WO2013114996A1 - 発泡成形品の製造方法および発泡成形品 - Google Patents
発泡成形品の製造方法および発泡成形品 Download PDFInfo
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- WO2013114996A1 WO2013114996A1 PCT/JP2013/051124 JP2013051124W WO2013114996A1 WO 2013114996 A1 WO2013114996 A1 WO 2013114996A1 JP 2013051124 W JP2013051124 W JP 2013051124W WO 2013114996 A1 WO2013114996 A1 WO 2013114996A1
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- duct
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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- B29L2031/3032—Air inlets
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Definitions
- the present invention relates to a method for manufacturing a foam molded product used for, for example, an air conditioning duct for a vehicle and a foam molded product.
- a foam molded product is sometimes used by being integrated with another member such as an instrument panel.
- another member such as an instrument panel.
- heat is generated in the contact portion by ultrasonic vibration generated by an ultrasonic welding machine while one member is pressed against the other member, and this heat causes the contact portion to surround it.
- a method of melting and welding is known.
- polyethylene resins are generally cheaper than polypropylene resins, it is often possible to manufacture foamed molded products with polyethylene resins at a lower cost than with polypropylene resins alone.
- instrument panels used in vehicles are often molded products made of polypropylene resin.
- a foam molded product composed only of an inexpensive polyethylene resin is not suitable for a polypropylene resin and a polyethylene resin. It was difficult to weld due to the difference in physical properties.
- the foamed molded article when applied as a vehicle-mounted component, it is desirable that the foamed molded article also has impact resistance up to a level where cracks are less likely to occur during use.
- Patent Document 1 has not been considered up to the fact that it is fused and integrated with such a molded product made of polypropylene resin.
- the present invention has been made in view of such a situation, and although it is a foam molded product using a polyethylene resin, it has excellent weldability to a molded product by a polypropylene resin and can also increase the expansion ratio.
- An object of the present invention is to provide a method for producing a foamed molded article having impact resistance up to a predetermined level and a foamed molded article.
- a method for producing a foam molded article according to the present invention includes foaming a base resin in which a first polyethylene resin, a second polyethylene resin, and a polypropylene resin are mixed.
- a method of manufacturing a foamed molded product to be molded The first polyethylene-based resin has a long-chain branched structure, has a density of 0.920 g / cm 3 or more
- the second polyethylene-based resin is produced by a low-pressure slurry method, has a long-chain branched structure, has a density of 0.920 g / cm 3 or less, and a melt tension at 160 ° C. of 70 mN or more.
- the polypropylene resin is characterized in that the blending ratio is 20% or more of the base resin by weight.
- the foam molded article according to the present invention is a foam molded article obtained by foaming and molding a base resin in which a first polyethylene resin, a second polyethylene resin, and a polypropylene resin are mixed. Because the first polyethylene-based resin has a long-chain branched structure, has a density of 0.920 g / cm 3 or more, The second polyethylene-based resin is produced by a low-pressure slurry method, has a long-chain branched structure, has a density of 0.920 g / cm 3 or less, and a melt tension at 160 ° C. of 70 mN or more.
- the polypropylene resin is characterized in that the blending ratio is 20% or more of the base resin by weight.
- the present invention while being a foam-molded product that can be reduced in cost using a polyethylene-based resin, it is excellent in weldability to a molded product by a polypropylene-based resin, and the expansion ratio can be increased. It can be made into the foaming molded article which also has impact resistance to a predetermined level.
- FIG. 10 It is a perspective view showing an example of duct 10 as an embodiment of the present invention. It is sectional drawing which shows the aspect at the time of blow-molding the duct 10 of FIG.
- the present invention is not limited to a vehicle air-conditioning duct.
- automotive interior parts such as door panels, instrument panels, and vehicle deck boards, residential interior wall materials, housings for electronic devices, gases other than those for vehicles
- the present invention can also be applied to other foamed molded products such as a duct for supplying a liquid.
- a duct 10 according to an embodiment of the present invention shown in FIG. 1 is configured so that air-conditioned air supplied from an air-conditioner unit (not shown) is circulated through a flow path inside the duct and is ventilated to a desired part. Further, it is welded to a molded product made of polypropylene resin such as an instrument panel of a vehicle, and is integrated into a vehicle.
