composition containing up to about 30 parts water and up to about 5 parts slip agent. Any one of all previous claims except claim 11 or 12 which is issued Method described. 15. polyhinyl alcohol in which the first water-soluble polymer is partially hydrolyzed; and the second relatively water-insoluble polymer (in some cases) is completely Any one of all previous claims which is a hydrolyzed polyvinyl alcohol The method described in. 16. Having two or more compression zones with a steam outlet between them to A screen with an extruded barrel configured to maintain a range of temperatures along its length. Each polymer composition is fed into a die through a die extruder. The method described in any one of the paragraphs. 17. It consists of an organic polymer that dissolves in water at a predetermined temperature, and the surface The organic polymer dissolves more slowly or not at all in water than the organic polymer. completely or partially coated with water to form a water-resistant protective coating. A polymer product or material characterized by: 18. 18. The product of claim 17, wherein the predetermined temperature is about room temperature (about 20°C). item or material. 19. All surfaces intended to be exposed to water during normal use should be 19. A product or material according to claim 17 or 18, coated with an ink. 20. the organic polymer is partially hydrolyzed polyvinyl alcohol A product or material according to any one of claims 17 to 19. 21. The ink coating layer is alcohol-based, hydrocarbon-free for flexographic printing. The product according to any one of the preceding claims, which is a dry residue of liquid ink. item or material. 22. A coating layer of liquid ink is applied to the entire or partial surface of the organic polymer. Then, the liquid ink is dried and slowly melts in water at a specified temperature, or 18. The polymer of claim 17, wherein the polymer forms a completely insoluble, water-resistant ink protective coating. – A method of forming a product or polymeric material. 23. The liquid ink is first transferred to a blank roller of a conventional film printing machine. and then a film of said liquid ink is applied to said organic polymer film. 23. The method according to claim 22. 24. A composite polymer article comprising first and second organic polymer layers adjacent to each other. A pressurized die assembly for coextrusion of polymeric materials. a first suction □ for receiving one of said polymer layers and said port being pressurized; a second suction port for receiving the other of the remer layers and discharging the composite polymer material; an elongated housing having an outlet downstream of an inlet for the purpose; A pair of mandrel members are housed, the first mandrel member is a first annular conduit, which is hollow along its length and surrounds a second mandrel; is formed on the outer periphery of the first mandrel, and the one organic polymer is conveyed from the outer surface of the first mandrel member to the outlet of the housing, and the second annular A conduit is formed on the outer periphery of the second mandrel member and is connected to the other organic port. conveying the reamer from the outer surface of the second mandrel member to the outlet of the housing; The first and second annular conduits are made of a composite polymer material in which the two polymers include a polymer layer. The material is discharged from the outlet of the housing and terminates together, and furthermore, the annular a port corresponding to one or each of the conduits, preferably wider than each said annular conduit; a reamer guide groove, and the polymer guide groove guides the polymer from each suction port to each of the mantles. It is characterized in that the drill member is conveyed to each of the annular conduits by passing around almost the entire outer surface of the drill member. Dia assembly. 25. A composite polymer article comprising first and second organic polymer layers adjacent to each other. Or a die assembly for co-extrusion of polymeric materials. a first suction port for receiving one of said pressurized polymer layers; a second suction port for receiving the other of the polymer layers; a housing having an outlet for discharging the polymeric material; a first elongated hole; Provided to communicate the first suction port with the first elongated hole, and widening in the direction of the elongated hole. first manifold channel means for extending polymer into said slotted hole; die means comprising; a second elongated hole; and a second suction port connected to the second elongated hole; The polymer is provided for communication and extends in the direction of the elongated hole to spread the polymer into the elongated hole. a die means defining a second manifold channel; and the second slot is a composite polymer material comprising two polymer layers. are discharged from the outlet of the housing and terminate together. Dia assembly. 26. The extrudable organic polymer plasticized composition is Injected into an extrusion die during the process of forming remer products or polymeric materials. A device that A barrel having two or more compression zones with a hole between some or all of them; , such that the barrel maintains a constant or a range of temperatures along its length. and control means, comprising a screw extruder. 27. Claim 26, wherein the die is a coextrusion die of claim 24 or 25. The device described in. 28. The screw extruder has a compression ratio of 1.1:1 to 5.6:1. 28. A device according to claim 26 or 27, configured to feed objects. 29. The screw extruder compresses the composition at a compression ratio of 1.5:1 to 6:1. 28. A device according to claim 26 or 27, adapted to feed. 30. The barrel is divided into three parts and the temperature is increased as it approaches the die. Apparatus according to any one of claims 26 to 29, characterized in that temperature control means are configured. . 31. The barrel is divided into three parts and its temperature is kept approximately constant or close to the die. The temperature control means is configured to gradually lower the temperature as the temperature increases. Apparatus according to any one of ranges 26 to 29. 32. For every 100 parts of polymer, about 1 to 60 parts of plasticizer, up to about 30 parts of water, Contains up to about 5 parts of slip agent and is made of partially hydrolyzed polyhinyl alcohol. Plasticizing composition. 33. For 100 parts of water limmer, add about 1 to 80 parts of plasticizer, up to about 30 parts of water, and Plasticized set of fully hydrolyzed polyhinyl alcohol containing about 5 parts of lipstick. A product. 34. Formed by the method according to any one of claims 1 to 16, 22, 23. products or materials that are 35. A product according to claim 27, formed into a sheet. 36. A product according to claim 27, formed in the shape of a container. 37. substantially all of the plastic parts are made from sheets according to claim 35; The outermost part contains water that does not come in contact with water during normal use until it is necessary to dispose of it. Sanitary products that can be disposed of in a flush toilet with a soluble layer. 38. Substantially all of the container is made of a polymeric material according to claim 36, with the innermost has a water-soluble layer that does not come into contact with water during normal use until disposal is required. A container for some non-aqueous substance (such as oil or petroleum). 39. It consists of an absorbent part and a plastic protective part, and is disposed of in a flush toilet. Almost all of the plastic parts can be completely decomposed by water, making it a flush toilet. Disposable sanitary products. 40. Degradable oil/petroleum that completely decomposes only when water is placed inside the container container.