WO2020179792A1 - Résine pour moulage par soufflage de mousse et procédé de production d'un article moulé par soufflage en mousse - Google Patents

Résine pour moulage par soufflage de mousse et procédé de production d'un article moulé par soufflage en mousse Download PDF

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Publication number
WO2020179792A1
WO2020179792A1 PCT/JP2020/008959 JP2020008959W WO2020179792A1 WO 2020179792 A1 WO2020179792 A1 WO 2020179792A1 JP 2020008959 W JP2020008959 W JP 2020008959W WO 2020179792 A1 WO2020179792 A1 WO 2020179792A1
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Prior art keywords
resin
foam
blow molding
foam blow
polypropylene
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PCT/JP2020/008959
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English (en)
Japanese (ja)
Inventor
尊 佐野
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キョーラク株式会社
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Publication of WO2020179792A1 publication Critical patent/WO2020179792A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—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
    • C08J9/12—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 physical blowing agent

Definitions

  • the present invention relates to a foam blow molding resin and a method for producing a foam blow molding using the same.
  • tubular air conditioning ducts are used to ventilate the air.
  • a foam blow-molded body using a foamed resin obtained by foaming a thermoplastic resin with a foaming agent is known.
  • Demand for foam blow-molded products is expanding because they can simultaneously achieve high heat insulation and weight reduction.
  • Patent Document 1 discloses a technique in which the melt tension (MT) is set to a predetermined value or more and the MT ⁇ melt flow rate (MFR) is set to a predetermined value or more in order to increase the expansion ratio of the foam blow-molded body in foam blow molding. It is disclosed.
  • Patent Document 1 Although the standard disclosed in Patent Document 1 is applicable to various raw material resins, regarding polypropylene used as the raw material resin for foam blow molding, MT and MT ⁇ MFR and the obtained foam blow molded article As a result of investigating the relationship between the foaming ratios, it was found that the foaming ratio may be low even though both MT and MT ⁇ MFR are relatively high values.
  • the present invention has been made in view of such circumstances, and provides a resin for foam blow molding containing polypropylene capable of increasing the expansion ratio.
  • a foam blow molding resin containing polypropylene wherein the polypropylene has a strain hardening degree/shear viscosity of 3.5 ⁇ 10 ⁇ 5 Pa ⁇ 1 ⁇ s ⁇ 1 or more.
  • a molding resin is provided.
  • the inventors of the present invention have made earnest studies and found that by using polypropylene having a strain hardening degree/shear viscosity of 3.5 ⁇ 10 ⁇ 5 Pa ⁇ 1 ⁇ s ⁇ 1 or more, a foam blow-molded article having a high expansion ratio can be obtained. They have found that they can be obtained, and have completed the present invention.
  • the foam blow molding resin described above, wherein the polypropylene is a foam blow molding resin having a strain curing degree of 0.25 to 1.00.
  • the foam blow molding resin described above, wherein the polypropylene is a foam blow molding resin having a shear viscosity of 1000 to 16000 Pa ⁇ s.
  • the foam blow molding resin described above, wherein the polypropylene is a foam blow molding resin having a melt flow rate of 2 to 20 g / 10 minutes.
  • the foam blow molding resin described above wherein the polypropylene is a foam blow molding resin having a melt tension of 10 to 500 mN.
  • the foam blow molding resin and the foaming agent described above are melt-kneaded in a foam extruder to extrude a melt-kneaded resin from the foam extruder to form a foam parison, and the foam parison is blow-molded to foam.
  • This is a method for producing a foam blow molded article, which comprises a step of obtaining a blow molded article.
  • the foam blow molding resin of one embodiment of the present invention is a foam blow molding resin containing polypropylene (hereinafter, “PP”), and the PP has a strain hardening degree/shear viscosity. 3.5 ⁇ 10 -5 Pa -1 ⁇ s -1 or more.
  • PP polypropylene
  • the strain hardening degree indicates the degree of hardening of a material when a strain is applied to the material.
  • ⁇ n is calculated from the uniaxial extensional viscosity ( ⁇ E ) by the following equation (1) (FIG. 1), and the slope obtained when the horizontal axis is strain ( ⁇ ) and the vertical axis is log ⁇ n is It is defined as the strain hardening degree (Fig. 2).
  • ⁇ n ⁇ E (t, ⁇ non-liner ) / ⁇ E (t, ⁇ liner ) ⁇ ⁇ ⁇ Equation (1)
  • ⁇ E (t, ⁇ non-liner ) is a measured value of extensional viscosity during strain hardening