- the shape of the duct 10 of this embodiment is not limited to what is shown in FIG. 1, The arbitrary shapes according to the use of the duct 10, an arrangement place, etc. may be sufficient.
- the duct 10 of the present embodiment is obtained by blow molding by sandwiching a foamed parison formed by extruding a foamable resin from an annular die of an extruder.
- the duct immediately after blow molding is in a state where both ends are closed, and both ends of the duct are cut into an open shape by trimming after blow molding. The blow molding will be described later.
- the average cell diameter of the cell in the thickness direction of the tube wall is preferably less than 300 ⁇ m. In this case, there is an advantage that the mechanical strength is further increased.
- the average cell diameter is more preferably less than 100 ⁇ m.
- the duct 10 has a closed cell structure with an expansion ratio of 1.5 times or more.
- the expansion ratio is a value obtained by dividing the density of the thermoplastic resin used for foam blow molding by the apparent density of the tube wall of the foam blow molded product.
- the closed cell structure is a structure having a plurality of bubble cells, and means a structure having at least a closed cell ratio of 70% or more.
- the weight can be further reduced and the heat insulating property can be further enhanced as compared with other cases. For this reason, even if it is a case where the air of cooling is distribute
- the duct 10 of the present embodiment preferably has impact resistance and rigidity that do not cause cracking or scattering cracking, for example, during duct transportation, assembly, or deployment of a vehicle airbag. .
- the height at which cracks are generated is preferably 30 cm or more. By being in this range, it is possible to achieve a level of impact resistance that is unlikely to cause cracks when the duct 10 is used for a vehicle or the like, as compared to the case of being outside the range. More preferably, the height at which the above cracks are generated is preferably 40 cm or more. By being in this range, it is possible to achieve sufficient impact resistance that hardly causes cracks even when the duct is transported, assembled, and used, as compared with the case of being outside the range.
- the tensile elasticity modulus in the tube wall of the duct 10 is 1,500 kg / cm ⁇ 2 > or more. By being in this range, it is possible to effectively prevent deformation of the duct even when the duct is transported, assembled, and used, as compared with the case where it is out of the range.
- the tensile modulus is a value measured at room temperature (23 ° C.) at a tensile speed of 50 mm / min at room temperature (23 ° C.) using a type 2 test piece in accordance with JIS K-7113.
- the duct 10 of the present embodiment is welded to a molded product made of polypropylene resin such as an instrument panel of the vehicle, and is integrated into the vehicle.
- the duct 10 of the present embodiment is pressed against the molded product of the polypropylene resin to be welded, and the duct 10 is vibrated using an ultrasonic welding machine, so that only around the contact portion. Heat, melt and weld. For this reason, it is calculated
- the duct 10 of this embodiment is obtained by adding a foaming agent to a base resin in which a polypropylene resin, a foaming polyethylene resin, and a low density polyethylene resin are mixed, and then performing blow molding. It is done.
- melt tension means melt tension.
- the polypropylene resin for foaming exhibits strain hardening and a high foaming ratio can be obtained.
- the foaming polyethylene resin and the low density polyethylene resin preferably have a long-chain branched structure.
- This long chain branched structure is a long chain in which the number of branches of hexyl group (carbon number 6) or more detected by 13 C-NMR measurement is 0.01 or more per 1,000 carbon atoms and 3 or less.
- the number of branches and the weight average molecular weight (Mw) are preferably 100,000 or more and 1,000,000 or less. When the number of branches is less than 0.01, a foamed layer cannot be formed. On the other hand, when the number exceeds 3, the heat resistance and rigidity are inferior. If the weight average molecular weight is less than 100,000, shape retention is difficult, and if it is greater than 1,000,000, molding becomes difficult.
- the high-density polyethylene-based resin for foaming preferably has a density of 0.920 g / cm 3 or more at normal temperature (23 ° C.) and a melt tension (MT) of 100 to 250 mN.
- the melt flow rate (MFR) is preferably 3 to 7 g / 10 min. When MT and MFR are out of this range, a good foamed layer cannot be obtained as compared with the case of being within the range.
