WO2012067231A1 - Polypropylene resin composition for thin wall injection molding, molded article and container - Google Patents

Polypropylene resin composition for thin wall injection molding, molded article and container Download PDF

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Publication number
WO2012067231A1
WO2012067231A1 PCT/JP2011/076671 JP2011076671W WO2012067231A1 WO 2012067231 A1 WO2012067231 A1 WO 2012067231A1 JP 2011076671 W JP2011076671 W JP 2011076671W WO 2012067231 A1 WO2012067231 A1 WO 2012067231A1
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Prior art keywords
resin composition
ethylene
injection molding
mass
propylene
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PCT/JP2011/076671
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French (fr)
Japanese (ja)
Inventor
中島　武
四十四 菅野
信幸 鶴見
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サンアロマー株式会社
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Priority to CN2011800551899A priority Critical patent/CN103210038A/en
Priority to KR1020137012280A priority patent/KR20140021517A/en
Publication of WO2012067231A1 publication Critical patent/WO2012067231A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2823/00—Use of polyalkenes or derivatives thereof as mould material
    • B29K2823/10—Polymers of propylene
    • B29K2823/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages

Definitions

  • the present invention relates to a polypropylene resin composition suitable for thin-wall injection molding.
  • the present invention also relates to a molded product obtained by injection molding the polypropylene resin composition and a container using the molded product.
  • Polypropylene resin compositions containing polypropylene as a main component are inexpensive and have excellent mechanical properties, and thus are used for various applications and widely used for food containers. Molded products such as food containers are manufactured by injection molding, but it is required to reduce the thickness in order to reduce the weight of the molded product.
  • Patent Document 1 discloses a composition containing polypropylene and an ethylene / 1-butene copolymer.
  • Patent Document 2 discloses a resin composition containing polypropylene, an ethylene / propylene copolymer, and a nucleating agent.
  • Patent Document 3 discloses a resin composition containing polypropylene, high-density polyethylene, and a lubricant.
  • the resin composition described in Patent Document 1 may be buckled when the molded product is taken out from a mold by thin-wall injection molding, and a dent (so-called “sink”) due to shrinkage may occur.
  • a resin composition that causes molding defects as described above in injection molding is not suitable for molding with a thin wall because it is necessary to increase the thickness of the molded product.
  • the molded product obtained from the resin composition described in Patent Document 2 has insufficient transparency and low-temperature impact strength, and tends to be whitened when an impact is applied. In the resin composition described in Patent Document 3, transparency and thin-wall moldability may be lowered.
  • the polypropylene resin composition for thin-wall injection molding of the present invention is a polypropylene resin composition for thin-wall injection molding containing a propylene-based resin material and a clearing nucleating agent, and is in a xylene-soluble portion of 135 ° C tetrahydronaphthalene.
  • the melt flow rate measured under the conditions of a temperature of 230 ° C.
  • the propylene-based resin material was obtained by polymerizing an ethylene / 1-butene copolymer having an ethylene unit of 74 to 86% by mass in the presence of an ethylene / propylene copolymer or homopolypropylene having an ethylene unit of 1.2% by mass or less.
  • the content of the ethylene / 1-butene copolymer when the polypropylene resin composition for thin-wall injection molding is 100% by mass is 2 to 32% by weight.
  • the content of the clearing nucleating agent is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the propylene-based resin material.
  • the molded product of the present invention is obtained by injection molding the above-described polypropylene resin composition for thin-wall injection molding.
  • the container of this invention is equipped with the said molded article.
  • the polypropylene resin composition for thin wall injection molding of the present invention is excellent in transparency, whitening resistance, low temperature impact strength and thin wall moldability.
  • the molded article and container of the present invention are excellent in transparency, whitening resistance, and low temperature impact strength.
  • the polypropylene resin composition for thin-wall injection molding of the present invention contains a propylene-based resin material and a clearing nucleating agent.
  • the intrinsic viscosity in tetrahydronaphthalene at 135 ° C. of the xylene-soluble component is 0.9 to 1.3 dl / g, and 0.95 to 1.15 dl / g. Is more preferable.
  • the intrinsic viscosity of the resin composition exceeds the upper limit, whitening resistance and transparency tend to be lowered.
  • the melt flow rate (MFR) of the resin composition is 30 to 70 g / 10 minutes, and more preferably 40 to 60 g / 10 minutes.
  • MFR is a value measured in accordance with JIS K 7210 under conditions of a temperature of 230 ° C. and a load of 21.6 N.
  • the propylene resin material is a reaction blend type polypropylene obtained by polymerizing an ethylene / 1-butene copolymer in the presence of ethylene / propylene copolymer or homopolypropylene in a polymerization reactor.
  • the ethylene / 1-butene copolymer is a rubber component.
  • the propylene-based resin material can be produced by multistage polymerization. For example, homopolypropylene or ethylene-propylene copolymer is polymerized in the first stage polymerization reactor, and the resulting homopolypropylene or ethylene-propylene copolymer is supplied to the second stage polymerization reactor and 2 A propylene-based resin material can be obtained by polymerizing the ethylene / 1-butene copolymer in the stage polymerization reactor. In this method, the homopolypropylene or ethylene-propylene copolymer and the resulting ethylene / 1-butene copolymer are mixed in the second stage polymerization reactor.
  • the multistage polymerization is not limited to the above method, and homopolypropylene or ethylene-propylene copolymer may be polymerized in a plurality of polymerization reactors, or ethylene / 1-butene copolymer may be polymerized in a plurality of polymerization reactors. May be polymerized.
  • a known olefin polymerization catalyst can be used. Among them, a Ziegler-Natta catalyst is preferable because a propylene-based resin material exhibiting desired physical properties can be easily produced.
