JP2015157358A - Manufacturing device and manufacturing method of partial depolymerization body powder of polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device and method capable of performing mass production of a partial depolymerization body powder of polyester resin used for a natural fiber reforming agent for making sublimation transfer print possible on the surface of cloth made of natural fiber.SOLUTION: Polyester resin and multi-hydric alcohol supplied from a polyester resin hopper 2 and a multi-hydric alcohol hopper 3 respectively are fused and kneaded by a fusion extruder 4 to obtain a fused partial depolymerization body of polyester resin. Further, fused material of a partial depolymerization body of polyester resin is cooled and solidified by a cooling device 6 while conveying the fused material of a partial depolymerization body of polyester resin with a conveyance device 5 and the solidified material is crushed and pulverized by a crushing device 7.

Description

  The present invention relates to an apparatus and a method for producing a polyester resin partial decomposition polymer powder used as a natural fiber modifier for enabling sublimation transfer printing on the surface of a natural fiber cloth.

  2. Description of the Related Art Conventionally, a method called sublimation transfer printing is known as a method for printing characters or designs (hereinafter simply referred to as “designs”) on cloth. Sublimation transfer printing uses a specific dye to print a design, etc. on transfer paper, overlays the transfer paper on which the design, etc. is printed on a cloth, and applies high temperature and pressure from the top of the transfer paper. In this method, the dye is vaporized (sublimated) by adding, and the design printed on the transfer paper is printed (transferred) on the cloth. This sublimation transfer printing can print a plurality of colors in a single process, and therefore has an advantage of low cost and short processing time. Furthermore, since there is no need to wash away excess dye soaked into the printed fabric, no waste liquid is generated and the environment is not adversely affected.

  However, the dyes that can be used for sublimation transfer printing are limited, and the dyes are strongly bonded to polyester fibers but weakly bonded to natural fibers such as cotton. For this reason, even if a pattern or the like is printed on a natural fiber cloth by sublimation transfer printing, there is a problem that when the cloth is dry-cleaned, the printed pattern or the like is easily discolored. Therefore, the use of sublimation transfer printing has been limited to the case where a design or the like is mainly printed on a polyester fiber cloth.

  However, in recent years, various attempts have been made to make it possible to print a pattern or the like on a natural fiber cloth by sublimation transfer printing. Non-Patent Document 1 discloses that a natural fiber modifier synthesized by reacting a partially decomposed polymer powder of a polyester resin and a blocked isocyanate crosslinking agent is used for a cotton cloth, thereby blocking the modifier blocked isocyanate. It has succeeded in chemically introducing a partially decomposed polymer of polyethylene terephthalate (PET) resin into a cotton cloth by reacting the crosslinking agent with the cellulose hydroxyl group of the cotton cloth. Further, Non-Patent Document 1 shows that as a result of printing a pattern or the like by sublimation transfer printing on the cotton cloth modified by the above method, the dye for sublimation transfer printing is introduced into the cotton cloth. By firmly bonding with the partially decomposed polymer of PET resin, it is difficult for the color to fade even when dry cleaning is performed, and the pattern printed on the cotton cloth by the sublimation transfer print loses color. It also reports that it has improved the problem.

Gifu Prefectural Industrial Technology Center report No. 4 (2010) pp. 20-23

  As described above, a partially decomposed polymer powder of a polyester resin is used for the natural fiber modifier described in Non-Patent Document 1. In Non-Patent Document 1, regarding the production of this polyester resin partial decomposition polymer powder, a small amount of polyester resin partial decomposition polymer is produced using laboratory equipment such as a flask. A partially decomposed polymer powder of a polyester resin is obtained by pulverizing it. However, in this method, it is difficult to mass-produce the polyester resin part decomposition polymer powder. In this regard, Non-Patent Document 1 does not show any solution.

  The objective of this invention is providing the manufacturing apparatus and manufacturing method of the polyester resin part decomposition polymer powder which can mass-produce the polyester resin part decomposition polymer powder.

An apparatus for producing a partially decomposed polymer powder of a polyester resin used as a natural fiber modifier for enabling sublimation transfer printing on the surface of a natural fiber cloth according to the present invention,
A polyester resin hopper for storing the polyester resin;
A polyhydric alcohol hopper for storing polyhydric alcohol;
A melt obtained by melting and kneading a polyester resin supplied from a polyester resin hopper and a polyhydric alcohol supplied from a polyhydric alcohol hopper and partially depolymerizing the polyester resin with a heatable casing A melt-extrusion apparatus for producing a product,
A transport device for transporting the melt of the partially decomposed polymer of the polyester resin extruded from the melt extrusion device while being flattened;
A cooling device for cooling and solidifying the partially decomposed polymer of the polyester resin developed on the conveying device;
And a pulverizing device for pulverizing and solidifying the solidified product of the partially decomposed polymer of the polyester resin.