- the above MT uses a melt tension tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), extrudes a strand from an orifice having a diameter of 2.095 mm and a length of 8 mm at a preheating temperature of 160 ° C. and an extrusion speed of 5.7 mm / min. Is a tension when the roller is wound around a roller having a diameter of 50 mm at a winding speed of 100 rpm.
- the above MFR is a value measured at a test temperature of 190 ° C. and a test load of 2.16 kg in accordance with JIS K-6922-1.
- a thing with a bending elastic modulus (JIS K6922) of 700 Mpa or more is preferable. By being in this range, the rigidity is further improved as compared to the case of being outside the range.
- the flexural modulus is a value measured according to JIS K6922-2.
- the low-density polyethylene-based resin is manufactured by a low-pressure slurry method, has a density of 0.920 g / cm 3 or less at normal temperature (23 ° C.), and has a melt tension (MT) of 70 mN at the above-mentioned preheating temperature of 160 ° C.
- the above is preferable. By being in this range, compared with the case where it is outside the range, the mixing of the polypropylene resin and the foaming polyethylene resin is improved, and the expansion ratio is easily increased. In addition, impact resistance at low temperatures can be improved.
- melt tension (MT) and MFR it is preferable that MT ⁇ MFR is 300 (mN ⁇ g / 10 minutes) or more. By being within this range, pinholes are less likely to occur when forming the irregular shape on the mold surface compared to the case outside the range, and the moldability is improved.
- the weight blending ratio of the polypropylene resin, the foaming polyethylene resin, and the low density polyethylene resin in the base resin is 20 to 70 wt% with respect to the total amount of the base resin.
- the weight blending ratio in the base resin is preferably 10 to 20 wt% of the low density polyethylene resin with respect to the total amount of the base resin. By making it within the range of this blending ratio, it is possible to ensure sufficient impact resistance that prevents cracks during transport, assembly, and use of the duct 10, and sufficient rigidity without deformation. .
- the weight blending ratio in the base resin is preferably 50 wt% or more of the foaming polyethylene resin with respect to the total amount of the base resin. By making it within the range of this blending ratio, the expansion ratio can be further increased.
- the base resin is foamed using a foaming agent before being blow-molded.
- foaming agents include inorganic foaming agents such as air, carbon dioxide gas, nitrogen gas, and water, or organic foaming agents such as butane, pentane, hexane, dichloromethane, and dichloroethane.
- inorganic foaming agents such as air, carbon dioxide gas, nitrogen gas, and water
- organic foaming agents such as butane, pentane, hexane, dichloromethane, and dichloroethane.
- a supercritical fluid as the foaming method. That is, it is preferable that carbon dioxide gas or nitrogen gas is in a supercritical state to foam the mixed resin. In this case, air bubbles can be uniformly and reliably formed.
- the supercritical fluid is nitrogen gas
- the conditions may be a critical temperature of 149.1 ° C. and a critical pressure of 3.4 MPa or more.
- the supercritical fluid is carbon dioxide gas
- the conditions are a critical temperature of 31 ° C.
- the critical pressure may be 7.4 MPa or more.
- FIG. 2 is a cross-sectional view showing an aspect when the duct 10 according to this embodiment is blow-molded.
- the above-described polypropylene resin, foaming polyethylene resin, and low density polyethylene resin are kneaded at a predetermined ratio to produce a base resin.
- the blending ratio in the base resin is 20 to 70 wt% of the polypropylene resin as a weight ratio with respect to the total amount of the base resin.
- the low density polyethylene resin is 10 to 20 wt%. More preferably, the foaming polyethylene resin is 50 wt% or more.
- the present invention is not limited to the case where the foamed molded product is molded by blow molding, and vacuum molding in which a molded product having a predetermined shape is molded by sucking the extruded parison into a mold may be used. Moreover, you may shape
- the duct 10 according to the present embodiment is obtained by adding a foaming agent to a base resin in which the above-described polypropylene resin, a foaming polyethylene resin, and a low density polyethylene resin are mixed. Manufactured by molding.
- the weight ratio of the polypropylene resin, the foaming polyethylene resin, and the low density polyethylene resin in the base resin is 20 to 70 wt% with respect to the total amount of the base resin.
