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WO2006038507A1 - Matériau de moulage en résine polyamide pour formation de films et procédé de fabrication desdits films - Google Patents

Matériau de moulage en résine polyamide pour formation de films et procédé de fabrication desdits films Download PDF

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Publication number
WO2006038507A1
WO2006038507A1 PCT/JP2005/017852 JP2005017852W WO2006038507A1 WO 2006038507 A1 WO2006038507 A1 WO 2006038507A1 JP 2005017852 W JP2005017852 W JP 2005017852W WO 2006038507 A1 WO2006038507 A1 WO 2006038507A1
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Prior art keywords
film
weight
polyamide resin
inorganic particles
molding material
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English (en)
Japanese (ja)
Inventor
Hajime Ooyama
Morio Tsunoda
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Mitsubishi Engineering Plastics Corp
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Mitsubishi Engineering Plastics Corp
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    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the present invention relates to a polyamide resin molding material suitable for producing a polyamide resin film excellent in transparency, slipperiness, printability, appearance and productivity, and a film obtained therefrom.
  • Polyamide resin films are excellent in gas barrier properties, mechanical 'thermal properties, etc., and therefore are mainly composed of food packaging, single layer films, multilayer films with other resins, and other materials. It is used in a wide range of applications as a laminated film.
  • the transparency of the polyamide resin film is an important characteristic because it greatly affects the appearance of the contents. In general, a film having good transparency is desired.
  • the slipperiness is poor, the film may be caught during bag making, or the ink may be misaligned during multicolor printing. For this reason, the slipperiness of the film is an extremely important characteristic of film productivity, quality and commercial value. Thus, it is necessary to achieve both transparency and slipperiness of the film, but the surface of the film with good transparency is smooth. The smooth surface of the film is slippery.
  • Patent Document 1 Japanese Patent Publication No.54-4741
  • Patent Document 2 Japanese Patent Publication No. 44-9825
  • Patent Document 3 Japanese Patent Application Laid-Open No. 63-251460
  • the present invention overcomes the disadvantages of the polyimide resin for film produced by the conventional method of blending inorganic particles as described above, and has excellent transparency, slipperiness and printability, and continuous film formation.
  • An object of the present invention is to provide a polyamide resin molding material for a film that does not easily cause appearance defects such as die lines and fish eyes even if it is performed.
  • the first gist of the present invention is that the total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets, and (B) polyamide resin 2-8% by weight of inorganic particles and Master batch 10 to 1 parts by weight blended bisamide compound 1-5 wt 0/0, (C) Bisua bromide compound powder 0.1 005-0. 1 made by mixing parts by weight film for polyamide ⁇ molding Lies in the material.
  • the second gist of the present invention is that the total of (A) and (B) is 100 parts by weight, (A) 90 to 99 parts by weight of polyamide resin pellets, and (B) inorganic particles in polyamide resin. and 2-8 weight 0/0 and bisamide compound 1-5 wt% masterbatch 10-1 parts by weight blended, (C) a bisamide compound powder 0.1 005-0. 1 part by weight of a film manufacturing extruder
  • the present invention resides in a method for producing a polyamide resin film characterized in that the film is formed into a film.
  • the third gist of the present invention resides in a polyamide resin film in which the above-mentioned polyamide resin molding material strength is also formed.
  • the polyamide resin molding material for film according to the present invention includes the components (A), (B), and (C) as compounding, as is apparent from the description of the present specification.
  • it is a material that is uniformly stirred and mixed (referred to as “dry blend”) in a mixing device such as a tumbler mixer or a nauter mixer, and is used for film production as it is.
  • a mixture obtained by stirring and mixing (A), (B), and (C) in a mixing apparatus as described above may be referred to as a dry blend.
  • the polyamide resin molding material of the present invention By using the polyamide resin molding material of the present invention, it is possible to continuously form a film for a long time without stopping production, and the resulting film has an appearance, transparency, The excellent slipperiness and printability can be expected to reduce the manufacturing cost and expand the application to food packaging of polyamide resin film.
  • the polyamide resin used in the polyamide resin pellet is a polyamide obtained by polycondensation of ratata having a three-membered ring or more, polymerizable ⁇ -amino acid, dibasic acid and diamine, and the like. ⁇ ⁇ can be used.