  • polymerization you may add hydrogen for adjustment of molecular weight as needed.
  • the mass average molecular weight of the propylene-based resin material is preferably 160,000 to 210,000.
  • the MFR of the resin composition can be easily set to 30 to 70 g / 10 minutes.
  • the ethylene unit content in the ethylene / propylene copolymer is preferably 1.2% by mass or less, and more preferably 0 to 0.6% by mass. If the ethylene unit content in the ethylene / propylene copolymer exceeds the upper limit, the rigidity and thin-wall moldability of the resulting resin composition may be lowered.
  • the ethylene unit content in the ethylene / 1-butene copolymer is preferably 74 to 86% by mass, more preferably 80 to 85% by mass. If the ethylene unit content in the ethylene / 1-butene copolymer exceeds the upper limit, the low-temperature impact strength of the resulting resin composition tends to decrease, and if it is less than the lower limit, the propylene-based resin material In addition to the tendency to be difficult to manufacture, the rigidity, transparency, and thin moldability of the resin composition may be reduced.
  • the content of the ethylene / 1-butene copolymer in the resin composition is 22 to 32% by mass, more preferably 25 to 30% by mass, based on 100% by mass of the resin composition.
  • the content of the ethylene / 1-butene copolymer exceeds the upper limit, production of a propylene-based resin material tends to be difficult, and when the content is less than the lower limit, the low-temperature impact strength of the resulting resin composition Tend to decrease.
  • the clearing nucleating agent promotes the formation of polypropylene crystal nuclei and improves the transparency of the resulting resin composition.
  • the haze value JIS K 7105, 1 mm thickness
  • the nucleating agent is not contained, not only the transparency is lowered but also the thin-wall moldability is impaired.
  • the clearing nucleating agent include sorbitol compounds, metal salts of carboxylic acids, aromatic phosphate ester compounds, silica, talc and the like. In terms of low odor, an aromatic phosphate ester compound is preferable.
  • sorbitol compound examples include dibenzylidene sorbitol, 1,3,2,4-di- (methylbenzylidene) sorbitol, 1,3,2,4- (ethylbenzylidene) sorbitol, 1,3,2,4- (Methoxybenzylidene) sorbitol, 1,3,2,4- (ethoxybenzylidene) sorbitol, 1,2,3-trideoxy-4,6-5,7-bis-o-[(4-propylphenyl) methylene] nonitol Etc.
  • metal salt of carboxylic acid examples include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, di-para-t-butylbenzoate Examples thereof include aluminum oxide, titanium di-para-t-butylbenzoate, chromium di-para-t-butylbenzoate, and aluminum hydroxy-di-t-butylbenzoate.
  • a triaminobenzene derivative can be used as a clearing nucleating agent.
  • the content of the clearing nucleating agent is preferably 0.01 to 0.5 parts by mass, and preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the propylene-based resin material.
  • the clearing nucleating agent is a triaminobenzene derivative
  • the amount is preferably 0.01 to 0.02 parts by mass. If the content of the clearing nucleating agent is at least the lower limit value, the transparency of the molded product obtained from the resin composition can be further increased, and if it is at most the upper limit value, odor can be suppressed.
  • the resin composition may contain other polymers as necessary.
  • known thermoplastic resins or thermosetting resins can be used.
  • the thermoplastic resin include ethylene or ⁇ -olefin homopolymer, ethylene or ⁇ -olefin copolymer having 3 to 10 carbon atoms, a mixture thereof, nylon, polycarbonate, polyphenylene oxide, petroleum resin, and the like. .
  • ethylene or ⁇ -olefin homopolymer examples include high-density polyethylene, low-density polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, and poly (3-methyl-1 -Pentene), poly (3-methyl-1-butene), poly (4-methyl-1-pentene), poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene , Polystyrene and combinations thereof.
  • polypropylene is preferable.
  • an antioxidant for example, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an antistatic agent, a flame retardant, and a dispersant.
  • Additives such as copper damage inhibitors, neutralizers, plasticizers, foaming agents, anti-bubble agents, cross-linking agents, and peroxides may be included.
  • the resin composition described above comprises a propylene-based resin material, a clearing nucleating agent, and other polymers and additives as necessary, and then a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader. It can be produced by melt kneading using a known kneader such as a roll mill.
  • the resin composition is processed into a thin molded product by injection molding.
  • the term “thin” means that the thickness of the molded product is 1.0 mm or less.
  • Thin-walled molded products are lightweight, but difficult to mold and mechanical properties tend to be insufficient, but the resin composition of the present invention is suitable for thin-wall injection molding by including the propylene resin material. In addition, sufficient mechanical properties are exhibited.
  • the conditions for injection molding are not particularly limited, and are appropriately selected according to the shape and size of the target molded product and the type and scale of the injection molding machine to be used.
  • the molding temperature is 200 to 260 ° C. Is preferred. If the molding temperature is equal to or higher than the lower limit value, sufficient moldability can be secured, and if the molding temperature is equal to or lower than the upper limit value, thermal deterioration of the resin composition can be prevented.
  • Examples 1 to 8, Comparative Examples 1 to 14 Using a polymerization apparatus equipped with all four-stage polymerization reactors in series, homopolypropylene or ethylene / propylene copolymer is polymerized in the two-stage polymerization reactor in the first stage, and these are fed to the second-stage polymerization reactor. In the subsequent two-stage polymerization reactor, ethylene / 1-butene copolymer (indicated as “C2C4” in Table 1) or ethylene / propylene copolymer (indicated as “C2C3” in Table 1). ) was polymerized.
  • the propylene-based resin material shown in Table 1 was obtained by adjusting the ethylene supply amount, the hydrogen supply amount, the polymerization temperature, the polymerization pressure, and the addition amount of the catalyst.