  In the production apparatus of the present invention, the pulverizer includes a dry pulverizer for pulverizing the solidified product of the partially depolymerized polyester resin, and a wet pulverizer for finely pulverizing the pulverized material pulverized by the dry pulverizer. And a pulverizer.

In the production apparatus of the present invention, the pulverized product obtained by the dry pulverization apparatus is preferably pulverized by the wet pulverization apparatus until the cumulative volume 50% diameter (D ₅₀ ) becomes 10 μm or less.

  In the production apparatus of the present invention, the polyester resin is preferably a polyethylene terephthalate resin, and the polyhydric alcohol is preferably glycerin.

  In the production apparatus of the present invention, the mixing ratio of the polyethylene terephthalate resin and glycerol is preferably 0.05 mol to 0.2 mol of glycerol with respect to 1 mol of the polyethylene terephthalate resin monomer.

  In the production apparatus of the present invention, the melt kneading of the polyethylene terephthalate resin and glycerin in the melt extrusion apparatus is preferably performed in a range of 260 ° C to 300 ° C.

  In the production apparatus of the present invention, the melt kneading of the polyethylene terephthalate resin and glycerin in the melt extrusion apparatus is preferably performed in a range of 1 minute to 10 minutes.

A method for producing a partially decomposed polymer powder of a polyester resin used as a natural fiber modifier for enabling sublimation transfer printing on the surface of a natural fiber cloth according to the present invention,
A melt-kneading step for producing a melt of a partially decomposed polymer of polyester resin by kneading with a polyhydric alcohol while heating and melting the polyester resin;
A cooling and solidifying step of cooling and solidifying the melt of the partially decomposed polymer of the polyester resin obtained by the melt-kneading step;
And a pulverizing step of pulverizing and solidifying the solidified product of the partially decomposed polymer of the polyester resin obtained in the cooling and solidifying step.

  In the production method of the present invention, the pulverization step includes a primary pulverization step in which the solidified product of the partially decomposed polymer of the polyester resin obtained in the cooling and solidification step is dry pulverized, and a pulverized product obtained in the primary pulverization step. And a pulverizing step of pulverizing by wet pulverization.

  In the production method of the present invention, the polyester resin is preferably a polyethylene terephthalate resin, and the polyhydric alcohol is preferably glycerin.

  According to the production apparatus of the present invention, mass production of a melt of the polyester resin part decomposition polymer can be performed by a melt extrusion apparatus. Then, the molten product is cooled and solidified by a cooling device while being conveyed by a conveying device, and the solidified material is pulverized by a pulverizing device, whereby mass production of the polyester resin part decomposition polymer powder can be performed.

  By crushing the solidified product of the polyester resin decomposition polymer to a certain fine particle size with a dry pulverizer, shortening the pulverization time with a wet pulverizer in the subsequent process, and with a pulverizer The resulting polyester resin part decomposition polymer powder can be atomized. In addition, by using a wet pulverizer as the fine pulverizer, the polyester resin part decomposition polymer powder can be atomized as compared with a case where a dry pulverizer is used as the fine pulverizer. Furthermore, by using a wet pulverizer as a fine pulverizer, the polyester resin part decomposition polymer powder is obtained in a state of being dispersed in a liquid. Since the natural fiber modifier is preferably in a liquid state, when a dry pulverizer is used as a fine pulverizer, the resulting polyester resin part decomposition polymer powder is used when the natural fiber modifier is produced. Although a step of mixing with the liquid is required, the mixing step can be omitted by using a wet pulverizer as the pulverizer.

When the obtained polyester resin partial decomposition polymer powder has a cumulative volume 50% diameter (D ₅₀ ) of 10 μm or less, when this polyester resin partial decomposition polymer powder is used as a natural fiber modifier, the polyester resin part The depolymerized powder is uniformly dispersed in the natural fiber cloth. Therefore, printing unevenness at the time of sublimation transfer printing can be prevented.

  Since the polyester resin is a polyethylene terephthalate resin and the polyhydric alcohol is glycerin, the raw material can be easily obtained and the raw material cost can be kept low.

  Use as a natural fiber modifier by setting the mixing ratio of polyethylene terephthalate resin and glycerin, the melt kneading time of polyethylene terephthalate resin and glycerin, and the melt kneading temperature of polyethylene terephthalate resin and glycerin to the above ranges. A polyester resin partial decomposition polymer powder having a possible molecular weight can be obtained.

  According to the production method of the present invention, mass production of a melt of the polyester resin part decomposition polymer can be performed. Then, the melted product is cooled and solidified, and the solidified product is pulverized, whereby mass production of the polyester resin part decomposition polymer powder can be performed.