  • ⁇ -force prolatatam aminocaproic acid, enantolactam and other ratatams
  • 7 aminoheptanoic acid 11 aminoundeca Polymers of ⁇ -amino acids such as acid, 9-aminononanoic acid, pyrrolidone, and ⁇ -piperidone
  • hexamethylenediamine nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine
  • examples thereof include polycondensates of diamines such as metaxylene diamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and glutaric acid, or copolymers thereof.
  • polyamide 4 6, 7, 8, 11, 12, 6, 6, 6, 10, 11, 6, 12, 6 ⁇ , 6/6-6, 6/12, 6 / 6 ⁇ , 6 ⁇ 6 ⁇ ⁇ ⁇ Illustrated.
  • These polyamide resin may be used alone or in combination of two or more.
  • polyamide 6 resin and polyamide 6-66 copolymer resin can be preferably used from the viewpoint of thermal and mechanical properties of the obtained film.
  • the shape of the polyamide resin pellets ( ⁇ ⁇ ⁇ ⁇ ) in the present invention may be any of a sphere, a cylinder, a prism, and a plate, but the pellet volume is preferably about 0.5 to 10 cm 3 Zg. More preferably, it is l-8cm 3 Zg.
  • pellets having a length of 1 to 5 mm and a diameter of 1 to 4 mm are easy to handle in the production of the polyamide resin material of the present invention, and bite into the extruder during film formation.
  • the stability force of is preferably used.
  • the viscosity number measured at 96% sulfuric acid concentration 1% and the temperature at 23 ° C is usually 115 to 300, preferably It is in the range of 130-210. If the viscosity number is too low, the resulting film has insufficient mechanical properties, and if it is too high, film formation becomes difficult.
  • the amount of water extract measured in accordance with JIS K6920-1 which is a method for measuring the content of low molecular weight substances in the polyamide resin used in the present invention is usually 1% by weight or less, Preferably it is 0.5 weight% or less.
  • the amount of water extraction is large, low molecular weight materials such as monomers and dimers easily adhere to the periphery of the die mouth, and such low molecular weight materials come into contact with or adhere to the film. Appearance defects are likely to occur.
  • the kind of the inorganic particles used in the present invention is not particularly limited, and any of the conventionally used inorganic fillers can be selected and used.
  • silica-alumina clay minerals hydroous aluminum silicates
  • kaolin kaolin
  • calcined kaolin silica-magnesium
  • talc calcium silicate
  • silica zeolite
  • alumina calcium carbonate
  • talc kaolin
  • calcined kaolin, silica and zeolite are also suitable for easy dispersibility.
  • silica and zeolite are particularly suitable.
  • These inorganic particles do not contain particles having a particle size of 10 ⁇ m or more and have an average particle size of 0.4 to 6
  • ⁇ / z m Those in the range of / z m are preferred. If the particle size is large, it will cause the generation of fish eyes. If the particle size is too large, the dispersibility will be poor, and it will be easy to cause fishery due to secondary aggregation of inorganic particles.
  • the inorganic particles are used alone or in combination of two or more.
  • any of so-called wet silica and dry silica can be used, and the specific surface area by the BET method is usually 50 m 2 Zg or more, preferably 100 m 2.
  • the oil absorption measured according to JIS K5101-13 is usually 50 mlZlOOg or more.
  • the zeolite that is preferably used as the inorganic particles of the present invention may be either amorphous or crystalline, but is preferably zeolite that is amorphous as measured by the X-ray method.
  • shape of zeolite it may be spherical or polygonal fine particles. Preferably, it has a spherical or cubic shape.
  • the amount of oil absorption measured by ZEOLITE by the JIS K5101-13 method is usually 1 to 70 mlZlOg, preferably 5 to 70 mlZlOOg. If the oil absorption is too low, the stretching stability will decrease, and if it is too high, the effect of improving the slipping property will be small when stretched. Also, the chemical composition of zeolite is: Si O force 0-60% by weight, Al O force 3 ⁇ 40-45% by weight, Na O 6-9% by weight, CaO 0-8%
  • the inorganic particles used in the present invention are surface-treated with a known surface treatment agent such as a silane coupling agent (silane treatment agent) or a titanium-based treatment agent, good dispersion is obtained. It is preferable because the transparency of the resulting film is improved at the same time that the properties are obtained.