  • a transparent nucleating agent Merirken 3988 mirrored 3988
  • melt flow rate (MFR), productivity, transparency, whitening resistance, flexural modulus, impact resistance at low temperature, and thin-wall formability of each resin composition were evaluated as follows. The evaluation results are shown in Tables 1 to 3.
  • MFR is a value measured under conditions of a temperature of 230 ° C. and a load of 21.6 N according to JIS K 7210.
  • the productivity of the resin composition was evaluated according to the following criteria.
  • Each resin composition was injection-molded at a molding temperature of 230 ° C. to produce a 1 mm thick plate-shaped test piece.
  • the surface impact strength was measured with a surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation) in an environment of ⁇ 20 ° C. Further, the test piece was impacted in the same manner as the measurement of the surface impact strength except that the temperature was 0 ° C., and the whitening resistance was evaluated according to the following criteria. ⁇ : Whitening was not observed. X: Whitening was observed.
  • the resin compositions of Examples 1 to 8 were excellent in transparency, whitening resistance, low-temperature impact strength, and thin-wall moldability. Production of the resin composition of Comparative Example 1 in which the rubber component was an ethylene / propylene copolymer was difficult. In the resin composition of Comparative Example 2 in which the rubber component was an ethylene / propylene copolymer and the ethylene unit of the ethylene / propylene copolymer was 35%, it was difficult to produce a propylene-based resin material by polymerization. Moreover, transparency and whitening resistance were low.
  • the resin composition of Comparative Example 5 containing an ethylene / 1-butene copolymer having an ethylene unit of 2.2% had low productivity and low rigidity and thin-wall moldability.
  • the resin composition of Comparative Example 6 in which the ethylene unit of the ethylene / 1-butene copolymer was 90% had low low-temperature impact strength.
  • the resin composition of Comparative Example 7 in which the ethylene unit of the ethylene / 1-butene copolymer was 70% it was difficult to produce a propylene-based resin material by polymerization.
  • the resin composition of Comparative Example 8 in which the ethylene / 1-butene copolymer content was 20% had low low-temperature impact strength.
  • the resin composition of Comparative Example 10 having an intrinsic viscosity of 1.4 dl / g it was difficult to produce a propylene-based resin material by polymerization, and transparency and whitening resistance were low.
  • the resin composition of Comparative Example 11 having an intrinsic viscosity of 0.7 dl / g it was difficult to produce a propylene-based resin material by polymerization.
  • the resin composition of Comparative Example 13 having an MFR of 20 g / 10 min had low thin moldability.
  • the resin composition of Comparative Example 14 that did not contain a clearing nucleating agent had low transparency and thin-wall moldability.
  • the resin composition of Comparative Example 15 in which polypropylene and ethylene / 1-butene copolymer were mixed by a compound had low productivity, low temperature impact strength, and low formability.
  • the resin composition of Comparative Example 16 using high-density polyethylene had low transparency and thin wall moldability.
  • the polypropylene resin composition for thin-wall injection molding of the present invention can be suitably used for various packaging containers such as food containers and cosmetic containers, and bottle lids.

Abstract

This polypropylene resin composition for thin wall injection molding comprises a propylene resin material and a clarifying nucleating agent, the limiting viscosity of xylene solubles being 0.9-1.3 dl/g, and the melt flow rate measured under conditions of a temperature of 230°C and a load of 21.6 N being 30-70 g/10 mins. In addition, the propylene resin material is an ethylene propylene copolymer with an ethylene unit of 1.2 mass% or less that is polymerized or an ethylene 1-butene copolymer with an ethylene unit of 74-86 mass% polymerized under the presence of homopolypropylene. Further, the ethylene 1-butene copolymer content is 22-32 mass% when the polypropylene resin composition for thin wall injection molding is 100 mass%. According to the present invention, a polypropylene resin composition for thin wall injection molding which has excellent blush resistance, low temperature impact strength and thin wall moldability can be provided.

Description

薄肉射出成形用ポリプロピレン樹脂組成物、成形品および容器Thin-wall injection molding polypropylene resin composition, molded product and container
　本発明は、薄肉射出成形に適したポリプロピレン樹脂組成物に関する。また、本発明は、上記ポリプロピレン樹脂組成物を射出成形して得た成形品及び、その成形品を用いた容器に関する。
　本願は、２０１０年１１月１８日に日本に出願された特願２０１０－２５７８６４号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a polypropylene resin composition suitable for thin-wall injection molding. The present invention also relates to a molded product obtained by injection molding the polypropylene resin composition and a container using the molded product.
This application claims priority based on Japanese Patent Application No. 2010-257864 for which it applied to Japan on November 18, 2010, and uses the content here.
　ポリプロピレンを主成分としたポリプロピレン樹脂組成物は、安価である上に機械的物性に優れることから、様々な用途に使用され、食品用の容器などにも広く使用されている。食品用の容器等の成形品は射出成形によって製造されるが、成形品を軽量化するためには薄肉化することが求められる。
　容器を製造するためのポリプロピレン樹脂組成物として、特許文献１には、ポリプロピレンとエチレン・１－ブテン共重合体とを含むものが開示されている。
　特許文献２には、ポリプロピレンとエチレン・プロピレン共重合体と核剤とを含有する樹脂組成物が開示されている。
　特許文献３には、ポリプロピレンと高密度ポリエチレンと滑剤とを含有する樹脂組成物が開示されている。 Polypropylene resin compositions containing polypropylene as a main component are inexpensive and have excellent mechanical properties, and thus are used for various applications and widely used for food containers. Molded products such as food containers are manufactured by injection molding, but it is required to reduce the thickness in order to reduce the weight of the molded product.