It is a figure showing the whole manufacturing apparatus of this invention. It is a figure showing the structure at the time of using a circulation type bead mill as a wet grinding apparatus.

  The apparatus and production method for producing the polyester resin part decomposition polymer powder for natural fiber modifier of the present invention will be described. In the present specification, “the polyester resin is partially depolymerized” means that the polyester resin is not depolymerized up to the monomer, but the polyester resin monomer is several to several tens of monomers. It means that the polymer is depolymerized to a state of individual polymerization. The “polyester resin partial decomposition polymer” means a substance obtained by partially depolymerizing a polyester resin. “Natural fiber cloth” means a cloth containing at least a portion of natural fibers, and includes, for example, natural fibers such as cotton and chemical fibers, polyester. A cloth made of natural fibers and chemical fibers, such as a cloth to be produced, is also included.

  Below, the manufacturing apparatus and manufacturing method of this invention are demonstrated, referring drawings. As shown in FIG. 1, a manufacturing apparatus 1 according to the present invention includes a polyester resin hopper 2 for storing a polyester resin (hereinafter simply referred to as “hopper 2”) and a polyhydric alcohol for storing a polyhydric alcohol. A hydration alcohol hopper 3 (hereinafter simply referred to as “hopper 3”), and a hopper 2 and a melt extrusion device 4 disposed below the hopper 3 are provided. The melt extrusion apparatus 4 is an apparatus for producing a melt obtained by melt-kneading the polyester resin supplied from the hopper 2 and the polyhydric alcohol supplied from the hopper 3 and partially depolymerizing the polyester resin. It is.

  And the manufacturing apparatus 1 of this invention cools the polyester resin part decomposition | disassembly polymer on the conveying apparatus 5 for conveying the melt of the polyester resin part decomposition | disassembly polymer extruded from the melt extrusion apparatus 4, and the conveyance apparatus 5 And a cooling device 6 for solidifying and a pulverizing device 7 for pulverizing and solidifying the solidified product of the polyester resin part decomposition polymer.

[Explanation of melt extrusion equipment and melt kneading process]
A discharge port 2 a for discharging the polyester resin is provided in the lower part of the hopper 2, and a gas introduction port 2 b is provided in the upper part of the hopper 2. A gas is introduced into the hopper 2 from the gas inlet 2b in order to prevent moisture absorption of the polyester resin in the hopper 2.

  A discharge port 3 a for discharging polyhydric alcohol is provided in the lower part of the hopper 3, and a gas introduction port 3 b is provided in the upper part of the hopper 3. A supply speed adjusting device 8 for adjusting the supply speed (supply amount per unit time) of the polyhydric alcohol supplied into the melt extrusion apparatus 4 is attached to the discharge port 3a. In the present embodiment, the supply speed adjusting device 8 is a gear pump. A gas is introduced into the hopper 3 from the gas inlet 3 b in order to prevent moisture absorption of the polyhydric alcohol in the hopper 3 and to pump the polyhydric alcohol through the gear pump 8 to the melt extruder 4.

  The manufacturing apparatus 1 of the present embodiment further includes a gas unit 9 for supplying gas into each hopper (2, 3). The gas unit 9 includes a gas tank 9a for storing gas, a single pipe 9b connected to the gas tank 9a, and two pipes 9b and a gas introduction port (2b, 3b) of each hopper (2, 3). Each of the pipes (9c, 9d) is connected to each pipe (9c, 9d) and instrumentation equipment for adjusting the gas pressure and the gas flow rate flowing through each pipe (9b, 9c, 9d).

  In the present embodiment, a pressure control valve 9e for adjusting the pressure of gas supplied from the gas tank 9a is attached to the pipe 9b as instrumentation equipment. A flow rate controller 9 f for adjusting the flow rate of the gas supplied into the hopper 2 is provided in the pipe 9 c that connects the pipe 9 b and the gas inlet 2 b of the hopper 2. In addition, a pressure adjusting valve 9g for adjusting the pressure of the gas supplied into the hopper 3 is provided in the pipe 9d that connects the pipe 9b and the gas inlet 3b of the hopper 3.

  The gas supplied into each hopper (2, 3) may be any gas that is inert with the polyester resin and polyhydric alcohol and has a reduced dew point. Examples of such a gas include nitrogen and Argon or the like can be suitably used.