- the weldability of the polypropylene resin to the molded product can be sufficiently secured.
- the expansion ratio can be 1.5 times or more, and for example, it can be a duct having lightness and heat insulation sufficient for applications such as vehicles. In addition, it is possible to ensure a level of impact resistance that is unlikely to crack when used in vehicles.
- the weight blending ratio in the base resin is preferably 10 to 20 wt% of the low density polyethylene resin with respect to the total amount of the base resin. Due to this blending ratio, for example, when it is applied to a so-called instrument panel duct that is welded to an instrument panel of a vehicle, it has sufficient impact resistance to prevent cracks during duct transportation, assembly, and use. It can be set as the duct which has property. And it can be set as the duct which has sufficient rigidity which does not deform
- the foaming polyethylene-based resin is 50 wt% or more with respect to the total amount of the base resin.
- this blending ratio it is possible to obtain a duct having a higher expansion ratio. For this reason, it can be set as the duct further excellent in the lightweight property and heat insulation.
- the polypropylene resin, the foaming polyethylene resin, and the low density polyethylene resin used as Examples and Comparative Examples are as follows.
- PP1 Block polypropylene (made by Nippon Polypro Co., Ltd., trade name “NOVATEC BC8”)
- PP2 Propylene homopolymer (manufactured by Borealis AG, trade name “Daploy WB140”)
- PE1 Linear long-chain branched high melt strength polyethylene produced by the low pressure slurry method (trade name “TOSOH-HMS”, product number “08S55A” manufactured by Tosoh Corporation)
- PE2 A linear long-chain branched high-melt strength polyethylene produced by a low-pressure slurry method (trade name “TOSOH-HMS JK17” manufactured by Tosoh Corporation)
- PE3 Reticulated long-chain branched low-density polyethylene produced by the high-pressure radical method (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikasen F108-1”)
- PE4 Linear short-chain branched polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name “Excellen FX201”)
- MT is a strand from an orifice having a diameter of 2.095 mm and a length of 8 mm at a preheating temperature of 230 ° C., an extrusion speed of 5.7 mm / min, using a melt tension tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.). The tension when the strand is wound around a roller having a diameter of 50 mm at a winding speed of 100 rpm is shown. However, the PP2 MT was measured at a winding speed of 0.8 m / min. MFR is a value measured at a test temperature of 230 ° C. and a test load of 2.16 kg according to JIS K-7210.
- the density is a value measured at normal temperature (23 ° C.).
- the tensile modulus is a value measured at room temperature (23 ° C.) with a No. 2 type test piece according to JIS K-7113 and at a normal temperature (23 ° C.) at a tensile rate of 50 mm / min.
- MT uses a melt tension tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), has a preheating temperature of 160 ° C., an extrusion rate of 5.7 mm / min, and is strand from an orifice of 2.095 mm in diameter and 8 mm in length.
- the tension when the strand is wound around a roller having a diameter of 50 mm at a winding speed of 100 rpm is shown.
- MFR is a value measured at a test temperature of 190 ° C. and a test load of 2.16 kg according to JIS K-6922-1.
- the density is a value measured at normal temperature (23 ° C.).
- the tensile modulus is a value measured at room temperature (23 ° C.) with a No. 2 type test piece according to JIS K-7113 and at a normal temperature (23 ° C.) at a tensile rate of 50 mm / min.
- the flexural modulus is a value measured according to JIS K6922-2.
- PP1 was mixed at 70 wt%, PE1 was mixed at 20 wt%, and PE2 was mixed at 10 wt% to obtain a base resin.
- An LDPE base masterbatch (made by Dainichi Seika Kogyo Co., Ltd., trade name “Fine Cell Master” containing supercritical nitrogen as a foaming agent and 20 wt% sodium hydrogen carbonate-based foaming agent as a nucleating agent is added to the base resin.
- 1.0 part by weight of P0217K ” and 1.0 part by weight of an LLDPE base masterbatch containing 40 wt% carbon black as a colorant were added and foamed to obtain a foamed resin.
- an in-die accumulator which is a cylindrical space between the mandrel and the die outer cylinder, and extruded into a split mold as a cylindrical parison using a ring-shaped piston, after clamping Blow-molded samples were obtained by blowing air into the parison at a pressure of 0.1 MPa.
