WO2019039458A1 - Matière de moulage à l'état fondu - Google Patents

Matière de moulage à l'état fondu Download PDF

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WO2019039458A1
WO2019039458A1 PCT/JP2018/030779 JP2018030779W WO2019039458A1 WO 2019039458 A1 WO2019039458 A1 WO 2019039458A1 JP 2018030779 W JP2018030779 W JP 2018030779W WO 2019039458 A1 WO2019039458 A1 WO 2019039458A1
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melt
evoh
water
molding material
acid
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PCT/JP2018/030779
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English (en)
Japanese (ja)
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康弘 野中
英里子 米谷
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株式会社クラレ
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Priority to CN201880054441.6A priority Critical patent/CN110945059B/zh
Priority to JP2019537632A priority patent/JP7160816B2/ja
Publication of WO2019039458A1 publication Critical patent/WO2019039458A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the present invention relates to melt molding materials.
  • Ethylene-vinyl alcohol copolymer (hereinafter, also referred to as "EVOH”) is excellent in gas barrier properties, transparency, oil resistance, non-charging properties, mechanical strength and the like, and various packaging materials such as films, sheets, and containers. It is widely used as etc.
  • the appearance characteristics generally refer to characteristics capable of obtaining a molded product having an excellent appearance, such as occurrence of gel and bumps and occurrence of coloring such as yellowing.
  • long run property means that physical properties such as viscosity do not change even during long-time molding, and a molded article free of streaks and the like can be obtained.
  • Thermal deterioration of EVOH is considered to be a factor that reduces the appearance characteristics and long run characteristics. Therefore, in Patent Documents 1 and 2, acids such as carboxylic acid and phosphoric acid, alkali metal salts and alkaline earth are required in Patent Documents 1 and 2 in order to improve the various properties required for a melt molding material containing EVOH, in particular, the appearance properties.
  • Various EVOH compositions in which EVOH contains a metal salt such as a metalloid salt at an appropriate content rate have been proposed. According to these EVOH compositions, thermal deterioration is suppressed, appearance characteristics and long-run properties are enhanced, and it is believed that a molded article having an excellent appearance even in continuous molding for a long time can be obtained.
  • the melt-formed material containing EVOH is required to suppress the sudden generation of sudden generation during continuous melt forming.
  • thermal deterioration hardly occurs by confirming the presence or absence of carbonyl group formation by infrared spectroscopy in this sudden change. That is, according to the findings of the present inventors, this sudden buildup is caused by a factor different from the gel, the buildup and the coloring produced due to the above-mentioned thermal deterioration, and the additives such as acid and metal salt are used. Addition is not enough solution.
  • the present invention has been made based on the above circumstances, and an object thereof is to provide a melt-forming material capable of suppressing the occurrence of sudden bumps during continuous melt-forming.
  • the invention made to solve the above problems is a columnar, flat or spherical melt-formed material containing ethylene-vinyl alcohol copolymer (EVOH), wherein the maximum height roughness (Rz) of the side surface is 300 ⁇ m or less It is a melt molding material.
  • EVOH ethylene-vinyl alcohol copolymer
  • the present inventors have found that the sudden spikes occur due to the following reasons.
  • the following phenomenon occurs when the melt-forming material (EVOH) is passed through the inside of the pipe by air flow transport and sent to the hopper or the like of the melt-forming machine in continuous melt-forming.
  • EVOH melt-forming material
  • a part of the melt-formed material is scraped and pulverized due to a collision of the melt-formed material on the inner surface of the pipe or a collision of the melt-formed materials.
  • the stagnation part such as a bent part of the pipe, the pulverized EVOH is melted by the frictional heat generated at the time of air flow conveyance to become a tape-like foreign substance.
  • the foreign matter flows out of the stagnant part discontinuously during continuous melt forming and is supplied to the melt forming machine together with the melt forming material.
  • the foreign matter since the foreign matter is in the form of a tape, it is difficult to be sheared and is not easily melted in the melt molding machine. Therefore, the foreign matter remains in the obtained melt-molded body, that is, bumps derived from the foreign matter are generated suddenly.
  • EVOH has a high glass transition temperature and is a hard resin having a hydroxyl group, so it is easily pulverized during air transportation, and it is easy to generate sudden bumps.
  • the melt-forming material of the present invention when the maximum height roughness (Rz) of the side surface is 300 ⁇ m or less, it is difficult to cause scraping when colliding with the inner surface of the pipe during air flow conveyance. Therefore, according to the said melt-forming material, generation
  • the arithmetic mean roughness (Ra) of the side surface is preferably 50 ⁇ m or less.
  • the arithmetic mean roughness (Ra) of the side surface is preferably 50 ⁇ m or less.
  • the full width at half maximum in the particle size distribution of the circle equivalent diameter of the said fusion molding material is 1 mm or less.
  • the ethylene unit content of the ethylene-vinyl alcohol copolymer is preferably 20 mol% or more and 60 mol% or less. By making ethylene unit content into the said range, melt moldability, gas barrier property, etc. can be exhibited with sufficient balance.
  • the biting property and the like at the time of melt-forming can be improved by the height being 1 to 20 mm and the diameter being 1 to 20 mm.
  • the biting property and the like at the time of melt-forming can be improved by the longitudinal length being 1 to 20 mm and the transverse length being 1 to 20 mm.
  • the melt-forming material of the present invention can suppress the occurrence of sudden bumps during continuous melt-forming.
  • (A) is a perspective view of a columnar fusion molding material concerning one embodiment of the present invention.