  The melt-extrusion apparatus 4 includes a casing 4a configured by a double casing including an inner casing and an outer casing. A screw (not shown) is provided in the inner casing of the casing 4a. On one end side of the casing 4a, a supply port 4b for receiving the polyester resin supplied from the hopper 2 and a supply port 4c for receiving the polyhydric alcohol supplied from the hopper 3 through the gear pump 8 are provided. And the supply port 4b of the melt extrusion apparatus 4 and the discharge port 2a of the hopper 2 are connected, and the supply port 4c of the melt extrusion apparatus 4 and the gear pump 8 are connected. Moreover, the discharge port 4d for discharging | emitting the melt of a polyester resin part decomposition polymer is provided in the other end side of the casing 4a.

  In the present embodiment, the melt extrusion device 4 is a uniaxial horizontal melt extrusion device in which one screw is disposed in the inner casing of the casing 4a. In addition, a heating wire is disposed on the outer peripheral surface of the inner casing of the casing 4a. When a current is passed through the heating wire, the heating wire generates heat and the inner casing of the casing 4a is heated.

  The discharge port 4d of the melt extrusion apparatus 4 is provided with a discharge speed adjusting device 10 for adjusting the discharge speed (discharge amount per unit time) of the melt of the polyester resin part decomposition polymer. In the present embodiment, the discharge speed adjusting device 10 is a gear pump.

  A base (die) 11 is attached to the discharge speed adjusting device 10, and the melt of the polyester resin portion decomposition polymer is discharged toward the transport device 5 through the base 11.

  In the present invention, the polyester resin supplied from the hopper 2 into the melt extrusion apparatus 4 is melted by being heated in the melt extrusion apparatus 4, and the polyvalent resin supplied from the hopper 3 into the melt extrusion apparatus 4. Kneaded with alcohol. In the melt-extrusion apparatus 4, the polyester resin and the polyhydric alcohol are melt-kneaded at a predetermined temperature and for a predetermined time, so that the polyester resin is partially depolymerized and a melt of the polyester resin part decomposition polymer is generated. The

  In the present invention, for example, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate resin (PTT resin), or polybutylene terephthalate resin (PBT resin) can be suitably used as the polyester resin. This polyester resin may be in the form of pellets or powder. As the polyhydric alcohol, for example, ethylene glycol (divalent alcohol), glycerin (trivalent alcohol), pentaerythritol (tetravalent alcohol), or the like can be preferably used. Of the combination of the polyester resin and the polyhydric alcohol, the combination of the PET resin and glycerin is preferable from the viewpoint of easy availability of raw materials and raw material costs.

  The mixing ratio of the PET resin and glycerin is preferably 0.05 mol to 0.2 mol of glycerin with respect to 1 mol of the PET resin monomer, and more preferably 0.1 mol of glycerin with respect to 1 mol of the PET resin monomer. .

  In the present invention, the purpose is not to depolymerize the polyester resin to the monomer but to depolymerize the polyester resin to a state where several to several tens of monomers are polymerized. Therefore, in order to obtain a polyester resin partial decomposition polymer having a desired molecular weight, it is avoided that the polyester resin is depolymerized to a monomer by supplying more polyhydric alcohol than necessary to the polyester resin. There is a need. That is, the supply amount of the polyhydric alcohol to the polyester resin needs to be precisely controlled.

  In this respect, in the present embodiment, since the supply speed adjusting device 8 (gear pump) is attached to the discharge port 3a of the hopper 3, it is possible to precisely control the supply speed of the polyhydric alcohol. In the present embodiment, it is possible to adjust the polyhydric alcohol supply speed by adjusting the rotational speed of the gear pump 8, and if the rotational speed of the gear pump 8 is increased, the polyhydric alcohol supply speed also increases. Conversely, if the rotational speed of the gear pump 8 is reduced, the polyhydric alcohol supply speed is also reduced. In addition, it is preferable to measure the relationship between the rotational speed of the gear pump 8 and the supply speed of the polyhydric alcohol to be supplied before the operation of the melt extrusion apparatus 4.

  The supply speed of the polyester resin is controlled by the rotation speed of the gear pump 10 and the rotation speed of the screw in the melt extrusion device 4. Therefore, it is preferable to measure in advance the relationship between the rotational speed of the gear pump 10 and the rotational speed of the screw in the melt-extrusion apparatus 4 and the polyester resin supply speed before the operation of the melt-extrusion apparatus 4.

  Further, in order to obtain a polyester resin partial decomposition polymer having a desired molecular weight, the melt kneading temperature and the melt kneading time in the melt extruder 4 need to be precisely controlled. In the present embodiment, the melt-kneading temperature can be adjusted by adjusting the heating temperature of the heating wire disposed on the outer peripheral surface of the inner casing of the casing 4a. In the present invention, the melt kneading temperature needs to be performed at a temperature equal to or higher than the melting point of the polyester resin. When a PET resin is used as the polyester resin and glycerin is used as the polyhydric alcohol, the melt-kneading temperature in the melt-extrusion apparatus 4 is preferably 260 ° C to 300 ° C. When the melt kneading temperature is below 260 ° C., the PET resin does not melt. When the melt kneading temperature exceeds 300 ° C., side reactions such as thermal decomposition of glycerin and cross-linking reaction of PET resin may proceed. The higher the melt kneading temperature is, the more the partial decomposition polymerization reaction proceeds, and the molecular weight of the resulting polyester resin partial decomposition polymer tends to decrease.

