WO2012073969A1 - 燃料バリア性に優れた成形加工品 - Google Patents
燃料バリア性に優れた成形加工品 Download PDFInfo
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- WO2012073969A1 WO2012073969A1 PCT/JP2011/077563 JP2011077563W WO2012073969A1 WO 2012073969 A1 WO2012073969 A1 WO 2012073969A1 JP 2011077563 W JP2011077563 W JP 2011077563W WO 2012073969 A1 WO2012073969 A1 WO 2012073969A1
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- WIPO (PCT)
- Prior art keywords
- screw
- containing polyamide
- metaxylylene group
- molded product
- ratio
- Prior art date
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Definitions
- the present invention relates to a molded product having excellent fuel barrier properties.
- HDPE high-density polyethylene
- HDPE containers high-density polyethylene
- a method in which a fuel barrier resin such as ethylene vinyl alcohol copolymer resin (hereinafter sometimes abbreviated as EVOH) is laminated on an intermediate layer of an HDPE container to make the HDPE container cross-sectional structure a multilayer structure.
- EVOH ethylene vinyl alcohol copolymer resin
- an HDPE container in which an EVOH layer is laminated can be provided with a fuel barrier property superior to that of a conventional HDPE container, and the thickness of the EVOH layer laminated on the intermediate layer of the HDPE container depends on the thickness of the container. Since the fuel barrier performance can be controlled, it is easy to manufacture a container having a desired fuel barrier performance.
- an HDPE container manufacturing apparatus in which EVOH layers are laminated includes a multilayer blower provided with at least three extruders for extruding HDPE, adhesive resin, and EVOH, respectively, into the HDPE container. It is necessary to provide a device. For this reason, the manufacturing apparatus of the HDPE container which laminated
- a container manufactured by the direct blow method always has a portion where the parison has been cut off by a mold called a pinch-off part. For this reason, in the said multilayer container, since the joint surface of inner layer HDPE is made in the cross section of the pinch-off part, the site
- a method for improving the fuel barrier property of the HDPE container a method is known in which a polyamide resin such as nylon 6 is blended with HDPE together with an adhesive resin to produce a single layer container from the composition (Patent Documents 3 and 4). reference).
- the equipment for producing a conventional HDPE container can be used almost as it is, and the polyamide resin is flaky in the composition, in other words, when viewed in a cross section of a molded product.
- a fuel barrier property close to a multilayer structure can be imparted to the HDPE container.
- the resin material constituting the HDPE container is the same as the resin material constituting the scraps and purge waste generated when the HDPE container is manufactured, the resin material of the HDPE container is the resin material of the fluorination treatment container. Unlike the case, it can be pulverized by a pulverizer, charged as a recycled material into an extruder, and reused as one of the materials constituting the container.
- a pulverizer charged as a recycled material into an extruder, and reused as one of the materials constituting the container.
- fuel permeation from the inner layer HDPE mating surface of the pinch-off portion can be achieved. It can also be reduced.
- polymetaxylylene adipamide mainly composed of metaxylylenediamine and adipic acid has excellent gas barrier properties such as oxygen and carbon dioxide, and is resistant to various organic solvents compared to other polyamides. Since the material is also excellent in resistance, a container that exhibits better fuel barrier properties than a container using nylon 6 can be easily obtained (see Patent Documents 5 and 6).
- the melting point of polymetaxylylene adipamide is often higher than the processing temperature for producing HDPE containers, while polymetaxylylene adipamide is dispersed in the form of flakes in the composition, There is a tendency that the range of molding processing conditions for achieving both prevention of HDPE degradation is narrow.
- the molding process conditions such as the extruder temperature and extrusion speed vary somewhat, the dispersion state of polymetaxylylene adipamide in the composition may change, and the fuel barrier performance of the resulting molded product may vary.
- the quality of the obtained product is closely inspected to determine whether a product that exhibits stable performance has been obtained. There was a problem that we had to check every time we performed, and the productivity was not good.
- the present invention provides a method for stably producing a molded processed article such as a sheet having a fuel barrier property or a hollow container, comprising a resin composition obtained by melt-kneading polyolefin, adhesive polyolefin, and metaxylylene group-containing polyamide. To do.
- the inventors of the present invention in manufacturing a molded product comprising a resin composition obtained by melt-kneading at least a polyolefin, an adhesive polyolefin, and a metaxylylene group-containing polyamide, simply melt-knead the resin material.
- a screw whose ratio of the length of the supply unit, compression unit, and metering unit constituting the screw shape is within a specific range is shown.
- the molded product obtained by (2) extruding the cylinder temperature setting and (3) the shear rate of the screw under specific production conditions is a resin composition constituting the molded product
- the metaxylylene group-containing polyamide resin is dispersed in the form of flakes, resulting in a molded product with high fuel barrier properties.
- the molded article can be easily obtained understand, and have completed the present invention.
- the present invention blends a resin material containing at least three types of polyolefin (A) 40 to 90 parts by mass, metaxylylene group-containing polyamide (B) 3 to 30 parts by mass, and adhesive polyolefin (C) 3 to 50 parts by mass.
- the molded raw material mixture is a molded product made of a resin composition obtained by melt-kneading the raw material mixture under the conditions (2) and (3) below using a single screw extruder that satisfies the following condition (1).
- the single screw extruder is A screw shaft and a threaded portion formed in a spiral shape on a side surface of the screw shaft, the threaded portion feeding the resin composition from the proximal end portion to the distal end portion of the screw shaft by rotation of the screw shaft.
- Screw A cylinder through which the screw is rotatably inserted, and an inner peripheral surface has a cylindrical inner surface shape; A plurality of temperature adjusters for adjusting the temperature of the resin composition sent from the base end portion to the tip end portion by rotation of the screw; A screw driving device that rotates the screw to a predetermined shear rate, and The screw shaft has a constant depth of a screw groove between the tip of the threaded portion and the surface of the screw shaft from the base end of the screw shaft toward the tip of the screw shaft. And the supply section, the compression section that is in a range where the depth of the screw groove is gradually shallower, and the compression section, and the depth of the screw groove is larger than that of the supply section.
- a measuring section that is shallow and constant The ratio of the length of the supply section to the effective screw length of the screw shaft is 0.40 to 0.55, the ratio of the length of the compression section is 0.10 to 0.30, the ratio of the length of the measuring section Is in the range of 0.10 to 0.40, and the sum of the ratio of the length of the supply section, the ratio of the length of the compression section, and the ratio of the length of the measuring section is 1.0.
- the upper limit of the temperature of the cylinder in the supply unit is (the melting point of the metaxylylene group-containing polyamide + 20 ° C.
- the predetermined shear rate is 14 / second or more.
- the obtained molded product is a molded product having a high fuel barrier property because the metaxylylene group-containing polyamide is dispersed in the form of flakes in the resin composition constituting the molded product. Can be easily obtained.
- the molded product obtained by the production method of the present invention has excellent fuel barrier performance and has little variation in quality within or between lots, and as a container for fuel, chemicals, agricultural chemicals, beverages, etc. Can be used.
- the polyolefin (A) used in the present invention is a main material constituting a molded product, but the main material can be used without limitation as long as it can be used as a material constituting the molded product, preferably Is a polyethylene represented by low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene and the like, propylene homopolymer, ethylene-propylene block copolymer, polypropylene represented by ethylene-propylene random copolymer, Copolymers of ethylene hydrocarbon homopolymers having 2 or more carbon atoms such as 1-polybutene and 1-polymethylpentene, homopolymers of ⁇ -olefins having 3 to 20 carbon atoms, and ⁇ -olefins having 3 to 20 carbon atoms Polymers, copolymers of ⁇ -olefins having 3 to 20 carbon atoms and cyclic olefins, etc.
- the main material is more preferably the above-described polyethylenes or polypropylenes, and more preferably high-density polyethylene (HDPE). These polyolefins can be used alone as a main material of a molded product, or can be used as a mixture of two or more kinds.
- HDPE high-density polyethylene
- the polyolefin used in the present invention is preferably one having a high melt viscosity in order to prevent the drawdown of the parison causing the uneven thickness of the molded product.
- the sheet preferably has a high melt viscosity for the purpose of preventing drawdown.
- the melt flow rate (MFR) is 0.03 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.) or more and 2 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.).
- Those within the following ranges are preferable, more preferably 0.15 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.) or more and 1 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.) or less. More preferably, 0.2 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.) or more and 0.8 g / 10 min (load: 2.16 kgf, temperature: 190 ° C.) It is in the following range.
- a polyolefin having an MFR in the above-mentioned range, a molded product having a small drawdown and a controlled wall thickness can be easily obtained.
- a metaxylylene group-containing polyamide (B) is contained in the resin composition. Therefore, the molded product can be made excellent in fuel barrier properties.
- the metaxylylene group-containing polyamide (B) used in the present invention contains a diamine unit containing 70 mol% or more of metaxylylenediamine units and a dicarboxylic acid unit containing 50 mol% or more of adipic acid units.
- the metaxylylene group-containing polyamide (B) used in the present invention may further contain other structural units as long as the effects of the present invention are not impaired.
- the unit derived from dicarboxylic acid and the unit derived from diamine are referred to as “dicarboxylic acid unit” and “diamine unit”, respectively.
- the diamine unit in the metaxylylene group-containing polyamide (B) is a metaxylylenediamine unit of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, from the viewpoint of improving the fuel barrier property of the molded product. including.
- compounds that can constitute diamine units in addition to metaxylylenediamine units include aromatic diamines such as paraxylylenediamine, 1,3-bis (aminomethyl), and the like.
- aromatic diamines such as paraxylylenediamine, 1,3-bis (aminomethyl), and the like.
- examples thereof include alicyclic diamines such as cyclohexane, 1,4-bis (aminomethyl) cyclohexane and tetramethylene diamine, and aliphatic diamines such as hexamethylene diamine, nonanemethylene diamine and 2-methyl-1,5-pentane diamine.
- aliphatic diamines such as hexamethylene diamine, nonanemethylene diamine and 2-methyl-1,5-pentane diamine.
- these can be used individually or in combination of 2 or more types.
- the dicarboxylic acid unit constituting the metaxylylene group-containing polyamide (B) is an ⁇ , ⁇ -fat from the viewpoint of avoiding an excessive decrease in crystallinity of the metaxylylene group-containing polyamide (B) and improving the fuel barrier performance of the molded product. It is appropriate to contain 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more of the group dicarboxylic acid unit.
- Examples of compounds that can constitute an ⁇ , ⁇ -aliphatic dicarboxylic acid unit include suberic acid, adipic acid, azelaic acid, sebacic acid, and dodecanoic acid, and the like, but the ability to maintain good fuel barrier properties and crystallinity. Adipic acid and sebacic acid are preferable, and adipic acid is particularly preferably used.
- examples of compounds that can constitute dicarboxylic acid units other than ⁇ , ⁇ -aliphatic dicarboxylic acid units include alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, Aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, xylylene dicarboxylic acid, naphthalene dicarboxylic acid and the like can be exemplified, but are not limited thereto.
- isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because a polyamide having excellent fuel barrier properties can be easily obtained without inhibiting the polycondensation reaction during the production of the metaxylylene group-containing polyamide (B).
- the content of the isophthalic acid unit and / or 2,6-naphthalenedicarboxylic acid unit is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less of the dicarboxylic acid unit.