As a polypropylene resin composition for producing a container, Patent Document 1 discloses a composition containing polypropylene and an ethylene / 1-butene copolymer.
Patent Document 2 discloses a resin composition containing polypropylene, an ethylene / propylene copolymer, and a nucleating agent.
Patent Document 3 discloses a resin composition containing polypropylene, high-density polyethylene, and a lubricant.
特開平７－３０８７号公報Japanese Patent Laid-Open No. 7-3087 特開平９－３１２６４号公報Japanese Patent Laid-Open No. 9-31264 特開平１０－１３９９７７号公報JP-A-10-139777
　しかしながら、特許文献１に記載の樹脂組成物では、薄肉射出成形して成形品を金型から取り出す際に座屈し、また、収縮による凹み（いわゆる「ヒケ」）が生じることがある。射出成形において前記のような成形不良が生じる樹脂組成物は、成形品の厚さを増やす必要があるため、薄肉での成形に適したものではない。
　特許文献２に記載の樹脂組成物から得られた成形品は透明性および低温での衝撃強度が不充分である上に、衝撃が加えられた際に白化しやすい傾向がある。
　特許文献３に記載の樹脂組成物では、透明性および薄肉成形性が低くなることがある。
　本発明は、透明性、耐白化性、低温衝撃強度および薄肉成形性に優れた薄肉射出成形用ポリプロピレン樹脂組成物を提供することを目的とする。また、透明性、耐白化性、低温衝撃強度に優れた成形品および容器を提供することを目的とする。 However, the resin composition described in Patent Document 1 may be buckled when the molded product is taken out from a mold by thin-wall injection molding, and a dent (so-called “sink”) due to shrinkage may occur. A resin composition that causes molding defects as described above in injection molding is not suitable for molding with a thin wall because it is necessary to increase the thickness of the molded product.
The molded product obtained from the resin composition described in Patent Document 2 has insufficient transparency and low-temperature impact strength, and tends to be whitened when an impact is applied.
In the resin composition described in Patent Document 3, transparency and thin-wall moldability may be lowered.
An object of this invention is to provide the polypropylene resin composition for thin-wall injection molding excellent in transparency, whitening resistance, low temperature impact strength, and thin-wall moldability. Another object of the present invention is to provide a molded product and a container excellent in transparency, whitening resistance, and low temperature impact strength.
　本発明の薄肉射出成形用ポリプロピレン樹脂組成物は、プロピレン系樹脂材料および透明化核剤を含有する薄肉射出成形用ポリプロピレン樹脂組成物であって、キシレン可溶分の、１３５℃のテトラヒドロナフタレン中での極限粘度が０．９～１．３ｄｌ／ｇであり、ＪＩＳ　Ｋ　７２１０に準拠し、温度２３０℃、荷重２１．６Ｎの条件で測定したメルトフローレートが３０～７０ｇ／１０分であり、前記プロピレン系樹脂材料は、エチレン単位が１．２質量％以下のエチレン・プロピレン共重合体またはホモポリプロピレンの存在下、エチレン単位が７４～８６質量％のエチレン・１－ブテン共重合体を重合させたものであり、薄肉射出成形用ポリプロピレン樹脂組成物を１００質量％とした際のエチレン・１－ブテン共重合体の含有量が２２～３２質量％である。
　本発明の薄肉射出成形用ポリプロピレン樹脂組成物においては、透明化核剤の含有量が、プロピレン系樹脂材料１００質量部に対して０．０１～０．５質量部であることが好ましい。
　本発明の成形品は、上記薄肉射出成形用ポリプロピレン樹脂組成物を射出成形して得られる。
　本発明の容器は、上記成形品を備えている。 The polypropylene resin composition for thin-wall injection molding of the present invention is a polypropylene resin composition for thin-wall injection molding containing a propylene-based resin material and a clearing nucleating agent, and is in a xylene-soluble portion of 135 ° C tetrahydronaphthalene. The melt flow rate measured under the conditions of a temperature of 230 ° C. and a load of 21.6 N in accordance with JIS K 7210 is 30 to 70 g / 10 minutes, The propylene-based resin material was obtained by polymerizing an ethylene / 1-butene copolymer having an ethylene unit of 74 to 86% by mass in the presence of an ethylene / propylene copolymer or homopolypropylene having an ethylene unit of 1.2% by mass or less. The content of the ethylene / 1-butene copolymer when the polypropylene resin composition for thin-wall injection molding is 100% by mass is 2 to 32% by weight.
In the polypropylene resin composition for thin-wall injection molding of the present invention, the content of the clearing nucleating agent is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the propylene-based resin material.
The molded product of the present invention is obtained by injection molding the above-described polypropylene resin composition for thin-wall injection molding.
The container of this invention is equipped with the said molded article.
　本発明の薄肉射出成形用ポリプロピレン樹脂組成物は、透明性、耐白化性、低温衝撃強度および薄肉成形性に優れている。
　本発明の成形品および容器は、透明性、耐白化性、低温衝撃強度に優れている。 The polypropylene resin composition for thin wall injection molding of the present invention is excellent in transparency, whitening resistance, low temperature impact strength and thin wall moldability.
The molded article and container of the present invention are excellent in transparency, whitening resistance, and low temperature impact strength.