  • (B) is a front view of the flat melt molding material which concerns on one Embodiment of this invention.
  • (A) is a photograph of the tape-like foreign material extract
  • FIG. The both ends of the foreign matter are fixed with tape and photographed with a ruler (in cm).
  • (B) is an enlarged photograph of the tape-like foreign substance obtained in Comparative Example 1.
  • the melt-forming material 1 of FIG. 1A is a columnar melt-forming material containing EVOH.
  • the melt molding material 1 may be particulates called pellets.
  • columnar refers to a shape having substantially parallel upper and lower surfaces.
  • substantially parallel means that the angle between the upper surface and the lower surface is within ⁇ 10 °.
  • the upper and lower surfaces are substantially planar but may be curved.
  • the upper and lower surfaces are generally of substantially the same shape but may be different.
  • the upper and lower surfaces are substantially the same size, but may be different.
  • the melt molding material 1 may be a straight pillar or a diagonal pillar, but is preferably a straight pillar.
  • the melt molding material 1 of FIG. 1 (a) is cylindrical.
  • the term “cylindrical shape” means a columnar shape whose cross section in a direction perpendicular to the central axis (axial direction) X is circular.
  • circular shape it is not limited to a perfect circle, An ellipse may be sufficient and it may be a circle which has a concave or a projected part.
  • the melt-forming material may have a prismatic shape such as a square pillar shape, a hexagonal pillar shape, or the like in addition to a cylindrical shape. However, it is preferable that it is cylindrical from the viewpoint that pulverization at the time of air flow conveyance is further suppressed.
  • the cylindrically shaped melt molding material 1 has an upper surface 3 a, a lower surface 3 b and a side surface 2.
  • the upper surface 3a and the lower surface 3b are circular in the same size.
  • the side in which the upper surface 3a or the lower surface 3b and the side surface 2 are in contact with each other may be rounded.
  • the size of the melt molding material 1 is not particularly limited, but the lower limit of the height A is preferably 1 mm, and more preferably 2 mm. On the other hand, 20 mm is preferable, as for the upper limit of height A, 10 mm is more preferable, and 5 mm is more preferable. Moreover, 1 mm is preferable and, as for the minimum of the diameter B of the fusion molding material 1, 2 mm is more preferable. On the other hand, 20 mm is preferable, 10 mm is more preferable, and 5 mm of the upper limit of the diameter B is more preferable.
  • the handleability, the conveyance property in airflow conveyance, biting property to an extruder, etc. can be improved.
  • the upper limit of the maximum height roughness (Rz) of the side surface 2 of the melt molding material 1 is 300 ⁇ m, preferably 200 ⁇ m, more preferably 150 ⁇ m, still more preferably 120 ⁇ m, and particularly preferably 100 ⁇ m.
  • the lower limit of the maximum height roughness (Rz) in the side surface 2 is preferably 10 ⁇ m, more preferably 30 ⁇ m, and still more preferably 50 ⁇ m.
  • the maximum height roughness (Rz) of the side surface 2 of the melt molding material 1 is preferably 10 ⁇ m, more preferably 30 ⁇ m, and still more preferably 50 ⁇ m.
  • the upper limit of the arithmetic average roughness (Ra) of the side surface 2 of the melt-forming material 1 is preferably 50 ⁇ m, more preferably 40 ⁇ m, still more preferably 30 ⁇ m, still more preferably 25 ⁇ m, even more preferably 20 ⁇ m, and most preferably 10 ⁇ m.
  • the arithmetic average roughness (Ra) is preferably 50 ⁇ m, more preferably 40 ⁇ m, still more preferably 30 ⁇ m, still more preferably 25 ⁇ m, even more preferably 20 ⁇ m, and most preferably 10 ⁇ m.
  • the lower limit of the arithmetic average roughness (Ra) in the side surface 2 is preferably 1 ⁇ m, more preferably 3 ⁇ m, still more preferably 3.5 ⁇ m, and even more preferably 5 ⁇ m.
  • the maximum height roughness (Rz) and the arithmetic average roughness (Ra) of the melt-formed material are each taken as the average value of the measured values of 100 arbitrarily selected melt-formed materials.
  • the measured values of the maximum height roughness (Rz) and arithmetic average roughness (Ra) of the melt-formed material are measured at a cutoff value ( ⁇ c) of 2.5 mm according to JIS B 0601 (2001). Value.
  • the evaluation surface is a non-contact type, and the evaluation area is the one measured at a maximum width of 1414 ⁇ m and a height of 1060 ⁇ m. When the melt-molded material is small, the evaluation area may be appropriately adjusted.
  • the melt molding material 11 of FIG. 1 (b) is a flat melt molding material containing EVOH.
  • the melt molding material 11 may be particulates called pellets.
  • "flat” refers to a shape in which a cross section having a plane including the rotation axis (central axis) Y as a cutting plane is elliptical.
  • the flat melt molding material 11 may be a spheroid.
  • a direction along a portion having the longest linear distance along the horizontal direction is taken as a longitudinal direction d (in FIG. 1 (b), horizontal direction And the direction perpendicular to the horizontal plane is the lateral direction c.
  • the short direction c is identical to the direction of the rotation axis Y.
  • the length C in the short direction c is shorter than the length D in the longitudinal direction d.
  • the melt molding material may be a spherical melt molding material containing EVOH.
  • Spherical means a shape whose cross section having a plane including the rotation axis Y as a cutting plane is circular. In FIG.1 (b), when the length C of the transversal direction c and the length D of the longitudinal direction d are the same length, the fusion molding material 11 becomes spherical.