- the dispersion state of the metaxylylene group-containing polyamide (B) in the resin composition becomes constant, and the fuel barrier performance of the molded product Can be realized.
- the copolymer units constituting the metaxylylene group-containing polyamide (B) may be lactams such as ⁇ -caprolactam and laurolactam, and aminocaproic acid as long as the effects of the present invention are not impaired.
- lactams such as ⁇ -caprolactam and laurolactam
- aminocaproic acid as long as the effects of the present invention are not impaired.
- aliphatic aminocarboxylic acids such as aminoundecanoic acid, aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid, and the like can be used.
- the metaxylylene group-containing polyamide (B) is produced by a melt polycondensation (melt polymerization) method. For example, there is a method in which a nylon salt composed of a diamine and a dicarboxylic acid is heated in the presence of water under pressure and polymerized in a molten state while removing added water and condensed water.
- the metaxylylene group-containing polyamide (B) can also be produced by a method in which a diamine is directly added to a molten dicarboxylic acid and polycondensed.
- diamine is continuously added to the dicarboxylic acid, and the temperature of the reaction system is raised so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide. And proceed with polycondensation.
- a phosphorus atom-containing compound may be added in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloring during polycondensation.
- Phosphorus atom-containing compounds include phosphinic compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, etc.
- hypophosphorous acid compounds phenylphosphonic acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, etc., phenylphosphonic acid, ethylphosphonic acid, Phosphonic acid compounds such as sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid, sodium hydrogen phosphite, sodium phosphite, Phosphorous acid Ethyl, phosphite compounds such as triphenyl phosphite, pyrophosphorous acid and phosphoric acid.
- hypophosphorous acid metal salts such as sodium hypophosphite, potassium hypophosphite, and lithium hypophosphite are particularly preferable because they have a high effect of promoting amidation reaction and are excellent in anti-coloring effect.
- sodium hypophosphite is preferably used, the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
- the addition amount of the phosphorus atom-containing compound added to the polycondensation system of the metaxylylene group-containing polyamide (B) is preferably 1 to 1000 ppm in terms of phosphorus atom concentration in the metaxylylene group-containing polyamide (B). More preferably, it is 5 to 450 ppm, and particularly preferably 10 to 400 ppm. Coloring of the xylylene group-containing polyamide (B) during polycondensation can be prevented by setting the addition amount of the phosphorus atom compound within the above range.
- the phosphorus atom-containing compound may be a xylylene group-containing polyamide (B). Therefore, it is preferable to coexist an alkali metal compound or an alkaline earth metal compound in order to adjust the amidation reaction rate.
- Such compounds include, for example, alkali metal / alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.
- alkali metal / alkaline earth metal acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, and barium acetate, but are limited to these compounds. Can be used without any problem.
- the molar ratio of the compound to the phosphorus atom-containing compound is 0.5 to 2.0. More preferably, it is 0.6 to 1.8, and more preferably 0.7 to 1.5.
- the metaxylylene group-containing polyamide (B) obtained by melt polycondensation is once taken out, pelletized and then used after drying, and may further be subjected to solid-phase polymerization in order to increase the degree of polymerization.
- a heating device used in drying or solid phase polymerization a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum type heating device called a rotary dryer, and an inside called a Nauta mixer rotate.
- a conical heating device having blades can be suitably used, but a known method and device can be used without being limited thereto.
- the rotary drum type heating device in the above-mentioned device can seal the inside of the system, and it is easy to proceed polycondensation in a state where oxygen causing coloring is removed.
- the rotary drum type heating device in the above-mentioned device can seal the inside of the system, and it is easy to proceed polycondensation in a state where oxygen causing coloring is removed.
- oxygen causing coloring is removed.
- the relative viscosity of the xylylene group-containing polyamide is preferably 2.0 to 4.5, more preferably 2.1 to 4.1, and still more preferably 2.3 to 4.0.
- Metaxylylene group-containing polyamide (B) has antioxidants, matting agents, heat stabilizers, weathering stabilizers, UV absorbers, nucleating agents, plasticizers, flame retardants, antistatics as long as the effects of the present invention are not impaired. Additives such as additives, anti-coloring agents, lubricants, anti-gelling agents, clays such as layered silicates, nanofillers, and the like can also be added.
- various polyamides such as nylon 6 and nylon 66, amorphous nylon using aromatic dicarboxylic acid as a monomer, and modified resins thereof, polyolefins as necessary Further, a modified resin thereof, an elastomer having styrene in the skeleton, and the like can be added.
- the present invention is not limited to those described above, and various materials may be mixed.
- the adhesive polyolefin (C) used in the present invention is obtained by graft-modifying the above-mentioned polyolefin (A) with an unsaturated carboxylic acid or an anhydride thereof, and is generally widely used as an adhesive resin.
- unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, chloromaleic acid, butenyl succinic acid, and the like. These acid anhydrides are mentioned. Of these, maleic acid and maleic anhydride are preferably used.
- Various known methods can be used as a method for obtaining a modified polyolefin by graft copolymerization of the unsaturated carboxylic acid or its anhydride onto a polyolefin.
- a method of melting a polyolefin using an extruder or the like and adding a graft monomer to copolymerize a method of dissolving a polyolefin in a solvent and adding a graft monomer to copolymerize, and a polyolefin in an aqueous suspension
- Examples thereof include a method in which a post-graft monomer is added and copolymerized.
- the adhesive polyolefin (C) preferably has a melt flow rate (MFR) of 0.01 to 5 (g / 10 minutes, 2.16 kgf) at 190 ° C. and a load of 2.16 kgf, more preferably 0. 0.02 to 4 (g / 10 min, 2.16 kgf), more preferably 0.03 to 3 (g / 10 min, 2.16 kgf).
- MFR melt flow rate
- the metaxylylene group-containing polyamide (B) can be easily dispersed in a flake form in the resin composition, and a molded product with high adhesion strength between the polyolefin and the metaxylylene group-containing polyamide can be obtained. It is done.
- the amount of the polyolefin (A) used in the present invention may be 40 to 90% by mass as the total content of the polyolefin (A), the metaxylylene group-containing polyamide (B), and the adhesive polyolefin (C). More preferably, it is 50 to 90% by mass, and still more preferably 60 to 80% by mass. By setting the amount of polyolefin used in the above-mentioned range, it is possible to minimize a decrease in strength of a molded product made of the resin composition.
- the amount of the metaxylylene group-containing polyamide (B) used in the present invention is 3 to 30% by mass as the content in the total amount of the polyolefin (A), the metaxylylene group-containing polyamide (B) and the adhesive polyolefin (C). It is preferably 5 to 25% by mass, more preferably 5 to 20% by mass.
- the amount of the adhesive polyolefin (C) used in the present invention is 3 to 50% by mass as the total content of the polyolefin (A), the metaxylene group-containing polyamide (B) and the adhesive polyolefin (C). Is more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass.
- the use ratio of the adhesive polyolefin (C) to the metaxylylene group-containing polyamide (B) is preferably 0.8 to 5.0, more preferably 1.0 to 4.5 in terms of mass ratio. More preferably, it is 1.0 to 4.0.
- the strength of the molded product can be increased.
- a hollow container which is a molded product, is prevented from peeling at the interface between the polyolefin dispersed in the resin composition and the metaxylylene group-containing polyamide even when subjected to an impact such as dropping, thereby improving the strength and fuel barrier properties of the hollow container. Can keep.
- the resin composition for forming a molded product by the production method of the present invention is thermoplastic for modification purposes.
- Elastomers, EEA (ethylene-ethyl acrylate), various copolymerized polyolefins such as EMA (ethylene-methyl acrylate), ionomers, etc. may be mixed, and purge waste and burrs generated in the manufacturing process of molded products, molding You may mix what grind
- the mixing ratio of the pulverized product is preferably 60% by mass or less, more preferably 50% by mass or less as the content in the resin composition in order to minimize the strength reduction of the molded product. More preferably, it is 40 mass% or less.
- the content of the metaxylylene group-containing polyamide (B) in the molded product may increase.
- the content of the adhesive polyolefin (C) with respect to the metaxylylene group-containing polyamide (B) is 0.8 to 5.0 times in mass ratio in order to prevent the strength of the molded product from greatly decreasing.
- the pulverized product is blended so that it becomes 1.0 to 4.5 times, more preferably 1.0 to 4.0 times.
- a direct blow method for the method for producing a hollow container which is a molded product of the present invention.
- a conventionally known method can be applied to the direct blow method. For example, using a device consisting of an extruder, an adapter, a cylindrical die, a mold, a cooling device, a mold clamping machine, etc., after melting and kneading the raw material mixture in the extruder, a hollow parison is removed from the cylindrical die via the adapter.
- a method of forming a molded product by extruding, extruding a certain amount, sandwiching a parison with a mold clamping machine, and then cooling while blowing air is mentioned.
- An accumulator may be used for the apparatus, or a molded product having an excellent thickness distribution can be produced by extruding a parison whose thickness is controlled using a parison controller. Further, it is preferable to employ a T-die-roll cooling method for the method for producing a sheet which is a molded product of the present invention. For example, using an extruder, an adapter, a T die, a take-off device attached to a cooling roll, etc., after melting and kneading the raw material mixture in the extruder, the molten resin sheet is extruded from the T die via the adapter and cooled.
- thermoforming the sheet is first heated at a temperature equal to or higher than the glass transition point and preheated and softened by a preheating zone for preheating the sheet and a mold having the shape of the molded product, and then the molded product has a shape.
- the shape of the molded product applied to the mold is formed on the sheet using vacuum or compressed air as necessary, and cooled to obtain the molded product.
- the metaxylylene group-containing polyamide (B) When the raw material mixture is melt-kneaded in the extruder, the metaxylylene group-containing polyamide (B) is softened by absorbing heat applied from the extruder heater, and then thinly stretched by receiving shear stress due to screw rotation. Then, it is further sheared and cut into flakes. Furthermore, the metaxylylene group-containing polyamide (B) that has been flaky in the resin composition is uniformly dispersed (dispersed) throughout the resin composition by mixing by screw rotation. Thus, the metaxylylene group-containing polyamide (B) is uniformly dispersed in the form of flakes in the resin composition, so that a molded product made of the resin composition exhibits fuel barrier performance.
- the dispersion state is not limited to the flake state, but is further cut into fine particles, and as a result, The fuel barrier performance of the molded product is reduced. Therefore, it is necessary to devise such that the metaxylylene group-containing polyamide (B) is not dispersed in the resin composition in a fine granular state due to excessive shear stress.
- the dispersion state of the metaxylylene group-containing polyamide (B) in the resin composition should not change even if the molding conditions slightly vary. is required.
- a raw material mixture obtained by blending resin materials containing at least three types of polyolefin (A) 40 to 90 parts by mass, metaxylylene group-containing polyamide (B) 3 to 30 parts by mass, and adhesive polyolefin (C) 3 to 50 parts by mass Is obtained by a method for producing a molded product comprising a resin composition melt-kneaded under the conditions (2) and (3) below using a single screw extruder that satisfies the following condition (1): It was found that the molded product had a high fuel barrier property when the metaxylylene group-containing polyamide (B) was dispersed in the form of flakes in the resin composition constituting the molded product.
- the single screw extruder is A screw shaft and a threaded portion formed in a spiral shape on a side surface of the screw shaft, the threaded portion feeding the resin composition from the proximal end portion to the distal end portion of the screw shaft by rotation of the screw shaft.