  Further, the longer the melt kneading time, the more the partial decomposition polymerization reaction proceeds, and the molecular weight of the resulting polyester resin partial decomposition polymer tends to decrease. When a PET resin is used as the polyester resin and glycerin is used as the polyhydric alcohol, the melt kneading in the melt extrusion apparatus 4 is preferably performed in the range of 1 minute to 10 minutes. If the melt-kneading time is shorter than 1 minute, the partial decomposition polymerization reaction may not proceed sufficiently. On the other hand, when the melt kneading time is longer than 10 minutes, there is a possibility that a side reaction such as a crosslinking reaction of the PET resin proceeds.

  In the present embodiment, as described above, since the discharge speed adjusting device (gear pump) 10 is attached to the discharge port 4d of the melt extrusion device 4, the polyester resin portion is decomposed by adjusting the rotation speed of the gear pump 10. The discharge rate of the polymer melt can be precisely controlled. That is, by adjusting the rotational speed of the gear pump 10, the residence time (melt kneading time) of the polyester resin and the polyhydric alcohol in the melt extrusion apparatus 4 can be adjusted. If the rotational speed of the gear pump 10 is slowed, the discharge speed of the melt of the polyester resin part decomposition polymer becomes small, so that the residence time of the polyester resin and polyhydric alcohol in the melt extrusion apparatus 4 becomes long. On the other hand, if the rotational speed of the gear pump 10 is increased, the discharge rate of the melt of the polyester resin part decomposition polymer increases, so the residence time of the polyester resin and polyhydric alcohol in the melt extrusion apparatus 4 is shortened.

[Description of Conveying Device and Cooling Device, and Conveying Step and Cooling Solidification Step]
The melt of the polyester resin part decomposition polymer extruded from the base 11 is received by the transport device 5 disposed below the base 11. In the present embodiment, the transport device 5 is a belt conveyor. Since the melt of the polyester resin part decomposition polymer has a very low viscosity, it is conveyed while being flatly developed on the Belcoton bear 5. The belt of the belt conveyor 5 is made of a material to which the melt of the polyester resin part decomposition polymer does not stick, and as such a material, for example, a fluorine-based resin such as Teflon (registered trademark) can be suitably used. .

  The cooling device 6 is provided for cooling and solidifying the melt of the polyester resin part decomposition polymer conveyed on the belt conveyor 5. In the present embodiment, the cooling device 6 is a cold air generator such as a cooler. FIG. 1 shows a state in which two cold air generators 6 are juxtaposed in the conveying direction of the belt conveyor 5. The cold air outlet of the cold air generator 6 is disposed so as to face the upper surface of the belt conveyor 5. And the melt of the polyester resin part decomposition polymer is cooled and solidified by blowing the cold air from the cold wind generator 6 with respect to the melt of the polyester resin part decomposition polymer conveyed on the belt conveyor 5. Is done.

  The cooled solidified product of the polyester resin part decomposition polymer becomes an elongated and thin plate-shaped solidified product. The solidified product of the polyester resin part decomposition polymer is very brittle and breaks easily. The elongated and thin polyester resin part decomposition polymer is cut into an appropriate length by a cutting device 12 provided in front of the front end of the belt conveyor 5. In this embodiment, the cutting device 12 is composed of a plate-like member 12a, and the plate-like member 12a has an inclined surface 12b that is inclined downward toward the conveying direction of the solidified product of the polyester resin part decomposition polymer. ing. The cutting device 12 is provided so that the inclined surface 12b is positioned in front of the front end portion of the belt conveyor 5 and on the horizontal extension line of the conveying surface of the belt conveyor 5.

  The solidified product of the polyester resin part decomposition polymer conveyed on the belt conveyor 5 collides with the inclined surface 12b of the plate-like member 12a, and then is forcibly bent downward along the inclination of the inclined surface 12b. Therefore, bending stress is applied to the solidified product of the polyester resin part decomposition polymer. As described above, the solidified product of the polyester resin partial decomposition polymer is very brittle, and therefore easily breaks even with a small bending stress. In this way, the solidified product of the polyester resin part decomposition polymer is cut into an appropriate length. In addition, the length after cutting | disconnection of the solidified material of a polyester resin part decomposition | disassembly polymer can be changed by adjusting the inclination-angle of the inclined surface 12b of the plate-shaped member 12a with respect to the conveyance surface of the belt conveyor 5. FIG. For example, by increasing the inclination angle of the inclined surface 12b with respect to the conveying surface of the belt conveyor 5, when the solidified product of the polyester resin portion decomposition polymer is forcibly bent along the inclined surface 12b, the polyester resin portion decomposition weight is reduced. The bending stress generated for the combined solidified product becomes large. As a result, the length after cutting of the solidified product of the polyester resin part decomposition polymer is shortened.