　本発明の薄肉射出成形用ポリプロピレン樹脂組成物（以下、「樹脂組成物」と略す。）は、プロピレン系樹脂材料および透明化核剤を含有する。
　本発明の樹脂組成物においては、キシレン可溶分の、１３５℃のテトラヒドロナフタレン中での極限粘度が０．９～１．３ｄｌ／ｇであり、０．９５～１．１５ｄｌ／ｇであることがより好ましい。この樹脂組成物の極限粘度が前記上限値を超えると、耐白化性および透明性が低下する傾向にある。樹脂組成物の極限粘度はプロピレン系樹脂材料の粘度に大きく依存するが、前記下限値未満にするための、プロピレン系樹脂材料は製造困難である。
　また、樹脂組成物のメルトフローレート（ＭＦＲ）は３０～７０ｇ／１０分であり、４０～６０ｇ／１０分であることがより好ましい。ここで、ＭＦＲは、ＪＩＳ　Ｋ　７２１０に準拠し、温度２３０℃、荷重２１．６Ｎの条件で測定した値である。この樹脂組成物のＭＦＲが前記下限値未満であると、薄肉成形性が低くなり、前記上限値を超えると、プロピレン系樹脂材料が製造困難になる上に、低温衝撃強度が低くなる。 The polypropylene resin composition for thin-wall injection molding of the present invention (hereinafter abbreviated as “resin composition”) contains a propylene-based resin material and a clearing nucleating agent.
In the resin composition of the present invention, the intrinsic viscosity in tetrahydronaphthalene at 135 ° C. of the xylene-soluble component is 0.9 to 1.3 dl / g, and 0.95 to 1.15 dl / g. Is more preferable. When the intrinsic viscosity of the resin composition exceeds the upper limit, whitening resistance and transparency tend to be lowered. Although the intrinsic viscosity of the resin composition largely depends on the viscosity of the propylene-based resin material, it is difficult to produce a propylene-based resin material for making it less than the lower limit.
The melt flow rate (MFR) of the resin composition is 30 to 70 g / 10 minutes, and more preferably 40 to 60 g / 10 minutes. Here, MFR is a value measured in accordance with JIS K 7210 under conditions of a temperature of 230 ° C. and a load of 21.6 N. When the MFR of the resin composition is less than the lower limit, the thin moldability is lowered. When the upper limit is exceeded, the propylene-based resin material becomes difficult to manufacture and the low-temperature impact strength is lowered.
（プロピレン系樹脂材料）
　プロピレン系樹脂材料は、重合反応器内で、エチレン・プロピレン共重合体またはホモポリプロピレンの存在下、エチレン・１－ブテン共重合体を重合させて得た反応ブレンド型ポリプロピレンである。なお、エチレン・１－ブテン共重合体はゴム成分である。
　エチレン・プロピレン共重合体またはホモポリプロピレンの存在下でエチレン・１－ブテン共重合体を重合させることにより、生産性が高くなる上に、分散性が高くなるため、物性バランスも向上する。 (Propylene resin material)
The propylene resin material is a reaction blend type polypropylene obtained by polymerizing an ethylene / 1-butene copolymer in the presence of ethylene / propylene copolymer or homopolypropylene in a polymerization reactor. The ethylene / 1-butene copolymer is a rubber component.
By polymerizing the ethylene / 1-butene copolymer in the presence of the ethylene / propylene copolymer or homopolypropylene, the productivity increases and the dispersibility increases, so that the physical property balance is also improved.
　上記プロピレン系樹脂材料は、多段重合により製造することができる。例えば、１段目の重合反応器にて、ホモポリプロピレンまたはエチレン－プロピレン共重合体を重合し、得られたホモポリプロピレンまたはエチレン－プロピレン共重合体を２段目の重合反応器に供給すると共に２段目の重合反応器にてエチレン・１－ブテン共重合体を重合することでプロピレン系樹脂材料を得ることができる。この方法では、２段目の重合反応器にて、ホモポリプロピレンまたはエチレン－プロピレン共重合体と、生成するエチレン・１－ブテン共重合体とを混合する。
　なお、多段重合は上記の方法に限らず、ホモポリプロピレンまたはエチレン－プロピレン共重合体を複数の重合反応器にて重合してもよいし、エチレン・１－ブテン共重合体を複数の重合反応器にて重合してもよい。
　重合に使用する触媒としては、公知のオレフィン重合触媒を用いることができるが、中でも、所望の物性が発現するプロピレン系樹脂材料を容易に製造できることから、チーグラー・ナッタ触媒が好ましい。
　また、重合の際には、必要に応じて、分子量の調整のために、水素を添加してもよい。 The propylene-based resin material can be produced by multistage polymerization. For example, homopolypropylene or ethylene-propylene copolymer is polymerized in the first stage polymerization reactor, and the resulting homopolypropylene or ethylene-propylene copolymer is supplied to the second stage polymerization reactor and 2 A propylene-based resin material can be obtained by polymerizing the ethylene / 1-butene copolymer in the stage polymerization reactor. In this method, the homopolypropylene or ethylene-propylene copolymer and the resulting ethylene / 1-butene copolymer are mixed in the second stage polymerization reactor.
The multistage polymerization is not limited to the above method, and homopolypropylene or ethylene-propylene copolymer may be polymerized in a plurality of polymerization reactors, or ethylene / 1-butene copolymer may be polymerized in a plurality of polymerization reactors. May be polymerized.
As the catalyst used for the polymerization, a known olefin polymerization catalyst can be used. Among them, a Ziegler-Natta catalyst is preferable because a propylene-based resin material exhibiting desired physical properties can be easily produced.
Moreover, in the case of superposition | polymerization, you may add hydrogen for adjustment of molecular weight as needed.
　プロピレン系樹脂材料の質量平均分子量は１６０，０００～２１０，０００であることが好ましい。プロピレン系樹脂材料の質量平均分子量が前記範囲であれば、樹脂組成物のＭＦＲを容易に３０～７０ｇ／１０分にできる。 The mass average molecular weight of the propylene-based resin material is preferably 160,000 to 210,000. When the mass average molecular weight of the propylene-based resin material is in the above range, the MFR of the resin composition can be easily set to 30 to 70 g / 10 minutes.