- Screw A cylinder through which the screw is rotatably inserted, and an inner peripheral surface has a cylindrical inner surface shape; A plurality of temperature adjusters for adjusting the temperature of the resin composition sent from the base end portion to the tip end portion by rotation of the screw; A screw driving device that rotates the screw to a predetermined shear rate, and The screw shaft has a constant depth of a screw groove between the tip of the threaded portion and the surface of the screw shaft from the base end of the screw shaft toward the tip of the screw shaft. And the supply section, the compression section that is in a range where the depth of the screw groove is gradually shallower, and the compression section, and the depth of the screw groove is larger than that of the supply section.
- a measuring section that is shallow and constant The ratio of the length of the supply section to the effective screw length of the screw shaft is 0.40 to 0.55, the ratio of the length of the compression section is 0.10 to 0.30, the ratio of the length of the measuring section Is in the range of 0.10 to 0.40, and the sum of the ratio of the length of the supply section, the ratio of the length of the compression section, and the ratio of the length of the measuring section is 1.0.
- the upper limit of the temperature of the cylinder in the supply unit is (the melting point of the metaxylylene group-containing polyamide + 20 ° C. or less), and the temperature of the cylinder in the compression unit and the metering unit is (the melting point of the metaxylylene group-containing polyamide) -30 ° C) to (the melting point of the metaxylylene group-containing polyamide + 20 ° C).
- the predetermined shear rate is 14 / second or more.
- the single screw extruder used in the present invention is a single screw extruder 100 as shown in FIG.
- the single-screw extruder 100 includes a hopper 110 into which a raw material mixture can be charged, a screw 150 for extruding a resin composition obtained by plasticizing and kneading while moving the resin mixture charged into the hopper 110, and a screw 150 A plurality of cylinders 140 whose inner peripheral surface 142 has a cylindrical inner side surface shape, and a resin composition that moves inside the cylinder 140 by the rotation of the screw 150 to adjust the temperature by heating or cooling.
- the screw 150 includes a screw shaft 152 and a threaded portion 154 formed in a spiral shape on the side surface of the screw shaft 152.
- the outer diameter D of the threaded portion 154 is set slightly smaller than the inner diameter of the inner peripheral surface 142.
- the screw shaft 152 includes a supply unit 150a, a compression unit 150b following the supply unit 150a, and a measuring unit 150c following the compression unit 150b from the base end of the screw shaft 152 toward the tip of the screw shaft 152.
- the supply unit 150a has a range in which the groove depth (also referred to as height or screw depth) is constant (groove depth dimension h2) from the beginning of threading, where the threaded portion 154 of the screw 150 is applied. This is where the raw material mixture is transported and preheated.
- the compression part 150b refers to a range in which the raw material mixture is melted by shearing within a range where the groove depth gradually decreases.
- the measuring unit 150c refers to a range in which the resin composition is conveyed in a range where the groove depth at the screw tip is shallow and constant (groove depth dimension h1).
- the supply unit 150a has a length L1 (supply length)
- the compression unit 150b has a length L2 (compression range)
- the weighing unit 150c has a length L3 (measurement length).
- the effective screw length L of the present invention refers to the length of the threaded portion 154 (from the beginning of threading to the final end of threading) of the screw 150 (the effective screw length L is the length L1 of the supply portion 150a and the compression portion 150b. It is equal to the sum of the length L2 and the length L3 of the measuring portion 150c.)
- the portion where the threading is not formed is shown below (a).
- the length of the portion is included in the effective screw length L, and in the case of (b) shown below, the length of the portion is not included in the effective screw length L.
- B) The diameter of the portion is different from the diameter d of the screw shaft 152 corresponding to the measuring portion 150c (for example, when the most distal portion of the screw has a conical shape or the like).
- the hopper 110 is formed with an opening 122 through which a raw material mixture can be poured from above, an insertion hole 124 formed below the opening 122, and a base end side of the screw shaft 152 being rotatably inserted therein, and a cooling water hole 130.
- the temperature controller 120 is provided.
- the temperature controller 120 is configured as a cooling unit that can cool the raw material mixture moved by the screw 150 in the vicinity of the opening 122 and adjust the temperature by circulating the cooling water through the cooling water hole 130, for example.
- the single screw extruder 100 used in the present invention is provided with three heaters as temperature controllers.
- the three heaters are respectively heaters C1, C2, and C3 in order from the base end portion of the screw shaft 152 toward the tip end portion of the screw shaft 152.
- the screw shape of the present invention will be described.
- the ratio of the length L1 of the supply unit 150a to the effective screw length L is 0.40 to 0.55
- the ratio of the length L2 of the compression unit 150b is 0.10 to 0.30
- the metering unit The ratio of the length L3 of 150c is in the range of 0.10 to 0.40, and the ratio of the length L1 of the supply unit 150a, the ratio of the length L2 of the compression unit 150b, and the length L3 of the weighing unit 150c.
- the screw shape of the present invention preferably has a ratio of the length L1 of the supply section 150a to the screw effective length L of 0.40 to 0.55, more preferably 0.43 to 0.55, Preferably, it is 0.50 to 0.55.
- the ratio of the length L1 of the supply portion 150a to the screw effective length L is less than 0.40, the polyolefin (A), the adhesive polyolefin (C) and the metaxylylene group-containing polyamide (B) which are resin materials to be used are used. It becomes difficult to give sufficient preheating.
- a crushed metaxylylene group-containing polyamide will come out.
- the ratio of the length L1 of the supply unit 150a to the screw effective length L is larger than 0.55, there is a restriction on the length of the cylinder 140 of the extruder 100, and the other compression units 150b and metering units 150c The desired length cannot be taken. Therefore, the ratio of the length L1 of the supply section 150a to the preferable screw effective length of the present invention is 0.40 to 0.55.
- the ratio of the length L2 of the compression portion 150b to the effective screw length L is preferably 0.10 to 0.30, and more preferably 0.20 to 0.30.
- the ratio of the length L2 of the compression part 150b to the screw effective length L exceeds 0.30, the resin composition is excessively subjected to shear stress, so that the dispersed state of the metaxylylene group-containing polyamide (B) in the resin composition is a flake.
- the shape becomes smaller. In other words, when the resin composition constituting the molded product is observed from a cross section, the linear dispersion of the metaxylylene group-containing polyamide in the resin composition is shortened and becomes almost granular.
- the fuel-barrier property of the obtained molded product will fall.
- the ratio of the length L2 of the compression portion 150b to the screw effective length L is less than 0.10, the shearing effect when the resin material is changed to the resin composition is lost, and the metaxylylene group-containing polyamide ( B) cannot be thinly stretched.
- the screw shape of the present invention preferably has a ratio of the length L3 of the measuring portion 150c to the effective screw length L of 0.10 to 0.40. More preferably, it is 0.20 to 0.40.
- a ratio of the length L3 of the measuring unit 150c to the screw effective length exceeds 0.40, a desired length ratio between the supply unit 150a and the compression unit 150b cannot be obtained.
- the ratio of the length L3 of the measuring portion 150c to the screw effective length L is less than 0.10, the fluctuation of the extrusion amount (surging phenomenon) increases, or the flakes of the metaxylylene group-containing polyamide (B) in the resin composition
- the dispersion of the shape tends to be biased and the size of the flake shape tends to be uneven.
- the screw shape of the present invention preferably has a compression ratio (C / R) of 2.3 to 3.5, more preferably 2.4 to 2.8.
- the resin composition of the polyolefin (A), the adhesive polyolefin (C), and the metaxylylene group-containing polyamide (B) can be given a shearing effect, and mainly the metaxylylene group-containing polyamide (B) is effectively thinly stretched. It becomes possible. Further, when the compression ratio is 3.5 or less, the dispersion of the meta-xylylene-based polyamide (B) in the resin composition does not reach a fine granular dispersion but remains in a flaky dispersion, and the molded product obtained The fuel barrier property is excellent.
- the groove depth in the screw shape of the present invention is the groove depth as described below.
- the groove depth h2 of the supply unit 150a for transporting the solid raw material mixture requires a groove depth that can send an amount of the resin composition corresponding to the molten resin capacity of the measuring unit 150c. In consideration of the bulk specific gravity of the resin and the molten resin, h2> h1 is necessarily satisfied.
- the groove depth h1 of the measuring part 150c is deep, the amount of extrusion increases and the shearing ability for melting is not accompanied.
- ⁇ D is generally used as the groove depth of the supply section 150a. ing.
- the metaxylylene group-containing polyamide (B) In order to maintain a high fuel barrier property in the molded product produced by the production method of the present invention, it is necessary to disperse the metaxylylene group-containing polyamide (B) in a flaky form in the resin composition, and vice versa. In other words, the metaxylylene group-containing polyamide is too dispersed to form a fine granular dispersion. Therefore, in the present invention, it is necessary to avoid excessive shearing, kneading, and dispersion by making the screw shape into a screw shape in which the length of the compression portion which is a dispersion kneading portion is relatively short.
- the groove depth h2 of the supply unit 150a can be made deeper than the general groove depth described above, preferably h2 is 0.10D to 0.30D, more preferably 0. 15D to 0.26D.
- the groove depth h2 of the supply unit 150a is less than 0.10D, the amount of extrusion is too small. In direct blow molding or the like, the parison drop time until the desired parison length corresponding to the mold shape is reached. Longer and longer molding cycle.
- the groove depth h2 of the supply unit 150a exceeds 0.30D, the amount of extrusion increases, so the load on the motor of the screw drive device 170 increases, and an extruder motor having a larger motor capacity is required. In other words, the screw breaks or the heater capacity of the heating section corresponding to the material capacity of the supply section tends to be insufficient.
- the screw shape is simply a full-flight screw with a constant screw thread pitch and continues to the forefront, or a supply of mixing such as dull mage or Murdoch in the measuring section to increase the shearing effect or improve dispersion
- a portion having unevenness different from a screw shape such as a portion is provided.
- a general screw can be used without limitation.
- a dalmage or Murdoch is used in order to prevent excessive dispersion and refinement of the metaxylylene group-containing polyamide (B) in the resin composition. It is preferable to use a so-called full flight type that does not have a mixing site such as mixing. Moreover, you may use the double flight type screw which made the number of flights of a supply part and a compression part two.
- the single screw extruder used in the present invention is preferably provided with three or more heaters.
- the number of rotations of the screw of the extruder is increased to increase the discharge rate.
- the time during which the raw material mixture stays in the extruder cylinder is shortened, and the preheating given to the raw material mixture in the supply unit is likely to be insufficient. Therefore, it is preferable to set the temperature of the supply section high in order to preheat the raw material mixture charged in the extruder cylinder at the supply section of the screw.
- the temperature setting in order to increase the temperature of the compression part to lower the viscosity to suppress heat generation due to the shearing of the resin, and conversely to suppress resin deterioration (yellowing, property deterioration) in the measuring part.
- an extruder having three or more heaters corresponding to each of the screw supply section, the compression section and the metering section is preferable.
- an extruder provided with three or more heaters is more preferable.
- the decomposition temperature of the polyolefin (A) and the melting point of the metaxylylene group-containing polyamide (B) are close to each other, the range of the molding temperature at which the resin composition of the present invention can be molded is naturally narrowed. Therefore, it is possible to suppress the decomposition of polyolefin by setting the cylinder temperature of the screw supply unit, compression unit and metering unit finely according to the state of equipment and the shape of the molded product, and the molding of the present invention. In the resin composition constituting the processed product, it is possible to perform a molding process in which the metaxylylene group-containing polyamide (B) is dispersed in a flaky shape.