  • the maximum height roughness (Rz) of the side surface 12 is 300 ⁇ m or less.
  • the side surface 12 is a curved surface portion of the surface of the melt molding material 11 whose normal is substantially perpendicular to the rotation axis Y (short direction c).
  • the side surface 12 is a curved surface portion along the circumferential direction including the so-called equator.
  • the side surface 12 is a region surrounded by a broken line along the longitudinal direction d (the same applies to the region corresponding to the back side of the paper surface of FIG. 1B).
  • the arbitrary parts of the surface are side surfaces.
  • the size of the melt molding material 11 is not particularly limited, but the lower limit of the length C in the short direction of the melt molding material 11 is preferably 1 mm, and more preferably 1.5 mm.
  • the upper limit of the length C in the short direction is preferably 20 mm, more preferably 10 mm, and still more preferably 5 mm.
  • 1 mm is preferable and, as for the minimum of longitudinal direction length D, 1.5 mm is more preferable.
  • the upper limit of the longitudinal direction length D is preferably 20 mm, more preferably 10 mm, and still more preferably 5 mm.
  • the upper limit of the maximum height roughness (Rz) of the side surface 12 of the melt molding material 11 is 300 ⁇ m, preferably 200 ⁇ m, more preferably 150 ⁇ m, still more preferably 120 ⁇ m, and particularly preferably 100 ⁇ m.
  • the lower limit of the maximum height roughness (Rz) of the side surface 12 is preferably 10 ⁇ m, more preferably 30 ⁇ m, and still more preferably 50 ⁇ m.
  • the maximum height roughness (Rz) of the side surface 12 of the melt molding material 11 is preferably 10 ⁇ m, more preferably 30 ⁇ m, and still more preferably 50 ⁇ m.
  • the upper limit of the arithmetic average roughness (Ra) of the side surface 12 of the melt-molded material 11 is preferably 50 ⁇ m, more preferably 40 ⁇ m, still more preferably 30 ⁇ m, still more preferably 25 ⁇ m, even more preferably 20 ⁇ m, and most preferably 10 ⁇ m.
  • the arithmetic average roughness (Ra) is preferably 50 ⁇ m, more preferably 40 ⁇ m, still more preferably 30 ⁇ m, still more preferably 25 ⁇ m, even more preferably 20 ⁇ m, and most preferably 10 ⁇ m.
  • the lower limit of the arithmetic average roughness (Ra) in the side surface 12 is preferably 1 ⁇ m, more preferably 3 ⁇ m, still more preferably 3.5 ⁇ m, and even more preferably 5 ⁇ m.
  • the maximum height roughness (Rz) and arithmetic average roughness (Ra) of the side surface 2 of the melt-forming material 1 and the side surface 12 of the melt-forming material 11 are gold when forming the melt-forming material as described later. It can be adjusted by controlling the surface roughness of the inner surface of the mold and the drying conditions of the melt-formed material.
  • the upper limit of the full width at half maximum (FWHM) in the particle size distribution of the circle-equivalent diameter (diameter) of melt-formed materials (hereinafter, column-shaped, flat, and spherical melt-formed materials may be simply referred to as melt-formed materials) 1 mm is preferable, 0.6 mm is more preferable, 0.5 mm is more preferable, and 0.4 mm is particularly preferable.
  • the size of the melt-formed material uniform by setting the half-width in the particle size distribution of the melt-formed material to 1 mm or less, biting into the extruder can be stabilized, and thickness unevenness of the obtained melt-formed product can be suppressed.
  • the lower limit of the full width at half maximum in this particle size distribution may be 0.1 mm, 0.2 mm, or 0.3 mm.
  • the particle size distribution of the circle equivalent diameter (radius) of the melt molding material is the circle equivalent diameter calculated by the dynamic image analysis method according to ISO 13322-2 (2006) using 500 g of the melt molding material Particle size distribution of
  • the particle size distribution of the melt-formed material can be adjusted by sieving the produced melt-formed material.
  • EVOH ethylene-vinyl ester copolymer
  • EVOH is a copolymer having ethylene units and vinyl alcohol units as main structural units.
  • EVOH may contain one or more other structural units in addition to the ethylene unit and the vinyl alcohol unit.
  • EVOH is usually obtained by polymerizing ethylene and a vinyl ester, and saponifying the resulting ethylene-vinyl ester copolymer. The polymerization and saponification can be carried out by methods known in the art.
  • the lower limit of the ethylene unit content of EVOH (that is, the ratio of the number of ethylene units to the total number of monomer units in EVOH) is preferably 20 mol%, more preferably 22 mol%, and still more preferably 24 mol%. On the other hand, 60 mol% is preferable, as for the upper limit of ethylene unit content of EVOH, 55 mol% is more preferable, and 50 mol% is more preferable. By making ethylene unit content of EVOH into the said range, sufficient melt moldability, gas barrier property, etc. can be exhibited.
  • the ethylene unit content of EVOH is set to 20 mol% or more, for example, the water resistance, hot water resistance, gas barrier property under high humidity, and melt formability of the obtained melt-formed product are enhanced.
  • the ethylene unit content of EVOH is set to 60 mol% or less, the gas barrier properties and the like of the obtained molded article can be enhanced.
  • the lower limit of the degree of saponification of EVOH (that is, the ratio of the number of vinyl alcohol units to the total number of vinyl alcohol units and vinyl ester units in EVOH) is preferably 80 mol%, more preferably 95 mol%, still more preferably 99 mol% .