　エチレン・プロピレン共重合体におけるエチレン単位含有量は１．２質量％以下であることが好ましく、０～０．６質量％であることがより好ましい。エチレン・プロピレン共重合体におけるエチレン単位含有量が前記上限値を超えると、得られる樹脂組成物の剛性、薄肉成形性が低下することがある。 The ethylene unit content in the ethylene / propylene copolymer is preferably 1.2% by mass or less, and more preferably 0 to 0.6% by mass. If the ethylene unit content in the ethylene / propylene copolymer exceeds the upper limit, the rigidity and thin-wall moldability of the resulting resin composition may be lowered.
　エチレン・１－ブテン共重合体におけるエチレン単位含有量は７４～８６質量％であることが好ましく、８０～８５質量％であることがより好ましい。エチレン・１－ブテン共重合体におけるエチレン単位含有量が前記上限値を超えると、得られる樹脂組成物の低温衝撃強度が低下する傾向にあり、前記下限値未満であると、プロピレン系樹脂材料の製造が困難になる傾向にある上に、樹脂組成物の剛性、透明性、薄肉成形性が低下することがある。 The ethylene unit content in the ethylene / 1-butene copolymer is preferably 74 to 86% by mass, more preferably 80 to 85% by mass. If the ethylene unit content in the ethylene / 1-butene copolymer exceeds the upper limit, the low-temperature impact strength of the resulting resin composition tends to decrease, and if it is less than the lower limit, the propylene-based resin material In addition to the tendency to be difficult to manufacture, the rigidity, transparency, and thin moldability of the resin composition may be reduced.
　樹脂組成物におけるエチレン・１－ブテン共重合体の含有量は、樹脂組成物を１００質量％とした際の２２～３２質量％であり、２５～３０質量％であることがより好ましい。エチレン・１－ブテン共重合体の含有量が前記上限値を超えると、プロピレン系樹脂材料の製造が困難になる傾向にあり、前記下限値未満であると、得られる樹脂組成物の低温衝撃強度が低下する傾向にある。 The content of the ethylene / 1-butene copolymer in the resin composition is 22 to 32% by mass, more preferably 25 to 30% by mass, based on 100% by mass of the resin composition. When the content of the ethylene / 1-butene copolymer exceeds the upper limit, production of a propylene-based resin material tends to be difficult, and when the content is less than the lower limit, the low-temperature impact strength of the resulting resin composition Tend to decrease.
（透明化核剤）
　透明化核剤は、ポリプロピレン結晶核の形成を促進させて、得られる樹脂組成物の透明性を向上させる。透明化核剤を含むことによって、ヘイズ値（ＪＩＳ　Ｋ　７１０５、１ｍｍ厚）を容易に３０％以下にできる。透明化核剤を含有しない場合には、透明性が低下するばかりか、薄肉成形性も損なわれる。 (Clearing nucleating agent)
The clearing nucleating agent promotes the formation of polypropylene crystal nuclei and improves the transparency of the resulting resin composition. By including a clearing nucleating agent, the haze value (JIS K 7105, 1 mm thickness) can be easily reduced to 30% or less. When the nucleating agent is not contained, not only the transparency is lowered but also the thin-wall moldability is impaired.
　透明化核剤の具体例としては、ソルビトール化合物、カルボン酸の金属塩、芳香族リン酸エステル系化合物、シリカ、タルクなどが挙げられる。臭気が少ない点では、芳香族リン酸エステル系化合物が好ましい。
　ソルビトール化合物としては、例えば、ジベンジリデンソルビトール、１，３，２，４－ジ－（メチルベンジリデン）ソルビトール、１，３，２，４－（エチルベンジリテン）ソルビトール、１，３，２，４－（メトキシベンジリデン）ソルビトール、１，３，２，４－（エトキシベンジリデン）ソルビトール、１，２，３－トリデオキシ－４，６－５，７－ビス－ｏ－［（４－プロピルフェニル）メチレン］ノニトールなどが挙げられる。
　カルボン酸の金属塩としては、例えば、アジピン酸ナトリウム、アジピン酸カリウム、アジピン酸アルミニウム、セバシン酸ナトリウム、セバシン酸カリウム、セバシン酸アルミニウム、安息香酸ナトリウム、安息香酸アルミニウム、ジ－パラ－ｔ－ブチル安息香酸アルミニウム、ジ－パラ－ｔ－ブチル安息香酸チタン、ジ－パラ－ｔ－ブチル安息香酸クロム、ヒドロキシ－ジ－ｔ－ブチル安息香酸アルミニウムなどが挙げられる。
　また、透明化核剤として、トリアミノベンゼン誘導体を用いることができる。 Specific examples of the clearing nucleating agent include sorbitol compounds, metal salts of carboxylic acids, aromatic phosphate ester compounds, silica, talc and the like. In terms of low odor, an aromatic phosphate ester compound is preferable.
Examples of the sorbitol compound include dibenzylidene sorbitol, 1,3,2,4-di- (methylbenzylidene) sorbitol, 1,3,2,4- (ethylbenzylidene) sorbitol, 1,3,2,4- (Methoxybenzylidene) sorbitol, 1,3,2,4- (ethoxybenzylidene) sorbitol, 1,2,3-trideoxy-4,6-5,7-bis-o-[(4-propylphenyl) methylene] nonitol Etc.
Examples of the metal salt of carboxylic acid include sodium adipate, potassium adipate, aluminum adipate, sodium sebacate, potassium sebacate, aluminum sebacate, sodium benzoate, aluminum benzoate, di-para-t-butylbenzoate Examples thereof include aluminum oxide, titanium di-para-t-butylbenzoate, chromium di-para-t-butylbenzoate, and aluminum hydroxy-di-t-butylbenzoate.