- the cylinder temperature of the supply section is preferably set to (melting point of metaxylylene group-containing polyamide + 20 ° C.) or lower. More preferably (melting point of metaxylylene group-containing polyamide + 10 ° C.) or lower, more preferably lower than melting point of metaxylylene group-containing polyamide, preferably 4 ° C. or higher, more preferably 15 ° C. or higher, more preferably (melting point of metaxylylene group-containing polyamide). ⁇ 70 ° C.) or higher, particularly preferably (melting point of the metaxylylene group-containing polyamide ⁇ 35 ° C.) or higher.
- a plurality of heater zones may be provided as described above.
- the temperature in the cylinder heating zone commonly referred to as C1
- C1 may also be set fairly low if it serves only to transport the raw material mixture and preheat a little. Whether the range is the range from C1 to C2 is derived from the length of the heater for heating, in other words, the number of divisions of the heater zone.
- the molding cycle can be shortened by increasing the screw rotation speed of the extruder and increasing the discharge rate of the extruder.
- the time during which the raw material mixture stays in the extruder cylinder is shortened, and the preheating given to the raw material mixture in the supply section is likely to be insufficient. Therefore, it is necessary to set the temperature of the supply section high in order to preheat the raw material mixture charged in the extruder cylinder at the supply section of the screw.
- the cylinder temperature setting in the supply section is in the range of 70% or more from the side adjacent to the compression section of the supply section (melting point of the metaxylylene group-containing polyamide -70 ° C.) to (metaxylylene group-containing polyamide). It is preferable that the temperature setting is (melting point of metaxylylene group-containing polyamide-35 ° C.) to (melting point of metaxylylene group-containing polyamide + 20 ° C.).
- the cylinder temperature of the compression part and the metering part is preferably (the melting point of the metaxylylene group-containing polyamide + 20 ° C.) or less, more preferably (the melting point of the metaxylylene group-containing polyamide + 10 ° C.) or less, more preferably the melting point of the metaxylylene group-containing polyamide. Further, (the melting point of the metaxylylene group-containing polyamide ⁇ 30 ° C.) or more is preferable, and more preferably, the temperature range of (the melting point of the metaxylylene group-containing polyamide ⁇ 20 ° C.) is preferable.
- the set temperature is determined based on the screw shape.
- the set temperature of the heater is preferably set to (the melting point of the metaxylylene group-containing polyamide + 20 ° C.) or less, more preferably (metaxylylene group-containing polyamide) Of the metaxylylene group-containing polyamide, more preferably 4 ° C. or more, more preferably 15 ° C. or more, and still more preferably (the melting point of the metaxylylene group-containing polyamide—70 ° C.) or more. Particularly preferred is (melting point of metaxylylene group-containing polyamide -35 ° C.) or higher.
- the temperature setting for an extruder with a large L / D that can lengthen the supply section, for example, a zone where the heater is turned off and the raw material mixture is simply sent without preheating at C1 is used. Good.
- the set temperature of the heater is from (melting point of the metaxylylene group-containing polyamide-30 ° C.) to (melting point of the metaxylylene group-containing polyamide + 20 ° C.). It is preferable to set.
- the heater that covers only the compression section that does not include the supply section and the metering section has a set temperature in the temperature range of (melting point of the metaxylylene group-containing polyamide ⁇ 30 ° C.) to (melting point of the metaxylylene group-containing polyamide + 20 ° C.). It is preferable to set.
- the cylinder temperature of the supply unit, the compression unit and the metering unit that are continuous with each other is set such that the cylinder temperature setting of the supply unit ⁇ the cylinder temperature setting of the compression unit ⁇ the cylinder temperature setting of the metering unit, or the cylinder of the supply unit It is preferable to set so that temperature setting ⁇ cylinder temperature setting of the compression section ⁇ cylinder temperature setting of the measurement section.
- set the set temperature of the metering section to the setting of the compression section. The temperature may be set lower by about 5 to 10 ° C.
- the raw material mixture is melt-kneaded to produce a resin composition in which the metaxylylene group-containing polyamide is dispersed in the form of flakes, and a screw having a screw shape within the scope of the present invention is inserted. This is achieved by using a single screw extruder in which the cylinder temperature is set and increasing the shear rate of the screw to 14 / second or more.
- the shearing action of a screw is proportional to the shear rate and is expressed by the following equation.
- ⁇ ⁇ ⁇ dc ⁇ n / (60 ⁇ h1)
- ⁇ shear rate (sec -1 or / sec)
- dc cylinder diameter (mm)
- n Number of rotations of the screw (rpm)
- h1 groove depth of the metering part of the screw (mm)
- the cylinder diameter dc is substantially the same as the screw diameter D. The reason is that the gap between the top of the screw screw and the cylinder wall surface is generally as narrow as 0.03 to 0.09 mm. If the clearance gap of the extrusion equipment which has the screw shape of this invention is also the said general range, it can be used without any problem.
- shear rate proportional to the shear stress is proportional to the screw rotation speed according to the above formula
- a moderate shearing action can be achieved with the material, extrusion equipment, and cylinder temperature setting within the scope of the present invention.
- 14 / second or more and more preferably 20 / second or more.
- the shear rate is less than 14 / second, the metaxylylene group-containing polyamide is likely to come out from the discharge port 162 of the single screw extruder 100 in a large particle state of 1 to 5 mm size or in an unmelted state as described above.
- the shear rate of the present application is a sufficiently wide practical shear rate range in a general single-screw extruder, no special motor capacity is required, and a practical and general single-screw extruder is used. Can be used.
- the screw width (flight width) w of the screw is generally about 1/10 of the screw screw pitch, and the flight width of the extrusion equipment having the screw shape of the present invention can be used without any problem as long as it is in a general size range. .
- a cylindrical die is disposed at the outlet of a single screw extruder into which a screw having the screw shape of the present invention has been inserted in advance.
- Parison controller for controlling the wall thickness of tank molded product or a certain amount of molten resin is stored at the outlet of the extruder in the cylindrical die, and the parison drop time is shortened by putting out the parison from the cylindrical die at once. It is also possible to install an accumulator tank whose purpose is to prevent the resin temperature from dropping.
- the resin composition constituting the molded product is obtained by using the screw shape, cylinder temperature setting, and shear rate of screw rotation of the present invention. It is possible to disperse the metaxylylene group-containing polyamide in the form of flakes. Furthermore, the parison of the molten resin composition extruded from the cylindrical die is guided to a mold having a cavity processed into a desired shape, and after being clamped, it is pressure-shaped with air or the like, and further cooled. After opening the mold, a tank molded product is obtained.
- the relationship between the discharge rate of the extruder and the shape of the molded product depends on the thickness of the molded product, but for thin molded products, the extruder can be operated continuously to shorten the molding cycle.
- the cooling time tends to be long, and in such a case, intermittent operation such as stopping the extruder every shot may be used.
- the metaxylylene group-containing polyamide can be dispersed in the flakes in the resin composition constituting the molded product. Is possible.
- a T die When a sheet molded product is obtained as a molded product, a T die is connected to the exit of the extruder.
- the molten resin composition extruded from the T die and formed into a flat plate shape is cooled by a roll and transferred to form a flat plate (sheet).
- a sheet having fuel barrier properties, in which the metaxylylene group-containing polyamide is dispersed in a flake form in the resin composition can be obtained.
- a container-shaped product can be obtained by post-processing thermoforming.
- a container molded product obtained by the method of the present invention or a container obtained by processing a sheet molded product obtained by the method of the present invention takes various shapes such as bottles, cups, trays, tanks, etc., tubes, etc. be able to.
- Items that can be stored include gasoline, kerosene, light oil and other fuels, lubricating oils such as engine oil and brake oil, various sanitary products such as bleach, detergent and shampoo, chemical substances such as ethanol and oxidol, vegetable juice and milk drinks And various articles such as seasonings.
- the container obtained by the present invention can be effectively used as a container that improves the storability of articles to be stored.
- Polyolefin 4 High-density polyethylene manufactured by Nippon Polyethylene Co
- Adhesive polyolefin 1 maleic anhydride-modified polyethylene manufactured by Nippon Polyethylene Co., Ltd., trade name: Adtex L6100M, density 0.92 g / cm 3
- Adhesive polyolefin 2 modified polypropylene manufactured by Nippon Polypro Co., Ltd., trade name: Modic P604V, density 0.9 g / cm 3
- pseudo gasoline common name: CE10
- the permeation amount of pseudo gasoline per day (g ⁇ mm / m 2 ⁇ day ⁇ atm) was determined from the decrease in the container weight.
- the tank molded product by blow molding measured the thickness of the trunk
- Tensile test A molded 2.5-mm thick sheet of No. 4 type test piece (total length including the grip part is 120 mm, width 10 mm is 50 mm long), and wood with a Thomson blade Punching was performed using a mold to prepare a test piece.
- the tensile (yield) strength was measured with a tensile tester (Strograph AP III, manufactured by Toyo Seiki Co., Ltd.) using a punched specimen.
- the test piece is punched in two directions: a direction in which the sheet flow direction is punched as the test piece longitudinal direction (MD direction) and a direction in which the test piece longitudinal direction is perpendicular to the sheet flow direction (TD direction). It was a piece. In each direction, the number of measurement samples was 5 / condition, and the average value of tensile (yield) strength was shown.
- the tensile test speed was 50 mm / min.
- Screw shape The screws used in Examples and Comparative Examples are the screws a to d having the shapes shown in Table 1.
- Example 1 In advance, 70 parts by mass of polyolefin 1, 20 parts by mass of adhesive polyolefin 1, and 10 parts by mass of metaxylylene group-containing polyamide 1 were dry-blended to prepare raw material mixture 1.
- This raw material mixture was fed into a ⁇ 25 mm single screw extruder (PTM25, manufactured by Plastic Engineering Laboratory Co., Ltd.) with a screw of shape a inserted therein, and the cylinder temperature of the supply unit was 225 ° C., the cylinder temperature of the compression unit was 225 ° C., and the measuring unit
- a sheet having a thickness of about 2.4 mm was produced at a roll temperature setting of 30 ° C.
- the obtained sheet was subjected to observation of a metaxylylene group-containing polyamide dispersion state, a tensile test and a fuel barrier property test I.
- the results are shown in Table 2.
- the metaxylylene group-containing polyamide is dispersed in a long linear (flaky) form in the resin composition, and the pseudo gasoline (CE10) transmittance per day is 10 g ⁇ mm / m 2 ⁇ day ⁇ atm, indicating a good fuel barrier property.
- Examples 2 to 7 A sheet was produced in the same manner as in Example 1 except that the types and blending amounts of the resin material, the setting of the cylinder temperature, and the molding conditions such as the shear rate of the screw were changed as shown in Table 2. The obtained sheet was subjected to observation of a metaxylylene group-containing polyamide dispersion state, a tensile test and a fuel barrier property test I. The results are shown in Table 2. The location where the metaxylylene group-containing polyamide was dispersed in a linear (flaky) form was confirmed, and each sheet exhibited good gasoline permeability.