[Description of crushing apparatus and crushing process]
The solidified product of the polyester resin part decomposition polymer cut to an appropriate length is put into a crushing device 7 disposed below the front end of the belt conveyor 5. In the present embodiment, the pulverizer 7 includes a first pulverizer 7a, a second pulverizer 7b, and a third pulverizer 7c. The solidified product of the polyester resin part decomposition polymer is first put into the first pulverizer 7a and crushed (preliminary pulverization), and then the crushed material crushed by the first pulverizer 7a is the second pulverizer 7b. The coarsely pulverized product is finally finely pulverized (second main pulverization) by the third pulverizer 7c to obtain a polyester resin part decomposition polymer powder. .

  The first crushing device 7 a is disposed below the front end portion of the belt conveyor 5 and receives and crushes the solidified product of the polyester resin part decomposition polymer cut by the cutting device 12. In the present embodiment, the first crusher 7a is a roll mill. The first crushing device 7a is provided as necessary, and the polyester resin part decomposition polymer solidified product cut by the cutting device 12 is small enough to be pulverized by the second crushing device 7b. It is not necessary to provide the first crushing device 7a.

  The second pulverizer 7b is disposed below the first pulverizer 7a, receives the crushed material crushed by the first pulverizer 7a, and further pulverizes (coarsely pulverizes) the crushed material. The second pulverizer 7b is preferably composed of a dry pulverizer having a classification mechanism. In the present embodiment, the second pulverizer 7b incorporates a mesh screen having a predetermined opening as a classification mechanism. This is a dry impact crusher. In the second pulverizer 7b, pulverization is repeatedly performed until the crushed material becomes smaller than the mesh screen opening. Then, the coarsely pulverized product that has become smaller than the mesh screen opening passes through the mesh screen and is collected by the cyclone type collecting device 13 connected to the second pulverizing device 7b.

  The coarsely pulverized material recovered by the recovery device 13 is supplied to the third pulverizing device 7c and further pulverized (finely pulverized). In the present embodiment, the third crusher 7c is a wet bead mill.

  When the wet bead mill 7c is used, the coarsely pulverized product and the liquid (for example, water) are agitated in advance with a stirrer rather than supplying the coarsely pulverized product to the bead mill 7c containing the liquid as it is. It is preferable to pulverize the slurry by supplying the slurry into the bead mill 7c containing the liquid. Thus, by preparing the slurry of the coarsely pulverized product in advance, the dispersibility of the coarsely pulverized product with respect to the liquid in the bead mill 7c is improved, and the pulverization time can be shortened. In addition, it is preferable to use the liquid which can be used as a natural fiber modifier mentioned later for the liquid used for the liquid at the time of producing the slurry and the bead mill 7c.

The bead mill 7c may be a batch type or a circulation type. In the case of circulation, as shown in FIG. 2, is connected to a discharge port 7c ₁ and the tank 15 of the bead 7c, the tank 15 and the pump 14 is connected, and a supply port 7c of the pump 14 and the bead 7c ₂ are connected. The circulating moves to the ground product and the tank 15 a portion of the liquid in the bead mill 7c during the grinding by the pump 14 from the discharge port 7c _1, then pulverized and the liquid again supply port is moved to the tank 15 7c ₂ returns to the bead mill 7c. By repeating such an operation continuously, the coarsely pulverized product passes through the bead mill 7c a plurality of times and is repeatedly pulverized, so that a powder having a sharp particle size distribution can be obtained. In addition, by providing the stirring blade in the tank 15, the tank 15 can be used as a stirrer for producing the slurry, and the pulverized material and liquid in the tank 15 can be stirred. It is possible to prevent the pulverized material moved from the bead mill 7c into the tank 15 from being precipitated in the tank 15.

  The polyester resin part decomposed polymer powder is pulverized in the liquid by the wet bead mill 7c, whereby the polyester resin part decomposed polymer powder is obtained in a dispersed state in the liquid. The natural fiber modifier is produced by adding and mixing an additive such as a crosslinking agent or a crosslinking catalyst in a liquid in which the polyester resin part decomposition polymer powder is dispersed. Then, the natural fiber cloth is impregnated with the liquid natural fiber modifier thus obtained, and then the cloth is squeezed and dried to complete the modification of the natural fiber cloth. .