  • the type of surface treatment agent and the surface treatment method are not particularly limited, but treatment with a silane coupling agent is preferred. In particular, when surface-treated silica or zeolite is used as the inorganic particles, favorable results are obtained in terms of transparency and slipperiness of the resulting film.
  • the silane coupling agent preferably used in the present invention has an organosiloxane group.
  • the organo group include alkyl groups such as methyl, ethyl and propyl; alkenyl groups such as butyl and allyl; cycloalkyl groups such as cyclopropyl and cyclohexyl; aryl groups such as phenyl and benzyl; ⁇ -Aminopropyl, ⁇ - ( ⁇ -aminoethyl) Contains functional groups such as chloro, thiol, and epoxy, such as aminoalkyl groups such as ⁇ -aminominopropyl, ⁇ -glycidoxy, ⁇ -chloropropyl, and ⁇ mercaptopropyl.
  • the amount of the silane coupling agent used is usually 1 to 99% by weight, preferably 2 to 70% by weight, more preferably 5 to 40% by weight, based on the inorganic particles. If the amount of the silane coupling agent used is less than 1% by weight relative to the inorganic particles, the effect of preventing film turbidity will be reduced. On the other hand, if it exceeds 99% by weight, the coupling agents will easily aggregate. There are features that cause poor appearance such as fish eyes in the film.
  • the method of surface treatment of inorganic particles with a silane coupling agent is not particularly limited, and is a method known per se. Specifically, for example, inorganic particles treated with a silane coupling agent are added to the inorganic particles with a silane coupling agent diluted with water under heating. Prepared and dried, blended during the production of the masterbatch (B), melt-kneaded, or dry blending of inorganic particles, silane coupling agent and polyamide resin, and blending For example, a method of melt-kneading a product to produce a master batch can be used.
  • the blending amount of the inorganic particles in the master batch (B) of the present invention is 2 to 8% by weight. If the amount of inorganic particles is less than 2% by weight, a large amount of masterbatch is used, resulting in poor thermal stability during film production and a reduction in film quality. On the other hand, when the content is more than 8% by weight, the dispersion of the inorganic particles is lowered and the appearance of the film such as fish eye is deteriorated.
  • the blending amount of the inorganic particles in the master batch is more preferably 2.5 to 7.5% by weight, particularly preferably 3 to 7% by weight.
  • R 1 represents a divalent hydrocarbon residue
  • R 2 and R 3 represent a monovalent hydrocarbon residue
  • R 4 and R 5 represent a hydrogen atom, or a monovalent hydrocarbon residue.
  • Examples of the bisamido compound of the general formula [I] include alkylene bis fatty acid amides and arylene bis fatty acid amides obtained by reaction of diamine and monocarboxylic acid.
  • Examples of the diamine include ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, otatamethylene diamine, dodecamethylene diamine etc.
  • arylene alkyldiamines such as arylenediamine and xylylenediamine.
  • Monocarboxylic acids include fatty acids such as stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, arachidic acid, behenic acid, oleic acid, elaidic acid, and montanic acid. Can be mentioned.
  • N, N'-methylenebis Mention may be made of the tea amide and N, N'-ethylenebisstearic amide.
  • the bisamido compound represented by the general formula [ ⁇ ] is obtained by the reaction of a monoamine and a dicarboxylic acid.
  • the monoamine include alkylamines such as ethylamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, dodecylamine, aralkylamines such as a-line and naphthylamine, aralkylamines such as benzylamine, and cyclohexylamine.
  • dicarboxylic acid examples include terephthalic acid, p-phenylene dipropionic acid, succinic acid, and adipic acid.
  • representative examples include dioctadecyl dibasic acid amides such as N, N′-dioctadecyl terephthalic acid amide.
  • the bisamidite compound is characterized by being divided and mixed in the master notch of the component (B) and the bisamidyl compound powder of the component (C).
  • component of the bi Suamido compound as the amount in (master batch), 1 to 5 wt 0/0, the amount of component (C) (powder) is,
  • A) component and (B) It is 0.005 to 0.1 part by weight with respect to 100 parts by weight of the total of the components, and the blending amount of the entire polyamide resin molding material of the present invention is preferably 0.005 with respect to the total polyamide resin.