  • 100 mol% is preferable and 99.99 mol% of the upper limit of the saponification degree of EVOH is more preferable.
  • the lower limit of the melt flow rate of EVOH (according to JIS K 7210, measured at a temperature of 210 ° C. and a load of 2160 g) is preferably 0.1 g / 10 min, more preferably 0.5 g / 10 min, 1 g / 10 min More preferably, 3 g / 10 min is particularly preferred.
  • the upper limit of the melt flow rate of EVOH is preferably 200 g / 10 min, more preferably 50 g / 10 min, still more preferably 30 g / 10 min, particularly preferably 15 g / 10 min, and most preferably 10 g / 10 min.
  • the lower limit of the content of EVOH in the melt molding material is preferably 50% by mass, more preferably 90% by mass, still more preferably 99% by mass, and particularly preferably 99.9% by mass.
  • the content of EVOH in the melt molding material may be 100% by mass.
  • the melt molding material may contain other components other than EVOH.
  • other components include carboxylic acids, carboxylic acid salts, phosphoric acid compounds and boron compounds. When these components are contained, appearance characteristics and long run characteristics can be enhanced.
  • the carboxylic acid may be a monocarboxylic acid or a polyvalent carboxylic acid.
  • monocarboxylic acids examples include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, acrylic acid, methacrylic acid, benzoic acid, 2-naphthoic acid and the like. These monocarboxylic acids may have a hydroxyl group or a halogen atom. Moreover, as a monocarboxylic acid ion, what the hydrogen ion of the carboxy group of each said monocarboxylic acid detached
  • the polyvalent carboxylic acid may have two or more carboxy groups in the molecule, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, malic acid, glutaric acid, adipic acid, Aliphatic dicarboxylic acids such as pimelic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as citric acid, isocitric acid and aconitic acid; 1,2,3,4-butanetetracarboxylic acid, Carboxylic acids having four or more carboxyl groups such as ethylenediaminetetraacetic acid; hydroxycarboxylic acids such as citric acid, isocitric acid, tartaric acid, malic acid, mucic acid, thaltronic acid, citromalic acid; oxaloacetic acid, mesooxalic acid, 2-ketoglutaric acid Ketocarboxylic acids such as
  • Examples of the phosphoric acid compound include oxygen acids of various types of phosphorus such as phosphoric acid and phosphorous acid and salts thereof.
  • the phosphate may be contained, for example, in any form of primary phosphate, secondary phosphate, and tertiary phosphate, and is not particularly limited as a counter cation species, but is an alkali metal salt. And alkaline earth metal salts are preferred.
  • Examples of the boron compound include boric acids, boric acid esters, boric acid salts, and borohydrides.
  • examples of boric acids include orthoboric acid (H 3 BO 3 ), metaboric acid, tetraboric acid and the like.
  • examples of boric acid esters include triethyl borate and trimethyl borate.
  • examples of the borate include alkali metal salts of various boric acids, alkaline earth metal salts, and borax.
  • the melt molding material contains an appropriate amount of additives such as a lubricant, a plasticizer, a stabilizer, a surfactant, a colorant, an ultraviolet absorber, an antistatic agent, a desiccant, a crosslinking agent, a filler, and various fibers. May be In addition, a lubricant or the like may be attached to the surface of the melt molding material. Furthermore, the said melt molding material may contain thermoplastic resins other than EVOH.
  • thermoplastic resins other than EVOH include polyolefin, nylon, polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene, polyacrylonitrile, polyurethane, polyacetal, modified polyvinyl alcohol and the like.
  • polystyrene resin examples include polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, ethylene-propylene copolymer, copolymer of ethylene and ⁇ -olefin having 4 or more carbon atoms, polyolefin and anhydride
  • examples thereof include copolymers with maleic acid, ethylene-vinyl ester copolymers, ethylene-acrylic acid ester copolymers, and modified polyolefins obtained by graft-modifying these with unsaturated carboxylic acids or their derivatives.
  • nylon examples include nylon-6, nylon-66, and nylon-6 / 66 copolymer.
  • These other components can be mixed with EVOH by known methods.
  • it can be mixed by a method of melt-kneading EVOH and other components, or a method of immersing EVOH in a solution containing other components.
  • the melt-forming material comprises, for example, a granulation step (step 1 (a), step 1 (b) or step 1 (c)) of obtaining a water-containing pellet of EVOH by a granulation operation from a solution containing EVOH It can obtain by passing through the drying process (step 2) to dry.
  • a sieving step (step 3) may be further provided.
  • the EVOH to be subjected to the step 1 can be obtained through the polymerization step and the saponification step which are conventionally known methods as described above.
  • Step 1 (a) In the production of a melt-molded material, EVOH is usually obtained as a solution dissolved in the solvent or the like used in the saponification reaction.
  • the solution is granulated to obtain a water-containing pellet containing EVOH.
  • the operation of granulation for obtaining such water-containing pellets is not particularly limited.
  • the strand-like solidified material can be cut by a strand cutter to obtain a pillar-shaped water-containing pellet of EVOH.
  • the coagulation bath for example, a mixed solvent of water and methanol is used.
  • the moisture content of the water-containing pellet obtained can be adjusted with the mass ratio etc. of this mixed solvent and EVOH.
  • Step 1 (b) a method of obtaining a water-containing pellet of flat (stone-like) to spherical EVOH by cutting with a blade etc. rotating immediately after extruding a solution of ethylene-vinyl alcohol copolymer into a coagulation bath, etc.
  • Known methods can be used.