- Example 2 20 wt% of PP1, 70 wt% of PE1, and 10 wt% of PE2 were mixed to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- Example 3 PP1 was mixed at 60 wt%, PE1 was mixed at 20 wt%, and PE2 was mixed at 20 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- Example 4 PP1 was mixed with 55 wt%, PE1 was mixed with 30 wt%, and PE2 was mixed with 15 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- PP1 was mixed with 65 wt%, PE1 with 30 wt%, and PE2 with 5 wt%, and a base resin was prepared. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- Example 6 PP1 was mixed with 50 wt%, PE1 was mixed with 20 wt%, and PE2 was mixed with 30 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- PP1 was mixed at 70 wt%
- PE1 was mixed at 20 wt%
- PE3 was mixed at 10 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- PP1 was mixed with 70 wt%
- PE1 was mixed with 20 wt%
- PE4 was mixed with 10 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- PP1 was mixed at 10 wt%, PE1 at 70 wt%, and PE2 at 20 wt% to form a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- Example 4 A base resin was prepared by mixing 80 wt% PE1 and 20 wt% PE2. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- PP1 was mixed at 60 wt%
- PP2 was mixed at 20 wt%
- PE2 was mixed at 20 wt% to obtain a base resin. Subsequent steps obtained a blow-molded sample by the same method as in Example 1.
- Samples of foam molded products obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were instrument panel members made of polypropylene resin using a 12 mm head of an ultrasonic welder SONOPET 335 manufactured by Seidensha Electronics Co., Ltd. For 5 seconds under conditions of a frequency of 39.5 Hz, normal temperature, and a pressing strength of 85 N, and then weld strength is adjusted at a tensile speed of 10 mm / min with a Tensilon universal material testing machine RTC-1325A manufactured by Orientec Co., Ltd. The case where the welding strength at the time of measurement was 10 kgf or more was marked as ⁇ , and the other cases were marked as x.
- ⁇ Foaming ratio The expansion ratio was calculated by dividing the density of the mixed resin used in Examples 1 to 6 and Comparative Examples 1 to 6 by the apparent density of the wall portion of the corresponding foam molded product sample.
- ⁇ Foaming properties The case where the foaming ratio calculated as described above was 1.5 times or more was marked as ⁇ , and the other cases were marked as x.
- ⁇ Rigidity> For the measurement of the tensile modulus, a No. 2 type test piece according to JIS K-7113 was used, and the value measured at room temperature (23 ° C.) at a tensile rate of 50 mm / min was 1,500 kg / cm 2 or more. ⁇ , and other cases were marked with ⁇ .
- the weight ratio of the polypropylene resin is 20 to 70 wt% with respect to the total amount of the base resin. With this blending ratio, the above-mentioned weldability and foamability could be sufficiently secured for all the samples, and impact resistance of about the evaluation level “ ⁇ ” or more could be secured.
- the weight blending ratio of the low density polyethylene resin is 10 to 20 wt% with respect to the total amount of the base resin. With this blending ratio, in addition to the weldability and foamability described above, the impact resistance and rigidity described above can be sufficiently secured.
- the weight blending ratio of the foaming polyethylene resin is 50 wt% or more with respect to the total amount of the base resin.
- the above-mentioned weldability, foamability, impact resistance, and rigidity were sufficiently ensured, and the expansion ratio could be 2.5 times.
- PP1 is reduced to 10 wt% as a weight blending ratio in the base resin, and 70 wt% of PE1, which is a polyethylene resin for foaming, is blended.
- PE1 which is a polyethylene resin for foaming
- the base resin is composed of PP1 of polypropylene resin and PE1 of polyethylene resin for foaming without blending the low density polyethylene resin, the above-described weldability and foamability are included. Was sufficiently secured, but the impact resistance was insufficient.
- the present invention is not limited to light-weight air conditioning ducts for vehicles, but can be used for, for example, automobiles, aircrafts, vehicles / ships, building materials, housings for various electrical equipment, sports / leisure structural members, etc. Can do. Also, when used as automotive structural members such as cargo floor boards, deck boards, rear parcel shelves, roof panels, door trims, interior panels, door inner panels, platforms, hard tops, sunroofs, bonnets, bumpers, floor spacers, devia pads, etc. Since the weight reduction of an automobile can be measured, fuel consumption can be improved.