  • the bisamide compound is blended mainly for the purpose of improving the transparency and slipperiness of the film, but the bisamide in the component (B) is the dispersibility of the inorganic particles.
  • the bisamide powder as component (C) is essential for the stability of biting into the extruder. Therefore, in the component (B), the blending ratio (weight ratio) of the inorganic particle Z bisamide compound is preferably in the range of 1 to 5.
  • the blending ratio is less than 1 and the blending amount of the bisamide compound is 5% by weight or more, the dispersibility of the inorganic particles, which is difficult to stably melt and knead during the production of the masterbatch, is also lowered. If the blending ratio is larger than 5, the resulting film is difficult to disperse, and poor appearance tends to occur.
  • the production method of the masterbatch that is the component (B) of the present invention is not particularly limited, and is produced by a known method, preferably in the form of pellets.
  • a certain amount of polyamide Master blend pellets can be obtained by dry blending the resin, inorganic particles and bisamide compound, then melting and kneading with an extruder, and pelletizing with a conventional method.
  • the shape and size of the masterbatch pellets are the same as or similar to those of the polyamide resin pellets (A). From the viewpoint of preventing separation of the masterbatch and the polyamide pellets.
  • the molding material of the present invention comprises the three components of polyamide resin, inorganic particles and bisamide compound as essential components.
  • the production of such a three-component composition is usually performed by dry blending the three components together or by adding inorganic particles internally during the polymerization of the polyamide and dry blending the biamide compound.
  • a masterbatch (B) was prepared by blending 2 to 8% by weight of inorganic particles and 1 to 5% by weight of a bisamide compound in polyamide, and the masterbatch (B) and bisamide compound powder (C) were prepared. And 3 types of polyamide rosin pellets (A).
  • the content is less than 1% by weight, the inorganic particles are dispersed unevenly in the film, resulting in uneven transparency. If it is more than 10% by weight, the thermal stability deteriorates during film production, and poor film appearance tends to occur.
  • the blending amount of the bisamide compound powder (C) is 0.005 to 0.1 parts by weight, preferably 0.01 to 0.08 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). is there. Less than 005 wt.%! / ⁇ and stable bite into the extruder during the manufacture of FINOLEM is not guaranteed, and if more than 0.1 wt.%, Stable bite into the beam extruder A failure occurs.
  • the polyamide used in the polyamide resin pellet (A) and the master notch (B) may be the same or different. If they are different, the melting point or melt viscosity of the polyamide in the masterbatch (B) is preferably lower than those of the polyamide resin pellet (A).
  • the bisamide compound in the master batch (B) and the bisamide compound in the bisamide compound powder (C) The compound may be the same or different.
  • the material according to the present invention is manufactured by mixing the components (A), (B), and (C).
  • A), (B) and (C) are dry blended and supplied to the hopper of an extruder for film production, and (A), (B) and (C) are separately supplied to the hopper of a film production extruder.
  • a method using a fixed amount feeder can be preferably used.
  • the material of the present invention can contain additives within a range that does not impair the effects of the present invention.
  • it contains a partial ester compound of tri- to hexavalent aliphatic alcohol and C10-22 fatty acid and magnesium metal salt of Z or hydroxy fatty acid Let me do it.
  • Examples of the aliphatic alcohol of a partial ester compound of a tri- to hexavalent aliphatic alcohol and a fatty acid having 10 to 22 carbon atoms include glycerin, trimethylpropane, pentaerythritol, mesoerythritol, and sorbitol. Carbon number
  • Examples of the fatty acids 10 to 22 include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like.
  • a substituent such as a hydroxyl group may be present in the carbon skeleton of the fatty acid.
  • Such an ester compound of an aliphatic alcohol and a fatty acid needs to be substantially a partial ester, and preferably 30% or more of the total hydroxyl groups in the polyhydric alcohol are not esterified and remain. Is used.
  • glycerin monostearate, glycerin distearate, glycerin monobehenate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol monobehenate, pentaerythritol dibehenate, etc. is preferred.
  • Such partial ester compounds can be used alone or in combination of a plurality of compounds.