  • Step 1 (c) Furthermore, in the granulation step, after a solution of ethylene-vinyl alcohol copolymer is brought into contact with steam by the method described in JP-A-2002-121290 or the like to obtain a water-containing resin composition of EVOH in advance, it is extruded into a coagulation bath A method of cutting this to obtain a water-containing pellet of EVOH, etc. can also be suitably used.
  • the inner surface of the mold used when extruding a solution of EVOH in particular, the inner surface of the outlet portion (die)
  • the surface roughness (maximum height roughness (Rz) and arithmetic average roughness (Ra) of the side surface 2 of the melt-formed material 1 and the side surface 12 of the melt-formed material 11 finally obtained by controlling the surface roughness ) Can be adjusted.
  • the surface shape of the inner surface of the mold outlet portion is transferred to a solution (water-containing pellet) of EVOH to be extruded. Therefore, the surface roughness of the resulting melt-formed material can be reduced by increasing the smoothness of the inner surface of the mold outlet portion.
  • the upper limit of the maximum height roughness (Rz) of the inner surface of the mold outlet portion is preferably 15 ⁇ m, more preferably 5 ⁇ m, still more preferably 3 ⁇ m, and particularly preferably 1 ⁇ m.
  • the lower limit of the maximum height roughness (Rz) may be 0.1 ⁇ m or 0.3 ⁇ m.
  • the upper limit of the arithmetic mean roughness (Ra) of the inner surface of the mold outlet portion is preferably 1.2 ⁇ m, more preferably 1 ⁇ m, still more preferably 0.5 ⁇ m, particularly preferably 0.2 ⁇ m, and most preferably 0.1 ⁇ m .
  • the lower limit of the arithmetic average roughness (Ra) may be 0.01 ⁇ m or 0.03 ⁇ m.
  • the maximum height roughness (Rz) and the arithmetic average roughness (Ra) of the inner surface of the mold outlet portion are respectively taken as the average values of the measurement values at 10 arbitrarily selected locations. Further, in the present specification, the measured values of the maximum height roughness (Rz) and the arithmetic average roughness (Ra) of the inner surface of the mold outlet portion are cut-off values (JIS B 0601 (1994)). c) 2.5 mm, evaluation length (l) 7.5 mm, values measured by a contact method.
  • the water-containing pellet thus obtained may be washed if necessary. By washing, for example, by-products and the like generated at the time of saponification can be removed.
  • the water-containing pellet may be subjected to a treatment of being immersed in a solution containing an additive such as a carboxylic acid, a phosphoric acid compound, or a boron compound. By such treatment, an additive such as carboxylic acid can be contained in the obtained melt-forming material.
  • Step 2 The water-containing pellet of EVOH obtained through the above steps is converted to a melt-formed material (pellets) containing EVOH through the drying step.
  • the upper limit of the water content in the water-containing pellets of EVOH to be subjected to the drying step is preferably 200% by mass, more preferably 150% by mass, still more preferably 120% by mass, particularly 80% by mass based on the dry mass of EVOH. preferable.
  • the water content of the water-containing pellet By setting the water content of the water-containing pellet to 200% by mass or less, drying can be performed under mild conditions, and the surface roughness of the resulting melt-formed material can be reduced.
  • the lower limit of the water content may be, for example, 30% by mass, and may be 50% by mass. The drying efficiency can be enhanced by setting the water content to 30% by mass or more.
  • drying method of a water-containing pellet there is no restriction
  • the drying process may be carried out by either a continuous system or a batch system, and when a plurality of drying systems are combined, the continuous system and the batch system can be freely selected for each drying system. Drying may be carried out under an air atmosphere, but it is also preferable to carry out drying under a low oxygen concentration or in an oxygen-free state, since deterioration due to oxygen during drying can be reduced.
  • the drying initial stage means the stage until the moisture content of a water-containing pellet becomes 10 mass%, for example.
  • 90 degreeC is preferable, as for the upper limit of the atmospheric temperature (temperature of the gas to blow) in a drying initial stage, 75 degreeC is more preferable, and 65 degreeC is more preferable.
  • the ambient temperature is preferably 40 ° C, and more preferably 50 ° C.
  • the lower limit of the dew point temperature of the gas (such as air) used for drying in the early stage of drying is preferably -35.degree. C., more preferably -25.degree. C., and still more preferably -15.degree.
  • the upper limit of the dew point temperature is preferably 10 ° C, more preferably 0 ° C, and still more preferably -5 ° C.
  • the upper limit of the drying rate in the early stage of drying is preferably 50 g / hr ⁇ 100 g-dry base, more preferably 30 g / hr ⁇ 100 g-dry base, and still more preferably 20 g / hr ⁇ 100 g-dry base.
  • the drying rate is preferably 5 g / hr ⁇ 100 g-dry base, and more preferably 10 g / hr ⁇ 100 g-dry base.
  • the drying efficiency can be enhanced by setting the drying rate to 5 g / hr ⁇ 100 g-dry base or more.
  • the drying rate of 50 g / hr ⁇ 100 g-dry base means that 50 g of water is volatilized per 100 g of EVOH on a dry weight basis per hour.
  • drying may be performed at high temperature and low dew point temperature. By doing this, the drying efficiency can be enhanced.
  • 1 mass% is preferable with respect to the whole pellet, as for the upper limit of the moisture content in the pellet (melt-forming material) obtained through the drying process, 0.8 mass% is more preferable, and 0.5 mass% is more preferable.