Abstract
Description
こうして発泡成形品を他部材と一体化させる場合、一方の部材を他方の部材に押し付けた状態で、超音波溶着機による超音波振動により接触部分に熱を発生させ、この熱で接触部分周りを溶融させて溶着させる方法などが知られている。
また、例えば車載用部品として適用する場合等、発泡成形品の実用上、使用時に亀裂が生じにくい程度のレベルまでは耐衝撃性も有していることが望ましい。
第1のポリエチレン系樹脂は、長鎖分岐構造を有し、密度0.920g/cm3以上であり、
第2のポリエチレン系樹脂は、低圧スラリー法で製造され、長鎖分岐構造を有し、密度0.920g/cm3以下、かつ160℃での溶融張力が70mN以上であり、
ポリプロピレン系樹脂は、配合比率が重量比で基材樹脂の20%以上であることを特徴とする。
第1のポリエチレン系樹脂は、長鎖分岐構造を有し、密度0.920g/cm3以上であり、
第2のポリエチレン系樹脂は、低圧スラリー法で製造され、長鎖分岐構造を有し、密度0.920g/cm3以下、かつ160℃での溶融張力が70mN以上であり、
ポリプロピレン系樹脂は、配合比率が重量比で基材樹脂の20%以上であることを特徴とする。
なお、本発明は、車両用空調ダクトに限らず、例えば、ドアパネル、インストルメントパネル、車両用デッキボードなどの自動車用内装部品、住宅用内装壁材、電子機器のハウジング、車両用以外の気体や液体を供給するダクトなど、他の発泡成形品にも適用することができる。
なお、本実施形態のダクト10の形状は図1に示すものに限定されず、ダクト10の用途や配置場所等に応じた任意の形状であってよい。
また、より好ましくは、上記のひび割れが発生する高さが40cm以上であることが好ましい。この範囲であることにより、範囲外である場合と対比して、ダクト運送時、組付け時、使用時においても亀裂がほとんど発生することのない十分な耐衝撃性とすることができる。
上記の引張弾性率は、常温(23℃)で、JIS K-7113に準じて2号形試験片とし、常温(23℃)にて、引張速度50mm/分で測定した値である。
分岐数が0.01個未満では発泡層を形成することができず、一方、3個を超えると耐熱性及び剛性に劣るようになる。重量平均分子量が100,000未満では、形状保持が困難となり、1,000,000より大きいと、成形が困難になる。
また、上記のMFRは、JIS K-6922-1に準じて試験温度190℃、試験荷重2.16kgにて測定を行った値である。
上記の曲げ弾性率は、JIS K6922-2に準じて測定した値である。
この配合比率の範囲内とすることにより、安価なポリエチレン系樹脂も用いた配合でありながら、ポリプロピレン系樹脂の成形品への溶着性を十分に確保することができる。また、発泡倍率も十分に高めることができ、車両用等での使用時にも亀裂が生じにくい程度のレベルの耐衝撃性も確保することができる。
この配合比率の範囲内とすることにより、ダクト10の運送時、組付け時、使用時などにも亀裂が発生しにくい十分な耐衝撃性、および変形のない十分な剛性を確保することができる。
こうした発泡剤としては、空気、炭酸ガス、窒素ガス、水等の無機系発泡剤、又は、ブタン、ペンタン、ヘキサン、ジクロロメタン、ジクロロエタン等の有機系発泡剤が挙げられる。
これらの中でも、発泡剤は、空気、炭酸ガス又は窒素ガスを用いることが好ましい。この場合、有体物の混入が防げるので、耐久性等の低下が抑制される。
なお、超臨界流体が窒素ガスの場合、条件は、臨界温度-149.1℃、臨界圧力3.4MPa以上とすればよく、超臨界流体が炭酸ガスの場合、条件は、臨界温度31℃、臨界圧力7.4MPa以上とすればよい。
図2は、本実施形態としてのダクト10をブロー成形する際の態様を示す断面図である。
そして、図2に示す環状ダイ21のダイスリットより、押出速度700kg/時以上で円筒状のパリソンPとして、型締装置30を構成する分割金型31、32の間に押し出す。
その後、分割金型31、32を型締めしてパリソンPを挟み込んで、パリソンP内に0.05~0.15MPaの範囲でエアを吹き込み、ダクト10を形成する。
このため、ポリプロピレン系樹脂に加えて安価なポリエチレン系樹脂を用いた発泡成形品でありながら、ポリプロピレン系樹脂の成形品への溶着性を十分に確保することができる。また、発泡倍率を1.5倍以上とすることができ、例えば車両用などの用途にも十分な軽量性、断熱性を有したダクトとすることができる。また、車両用等での使用時にも亀裂が生じにくい程度のレベルの耐衝撃性も確保することができる。