- Example 8 In advance, 70 parts by mass of polyolefin 1, 20 parts by mass of adhesive polyolefin 1, and 10 parts by mass of metaxylylene group-containing polyamide 1 were dry blended to prepare raw material mixture 8. This is a ⁇ 55 mm single screw extruder (manufactured by Tsuseki Industry Co., Ltd.) with a screw of shape b inserted therein.
- Cylinder temperature 210-225 ° C in the supply section, cylinder temperature 235 ° C in the compression section, cylinder temperature 235-in the measurement section 233 ° C, similarly, the head is 233 ° C, the adapter is 225 ° C, the T die is 215 ° C, and the rotational speed is 22 rpm (shear rate 14 / sec) to cool the cylindrical die-die
- a 0.5 L tank molded product was obtained by continuous extrusion molding with a molding cycle of 24 seconds by the direct blow method.
- the mold cooling water temperature was about 20-30 ° C.
- the thickness of the central part of the tank body was about 2 mm.
- Example 9 Except for changing the molding conditions such as the type and blending amount of the resin material and the temperature of the cylinder, the shear rate of the screw and the like as described in Table 3, the same as in Example 8, A 0.5 L tank molded product having a thickness of about 4 mm at the center of the body was produced by intermittent extrusion molding. Each of the obtained molded tanks was observed for metaxylylene group-containing polyamide dispersion and subjected to a fuel barrier property test II. The results are shown in Table 3. The locations where the metaxylylene group-containing polyamide was dispersed in a linear (flaky) form were confirmed, and each tank molded product showed good gasoline permeability.
- Example 14 to 18 A sheet was produced in the same manner as in Example 1 except that the molding conditions such as the type and blending amount of the resin material, the setting of the cylinder temperature, and the shear rate of the screw were changed as shown in Table 4.
- Each of the obtained sheets was subjected to observation of a metaxylylene group-containing polyamide dispersion state and a fuel barrier property test I. The results are shown in Table 4. About each sheet
- Example 19 A sheet was produced in the same manner as in Example 1 except that the types and blending amounts of the resin material, the setting of the cylinder temperature, and the molding conditions such as the shear rate of the screw were changed as shown in Table 5.
- Each of the obtained sheets was subjected to observation of a metaxylylene group-containing polyamide dispersion state, a tensile test, and a fuel barrier property test I. The results are shown in Table 5. About each sheet
- Comparative Example 1 Except having used the screw of shape c, it implemented similarly to Example 1 and produced the sheet
- Example 4 Except having changed the compounding quantity of the resin material as described in Table 7, it implemented similarly to Example 1 and produced the sheet
- the obtained sheet was subjected to observation of metaxylylene group-containing polyamide dispersion state, tensile test and fuel barrier property test I. The results are shown in Table 7. Since the content of the metaxylylene group-containing polyamide in the resin composition constituting the sheet is large, the cross section of the obtained sheet is dotted with a place where the metaxylylene group polyamide is linear and a large lump. . In addition, the lump was defective in appearance that appeared as white spots on the sheet surface. In the fuel barrier property test, good fuel barrier property was obtained, but it was inferior in practicality with poor appearance.
- Example 5 A sheet was produced in the same manner as in Example 7 except that the temperature of the cylinder and the number of rotations of the screw were changed as described in Table 7. The obtained sheet was subjected to observation of metaxylylene group-containing polyamide dispersion state, tensile test and fuel barrier property test I, and the results are shown in Table 7. Since the temperature of was too high, the metaxylylene group-containing polyamide in the resin composition constituting the obtained sheet was excessively dispersed to form a granular dispersion, resulting in poor fuel barrier properties.
- Example 6 As described in Table 7, a sheet was produced in the same manner as in Example 1 except that the screw rotation speed was reduced and the screw shear rate was changed. The obtained sheet was observed for a metaxylylene group-containing polyamide dispersion state and a fuel barrier property test I. The results are shown in Table 7. In the resin composition, an unmelted state of the metaxylylene group-containing polyamide was generated, and the portions dispersed in a linear shape (flaky shape) could not be confirmed. The gasoline transmission rate was also bad.
- Example 7 A 0.5 L tank molded product was produced in the same manner as in Example 8 except that the screw of shape d was used and the molding conditions such as cylinder temperature setting and screw shear rate were changed as shown in Table 8. did. In the continuous extrusion molding, the molding cycle was 24 seconds and the tank molded product had a thickness of about 2 mm. Observation of the metaxylylene group-containing polyamide dispersion state and fuel barrier property test II were performed on the obtained tank molded product, and the results are shown in Table 8. In Comparative Example 7, since the length ratio of the compression portion of the screw used for molding is large, the metaxylylene group-containing polyamide is excessively dispersed in the resin composition constituting the sheet, resulting in granular dispersion. The result was not so good.
- Comparative Example 9 since the cylinder temperature of the supply part and the compression part was low, the metaxylylene group-containing polyamide was unmelted. In Comparative Example 10, since the cylinder temperature of the supply unit was high, the metaxylylene group-containing polyamide was excessively dispersed in the resin composition constituting the tank, resulting in a granular dispersion, resulting in poor fuel barrier properties.