  • the water content By setting the water content to 1% by mass or less, it is possible to suppress molding problems such as the generation of voids due to foaming or the like during melt molding processing.
  • Step 3 The pellets (melt-formed material) obtained through the drying step can be further sieved to adjust the particle size distribution.
  • the number of sieves used is appropriately set according to the size of the melt-formed resin, but can be, for example, 4 mesh or more and 10 mesh or less.
  • the particle size can be adjusted by passing through a plurality of sieves with different meshes (number of eyes).
  • the lower limit of the sieving time is preferably 1 minute, more preferably 5 minutes.
  • the upper limit may be, for example, one hour, 20 minutes is preferable, and 15 minutes is more preferable.
  • the said melt-forming material is shape
  • melt molding method extrusion molding, inflation extrusion, blow molding, melt spinning, injection molding and the like are possible.
  • the said melt-forming material is continuously conveyed by the air flow conveyance normally at the time of continuous melt-forming to injection
  • throwing-in openings such as a hopper of a melt forming machine.
  • the circulating gas used for air flow transportation and in general, air can be used, or an inert gas such as nitrogen gas may be used.
  • the lower limit of the temperature of the flowing gas is, for example, 0 ° C., and may be 10 ° C.
  • an upper limit is 100 degreeC, for example, may be 80 degreeC, and may be 60 degreeC.
  • the flow velocity of the flowing gas is usually 10 m / sec or more and 100 m / sec or less, though it depends on the size of the melt molding material, the pipe diameter and the like.
  • the particle size distribution of the circle equivalent diameter (radius) of the melt molding material is about 500 g of the melt molding material, using "CAMSIZER XT" of Varda Scientific Co., Ltd. It was determined from the equivalent circle diameter calculated by the dynamic image analysis method based on 13322-2 (2006). The full width at half maximum (mm) was determined from the obtained particle size distribution.
  • melt-molded material used in the test the one from which fine powder was removed to 10 ppm or less by a fine powder remover was used.
  • Synthesis Example 1 Synthesis of EVOH (Polymerization of Ethylene-Vinyl Acetate Copolymer) 83.0 kg of vinyl acetate and 26.6 kg of methanol are charged into a 250 L pressure reaction tank equipped with a stirrer, nitrogen inlet, ethylene inlet, initiator addition port and delay (additional addition) solution addition port, and the temperature is raised to 60 ° C. After warming, the system was purged with nitrogen by bubbling nitrogen for 30 minutes. Next, ethylene was charged so that the reactor pressure would be 3.6 MPa.
  • EVOH Polymerization of Ethylene-Vinyl Acetate Copolymer
  • AMV 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
  • the neutralized reaction solution was transferred from the reactor to a drum, allowed to stand at room temperature for 16 hours, and allowed to cool and solidify into a cake. Thereafter, the cake-like resin was drained using a centrifuge ("H-130" rotation speed: 1200 rpm, manufactured by Kokusan Centrifuge Co., Ltd.). Next, it wash
  • the resultant mixture was cut and cut to obtain a water-containing EVOH pellet having a diameter of about 4 mm and a length of about 5 mm.
  • die it is hard chromium plating and the maximum height roughness (Rz) of die (outlet part) inner surface used a metal mold whose arithmetic average roughness (Ra) is 0.6 micrometer and is 0.05 micrometer. .
  • the water-containing EVOH pellet (w-EVOH-1) after the immersion treatment was dewatered by centrifugal drainage.
  • the water content of the obtained water-containing EVOH pellet (w-EVOH-1) was 60% by mass.
  • the obtained water-containing EVOH pellet (w-EVOH-1) was dried by the following operation. First, it was dried at 60 ° C. for 5 hours in a hot air dryer using air with a dew point temperature of ⁇ 10 ° C. to make the water content 10 mass%. Subsequently, it was dried at 120 ° C. for 24 hours in hot air drying air using air having a dew point temperature of ⁇ 20 ° C.
  • Example 1 The dried pellet is sieved in the order of 6.5 mesh, 7 mesh and 8 mesh for 10 minutes, and the pellet remaining on 8 mesh is collected to obtain the dried EVOH pellets of Example 1 (melt forming The material was obtained.
  • the obtained melt-formed material was cylindrical and had a height of 3.2 mm and a diameter of 2.8 mm.
  • the water-containing pellet (w-EVOH-2) was dried by the following procedure. First, it was dried at 70 ° C. for 4 hours in a hot air drier using air with a dew point temperature of ⁇ 20 ° C. to make the water content 10 mass%. Subsequently, it was dried at 120 ° C. for 24 hours in hot air drying air using air having a dew point temperature of ⁇ 20 ° C. Thereafter, the same sieving as in Example 1 was carried out to obtain dried EVOH pellets (melt-formed material).
  • the water-containing pellet (w-EVOH-3) was dried by the following operation. First, it was dried at 80 ° C. for 4 hours in a hot air drier using air with a dew point temperature of ⁇ 30 ° C. to make the water content 10 mass%. Subsequently, it was dried at 120 ° C. for 24 hours using air with a dew point temperature of ⁇ 20 ° C. Thereafter, the same sieving as in Example 1 was carried out to obtain dried EVOH pellets (melt-formed material).
  • Example 4 As a mold for extruding a solution of EVOH, use is made of a mold that is hard chromium plated and has a maximum height roughness (Rz) of 1.5 ⁇ m on the inner surface of the die (exit part) and an arithmetic mean roughness (Ra) of 0.43 ⁇ m. The same procedure as in Example 2 was carried out except for the fact that dry EVOH pellets (melted material) were obtained.