  As described above, since the natural fiber modifier is preferably in a liquid state, when a dry pulverizer is used as the third pulverizer 7c, a polyester resin depolymerized powder is obtained, and then the polyester resin is obtained. A step of mixing the depolymerized powder and the liquid is necessary. However, as in the present embodiment, by using a wet pulverizer as the third pulverizer 7c, the step of mixing the polyester resin depolymer powder and the liquid when producing the natural fiber modifier is performed. Can be omitted.

Further, the third crushing device 7c, the cumulative 50% volume size of the polyester resin portion decomposed polymer powder obtained (D ₅₀₎ is preferably to be ground until 10μm or less. When the polyester resin partial decomposition polymer powder has a cumulative volume 50% diameter (D ₅₀ ) of 10 μm or less, when this polyester resin partial decomposition polymer powder is used as a natural fiber modifier, the polyester resin partial decomposition weight The coalesced powder is uniformly dispersed in the natural fiber cloth. Therefore, printing unevenness at the time of sublimation transfer printing can be prevented.

[Other Embodiments]
Although the case where the uniaxial melt extrusion apparatus was used for the melt extrusion apparatus 4 was demonstrated in the said embodiment, the melt extrusion apparatus 4 may be a biaxial melt extrusion apparatus. The casing 4a may be a jacket-type casing, and the casing 4a may be heated by flowing steam or heated oil as a heating medium through the jacket.

  Moreover, at the time of melt-kneading the polyester resin and the polyhydric alcohol in the melt extrusion apparatus 4, for example, an additive such as a catalyst for promoting partial decomposition polymerization of the polyester resin may be added as necessary.

  Further, instead of directly blowing cold air to the melt of the polyester resin partial decomposition polymer on the belt conveyor 5 by the cold air generator 6, it is applied to the back side of the conveying surface of the belt conveyor 5 (back side of the belt of the belt conveyor 5). Cold air may be blown. In other words, the polyester resin partial decomposition polymer is melted indirectly by blowing cold air on the belt of the belt conveyor 5 to cool the belt instead of directly blowing cold air on the melt of the polyester resin partial decomposition polymer. The object may be cooled.

[Experimental conditions]
The polyester resin part decomposition polymer powder was manufactured using the manufacturing apparatus 1 shown in FIG. First, in accordance with the experimental conditions below, a melt of the polyester resin part decomposition polymer was produced by the melt extrusion apparatus 4.
Polyester resin: PET resin pellet (weight average molecular weight Mw about 30,000)
Polyhydric alcohol: Glycerin Mixing ratio of PET resin monomer and glycerin: 0.1 mol of glycerin with respect to 1 mol of PET resin monomer
Melt kneading temperature: 270 ° C
Melt kneading time: 5 minutes

  Next, while the melt of the polyester resin partial decomposition polymer produced under the above conditions was transported by the belt conveyor 5, cold air was blown from the cold air generator 6 to be cooled and solidified. Then, the solidified product was pulverized by the first pulverizing device 7a, the second pulverizing device 7b, and the third pulverizing device 7c to obtain a polyester resin part decomposition polymer powder. The first pulverizer 7a has a roll mill, the second pulverizer 7b has a dry impact pulverizer incorporating a mesh screen (mesh size: φ0.3 mm) as a classification mechanism, and the third pulverizer 7c Used a circulation type bead mill (bead diameter: φ1 mm, liquid: water) shown in FIG. 2. In the bead mill, the grinding time was 30 minutes.

[Molecular weight measurement]
The molecular weight of the obtained polyester resin part decomposition polymer powder was measured. The molecular weight was evaluated using the weight average molecular weight Mw. The molecular weight measurement was performed using gel permeation chromatography (e2695 manufactured by Nippon Waters Co., Ltd., column: two Shodex HFIP-606M manufactured by Showa Denko KK, detector: e2914 RI detector manufactured by Nippon Waters Co., Ltd.). . First, polyester resin partial decomposition polymer powder and polymethyl methacrylate (standard material) are added to 1,1,1,3,3,3-hexa so that the concentration of the polyester resin partial decomposition polymer is 0.4 mg / mL. The sample solution was prepared by dissolving in fluoro-2-propanol and filtering the solution through a membrane filter (pore size: 0.2 μm). 100 μL of this sample solution was injected into the measuring apparatus, and measurement was performed under the following conditions.
Eluent: 1,1,1,3,3,3-hexafluoro-2-propanol column with 5 mM sodium trifluoroacetate added Temperature: 40 ° C.
Flow rate: 0.4 mL / min

[Particle size measurement]
The particle diameter of the obtained polyester resin part decomposition polymer powder was measured. The particle diameter was evaluated using a 50% cumulative volume diameter (D ₅₀ ). The particle size was measured by a wet method (solvent: water) using a laser diffraction particle size distribution analyzer (SALD-2000 manufactured by Shimadzu Corporation).