この配合比率により、例えば車両のインストラメントパネルに溶着されて用いられるいわゆるインパネダクトなどに適用された場合であっても、ダクト運送時、組付け時、使用時に亀裂が発生しにくい十分な耐衝撃性を有するダクトとすることができる。かつ、ダクト運送時、組付け時、使用時にも変形することのない十分な剛性を有するダクトとすることができる。
PP1:ブロックポリプロピレン(日本ポリプロ株式会社製、商品名「ノバテックBC8」)
PP2:プロピレン単独重合体(ボレアリス社(Borealis AG)製、商品名「Daploy WB140」)
PE1:低圧スラリー法により製造される直鎖状長鎖分岐ハイメルトストレングス・ポリエチレン(東ソー株式会社製、商品名「TOSOH-HMS」、品番「08S55A」)
PE2:低圧スラリー法により製造される直鎖状長鎖分岐ハイメルトストレングス・ポリエチレン(東ソー株式会社製、商品名「TOSOH-HMS JK17」)
PE3:高圧ラジカル法により製造される網目状長鎖分岐低密度ポリエチレン(住友化学株式会社製、商品名「スミカセンF108-1」)
PE4:直鎖状短鎖分岐ポリエチレン(住友化学工業株式会社製、商品名「エクセレンFX201」)
また、MFRは、JIS K-7210に準じて試験温度230℃、試験荷重2.16kgにて測定を行った値である。
また、密度は、常温(23℃)で測定した値である。
また、引張弾性率は、常温(23℃)で、JIS K-7113に準じて2号形試験片とし、常温(23℃)にて、引張速度50mm/分で測定した値である。
また、MFRは、JIS K-6922-1に準じて試験温度190℃、試験荷重2.16kgにて測定を行った値である。
また、密度は、常温(23℃)で測定した値である。
また、引張弾性率は、常温(23℃)で、JIS K-7113に準じて2号形試験片とし、常温(23℃)にて、引張速度50mm/分で測定した値である。
また、曲げ弾性率は、JIS K6922-2に準じて測定した値である。
PP1を70wt%、PE1を20wt%、PE2を10wt%、混合して、基材樹脂とした。
そして、この基材樹脂に、発泡剤として超臨界状態の窒素、核剤として20wt%の炭酸水素ナトリウム系発泡剤を含むLDPEベースマスターバッチ(大日精化工業株式会社製、商品名「ファインセルマスターP0217K」)を1.0重量部、および着色剤として40wt%のカーボンブラックを含むLLDPEベースマスターバッチ1.0重量部を添加して発泡させ発泡樹脂とした。これを、押出機で混練した後にマンドレルとダイ外筒の間の円筒状空間であるダイ内アキュムレーターに貯留し、リング状ピストンを用いて円筒状のパリソンとして分割金型に押出し、型締め後パリソン内に0.1MPaの圧力でエアを吹き込むことにより、ブロー成形されたサンプルを得た。
PP1を20wt%、PE1を70wt%、PE2を10wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を60wt%、PE1を20wt%、PE2を20wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を55wt%、PE1を30wt%、PE2を15wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を65wt%、PE1を30wt%、PE2を5wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を50wt%、PE1を20wt%、PE2を30wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を70wt%、PE1を20wt%、PE3を10wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を70wt%、PE1を20wt%、PE4を10wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を10wt%、PE1を70wt%、PE2を20wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PE1を80wt%、PE2を20wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を70wt%、PE1を30wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