  • the magnesium metal salt of hydroxy fatty acid is a salt of hydroxycarbonic acid having 12 to 30 carbon atoms and magnesium, for example, by direct reaction with hydroxycarboxylic acid and magnesium oxide or hydroxide. Can be obtained. In this case, a better result can be obtained by adding magnesium oxide or hydroxide in excess to synthesize a highly basic hydroxy fatty acid magnesium salt.
  • lauric acid, myristic acid A magnesium salt of a compound obtained by hydroxylating an aliphatic carboxylic acid such as palmitic acid, stearic acid or behenic acid. If the fatty acid has a small number of carbon atoms, a predetermined effect cannot be obtained.
  • the blending amount of the partial ester compound of aliphatic alcohol and fatty acid and the magnesium salt of hydroxy fatty acid is usually from 0.01 to 0.7 parts by weight, preferably from 0.03 to 0.7 parts per 100 parts by weight of the polyamide resin. 0. 4 parts by weight. If the blending amount is small, the effect of improving the appearance of the resulting film is insufficient, and if the blending amount is too large, the printing characteristics deteriorate.
  • the combination of the partial ester of the polyhydric alcohol and the magnesium metal salt of the hydroxy fatty acid may be a so-called external addition method in which dry blending is performed on the pelletized raw material of polyamide resin, a kneading method in which melt mixing is performed, or a high concentration
  • a so-called master one-batch method in which the raw materials contained in the compound are blended or an internal addition method to be added during polymerization can be used.
  • additives well known to those skilled in the art for example, hindered phenol, anti-oxidation agents such as phosphate ester and phosphite ester, and weather resistance improvement of triazine compounds, etc.
  • Contains colorants such as colorants, pigments and dyes, antistatic agents, lubricants, and surfactants.
  • the predetermined amount of component (C) and, if necessary, other additives may be dry blended in advance, or supplied to a molding machine for film production without preblending, and film formation may be performed according to a conventional method.
  • the film forming method to which the molding material of the present invention is applied is a force to which any of the known film forming methods can be applied, preferably the T-die method, the inflation method and the like.
  • the polyamide film of the present invention is used as an unstretched film or as a stretched film through a stretching process such as uniaxial stretching or biaxial stretching.
  • the film using the molding material of the present invention may be a single-layer polyamide film or a laminated film with other resin by coextrusion or lamination.
  • the thickness of the polyamide resin film of the present invention is not particularly limited, but if it is thick, the gas-noirality is improved, but the transparency is lowered. The strength you have is reduced.
  • the thickness of the polyamide resin monolayer is usually 2 to 100 ⁇ m for an unstretched film and usually 2 to 50 ⁇ m for a stretched film.
  • the thickness is usually about 10 to 300 m, and the thickness of the polyamide resin layer is preferably in the same range as the thickness of the single layer.
  • Polyamide resin Polyamide-6, “Novamid (registered trademark) 1020J” manufactured by Mitsubishi Engineering Plastics Co., Ltd., Viscosity number 182, Pellet size: Cylindrical shape with a length of 3mm and a diameter of 2.5mm
  • Inorganic particles 1 Silica, “Silysia 310” manufactured by Fuji Silysia Chemical Ltd., average particle size 2.5 m, specific surface area 300 m 2 Zg, oil absorption 310 ml ZlOOg.
  • Inorganic particles 2 Zeolite, “Silton JC20” manufactured by Mizusawa Chemical Co., Ltd., average particle size 2 .: L m, oil absorption 50 ml ZlOOg.
  • Inorganic particles 3 calcined kaolin, “Satinton No. 5” manufactured by Engelnodne earth, average particle size of 0.8 ⁇ .
  • Silane coupling agent y-aminopropyltriethoxysilane, “A 1100” manufactured by Nippon Kayaku Co., Ltd.
  • Polyamide resin, surface-treated inorganic particles 1 (silica), and bisamide compound are dry blended at a compounding ratio of 92/5/3 (weight ratio), and a twin screw extruder (“TEX30” manufactured by Nippon Steel) The mixture was melt-kneaded at 250 ° C, pelletized and dried to obtain a masterbatch containing inorganic particles and bisamido compound. 1.5 parts by weight of the master batch and 0.05 parts by weight of the bisamide compound powder were dry blended with 100 parts by weight of polyamide resin to obtain a molding material for film.