Moreover, a triaminobenzene derivative can be used as a clearing nucleating agent.
　透明化核剤の含有量は、プロピレン系樹脂材料１００質量部に対して、０．０１～０．５質量部であることが好ましく、０．１～０．４質量部であることが好ましい。ただし、透明化核剤がトリアミノベンゼン誘導体である場合には０．０１～０．０２質量部であることが好ましい。透明化核剤の含有量が前記下限値以上であれば、樹脂組成物から得られる成形品の透明性をより高くでき、前記上限値以下であれば、臭気を抑制できる。 The content of the clearing nucleating agent is preferably 0.01 to 0.5 parts by mass, and preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the propylene-based resin material. However, when the clearing nucleating agent is a triaminobenzene derivative, the amount is preferably 0.01 to 0.02 parts by mass. If the content of the clearing nucleating agent is at least the lower limit value, the transparency of the molded product obtained from the resin composition can be further increased, and if it is at most the upper limit value, odor can be suppressed.
（他の重合体）
　樹脂組成物には、必要に応じて、他の重合体が含まれてもよい。
　他の重合体としては、公知の熱可塑性樹脂または熱硬化性樹脂を用いることができる。
　熱可塑性樹脂としては、例えば、エチレン又はα－オレフィン単独重合体、エチレンまたは炭素数３～１０のα－オレフィンの共重合体、これらの混合物、ナイロン、ポリカーボネート、ポリフェニレンオキサイド、石油樹脂などが挙げられる。
　エチレン又はα－オレフィン単独重合体としては、具体的に、高密度ポリエチレン、低密度ポリエチレン、ポリプロピレン、ポリ－１－ブテン、ポリ－１－ペンテン、ポリ－１－ヘキセン、ポリ（３－メチル－１－ペンテン）、ポリ（３－メチル－１－ブテン）、ポリ（４－メチル－1－ペンテン）、ポリ－１－ヘキセン、ポリ－１－へプテン、ポリ－１－オクテン、ポリ－１－デセン、ポリスチレン及びこれらの組み合わせが挙げられる。これらの中でも、ポリプロピレンが好ましい。 (Other polymers)
The resin composition may contain other polymers as necessary.
As other polymers, known thermoplastic resins or thermosetting resins can be used.
Examples of the thermoplastic resin include ethylene or α-olefin homopolymer, ethylene or α-olefin copolymer having 3 to 10 carbon atoms, a mixture thereof, nylon, polycarbonate, polyphenylene oxide, petroleum resin, and the like. .
Specific examples of the ethylene or α-olefin homopolymer include high-density polyethylene, low-density polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, and poly (3-methyl-1 -Pentene), poly (3-methyl-1-butene), poly (4-methyl-1-pentene), poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-decene , Polystyrene and combinations thereof. Among these, polypropylene is preferable.
（添加剤）
　本発明の樹脂組成物には、任意成分として、例えば、酸化防止剤、塩酸吸収剤、耐熱安定剤、光安定剤、紫外線吸収剤、内部滑剤、外部滑剤、帯電防止剤、難燃剤、分散剤、銅害防止剤、中和剤、可塑剤、発泡剤、気泡防止剤、架橋剤、過酸化物等の添加剤が含まれてもよい。 (Additive)
In the resin composition of the present invention, as optional components, for example, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an antistatic agent, a flame retardant, and a dispersant. Additives such as copper damage inhibitors, neutralizers, plasticizers, foaming agents, anti-bubble agents, cross-linking agents, and peroxides may be included.
（製造方法）
　上述した樹脂組成物は、プロピレン系樹脂材料と透明化核剤と、必要に応じて、他の重合体、添加剤とを配合した後、単軸押出機、二軸押出機、バンバリーミキサー、ニーダー、ロールミル等公知の混練機を用いて溶融混練することにより製造することができる。 (Production method)
The resin composition described above comprises a propylene-based resin material, a clearing nucleating agent, and other polymers and additives as necessary, and then a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader. It can be produced by melt kneading using a known kneader such as a roll mill.
（成形品）
　上記樹脂組成物は、射出成形により薄肉の成形品に加工される。ここで、薄肉とは、成形品の厚さが１．０ｍｍ以下であることを示す。薄肉の成形品は軽量である反面、成形しにくくなる上に機械的物性が不充分になりやすいが、本発明の樹脂組成物は、前記プロピレン系樹脂材料を含むことで、薄肉射出成形に適し且つ充分な機械的物性を発揮する。
　射出成形の際の条件は特に制限されず、目的の成形品の形状や大きさ、使用する射出成形機の種類や規模に応じて適宜選択されるが、成形温度は２００～２６０℃であることが好ましい。成形温度が前記下限値以上であれば、充分な成形性を確保でき、前記上限値以下であれば、樹脂組成物の熱劣化を防止できる。 (Molding)
The resin composition is processed into a thin molded product by injection molding. Here, the term “thin” means that the thickness of the molded product is 1.0 mm or less. Thin-walled molded products are lightweight, but difficult to mold and mechanical properties tend to be insufficient, but the resin composition of the present invention is suitable for thin-wall injection molding by including the propylene resin material. In addition, sufficient mechanical properties are exhibited.
The conditions for injection molding are not particularly limited, and are appropriately selected according to the shape and size of the target molded product and the type and scale of the injection molding machine to be used. The molding temperature is 200 to 260 ° C. Is preferred. If the molding temperature is equal to or higher than the lower limit value, sufficient moldability can be secured, and if the molding temperature is equal to or lower than the upper limit value, thermal deterioration of the resin composition can be prevented.