- Comparative Example 11 As described in Table 9, a 0.5 L tank molded product was produced in the same manner as in Example 8 except that the screw rotation speed was reduced and the screw shear rate was changed. Observation of the metaxylylene group-containing polyamide dispersion state and fuel barrier property test II were performed on the obtained tank molded product, and the results are shown in Table 9. In Comparative Example 11, since the shear rate during the molding process was low, the taxylylene group-containing polyamide was unmelted. The fuel barrier property was also poor.
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Abstract
Description
(1)前記単軸押出機は、
スクリュー軸と前記スクリュー軸の側面に螺旋状に形成されたねじ切り部であって前記樹脂組成物を前記スクリュー軸の回転によって前記スクリュー軸の基端部から先端部に向けて送るねじ切り部とを有するスクリューと、
前記スクリューを回転可能に挿通し、内周面が円筒内側面形状を有するシリンダーと、
前記スクリューの回転によって前記基端部から前記先端部に送られる樹脂組成物の温度を調節する複数の温度調節器と、
前記スクリューを所定の剪断速度となるように回転させるスクリュー駆動装置と、を備え、
前記スクリュー軸は、前記スクリュー軸の基端部から前記スクリュー軸の先端部に向けて、前記ねじ切り部の先端と前記スクリュー軸の表面との間のスクリュー溝の深さが一定となっている範囲である供給部と、前記供給部に続き、前記スクリュー溝の深さが徐々に浅くなっている範囲である圧縮部と、前記圧縮部に続き、前記スクリュー溝の深さが前記供給部よりも浅くかつ一定となっている範囲である計量部とを有し、
前記スクリュー軸のスクリュー有効長に対する前記供給部の長さの比が0.40~0.55、前記圧縮部の長さの比が0.10~0.30、前記計量部の長さの比が0.10~0.40の範囲であり、かつ前記供給部の長さの比、前記圧縮部の長さの比、及び前記計量部の長さの比の合計が1.0である。
(2)前記供給部における前記シリンダーの温度の上限は(メタキシリレン基含有ポリアミドの融点+20℃以下)であり、前記圧縮部と前記計量部とにおける前記シリンダーの温度は、(メタキシリレン基含有ポリアミドの融点-30℃)~(メタキシリレン基含有ポリアミドの融点+20℃)の範囲である。
(3)前記所定の剪断速度は、14/秒以上である。
イソフタル酸単位及び/又は2,6-ナフタレンジカルボン酸単位の含有量は、ジカルボン酸単位の30モル%以下が好ましく、より好ましくは20モル%以下であり、更に好ましくは15モル%以下である。イソフタル酸単位及び/又は2,6-ナフタレンジカルボン酸の含有量を上記範囲にすることで、樹脂組成物中のメタキシリレン基含有ポリアミド(B)の分散状態が一定となり、成形加工品の燃料バリア性能を実現することが可能となる。
相対粘度=t/t0
また本発明の成形加工品であるシートの製造方法には、Tダイ-ロール冷却法を採用することが好ましい。例えば、押出機、アダプター、Tダイ、冷却ロール付属の引き取り装置等を用いて、押出機にて原料混合物を溶融混練した後、アダプターを経由してTダイから溶融状態の樹脂シートを押し出し、冷却ロールで挟み、シート面をロール面にて転写させて冷却させて、その後ハサミや鋸刃で切断して、板状のシートを作製する。その後、熱成形により所望形状の成形加工品を作製することもできる。
熱成形は、シートを予熱する予熱ゾーンと成形加工品の形状を有する金型とによって、まずシートをガラス転移点以上の温度で加熱し予熱して軟化させた後、成形加工品の形状を有した金型で挟み、必要に応じて真空や圧空を用いてシートに金型に施された成形加工品の形状を賦形し、冷却させて成形加工品を得る方法である。
しかし、メタキシリレン基含有ポリアミド(B)が樹脂組成物中で過度の剪断応力を受けた場合、その分散状態は、薄片状態にとどまらず、更に微細な粒状に切断された状態になり、その結果、成形加工品の燃料バリア性能が低下する。
よって、メタキシリレン基含有ポリアミド(B)を樹脂組成物中で過度の剪断応力により微細な粒状となって分散させないような工夫が必要となる。
スクリュー軸と前記スクリュー軸の側面に螺旋状に形成されたねじ切り部であって前記樹脂組成物を前記スクリュー軸の回転によって前記スクリュー軸の基端部から先端部に向けて送るねじ切り部とを有するスクリューと、
前記スクリューを回転可能に挿通し、内周面が円筒内側面形状を有するシリンダーと、
前記スクリューの回転によって前記基端部から前記先端部に送られる樹脂組成物の温度を調節する複数の温度調節器と、
前記スクリューを所定の剪断速度となるように回転させるスクリュー駆動装置と、を備え、
前記スクリュー軸は、前記スクリュー軸の基端部から前記スクリュー軸の先端部に向けて、前記ねじ切り部の先端と前記スクリュー軸の表面との間のスクリュー溝の深さが一定となっている範囲である供給部と、前記供給部に続き、前記スクリュー溝の深さが徐々に浅くなっている範囲である圧縮部と、前記圧縮部に続き、前記スクリュー溝の深さが前記供給部よりも浅くかつ一定となっている範囲である計量部とを有し、
前記スクリュー軸のスクリュー有効長に対する前記供給部の長さの比が0.40~0.55、前記圧縮部の長さの比が0.10~0.30、前記計量部の長さの比が0.10~0.40の範囲であり、かつ前記供給部の長さの比、前記圧縮部の長さの比、及び前記計量部の長さの比の合計が1.0である。
なお、スクリュー軸152の最先端部側(図1において右端部側)の部分において、ねじ切りが形成されていない部分(図1において、ねじ切り部154の右側の部分)が、以下に示す(a)の場合、その部分の長さ寸法はスクリュー有効長Lに含め、以下に示す(b)の場合、その部分の長さ寸法はスクリュー有効長Lに含めない。
(a)その部分の径と計量部150cに対応するスクリュー軸152の径dとが同一とみなせる。
(b)その部分の径と計量部150cに対応するスクリュー軸152の径dとが異なる(例えば、スクリュー最先端部が円錐形状等になっている場合)。
また、本発明において使用する単軸押出機100は、温度調節器として、3つの加熱ヒーターが備えられている。3つの加熱ヒーターは、それぞれ、スクリュー軸152の基端部からスクリュー軸152の先端部に向けて、順番にヒーターC1、C2、C3とされている。
スクリュー有効長Lに対する供給部150aの長さL1の比が0.40未満であると、使用する樹脂材料であるポリオレフィン(A)や接着性ポリオレフィン(C)、及びメタキシリレン基含有ポリアミド(B)に充分な予熱を与えにくくなる。特にポリオレフィン(A)(融点=130℃前後)よりも融点の高いメタキシリレン基含有ポリアミド(B)(融点=240℃前後)に対する予熱が足りなくなり、単軸押出機100の吐出口162より未溶融や、押しつぶされた状態のメタキシリレン基含有ポリアミドが出てきてしまう。また、スクリュー有効長Lに対する供給部150aの長さL1の比が0.55より大きい場合には、押出機100のシリンダー140の長さの制約があり、他の圧縮部150bや計量部150cの所望の長さがとれなくなってしまう。よって本発明の好ましいスクリュー有効長に対する供給部150aの長さL1の比は0.40~0.55である。
スクリュー有効長Lに対する圧縮部150bの長さL2の比が0.30を超えると、樹脂組成物に剪断応力がかかりすぎるため、樹脂組成物中のメタキシリレン基含有ポリアミド(B)の分散状態は薄片状が小さくなる。換言すると成形加工品を構成する樹脂組成物を断面から観察した場合、樹脂組成物中のメタキシリレン基含有ポリアミドの線状分散が短くなり、ほとんど粒状になってしまう。そして、このような粒状の分散になってしまうと、得られた成形加工品の燃料バリア性が低下する。
また、スクリュー有効長Lに対する圧縮部150bの長さL2の比が0.10未満であると、樹脂材料から樹脂組成物にする際の剪断効果が無くなり、樹脂組成物中でメタキシリレン基含有ポリアミド(B)を薄く引き延ばすことができなくなる。
スクリュー有効長に対する計量部150cの長さL3の比が0.40を超えると、供給部150aと圧縮部150bの所望の長さ比が取れなくなる。またスクリュー有効長Lに対する計量部150cの長さL3の比が0.10未満であると押し出し量の変動(サージング現象)が大きくなったり、樹脂組成物中のメタキシリレン基含有ポリアミド(B)の薄片状の分散が偏ったり、薄片状の大きさが不均一になりやすい。
ここで、圧縮比(C/R)とは、供給部150aの1ピッチ分の樹脂容量(体積)と計量部150cの1ピッチ分の樹脂容量(体積)の比で表され、以下の式で一般的に計算される。
圧縮比(compression ratio)=C/R
C/R=h2(D-h2)/(h1(D-h1))
h2=供給部の溝深さ(mm)
h1=計量部の溝深さ(mm)
D=スクリューの直径(mm)
スクリューの圧縮比が2.3以上であれば、樹脂組成物を十分に溶融できる。また、ポリオレフィン(A)、接着性ポリオレフィン(C)、及びメタキシリレン基含有ポリアミド(B)の樹脂組成物に剪断効果を与えることができ、主にメタキシリレン基含有ポリアミド(B)を効果的に薄く引き延ばすことが可能となる。また、圧縮比が3.5以下であると、樹脂組成物中のメタキリシレン基ポリアミド(B)の分散が、微細な粒状分散には至らずに薄片状の分散に留まり、得られた成形加工品の燃料バリア性は優れたものとなる。
本願発明のスクリュー150において、分散混錬性の良好なスクリュー形状において溝深さは、以下に述べるような溝深さである。固体の原料混合物を運搬する供給部150aの溝深さh2は、計量部150cの溶融された樹脂容量に見合った量の樹脂組成物を送ることができる溝深さが必要になるが、ペレット状態の樹脂と溶融状態の樹脂の嵩比重を踏まえると、必然的にh2>h1となる。計量部150cの溝深さh1が深いと押出量が多くなり、溶融させる為の剪断能力が伴わなくなる。計量部150cの溝深さh1が逆に浅いと押出量が少なくなる。
例えば、文献「押出成形 第7版改訂」監修 村上健吉に開示されているように、一般的に供給部150aの溝深さは、h2=(0.10~0.15)×Dが用いられている。
供給部150aの溝深さh2が0.10D未満である場合、押出量が少なくなり過ぎるので、ダイレクトブロー成形等では、金型形状に見合った所望のパリソン長さになるまでのパリソン降下時間が長くなり、成形サイクルが長くなってしまう。逆に供給部150aの溝深さh2が0.30Dを超えると、押出量が増えるので、スクリュー駆動装置170のモーターの負荷が大きくなり、より大きなモーター容量をもった押出機モーターが必要となることや、スクリューが破断したり、供給部の材料容量に見合った加熱部のヒーター容量が不足したりすることが起こりやすくなる。
更に、一般的にC1と呼称されるシリンダー加熱ゾーンの温度も、単に原料混合物を輸送し、若干予熱するだけの役目の場合には、温度設定をかなり低く設定することがある。その範囲がC1からC2までの範囲なのかは、あくまでも加熱用ヒーターの長さ、換言すれば、ヒーターゾーンの分割数に由来する。
一方で、L/Dが小さい押出機でやや大きめの成形加工品を製造する場合は、押出機のスクリューの回転数を上げて押出機の吐出量を上げることで、成形サイクルの短縮を図るが、その際には押出機シリンダー内の原料混合物が滞留する時間が短くなり、供給部における原料混合物に与える予熱が不足する状態に陥りやすくなる。よって押出機シリンダー内に投入された原料混合物にスクリューの供給部で予熱を与える為に供給部の温度を高く設定する必要がある。
このことから、供給部におけるシリンダー温度設定は、供給部の圧縮部に隣接される側から7割以上の長さの範囲が、(メタキシリレン基含有ポリアミドの融点-70℃)~(メタキシリレン基含有ポリアミドの融点+20℃)の温度設定であることが好ましく、(メタキシリレン基含有ポリアミドの融点-35℃)~(メタキシリレン基含有ポリアミドの融点+20℃)がより好ましい。
供給部におけるシリンダー温度を、供給部の圧縮部に隣接される側から7割以上の長さの範囲において、(メタキシリレン基含有ポリアミドの融点-70℃)以上に設定することで、原料混合物のブロッキングを防止することができ、かつメタキシリレン基含有ポリアミドが未溶融のまま押出機の出口から出てくることを防止することが可能になる。また、供給部におけるシリンダー温度を、(メタキシリレン基含有ポリアミドの融点+20℃)以下に設定することで、過剰な予熱を原料混合物に与えることなく、樹脂組成物中でのメタキシリレン基含有ポリアミドが薄片状の分散にとどめることができるため、得られる成形加工品の燃料バリア性は優れたものとなる。
圧縮部と計量部とのシリンダー温度設定が(メタキシリレン基含有ポリアミドの融点-30℃)未満である場合、メタキシリレン基含有ポリアミドの未溶融物が発生しやすくなる。
また、圧縮部と計量部とのシリンダー温度設定が(メタキシリレン基含有ポリアミドの融点+20℃)を超えると、ポリオレフィンの溶融粘度が低下し、成形加工品が黄変色しやすくなり、また容器成形等のダイレクトブロー成形では、押出機出口より出てきた樹脂の溶融粘度が低下し、パリソンのドローダウンが発生して、所望のパリソン径(幅)が得られにくくなる。
なお、温度設定については、L/Dの大きい押出機で供給部を長くすることができるものについては、例えばヒーターをOFFとしC1で予熱を与えないで単に原料混合物を送るだけのゾーンにしてもよい。
供給部も計量部も含まれない圧縮部のみを覆っている加熱ヒーターは、その設定温度を(メタキシリレン基含有ポリアミドの融点-30℃)~(メタキシリレン基含有ポリアミドの融点+20℃)の温度範囲に設定することが好ましい。
更に、互いに連続する供給部、圧縮部及び計量部のシリンダー温度の設定については、供給部のシリンダー温度設定≦圧縮部のシリンダー温度設定≦計量部のシリンダー温度設定とするか、又は供給部のシリンダー温度設定≧圧縮部のシリンダー温度設定≧計量部のシリンダー温度設定となるように設定することが好ましい。
また、パリソンのドローダウン防止のためにアダプターや円筒ダイの設定温度を低くして、樹脂温度を低下させることにより樹脂粘度の低下を抑制する際には、計量部の設定温度を圧縮部の設定温度に対して5~10℃程度低く設定することもある。
γ=π×dc×n/(60×h1)
γ=剪断速度(sec-1 又は /秒 )
dc=シリンダー直径(mm)
n=スクリューの回転数(rpm)
h1=スクリューの計量部の溝深さ(mm)