  • TEX30 twin screw extruder
  • This molding material is supplied to a hopper of a T-die type film-forming machine that has a T-die having a diameter of 600 mm and a T-die having a diameter of 600 mm.
  • a film having a thickness of 135 m was formed at ° C.
  • the bite into the extruder was stable and the film was formed smoothly.
  • use the film 2 hours, 4 hours, 6 hours after the start of film formation The stability of the film formation for a long time was evaluated by observing with the naked eye the presence or absence of streaky appearance defects called die lines.
  • the film 1 hour after the start of film formation was cut into a 120 mm x 120 mm square and simultaneously biaxially stretched 3 x 3 times at 80 ° C with a TM-Long biaxial stretching machine, and then 200 The film was heat fixed in a hot air oven at ° C for 30 seconds to obtain a biaxially stretched film with a thickness of 15 ⁇ m.
  • the haze value and static friction coefficient of the stretched film were measured. The results are shown in Table 2.
  • Polyamide resin, surface-treated inorganic particles 1 (silica), and bisamide compound were dry blended at a blending ratio of 99.83 / 0.075 / 0.095 (weight ratio) to obtain a molding material for film.
  • a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • Surface-treated inorganic particles 1 (silica) was added in an amount of 0.05 to 5% by weight with respect to polyamide 6 during polymerization of polyamide 6, and polymerized by a conventional method to obtain polyamide 6 resin having a viscosity number of 182. .
  • a film molding material was obtained by dry blending the silica-containing polyamide 6 rosin pellets (3 mm in length and 2.5 mm in diameter) into a bisamide compound in an amount of 0.095% by weight. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.
  • Polyamide rosin and surface-treated inorganic particles 1 were dry blended at a blending ratio of 95Z5 (weight ratio), and melt-kneaded in the same manner as in Example 1 to obtain a master batch in which inorganic particles were blended.
  • 1.5 parts by weight of the master batch and 0.095 parts by weight of the bisamide compound powder were dry blended with 100 parts by weight of polyamide resin to obtain a molding material for film. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.
  • Polyamide, surface-treated inorganic particles 1 (silica), and a bisamide compound were dry blended at a blending ratio of 87Z10Z3 (weight ratio), and melt-kneaded in the same manner as in Example 1 to blend inorganic particles and a bisamide compound.
  • a master batch was obtained. 0.775 parts by weight of the masterbatch Then, 0.0725 parts by weight of bisamide compound powder and 100 parts by weight of polyamide resin were dry blended to obtain a molding material for film. Using this molding material, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.
  • Polyamide rosin, surface-treated inorganic particles 1 (silica), and bisamide compound were dry blended at a blending ratio of 88.67 / 5 / 6.33 (weight ratio), and melt-kneaded in the same manner as in Example 1 to make inorganic
  • a master batch containing the particles and the bisamide compound was obtained. 1.5 parts by weight of the master batch and 100 parts by weight of polyamide resin were dry blended. Next, using this blend, film formation and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.
  • a film molding material was obtained in the same manner as in Example 1 except that the inorganic particles 1 (silica) used in Example 1 were changed to surface-treated inorganic particles 2 (zeolite), and a film was formed. Evaluation was performed. The results are shown in Table 3.
  • a molding material for a film was obtained in the same manner as in Comparative Example 3 except that the inorganic particles 1 (silica) used in Comparative Example 3 were changed to surface-treated inorganic particles 2 (zeolite), and a film was formed. Evaluation was performed. The results are shown in Table 3.
  • a film molding material was obtained in the same manner as in Example 1 except that the inorganic particles 1 (silica) used in Example 1 were changed to surface-treated inorganic particles 3 (calcined kaolin). Went. The results are shown in Table 5.
  • the film of Example 1 formed using the molding material for film of the present invention was the film of Comparative Examples 1 to 3 formed using a material having the same additive composition. Compared with the film quality, the film quality such as transparency, slipperiness, presence of fish eyes and die lines was excellent, and the long-term stability of the film formation was also good.