PP1を60wt%、PP2を20wt%、PE2を20wt%、混合して、基材樹脂とした。
その後の工程は、実施例1と同様の方法によりブロー成形されたサンプルを得た。
精電舎電子工業株式会社製の超音波溶着機SONOPET 335の12mmヘッドにより、実施例1~6および比較例1~6で得られた発泡成形品のサンプルを、ポリプロピレン系樹脂によるインストラメントパネル部材に周波数39.5Hz、常温、押し付け強度85Nの条件で5秒間押し付けて溶着し、その後、株式会社オリエンテック製のテンシロン万能材料試験機RTC-1325Aにより、引張速度10mm/分の条件で溶着強度を測定した際の、溶着強度が10kgf以上である場合を〇として、他の場合を×とした。
<発泡倍率>
実施例1~6及び比較例1~6で用いた混合樹脂の密度を、対応する発泡成形品サンプルの壁部の見かけ密度で割ることにより、発泡倍率を算出した。
<発泡性>
上述のようにして算出された発泡倍率が1.5倍以上である場合を〇として、他の場合を×とした。
<耐衝撃性>
耐衝撃性は、実施例1~6および比較例1~6で得られた発泡成形品のサンプルに、マイナス10℃において、1kg球を落下させた際にひび割れが発生する高さが40cm以上である場合を〇とし、40cm未満かつ30cm以上である場合を△、他の場合を×とした。
<剛性>
引張弾性率の測定として、JIS K-7113に準じて2号形試験片とし、常温(23℃)にて、引張速度50mm/分で測定した値が1,500kg/cm2以上である場合を〇として、他の場合を×とした。
21 環状ダイ
30 型締装置
31、32 分割金型
P 発泡パリソン
Claims (4)
- 第1のポリエチレン系樹脂と、第2のポリエチレン系樹脂と、ポリプロピレン系樹脂とを混合した基材樹脂を発泡させて成形する発泡成形品の製造方法であって、
前記第1のポリエチレン系樹脂は、長鎖分岐構造を有し、密度0.920g/cm3以上であり、
前記第2のポリエチレン系樹脂は、低圧スラリー法で製造され、長鎖分岐構造を有し、密度0.920g/cm3以下、かつ160℃での溶融張力が70mN以上であり、
前記ポリプロピレン系樹脂は、配合比率が重量比で前記基材樹脂の20%以上であることを特徴とする発泡成形品の製造方法。 - 前記第2のポリエチレン系樹脂は、配合比率が重量比で前記基材樹脂の10~20%であることを特徴とする発泡成形品の製造方法。
- 前記第1のポリエチレン系樹脂は、配合比率が重量比で前記基材樹脂の50%以上であることを特徴とする発泡成形品の製造方法。
- 第1のポリエチレン系樹脂と、第2のポリエチレン系樹脂と、ポリプロピレン系樹脂とを混合した基材樹脂を発泡させて成形して得られた発泡成形品であって、
前記第1のポリエチレン系樹脂は、長鎖分岐構造を有し、密度0.920g/cm3以上であり、
前記第2のポリエチレン系樹脂は、低圧スラリー法で製造され、長鎖分岐構造を有し、密度0.920g/cm3以下、かつ160℃での溶融張力が70mN以上であり、
前記ポリプロピレン系樹脂は、配合比率が重量比で前記基材樹脂の20%以上であることを特徴とする発泡成形品。
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JP2018069557A (ja) * | 2016-10-28 | 2018-05-10 | 株式会社イノアックコーポレーション | 刻印を有する成形体と刻印を有する成形体の製造方法 |
WO2019044650A1 (ja) * | 2017-08-30 | 2019-03-07 | キョーラク株式会社 | 発泡成形用樹脂、発泡成形体、発泡成形体の製造方法 |
WO2019188764A1 (ja) * | 2018-03-29 | 2019-10-03 | キョーラク株式会社 | 発泡成形体の製造方法 |
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JP6920610B2 (ja) * | 2017-04-27 | 2021-08-18 | キョーラク株式会社 | 発泡ダクト |
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