  • ⁇ E (t, ⁇ liner ) is a measured value of extensional viscosity when not strain hardened.
  • the uniaxial elongation viscosity ⁇ E (t, ⁇ non-liner ) is a value obtained by measuring with ARES-G2 (manufactured by TA INSTRUMENTS) at a strain rate of 1s -1 and a measurement temperature of 180 ° C.
  • the uniaxial extensional viscosity ⁇ E (t, ⁇ liner ) means a value obtained by using ARES-G2 (manufactured by TA INSTRUMENTS) at a strain rate of 0.1 s ⁇ 1 and a measurement temperature of 180° C. To do.
  • Shear viscosity is the degree of stress generated when shear strain is applied to a material.
  • the shear viscosity means a value obtained by measuring at a test temperature of 200 ° C. and an apparent shear rate of 1 second according to JIS K-7199.
  • the expansion ratio tends to increase. It is based on what I discovered. A large value of strain hardening degree / shear viscosity means that the material is easily hardened and the stress is unlikely to increase when strain is applied to the material. Therefore, when this value is equal to or greater than a predetermined threshold value, during foam blow molding, the resin is likely to flow and the resin is less likely to be locally stretched, so that foam breakage is suppressed and the expansion ratio is increased. It is thought that it tends to be high.
  • the strain hardening degree / shear viscosity [ ⁇ 10 -5 Pa -1 ⁇ s -1 ] is, for example, 3.5 to 35, and specifically, for example, 3.5, 4.0, 4.5, 5. 0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 20, 30, 35, where It may be in the range between any two of the illustrated values.
  • the strain hardening degree is preferably 0.25 to 1.00, specifically, for example, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0. It is .60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.00, and the range between any two of the numerical values exemplified here. It may be inside.
  • the shear viscosity [Pa ⁇ s] is preferably 1000 to 16000, and specifically, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000. , 16000, and may be in the range between any two of the numerical values exemplified here.
  • the MFR [g / 10 minutes] of the PP of the present embodiment is preferably 2 to 20, specifically, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 , 14, 15, 16, 17, 18, 19, 20 and may be within a range between any two of the numerical values exemplified here. In this case, the expansion ratio tends to be particularly high.
  • MFR means a value obtained by measuring at a test temperature of 190 ° C. and a test load of 2.16 kg according to JIS K-7210.
  • the MT [mN] of PP of this embodiment is preferably 10 to 500, and specifically, for example, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, 450, 500, and may be in the range between any two of the numerical values exemplified here. In this case, the foaming ratio tends to be particularly high.
  • MT is a melt tension tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a strand is extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a test temperature of 190° C. and an extrusion rate of 10 mm/min. It means the tension when the strand is wound on a roller having a diameter of 80 mm at a winding speed of 16 rpm.
  • the PP of the present embodiment may be a homo-PP or a copolymer of another olefin and PP (preferably a block copolymer). Further, the PP of the present embodiment is preferably a PP having a long-chain branched structure, and more preferably a homo PP having a long-chain branched structure (long-chain branched homo PP).
  • the foam blow molding resin of the present embodiment may include only the above PP or may include a resin other than the above PP.
  • the proportion of the PP in the resin for foam blow molding is preferably 40% by mass or more, and specifically, for example, 40, 50, 60, 70, 80, 90, 100% by mass. It may be within the range between any two.
  • the resin other than the PP include resins having at least one of composition and structure different from those of the above PP, such as long chain branched block PP, linear homo PP, linear block PP, polyethylene (LDPE, LLDPE, HDPE, etc.). Is exemplified.
  • the length in the thickness direction of the bubbles formed in the foam blow-molded product is preferably 50 to 100 ⁇ m. This is because if the thickness is 50 ⁇ m, the growth of bubbles is insufficient and the expansion ratio tends to be small, and if it exceeds 100 ⁇ m, the bubbles are broken and pinholes are easily generated.
  • a melt-kneaded resin obtained by melt-kneading the above-mentioned foam blow-molding resin and a foaming agent in a foam extruder is used for the foam extrusion.
  • the obtained foam blow molded article can be used, for example, in an air conditioning duct for a vehicle.
  • the foam extruder 1 includes a cylinder 3, a resin inlet 5, a screw 7, a foaming agent injection port P, a temperature control unit 9, a resin extrusion port 11, and a die head 12.
  • the resin input port 5 is a so-called hopper, from which the raw material resin is input.