シリンダー直径dcはスクリュー径Dとほぼ同一寸法である。理由は、スクリューネジの山頂とシリンダー壁面の隙間は一般的には0.03~0.09mmと非常に狭く小さいからである。本発明のスクリュー形状を有した押出設備の隙間も前記一般的な範囲であれば何ら問題無く使用できる。
剪断応力(剪断作用)に比例する剪断速度は、上式によりスクリュー回転数に比例するので、本発明の範囲内の材料、押出設備、シリンダー温度設定にて、適度な剪断作用をメタキシリレン基含有ポリアミドに与えるには、14/秒以上が好ましく、より好ましくは20/秒以上であることがわかった。剪断速度が14/秒を下回ると、前記したようにメタキシリレン基含有ポリアミドが1~5mmサイズの大きな粒状態や、未溶融の状態で単軸押出機100の吐出口162から出てきやすくなる。
また、本願の剪断速度は、一般的な単軸押出機においては、充分に広い実用的な剪断速度範囲であるため、特別なモーター容量を必要とせず、実用的、一般的な単軸押出機を使用することができる。
なお、実施例及び比較例で使用する樹脂材料、各種試験方法、押出機及びスクリュー形状は次に示すとおりである。
ポリオレフィン1:日本ポリエチレン社製高密度ポリエチレン、商品名:ノバテックHD HB332R、MFR=0.3g/10分(荷重:2.16kgf、温度:190℃)、密度0.952g/cm3
ポリオレフィン2:日本ポリエチレン社製高密度ポリエチレン、商品名:ノバテックHD HB420R、MFR=0.2g/10分(荷重:2.16kgf、温度:190℃)、密度0.956g/cm3
ポリオレフィン3:日本ポリエチレン社製高密度ポリエチレン、商品名:ノバテックHD HB323R、MFR=0.15g/10分(荷重:2.16kgf、温度:190℃)、密度0.953g/cm3
ポリオレフィン4:日本ポリエチレン社製高密度ポリエチレン、商品名:ノバテックHD HB111R、MFR=0.05g/10分(荷重:2.16kgf、温度:190℃)、密度0.945g/cm3
ポリオレフィン5:日本ポリプロ社製ポリプロプレン、商品名:EC9、MFR=0.5g/10分(荷重:2.16kgf、温度:190℃)、密度0.9g/cm3
ポリオレフィン6:プライムポリマー社製高密度ポリエチレン、商品名:ハイゼックス 520B、MFR=0.32g/10分(荷重:2.16kgf、温度:190℃)、密度0.96g/cm3
ポリオレフィン7:プライムポリマー社製高密度ポリエチレン、商品名:ハイゼックス 537B、MFR=0.27g/10分(荷重:2.16kgf、温度:190℃)、密度0.95g/cm3
ポリオレフィン8:プライムポリマー社製高密度ポリエチレン、商品名:ハイゼックス 520MB、MFR=0.25g/10分(荷重:2.16kgf、温度:190℃)、密度0.96g/cm3
ポリオレフィン9:プライムポリマー社製高密度ポリエチレン、商品名:ハイゼックス 8200B、MFR=0.03g/10分(荷重:2.16kgf、温度:190℃)、密度0.95g/cm3
メタキシリレン基含有ポリアミド1:三菱ガス化学社製ポリメタキシリレンアジパミド、商品名:MXナイロンS6121、相対粘度=3.5、融点=243℃
メタキシリレン基含有ポリアミド2:三菱ガス化学社製イソフタル酸変性メタキシリレン基含有ポリアミド、商品名:MXナイロンS7007、相対粘度=2.7、融点=230℃
試料1gを精秤し、96%硫酸100mLに20~30℃で攪拌溶解し、完全に溶解した後、速やかにキャノンフェンスケ型粘度計に溶液5mlを取り、25℃の恒温層中で10分間放置後、落下時間tを測定した。また同様の条件で96%硫酸そのものの落下時間t0を測定した。落下時間t及び落下時間t0から次式により相対粘度を算出した。
相対粘度=t/t0
接着性ポリオレフィン1:日本ポリエチレン社製無水マレイン酸変性ポリエチレン、商品名:Adtex L6100M、密度0.92g/cm3
接着性ポリオレフィン2:日本ポリプロ社製変性ポリプロピレン、商品名:モディック P604V、密度0.9g/cm3
2.5mm厚となるようにシートに成形し、該シートからφ70mmの円板を打ち抜き、試験片とした。
次に内容積120mlのアルミ製試験容器に、イソオクタン/トルエン/エタノール=45/45/10vol%からなる擬似ガソリン(通称:CE10)を100ml充填し、φ70mm円板の試験片を2組のバイトン製パッキンとワッシャにて挟み、その後φ55mmの開口部を持つネジ込み式の蓋を用いて試験片を試験容器に装着し、擬似ガソリン封入直後の容器総重量を測定した。次に、40℃の防爆型熱風乾燥機に保管、総重量の経時変化を調査し、1日当たりの燃料透過量が平衡となるまで保存した。そして燃料透過量が平衡となったのちに、保存する容器重量の減少量から一日当たりの擬似ガソリンの透過量(g・mm/m2・day・atm)を求めた。
0.5Lタンク成形加工品に、イソオクタン/トルエン/エタノール=45/45/10vol%からなる擬似ガソリン(CE10)を200ml充填し、口栓開口部をアルミ箔積層フィルムでシールし、キャップを閉めた後、アルミテープでキャップを緩まないように固定した。更に擬似ガソリン封入後の容器総重量を測定した。次に、40℃の熱風乾燥機に保管、総重量の経時変化を調査し、1日当たりの燃料透過量が平衡となるまで保存した。そして燃料透過量が平衡となったのちに、保容器重量の減少量から一日当たりの擬似ガソリンの透過量(g・mm/m2・day・atm)を求めた。なお、ブロー成形によるタンク成形品は、タンク成形加工品の胴体中央部の厚みを測定し、この厚みで擬似ガソリンの透過量を示し、比較した。
成形したシート又はタンクを切断し、断面をカッターで平滑にした後、希ヨードチンキ(月島薬品株式会社製)を断面に塗布してメタキシリレン基含有ポリアミド部分を染色した後、実体顕微鏡により拡大して樹脂組成物中のメタキシリレン基含有ポリアミドの分散状態を観察した。
成形した約2.5mm厚シートを4号型試験片形状(把持部を含めた全長が120mmで、幅10mmが50mm長さの形状)を有し、トムソン刃を有した木型を用いて打ち抜きを行い、試験片を作製した。慨打ち抜き試験片を用いて引張り試験機(東洋精機(株)製 ストログラフAP III)にて、引張り(降伏)強度を測定した。なお、試験片は、シート流れ方向を試験片長手方向として打ち抜いた方向(MD方向)と、シート流れ方向に対して試験片長手方向が垂直になる方向(TD方向)の2方向で打ち抜き、試験片とした。各方向共、測定サンプル数を5本/条件とし、引張り(降伏)強度の平均値で示した。また引張り試験速度は50mm/minで実施した。
φ25mm単軸押出機(株式会社プラスチック工学研究所製、PTM25)
φ55mm単軸押出機(津関工業株式会社製)
実施例及び比較例で使用するスクリューは、表1に記載する形状のスクリューa~dである。
予め、ポリオレフィン1を70質量部、接着性ポリオレフィン1を20質量部、及びメタキシリレン基含有ポリアミド1を10質量部ドライブレンドし、原料混合物1を作製した。
この原料混合物を、形状aのスクリューを挿入した、φ25mm単軸押出機((株)プラスチック工学研究所製、PTM25)で、供給部のシリンダー温度225℃、圧縮部のシリンダー温度225℃、計量部のシリンダー温度225℃、同様にヘッド部、アダプター部、Tダイも225℃に設定にて、回転数を110rpm(剪断速度=90/秒)で樹脂組成物を押し出して、Tダイ-ロール冷却法により、ロール温度設定30℃にて厚み約2.4mmのシートを作製した。
得られたシートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表2に記載した。
表2から分かるように、メタキシリレン基含有ポリアミドは、樹脂組成物中で長い線状(薄片状)となって分散しており、また一日あたりの疑似ガソリン(CE10)透過率は10g・mm/m2・day・atmであり、良好な燃料バリア性を示した。
樹脂材料の種類と配合量及びシリンダーの温度の設定、スクリューの剪断速度等の成形条件を表2に記載したように変更した以外は、実施例1と同様に実施して、シートを作製した。
得られたシートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表2に記載した。
メタキシリレン基含有ポリアミドが線状(薄片状)となって分散している箇所を確認し、また、各シートは良好なガソリン透過率を示した。
予め、ポリオレフィン1を70質量部、接着性ポリオレフィン1を20質量部、及びメタキシリレン基含有ポリアミド1を10質量部、ドライブレンドし、原料混合物8を作製した。
これを、形状bのスクリューを挿入したφ55mm単軸押出機(津関工業株式会社製)で、供給部のシリンダー温度210~225℃、圧縮部のシリンダー温度235℃、計量部のシリンダー温度235~233℃、同様にヘッド部は233℃、アダプター部は225℃、Tダイ部は215℃に設定にて、回転数を22rpm(剪断速度=14/秒)で押し出して、円筒ダイ-金型冷却によるダイレクトブロー法により、成形サイクル24秒の連続押し出し成形にて、0.5Lタンク成形加工品を得た。
金型冷却水温度は約20~30℃であった。タンク胴体中央部の厚みは約2mmであった。
得られたタンク成形品について、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験IIを行い、その結果を表3に記載した。
タンク成形品の胴体部、ピンチオフ部共に、メタキシリレン基含有ポリアミドが長い線状(薄片状)となって分散していることを確認した。
また、一日あたりの疑似ガソリン(CE10)の透過率は、18g/m2・dayであり、良好な燃料バリア性を示した。
樹脂材料の種類と配合量及びシリンダーの温度の設定、スクリューの剪断速度等の成形条件を表3に記載したように変更した以外は、実施例8と同様に実施して、成形サイクル90秒の間欠押し出し成形にて、胴体中央部が約4mm厚の0.5Lタンク成形品を作製した。
得られた各タンク成形品について、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験IIを行い、その結果を表3に記載した。
メタキシリレン基含有ポリアミドが線状(薄片状)となって分散している箇所を確認し、また、各タンク成形品は良好なガソリン透過率を示した。
樹脂材料の種類と配合量及びシリンダーの温度の設定、スクリューの剪断速度等の成形条件を表4に記載したように変更した以外は、実施例1と同様に実施してシートを作製した。
得られた各シートについて、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験Iを行い、その結果を表4に記載した。
各シートについて、メタキシリレン基含有ポリアミドが長い線状(薄片状)となって分散している箇所を確認し、良好な燃料バリア性を示すことを確認した。
樹脂材料の種類と配合量及びシリンダーの温度の設定、スクリューの剪断速度等の成形条件を表5に記載したように変更した以外は、実施例1と同様に実施してシートを作製した。
得られた各シートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表5に記載した。
各シートについて、メタキシリレン基含有ポリアミドが長い線状(薄片状)となって分散している箇所を確認し、良好な燃料バリア性を示すことを確認した。
形状cのスクリューを用いた以外は、実施例1と同様に実施して、シートを作製した。但し、スクリュー回転数は実施例1と同一であるが、剪断速度はスクリュー形状が異なる為、表6に示すように実施例1とは異なった。
得られた各シートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表6に記載した。
比較例1では、成形に使用したスクリューの圧縮部の長さ割合が大きいために、シートを構成する樹脂組成物中のメタキシリレン基含有ポリアミドは過度に分散し、粒状分散となったため、燃料バリア性は良くない結果であった。
形状cのスクリューを用い、樹脂材料の配合量、シリンダーの温度、及びスクリュー剪断速度の設定等の成形条件を表6に記載したように変更した以外は、実施例1と同様に実施してシートを作製した。
得られた各シートについて、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験Iを行い、その結果を表6に記載した。
比較例2では成形に使用したスクリューの圧縮部の長さ割合が大きいために、シートを構成する樹脂組成物中でメタキシリレン基含有ポリアミドは過度に分散し、粒状分散となったため、燃料バリア性は良くない結果であった。
比較例3では供給部と圧縮部のシリンダー温度が低いため、得られたシート中にメタキシリレン基含有ポリアミドが未溶融の状態が発生した。
樹脂材料の配合量を表7に記載したように変更した以外は、実施例1と同様に実施して、シートを作製した。
得られたシートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表7に記載した。
シートを構成する樹脂組成物中のメタキシリレン基含有ポリアミドの含有量が多いため、得られたシートの断面は、メタキシリレン基ポリアミドが線状となっているところと大きな塊となっているところが点在した。またその塊が、シート表面の外観として白い斑点となって見える外観不良となった。燃料バリア性試験では良好な燃料バリア性は得られたが、外観の悪い実用性に劣るものであった。
シリンダーの温度を及びスクリュー回転数を表7に記載したように変更した以外は、実施例7と同様に実施してシートを作製した。
得られたシートについて、メタキシリレン基含有ポリアミド分散状態の観察、引っ張り試験及び燃料バリア性試験Iを行い、その結果を表7に記載したが、成形加工時の供給部、圧縮部、計量部のいずれの温度も高すぎるため、得られたシートを構成する樹脂組成物中のメタキシリレン基含有ポリアミドが過度に分散し粒状分散となったため、燃料バリア性結果も悪かった。
表7に記載したように、スクリュー回転数を低減して、スクリュー剪断速度を変更した以外は、実施例1と同様に実施して、シートを作製した。
得られたシートについて、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験Iを行い、その結果を表7に記載した。
樹脂組成物中にメタキシリレン基含有ポリアミド未溶融の状態が発生し、線状(薄片状)に分散している箇所は確認できなかった。またガソリン透過率も悪い結果であった。
形状dのスクリューを用い、シリンダーの温度設定、スクリュー剪断速度等の成形条件は表8に記載したように変えた以外は、実施例8と同様に実施して、0.5Lタンク成形品を作製した。連続押し出し成形にて、成形サイクルは24秒で、厚み約2mmのタンク成形品であった。