  • the film formed from the material of Comparative Examples 4 and 5 in which the blending amount of the inorganic particles and the bisamido compound in the master batch is out of the scope of the present invention is stable in fish eyes and long-term film formation. Problems occur. For this reason, the ratio of inorganic particles to bisamide compounds in the masterbatch affects the dispersion of inorganic particles, and coarse particles due to aggregation are It is presumed that this will affect the generation of die and the generation of die lines due to the turbulent flow of grease near the die outlet.
  • the molding material of the present invention is excellent in transparency and slipperiness of the obtained film, can prevent appearance defects such as die lines, and can be continuously stable for a long time. It was. In addition, since it is excellent in slipperiness, it is apparently excellent in printability. Industrial applicability
  • the molding material for polyamide resin film of the present invention is excellent in long-term continuous film-forming stability, and the resulting film has good transparency, slipperiness and printability, and has poor appearance such as die lines. Since it has few excellent characteristics, it is useful for a wide range of food packaging 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention a pour objet un matériau de moulage en résine polyamide pour formation de films, qui est obtenu en mélangeant (A) entre 90 et 99 parts en masse de granules de résine polyamide, (B) entre 10 et 1 parts en masse d’un mélange maître comprenant une résine polyamide et, incorporées audit mélange, entre 2 et 8 % en masse de particules inorganiques et entre 1 et 5 % en masse d'un dérivé de bisamide, et (C) entre 0,005 et 0,1 part en masse d’un dérivé de bisamide en poudre. La somme de (A) et de (B) est de 100 parts en masse. Ledit matériau de moulage en résine polyamide peut être employé pour fabriquer un film de résine polyamide dont les propriétés de transparence, de glissement et d'imprimabilité sont excellentes, et qui est moins sujet à l’apparition de défauts d’apparence tels que lignes de moulage et yeux de poissons même lorsqu’il est mis en forme en procédé continu.
PCT/JP2005/017852 2004-10-06 2005-09-28 Matériau de moulage en résine polyamide pour formation de films et procédé de fabrication desdits films Ceased WO2006038507A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012001710A (ja) * 2010-05-18 2012-01-05 Ube Industries Ltd ポリアミド樹脂組成物
EP2080788A4 (fr) * 2006-11-01 2012-01-25 Mitsubishi Eng Plastics Corp Mélange de granules d'une composition de résine de polyamide, article moulé et procédé de production du mélange de granules

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103132172B (zh) * 2011-11-29 2015-07-22 杜邦兴达（无锡）单丝有限公司 具有改善的刚度的磨料丝、包含其的工业用刷及该工业用刷的用途
CN107915987B (zh) * 2016-10-11 2021-01-05 中国石油化工股份有限公司 一种用于制备聚酰胺薄膜的组合原料及其制备方法

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Publication number Priority date Publication date Assignee Title
JPH06340807A (ja) * 1992-12-28 1994-12-13 Du Pont Kk ポリアミド樹脂組成物および成型品の製造方法
JP2000309702A (ja) * 1999-04-27 2000-11-07 Mitsubishi Chemicals Corp ポリアミド系樹脂組成物及びそれからなる包装用フィルム
JP2002348465A (ja) * 2001-05-28 2002-12-04 Unitika Ltd ２軸延伸ポリアミドフィルム

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Publication number Priority date Publication date Assignee Title
JP2001310956A (ja) * 2000-04-28 2001-11-06 Unitika Ltd 熱収縮性フィルム

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH06340807A (ja) * 1992-12-28 1994-12-13 Du Pont Kk ポリアミド樹脂組成物および成型品の製造方法
JP2000309702A (ja) * 1999-04-27 2000-11-07 Mitsubishi Chemicals Corp ポリアミド系樹脂組成物及びそれからなる包装用フィルム
JP2002348465A (ja) * 2001-05-28 2002-12-04 Unitika Ltd ２軸延伸ポリアミドフィルム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2080788A4 (fr) * 2006-11-01 2012-01-25 Mitsubishi Eng Plastics Corp Mélange de granules d'une composition de résine de polyamide, article moulé et procédé de production du mélange de granules
JP2012001710A (ja) * 2010-05-18 2012-01-05 Ube Industries Ltd ポリアミド樹脂組成物

Also Published As

Publication number Publication date
CN101031617A (zh) 2007-09-05
TWI370832B (fr) 2012-08-21
CN100532455C (zh) 2009-08-26
TW200628550A (en) 2006-08-16

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