  • the form of the raw material resin is not particularly limited, but is usually in the form of pellets.
  • the raw material resin is the foam blow molding resin according to the embodiment of the present invention described above.
  • the raw material resin is charged into the cylinder 3 from the resin input port 5 and then melted by being heated in the cylinder 3 to become a molten resin. Further, by the rotation of the screw 7 arranged in the cylinder 3, the screw 7 is conveyed toward the resin extrusion port 11 provided at one end of the cylinder 3.
  • the screw 7 is arranged in the cylinder 3 and conveys the molten resin toward the resin extrusion port 11 while kneading the molten resin by the rotation thereof.
  • a gear device 15 is provided at one end of the screw 7, and the screw 7 is rotationally driven by the gear device 15.
  • the cylinder 3 is provided with a foaming agent injection port P for injecting a foaming agent into the cylinder 3.
  • the foaming agent injected from the foaming agent injection port P include a physical foaming agent, a chemical foaming agent, and a mixture thereof, and a physical foaming agent is preferable.
  • the physical foaming agent an inorganic physical foaming agent such as air, carbon dioxide gas, nitrogen gas, or water, and an organic physical foaming agent such as butane, pentane, hexane, dichloromethane, dichloroethane, or a supercritical fluid thereof is used. be able to.
  • the critical temperature is -149.1 ° C
  • the critical pressure is 3.4 MPa or more
  • the critical temperature is 31 ° C, the critical pressure. It is obtained by setting it to 7.4 MPa or more.
  • the chemical foaming agent include those that generate carbon dioxide gas by a chemical reaction between an acid (eg, citric acid or a salt thereof) and a base (eg, baking soda). Instead of injecting the chemical foaming agent from the foaming agent injection port P, it may be injected from the resin injection port 5.
  • the temperature control unit 9 is configured to individually control a plurality of temperature control units provided along the cylinder 3 to control the temperature of each portion of the cylinder 3. Further, the temperature control unit 9 can also control the temperature of the die head 12 for forming the parison and the temperature of the connecting portion 10 between the cylinder 3 and the die head 12.
  • the die head 12 includes a cylindrical die outer cylinder 41 and a mandrel 43 accommodated therein, and stores a melt-kneaded resin extruded from the cylinder 3 in a space 47 therebetween.
  • the die head 12 for forming the cylindrical foam parison 13 is shown here, the die head 12 may be for forming a sheet foam parison.
  • ⁇ Split mold 14> The foamed parison 13 is guided between the pair of split molds 14. A foam blow-molded body is obtained by performing blow molding of the foam parison 13 using the split mold 14.
  • a foam blow molded product was produced using the foam extruder 1 and the split mold 14 shown in FIG. 3, and the foam blow moldability was evaluated.
  • the polypropylene shown in Table 1 was used as the raw material resin.
  • 1.0% of LDPE base masterbatch manufactured by Dainichiseika Kogyo Co., Ltd., trade name "Finecell Master P0217K"
  • 20 wt% of sodium hydrogencarbonate-based foaming agent as a nucleating agent was added to 100 parts by mass of the resin.
  • the temperature control unit 9 was set so that the temperature of the foamed parison 13 was 190 to 200 ° C.
  • the rotation speed of the screw 7 was 60 rmm, and the extrusion rate was 20 kg/hr.
  • the foaming agent using N 2 gas was injected from the blowing agent injection port P provided at the center in the longitudinal direction of the cylinder 3. The expansion ratio was adjusted by changing the amount of injected gas.
  • Blow molding was performed using the foam parison formed under the above conditions.
  • the foam parison was formed to have an outer diameter of 50 mm and a thickness of 2.5 mm. Blow molding was performed so that the outer diameter of the molded body was 100 mm.
  • Table 1 also shows the values of MFR, MT, MFR ⁇ MT, strain hardening degree, shear viscosity and strain hardening degree / shear viscosity.
  • MT, MFR, strain cure, and shear viscosity were measured by the methods described in the embodiments.
  • Example 1 and 2 and Comparative Examples 5 to 7 the above-mentioned commercially available polypropylene was used after being modified under the condition A or B.
  • the modification process the process of producing a foam parison in the foam extruder 1 and crushing it into pellets was repeated three times. Under the conditions A and B, the temperature of the foam parison 13 was controlled so as to be 230° C. and 215° C., respectively.
  • the maximum expansion ratio was higher in all the examples than in all the comparative examples.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