  • Example 5 Pellets of dried EVOH in the same manner as in Example 4 except that the dried pellets were sieved in the order of 5 mesh, 7 mesh and 8 mesh for 10 minutes and the pellet remaining on 8 mesh was collected (Fusing material) was obtained.
  • Example 6 Pellets of dried EVOH in the same manner as in Example 4 except that the dried pellets were sieved in the order of 5 mesh, 7 mesh and 9 mesh for 10 minutes and the pellet remaining on 9 mesh was collected (Fusing material) was obtained.
  • Example 7 Pellets of dried EVOH in the same manner as in Example 4 except that the dried pellet was sieved in the order of 4 mesh, 7 mesh and 9 mesh for 10 minutes and the pellet remaining on 9 mesh was collected (Fusing material) was obtained.
  • Example 8 As a mold for extruding a solution of EVOH, use is made of a mold that is hard chromium plated and has a maximum height roughness (Rz) of 14.5 ⁇ m on the inner surface of the die (outlet part) and an arithmetic mean roughness (Ra) of 0.99 ⁇ m. The same procedure as in Example 2 was carried out except for the fact that dry EVOH pellets (melted material) were obtained.
  • Example 9 The same procedure as in Example 8 was carried out except that the dried pellets were sieved for 30 minutes, to obtain dried EVOH pellets (melt-formed material).
  • the water content is 45% by mass in the same manner as in Example 1 except that a mold having a maximum height roughness (Rz) of 0.5 ⁇ m on the inner surface and an arithmetic mean roughness (Ra) of 0.05 ⁇ m is used.
  • a water-containing pellet (w-EVOH-4) of The water-containing pellet (w-EVOH-4) was dried by the following procedure. First, it was dried at 60 ° C.
  • Example 2 the same sieving as in Example 1 was carried out to obtain dried EVOH pellets (melt-formed material).
  • Comparative Example 1 As a mold for extruding the solution of EVOH, using a mold which is hard chromium plated, the maximum height roughness (Rz) of the inner surface of the die (outlet portion) is 18.2 ⁇ m, and the arithmetic average roughness (Ra) is 1.34 ⁇ m Dry the dried EVOH by following the same procedure as in Example 2 except that the dried pellet was sieved in the order of 4 mesh, 7 mesh and 9 mesh for 10 minutes and the pellet remaining on 9 mesh was collected. Pellets (melt molding material) were obtained.
  • Example 11 A water-containing EVOH having a water content of 50 mass% by drying the water-containing EVOH pellet w-EVOH-1 obtained in Example 1 at 80 ° C. in a hot air dryer for 1 hour using air with a dew point of -30 ° C. Pellets were obtained. The obtained water-containing EVOH pellet is charged into a twin-screw extruder (details shown below) at 10 kg / hr, the resin temperature of the discharge port is set to 100 ° C., and the solution addition shown in FIG.
  • the obtained water-containing EVOH pellets were dried at 60 ° C. for 102 minutes in a hot air drier using air at a dew point of ⁇ 10 ° C. to make the water content to 10 mass%. Subsequently, it was dried at 120 ° C. for 24 hours in hot air drying air using air having a dew point temperature of ⁇ 20 ° C. Thereafter, the dried pellet is sieved in the order of 6.5 mesh, 7 mesh and 8 mesh for 10 minutes, and the pellet remaining on 8 mesh is collected to obtain dried EVOH pellets (melt-formed material). The The obtained melt-formed material was flat and had a length in the longitudinal direction of 3.2 mm and a length in the lateral direction of 2.1 mm.
  • Comparative Example 2 A water-containing EVOH having a water content of 50 mass% by drying the water-containing EVOH pellet w-EVOH-1 obtained in Example 1 at 80 ° C. in a hot air dryer for 1 hour using air with a dew point of -30 ° C. Pellets were obtained. The obtained water-containing EVOH pellets were charged into a twin-screw extruder (details shown below) at 8 kg / hr, the resin temperature of the discharge port was 100 ° C., and the solution addition shown in FIG.
  • an aqueous solution containing 5.0 g / L of acetic acid, 3.6 g / L of sodium acetate, 0.06 g / L of phosphoric acid, and 4.9 g / L of boric acid was added at 1.2 L / hr.
  • Hard chrome plating was used as a mold for extruding a solution of EVOH, and the maximum height roughness (Rz) of the inner surface of the die (outlet portion) was 19.2 ⁇ m, and the arithmetic average roughness (Ra) was 1.45 ⁇ m.
  • Example 12 The water-containing pellet (w-EVOH-3) is first dried in a hot air drier at 60 ° C. for 3.7 hours using air with a dew point temperature of ⁇ 35 ° C. to make the water content to 10 mass%, and then the dew point temperature is ⁇ 20 Dried EVOH pellets (melt-molded material) were obtained in the same manner as in Example 3 except that drying was performed at 120 ° C. for 24 hours in hot air drying air using air of ° C.
  • Example 13 The water-containing pellet (w-EVOH-3) is first dried in a hot air drier at 60 ° C. for 13 hours using air with a dew point temperature of -30 ° C. to make the water content 10% by mass, and then the dew point temperature is -20 ° C. Dried EVOH pellets (melt-molded material) were obtained in the same manner as in Example 3 except that air was used and dried at 120 ° C. for 24 hours in hot air drying air.