得られたタンク成形品について、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験IIを行い、その結果を表8に記載した。
比較例7では成形に使用したスクリューの圧縮部の長さ割合が大きいために、シートを構成する樹脂組成物中でメタキシリレン基含有ポリアミドは過度に分散し、粒状分散となったため、燃料バリア性はあまり良くない結果であった。
形状bのスクリューを用いて、シリンダーの温度設定とスクリュー回転数を表9に記載したように変更した以外は、実施例11と同様に実施して、0.5Lタンク成形品を作製した。
得られたタンク成形品について、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験IIを行い、その結果を表9に記載した。
比較例8では、供給部と計量部のシリンダー温度が高いため、タンクを構成する樹脂組成物中でメタキシリレン基含有ポリアミドは過度に分散し、粒状分散となったため、燃料バリア性は良くない結果であった。
比較例9では、供給部と圧縮部のシリンダー温度が低いため、メタキシリレン基含有ポリアミドが未溶融の状態が発生した。
比較例10では、供給部のシリンダー温度が高いため、タンクを構成する樹脂組成物中でメタキシリレン基含有ポリアミドは過度に分散し、粒状分散となったため、燃料バリア性は良くない結果であった。
表9に記載したように、スクリュー回転数を低減して、スクリュー剪断速度を変更した以外は、実施例8と同様に実施して、0.5Lタンク成形品を作製した。
得られたタンク成形品について、メタキシリレン基含有ポリアミド分散状態の観察及び燃料バリア性試験IIを行い、その結果を表9に記載した。
比較例11では、成形加工時の剪断速度が遅いため、タキシリレン基含有ポリアミドが未溶融の状態が発生した。また燃料バリア性も悪い結果であった。
110 ホッパー
140 シリンダー
142 シリンダーの内周面
120 ホッパーに設けられた温度調節器
130 冷却水用穴
150 スクリュー
150a 供給部
150b 圧縮部
150c 計量部
152 スクリュー軸
154 ねじ切り部
170 スクリュー駆動装置
h1 計量部の溝深さ
h2 供給部の溝深さ
dc シリンダー直径
C1、C2、C3 ヒーター(温度調節器)
D スクリューの直径(ねじ切り部を含めた直径すなわちスクリューの外径)
d スクリュー軸の直径(ねじ切り部を含めない直径)
w スクリューのネジ幅(フライト幅)
Claims (7)
- ポリオレフィン(A)40~90質量部、メタキシリレン基含有ポリアミド(B)3~30質量部、及び接着性ポリオレフィン(C)3~50質量部の少なくとも3種類を含む樹脂材料をブレンドした原料混合物を、以下の(1)の条件を満たす単軸押出機を使用し、以下の(2)、(3)の条件にて溶融混練した樹脂組成物からなる成形加工品。
(1)前記単軸押出機は、
スクリュー軸と前記スクリュー軸の側面に螺旋状に形成されたねじ切り部であって前記樹脂組成物を前記スクリュー軸の回転によって前記スクリュー軸の基端部から先端部に向けて送るねじ切り部とを有するスクリューと、
前記スクリューを回転可能に挿通し、内周面が円筒内側面形状を有するシリンダーと、
前記スクリューの回転によって前記基端部から前記先端部に送られる樹脂組成物の温度を調節する複数の温度調節器と、
前記スクリューを所定の剪断速度となるように回転させるスクリュー駆動装置と、を備え、
前記スクリュー軸は、前記スクリュー軸の基端部から前記スクリュー軸の先端部に向けて、前記ねじ切り部の先端と前記スクリュー軸の表面との間のスクリュー溝の深さが一定となっている範囲である供給部と、前記供給部に続き、前記スクリュー溝の深さが徐々に浅くなっている範囲である圧縮部と、前記圧縮部に続き、前記スクリュー溝の深さが前記供給部よりも浅くかつ一定となっている範囲である計量部とを有し、
前記スクリュー軸のスクリュー有効長に対する前記供給部の長さの比が0.40~0.55、前記圧縮部の長さの比が0.10~0.30、前記計量部の長さの比が0.10~0.40の範囲であり、かつ前記供給部の長さの比、前記圧縮部の長さの比、及び前記計量部の長さの比の合計が1.0である。
(2)前記供給部における前記シリンダーの温度の上限は(メタキシリレン基含有ポリアミドの融点+20℃以下)であり、前記圧縮部と前記計量部とにおける前記シリンダーの温度は、(メタキシリレン基含有ポリアミドの融点-30℃)~(メタキシリレン基含有ポリアミドの融点+20℃)の範囲である。
(3)前記所定の剪断速度は、14/秒以上である。 - 前記単軸押出機において、前記スクリューの形状が以下の(1)から(3)条件を満足する請求項1記載の成形加工品。
(1)前記ねじ切り部の先端の直径Dに対する前記スクリュー有効長Lの比(L/D比)が22~32の範囲であり、
(2)前記供給部における前記スクリュー溝の深さh2が0.1D~0.3Dの範囲であり、
(3)前記供給部の断面積と前記計量部の断面積との比である圧縮比が2.3~3.5の範囲にある。 - 前記メタキシリレン基含有ポリアミド(B)がメタキシリレンジアミン単位を70モル%以上含むジアミン単位と、α,ω-脂肪族ジカルボン酸単位を50モル%以上含むジカルボン酸単位とを含むポリアミドである請求項1又は2に記載の成形加工品。
- 前記メタキシリレン基含有ポリアミド(B)の相対粘度が2.0~4.5である請求項1又は2に記載の成形加工品。
- 前記ポリオレフィン(A)のメルトフローレート(MFR)が、0.03g/10分(荷重:2.16kgf、温度:190℃)以上、かつ2g/10分(荷重:2.16kgf、温度:190℃)以下の範囲の高密度ポリエチレンである請求項1又は2に記載の成形加工品。
- 前記成形加工品がダイレクトブロー法により成形して得られる中空容器である請求項1~5のいずれかに記載の成形加工品。
- 前記成形加工品がTダイーロール冷却法により成形して得られるシートである請求項1~5のいずれかに記載の成形加工品。
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2011
- 2011-11-29 US US13/989,936 patent/US20130251927A1/en not_active Abandoned
- 2011-11-29 BR BR112013013449-6A patent/BR112013013449A2/pt not_active Application Discontinuation
- 2011-11-29 CN CN201180057193.9A patent/CN103260849B/zh active Active
- 2011-11-29 CA CA2819210A patent/CA2819210A1/en not_active Abandoned
- 2011-11-29 RU RU2013126625/05A patent/RU2565685C2/ru not_active IP Right Cessation
- 2011-11-29 PE PE2013001056A patent/PE20140016A1/es not_active Application Discontinuation
- 2011-11-29 EP EP11844709.3A patent/EP2647483B1/en active Active
- 2011-11-29 AU AU2011337681A patent/AU2011337681B2/en not_active Ceased
- 2011-11-29 JP JP2012546891A patent/JP5835226B2/ja active Active
- 2011-11-29 ES ES11844709.3T patent/ES2647869T3/es active Active
- 2011-11-29 WO PCT/JP2011/077563 patent/WO2012073969A1/ja active Application Filing
- 2011-11-29 KR KR1020137012915A patent/KR20140027061A/ko not_active Application Discontinuation
- 2011-11-29 MX MX2013005891A patent/MX342042B/es active IP Right Grant
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2013
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JP2014129487A (ja) * | 2012-12-28 | 2014-07-10 | Mitsubishi Gas Chemical Co Inc | ポリエチレン系構造体 |
CN105517774A (zh) * | 2013-09-11 | 2016-04-20 | 三菱瓦斯化学株式会社 | 聚烯烃系结构物的制造方法 |
WO2015037459A1 (ja) | 2013-09-11 | 2015-03-19 | 三菱瓦斯化学株式会社 | ポリオレフィン系構造体の製造方法 |
JP5790888B2 (ja) * | 2013-09-11 | 2015-10-07 | 三菱瓦斯化学株式会社 | ポリオレフィン系構造体の製造方法 |
CN105517774B (zh) * | 2013-09-11 | 2017-06-20 | 三菱瓦斯化学株式会社 | 聚烯烃系结构物的制造方法 |
KR20160054478A (ko) | 2013-09-11 | 2016-05-16 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 폴리올레핀계 구조체의 제조방법 |
EP3045291A1 (en) * | 2013-09-11 | 2016-07-20 | Mitsubishi Gas Chemical Company, Inc. | Method for producing a polyolefin structure |
KR102168386B1 (ko) | 2013-09-11 | 2020-10-21 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 폴리올레핀계 구조체의 제조방법 |
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EP3045291A4 (en) * | 2013-09-11 | 2017-04-26 | Mitsubishi Gas Chemical Company, Inc. | Method for producing a polyolefin structure |
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WO2016017518A1 (ja) * | 2014-07-30 | 2016-02-04 | 三菱瓦斯化学株式会社 | ポリアミドペレット、ポリアミドペレットの製造方法、及びポリアミド成形体の製造方法 |
JPWO2016017518A1 (ja) * | 2014-07-30 | 2017-05-18 | 三菱瓦斯化学株式会社 | ポリアミドペレット、ポリアミドペレットの製造方法、及びポリアミド成形体の製造方法 |
US10786928B2 (en) | 2014-07-30 | 2020-09-29 | Mitsubishi Gas Chemical Company, Inc. | Polyamide pellets, method for producing polyamide pellets, and method for producing polyamide molded article |
JP2017035801A (ja) * | 2015-08-07 | 2017-02-16 | 東洋製罐株式会社 | 押出機 |
WO2017098892A1 (ja) * | 2015-12-11 | 2017-06-15 | 三菱瓦斯化学株式会社 | 中空容器及びその製造方法 |
JP2018203859A (ja) * | 2017-06-02 | 2018-12-27 | 日本ポリプロ株式会社 | 熱成形シート用樹脂組成物およびその成形体 |
JP7024214B2 (ja) | 2017-06-02 | 2022-02-24 | 日本ポリプロ株式会社 | 成形体 |
JP2020116912A (ja) * | 2019-01-28 | 2020-08-06 | 東ソー株式会社 | 高純度薬品容器の製造方法 |
JP7243223B2 (ja) | 2019-01-28 | 2023-03-22 | 東ソー株式会社 | 高純度薬品容器の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CO6741159A2 (es) | 2013-08-30 |
JP5835226B2 (ja) | 2015-12-24 |
EP2647483A4 (en) | 2015-01-21 |
MX342042B (es) | 2016-09-12 |
CA2819210A1 (en) | 2012-06-07 |
MX2013005891A (es) | 2013-10-25 |
RU2013126625A (ru) | 2015-01-10 |
BR112013013449A2 (pt) | 2020-08-11 |
ES2647869T3 (es) | 2017-12-27 |
US20130251927A1 (en) | 2013-09-26 |
EP2647483B1 (en) | 2017-09-06 |
PE20140016A1 (es) | 2014-01-23 |
RU2565685C2 (ru) | 2015-10-20 |
CN103260849B (zh) | 2015-05-13 |
US20150108696A1 (en) | 2015-04-23 |
AU2011337681A1 (en) | 2013-05-02 |
CN103260849A (zh) | 2013-08-21 |
JPWO2012073969A1 (ja) | 2014-05-19 |
EP2647483A1 (en) | 2013-10-09 |
KR20140027061A (ko) | 2014-03-06 |
ZA201303413B (en) | 2014-07-30 |
AU2011337681B2 (en) | 2014-11-13 |
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