La présente invention concerne une résine pour moulage par soufflage de mousse, qui contient un polypropylène et est capable d'améliorer le taux d'expansion.　La présente invention concerne une résine pour moulage par soufflage de mousse, qui contient un polypropylène, et qui est configurée de telle sorte que le polypropylène a un rapport (degré de durcissement de contrainte) / (viscosité de cisaillement) de 3,5 × 10-5 Pa-1∙s-1 ou plus.
PCT/JP2020/008959 2019-03-06 2020-03-03 Résine pour moulage par soufflage de mousse et procédé de production d'un article moulé par soufflage en mousse WO2020179792A1 (fr)

Applications Claiming Priority (2)

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JP2019-040156 2019-03-06
JP2019040156A JP7201910B2 (ja) 2019-03-06 2019-03-06 発泡ブロー成形用樹脂、発泡ブロー成形体の製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023058525A1 (fr) * 2021-10-04 2023-04-13 キョーラク株式会社 Résine pour moulage par expansion, procédé de production associé, procédé de production d'un corps moulé par expansion et procédé de production de structure

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147110A (ja) * 2001-11-09 2003-05-21 Mitsui Chemicals Inc ポリオレフィン系重合体組成物発泡体およびその製造方法
WO2006101142A1 (fr) * 2005-03-22 2006-09-28 Prime Polymer Co., Ltd. Mousse extrudee en resine de propylene et son procede de fabrication
JP2015196711A (ja) * 2014-03-31 2015-11-09 サンアロマー株式会社 ポリプロピレン樹脂組成物及びその成形品
WO2016098695A1 (fr) * 2014-12-18 2016-06-23 株式会社ジェイエスピー Procédé de fabrication d'un objet en mousse, moulé par soufflage
WO2017030116A1 (fr) * 2015-08-18 2017-02-23 キョーラク株式会社 Résine pour le moulage de mousse et procédé de fabrication d'un article moulé en mousse
JP2017066204A (ja) * 2015-09-28 2017-04-06 日本ポリプロ株式会社 発泡成形用ポリプロピレン樹脂および成形体
WO2017170481A1 (fr) * 2016-03-29 2017-10-05 積水化成品工業株式会社 Résine à base de polypropylène modifié et procédé de production de résine à base de polypropylène modifié
JP2018047555A (ja) * 2016-09-20 2018-03-29 日本ポリプロ株式会社 ポリプロピレン樹脂製多層発泡シート

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003147110A (ja) * 2001-11-09 2003-05-21 Mitsui Chemicals Inc ポリオレフィン系重合体組成物発泡体およびその製造方法
WO2006101142A1 (fr) * 2005-03-22 2006-09-28 Prime Polymer Co., Ltd. Mousse extrudee en resine de propylene et son procede de fabrication
JP2015196711A (ja) * 2014-03-31 2015-11-09 サンアロマー株式会社 ポリプロピレン樹脂組成物及びその成形品
WO2016098695A1 (fr) * 2014-12-18 2016-06-23 株式会社ジェイエスピー Procédé de fabrication d'un objet en mousse, moulé par soufflage
WO2017030116A1 (fr) * 2015-08-18 2017-02-23 キョーラク株式会社 Résine pour le moulage de mousse et procédé de fabrication d'un article moulé en mousse
JP2017066204A (ja) * 2015-09-28 2017-04-06 日本ポリプロ株式会社 発泡成形用ポリプロピレン樹脂および成形体
WO2017170481A1 (fr) * 2016-03-29 2017-10-05 積水化成品工業株式会社 Résine à base de polypropylène modifié et procédé de production de résine à base de polypropylène modifié
JP2018047555A (ja) * 2016-09-20 2018-03-29 日本ポリプロ株式会社 ポリプロピレン樹脂製多層発泡シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023058525A1 (fr) * 2021-10-04 2023-04-13 キョーラク株式会社 Résine pour moulage par expansion, procédé de production associé, procédé de production d'un corps moulé par expansion et procédé de production de structure

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JP7201910B2 (ja) 2023-01-11
JP2020143208A (ja) 2020-09-10

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