  • Example 14 The water-containing pellet (w-EVOH-4) is first dried in a hot air drier at 55 ° C. for 5 hours using air with a dew point temperature of -10 ° C. to make the water content 10 mass%, and subsequently, the dew point temperature is -20 ° C. Dried EVOH pellets (melt-molded material) were obtained in the same manner as in Example 10 except that using air and drying at 100 ° C. for 36 hours in hot air drying air.
  • the water content is 50% by mass in the same manner as in Example 1 except that a mold having a maximum height roughness (Rz) of the inner surface of 18.2 ⁇ m and an arithmetic mean roughness (Ra) of 1.34 ⁇ m is used.
  • Water-containing pellets (w-EVOH-5) of The water-containing pellet (w-EVOH-5) was dried by the following procedure. First, it was dried at 75 ° C.
  • Example 2 the same sieving as in Example 1 was carried out to obtain dried EVOH pellets (melt-formed material).
  • the occurrence of sudden bumps in continuous melt molding is suppressed.
  • the thickness unevenness of the obtained melt-formed product is obtained by reducing the maximum height roughness (Rz) and arithmetic mean roughness (Ra) of the side surface of the melt-formed material, or reducing the full width at half maximum of the melt formed material. It is reduced more.
  • the amount of fine powder generated can be reduced by reducing the arithmetic mean roughness (Ra) of the side surface of the melt-molded material.
  • FIG. 2 (a) is a photograph of a tape-like foreign substance collected from the hopper when forming a single layer film from the melt-formed material obtained in Comparative Example 1. As shown in FIG. The both ends of the foreign matter are fixed with tape and photographed with a ruler (in cm). Further, FIG. 2 (b) shows an enlarged photograph of the tape-like foreign substance. It has been confirmed that such foreign matter is a cause of sudden spikes.
  • the melt molding material of the present invention can be suitably used as a material for continuous melt molding such as a film, a sheet, a container and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une matière de moulage à l'état fondu dans laquelle la production inattendue de particules pendant le moulage à l'état fondu en continu peut être inhibée. Plus précisément, la présente invention concerne une matière de moulage à l'état fondu, colonnaire, plate ou sphérique, comprenant un copolymère d'éthylène/alcool vinylique, la surface latérale ayant une rugosité (Rz) (hauteur maximale du profil) inférieure ou égale à 300 µm. Il est préférable que la surface latérale ait une rugosité (Ra) (écart moyen arithmétique du profil) inférieure ou égale à 50 µm. Il est préférable que la matière de moulage à l'état fondu ait une distribution des tailles des particules en termes de diamètre circulaire équivalent, qui a une largeur à mi-hauteur inférieure ou égale à 1 mm. Le copolymère d'éthylène/alcool vinylique a de préférence une teneur en motifs éthylène de 20 à 60 % en mole.
PCT/JP2018/030779 2017-08-21 2018-08-21 Matière de moulage à l'état fondu WO2019039458A1 (fr)

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WO2022168840A1 (fr) * 2021-02-02 2022-08-11 株式会社クラレ Pastilles poreuses de copolymère d'éthylène-alcool de vinyle et leur procédé de fabrication
US20220403212A1 (en) * 2021-06-16 2022-12-22 Chang Chun Petrochemical Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same
KR20220168541A (ko) * 2021-06-16 2022-12-23 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
KR20220168544A (ko) * 2021-06-16 2022-12-23 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
KR20220168542A (ko) * 2021-06-16 2022-12-23 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
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WO2022168840A1 (fr) * 2021-02-02 2022-08-11 株式会社クラレ Pastilles poreuses de copolymère d'éthylène-alcool de vinyle et leur procédé de fabrication
KR102502822B1 (ko) 2021-06-16 2023-02-23 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
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KR20220168541A (ko) * 2021-06-16 2022-12-23 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
JP2022191995A (ja) * 2021-06-16 2022-12-28 長春石油化學股▲分▼有限公司 エチレン－ビニルアルコール共重合体樹脂組成物、それにより形成されるエチレン－ビニルアルコール共重合体フィルム及びそれを含む多層構造体
KR102511213B1 (ko) * 2021-06-16 2023-03-16 장 춘 페트로케미컬 컴퍼니 리미티드 에틸렌-비닐 알코올 공중합체 수지 조성물, 이로부터 형성된 에틸렌-비닐 알코올 공중합체 필름, 및 이를 함유하는 다층 구조체
US11643575B2 (en) 2021-06-16 2023-05-09 Chang Chun Petrochemical Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same
JP7279136B2 (ja) 2021-06-16 2023-05-22 長春石油化學股▲分▼有限公司 エチレン－ビニルアルコール共重合体樹脂組成物
US11655317B2 (en) 2021-06-16 2023-05-23 Chang Chun Petrochemical Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same
JP7285298B2 (ja) 2021-06-16 2023-06-01 長春石油化學股▲分▼有限公司 エチレン－ビニルアルコール共重合体樹脂組成物
US11685824B2 (en) 2021-06-16 2023-06-27 Chang Chun Petrochemical Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same
JP7303276B2 (ja) 2021-06-16 2023-07-04 長春石油化學股▲分▼有限公司 エチレン－ビニルアルコール共重合体樹脂組成物
US11746170B2 (en) 2021-06-16 2023-09-05 Chang Chun Petrochemical Co., Ltd. Ethylene-vinyl alcohol copolymer resin composition, ethylene-vinyl alcohol copolymer film formed therefrom, and multilayer structure containing the same
WO2023033171A1 (fr) * 2021-09-06 2023-03-09 住友化学株式会社 Pastilles de résine thermoplastique et procédé de fabrication de pastilles de résine thermoplastique

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CN110945059A (zh) 2020-03-31
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