[Experimental result]
As a result of experiments under the above conditions, the weight average molecular weight of the obtained polyester resin part decomposition polymer powder was about 1880. This corresponds to the molecular weight when about 10 PET resin monomers are polymerized. Moreover, the cumulative volume 50% diameter of the obtained polyester resin part decomposition polymer powder was about 10 μm.

  The present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 2 Polyester resin hopper 2a Discharge port 2b Gas introduction port 3 Polyhydric alcohol hopper 3a Discharge port 3b Gas introduction port 4 Melt extrusion apparatus 4a Casing 4b Polyester resin supply port 4c Polyhydric alcohol supply port 4d Discharge port 5 Conveying device 6 Cooling device 7 Crushing device 7a First crushing device 7b Second crushing device 7c Third crushing device 7c ₁ Discharge port 7c ₂ Supply port 8 Supply speed adjusting device 9 Gas unit 9a Gas tank 9b Piping 9c Piping 9d Pipe 9e Pressure control valve 9f Flow rate controller 9g Pressure control valve 10 Discharge speed control device 11 Base 12 Cutting device 12a Plate member 12b Inclined surface 13 Collection device 14 Pump 15 Tank

Claims (10)

An apparatus for producing a partially decomposed polymer powder of a polyester resin used as a natural fiber modifier for enabling sublimation transfer printing on the surface of a natural fiber cloth, the production apparatus comprising:
A polyester resin hopper for storing the polyester resin;
A polyhydric alcohol hopper for storing polyhydric alcohol;
A polyester resin supplied from the polyester resin hopper and a polyhydric alcohol supplied from the polyhydric alcohol hopper are melted and kneaded to partially depolymerize the polyester resin. A melt extrusion apparatus for producing the obtained melt,
A transport device for transporting the melt of the partially decomposed polymer of the polyester resin extruded from the melt extrusion device while being flattened;
A cooling device for cooling and solidifying the partially decomposed polymer of the polyester resin developed on the conveying device;
And a pulverizing device for pulverizing and solidifying the solidified product of the partially decomposed polymer of the polyester resin.   The pulverization apparatus comprises a dry pulverization apparatus for pulverizing the solidified product of the partially depolymerized polyester resin, and a wet pulverization apparatus for finely pulverizing the pulverized substance pulverized by the dry pulverization apparatus; The manufacturing apparatus according to claim 1, comprising: The manufacturing apparatus according to claim 2, wherein the pulverized product obtained by the dry pulverizer is pulverized by the wet pulverizer until a cumulative volume 50% diameter (D ₅₀ ) is 10 µm or less.   The manufacturing apparatus according to any one of claims 1 to 3, wherein the polyester resin is a polyethylene terephthalate resin and the polyhydric alcohol is glycerin.   The manufacturing apparatus according to claim 4, wherein a mixing ratio of the polyethylene terephthalate resin and the glycerin is 0.05 mol to 0.2 mol of the glycerin with respect to 1 mol of the polyethylene terephthalate resin monomer.   The manufacturing apparatus according to claim 4 or 5, wherein the melt kneading of the polyethylene terephthalate resin and the glycerin in the melt extrusion apparatus is performed in a range of 260 ° C to 300 ° C.   The manufacturing apparatus according to any one of claims 4 to 6, wherein the melt kneading of the polyethylene terephthalate resin and the glycerin in the melt extrusion apparatus is performed in a range of 1 minute to 10 minutes. A method for producing a partially decomposed polymer powder of a polyester resin used as a natural fiber modifier for enabling sublimation transfer printing on the surface of a natural fiber cloth, the production method comprising:
A melt-kneading step for producing a melt of a partially decomposed polymer of polyester resin by kneading with a polyhydric alcohol while heating and melting the polyester resin;
A cooling and solidifying step of cooling and solidifying the melt of the partially decomposed polymer of the polyester resin obtained by the melt-kneading step;
And a pulverizing step of pulverizing and solidifying the solidified product of the partially decomposed polymer of the polyester resin obtained in the cooling and solidifying step.   In the pulverization step, the solidified product of the partially decomposed polymer of the polyester resin obtained in the cooling and solidifying step is crushed by dry pulverization, and the pulverized product obtained in the pulverized step is wet pulverized. The manufacturing method according to claim 8, comprising a pulverizing step of pulverizing.   The production method according to claim 8 or 9, wherein the polyester resin is a polyethylene terephthalate resin and the polyhydric alcohol is glycerin.

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