　以下の実施例および比較例において、「％」は「質量％」、「部」は「質量部」のことを意味する。 In the following Examples and Comparative Examples, “%” means “mass%” and “part” means “part by mass”.
（実施例１～８、比較例１～１４）
　全４段の重合反応器を直列に備える重合装置を用い、前段２段の重合反応器にてホモポリプロピレンまたはエチレン・プロピレン共重合体を重合し、それらを後段２段の重合反応器に供給し、後段２段の重合反応器にてエチレン・１－ブテン共重合体（表１では、「Ｃ２Ｃ４」と表記する。）またはエチレン・プロピレン共重合体（表１では、「Ｃ２Ｃ３」と表記する。）を重合した。その際、エチレン供給量、水素供給量、重合温度、重合圧力、触媒の添加量を調整することによって、表１に示すプロピレン系樹脂材料を得た。
　そのプロピレン系樹脂材料１００部に透明化核剤（ミリケン社製ミラード３９８８）０．２部を配合し、押出機を用いて２３０℃で溶融混練して、樹脂組成物を得た。 (Examples 1 to 8, Comparative Examples 1 to 14)
Using a polymerization apparatus equipped with all four-stage polymerization reactors in series, homopolypropylene or ethylene / propylene copolymer is polymerized in the two-stage polymerization reactor in the first stage, and these are fed to the second-stage polymerization reactor. In the subsequent two-stage polymerization reactor, ethylene / 1-butene copolymer (indicated as “C2C4” in Table 1) or ethylene / propylene copolymer (indicated as “C2C3” in Table 1). ) Was polymerized. At that time, the propylene-based resin material shown in Table 1 was obtained by adjusting the ethylene supply amount, the hydrogen supply amount, the polymerization temperature, the polymerization pressure, and the addition amount of the catalyst.
Into 100 parts of the propylene-based resin material, 0.2 part of a transparent nucleating agent (Mirken 3988 mirrored 3988) was blended and melt kneaded at 230 ° C. using an extruder to obtain a resin composition.
（比較例１５）
　ホモポリプロピレン（サンアロマー社製ＰＭＢ０２Ａ）７４部とエチレン・１－ブテン共重合体２６部と、透明化核剤（ミリケン社製ミラード３９８８）０．２部とを配合し、押出機を用いて２３０℃で溶融混練して、樹脂組成物を得た。 (Comparative Example 15)
74 parts of homopolypropylene (Sun Allomer PMB02A), 26 parts of an ethylene / 1-butene copolymer, and 0.2 part of a clarifying nucleating agent (Milken Mirrored 3988) were blended, and 230 ° C. using an extruder. And kneaded to obtain a resin composition.
（比較例１６）
　高密度ポリエチレン（旭化成社製Ｊ３００）をそのまま用いた。 (Comparative Example 16)
High density polyethylene (J300 manufactured by Asahi Kasei Co., Ltd.) was used as it was.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　各樹脂組成物のメルトフローレート（ＭＦＲ）、生産性、透明性、耐白化性、曲げ弾性率、低温での耐衝撃性、薄肉成形性を以下のように評価した。評価結果を表１～３に示す。 The melt flow rate (MFR), productivity, transparency, whitening resistance, flexural modulus, impact resistance at low temperature, and thin-wall formability of each resin composition were evaluated as follows. The evaluation results are shown in Tables 1 to 3.
［ＭＦＲ］
　ＭＦＲは、ＪＩＳ　Ｋ　７２１０に準拠し、温度２３０℃、荷重２１．６Ｎの条件で測定した値である。 [MFR]
MFR is a value measured under conditions of a temperature of 230 ° C. and a load of 21.6 N according to JIS K 7210.
［生産性］
　樹脂組成物の生産性を以下の基準で評価した。
　◎：重合反応器での連続生産可能で、且つ、生産速度が高い。
　○：重合反応器での連続生産可能で、且つ、生産速度が中程度。
　△：重合反応器での連続生産可能であるが、生産速度を下げる必要がある。
　×：重合反応器での連続生産は不能。 [productivity]
The productivity of the resin composition was evaluated according to the following criteria.
A: Continuous production in a polymerization reactor is possible and the production rate is high.
○: Continuous production in a polymerization reactor is possible and the production rate is moderate.
(Triangle | delta): Although continuous production with a polymerization reactor is possible, it is necessary to reduce a production rate.
X: Continuous production in the polymerization reactor is impossible.
［透明性］
　各樹脂組成物を成形温度２３０℃で射出成形して、１ｍｍ厚の板状の試験片を作製した。この試験片を用い、ＪＩＳ　Ｋ７１０５に従い、ヘイズ測定装置（（株）村上色彩技術研究所製ＨＭ－１５０型）によりヘイズを測定した。ヘイズの値が小さい程、透明性に優れる。 [transparency]
Each resin composition was injection-molded at a molding temperature of 230 ° C. to produce a 1 mm thick plate-shaped test piece. Using this test piece, haze was measured according to JIS K7105 using a haze measuring device (HM-150 type, manufactured by Murakami Color Research Laboratory Co., Ltd.). The smaller the haze value, the better the transparency.
［低温での耐衝撃性、耐白化性］
　各樹脂組成物を成形温度２３０℃で射出成形して、１ｍｍ厚の板状の試験片を作製した。この試験片を用い、－２０℃の環境下、面衝撃強度測定装置（島津製作所社製ハイドロショット）により、面衝撃強度を測定した。
　また、温度を０℃にしたこと以外は上記面衝撃強度の測定と同様にして試験片に衝撃を与え、以下の基準で耐白化性を評価した。
○：白化が見られなかった。
×：白化が見られた。 [Shock resistance and whitening resistance at low temperatures]
Each resin composition was injection-molded at a molding temperature of 230 ° C. to produce a 1 mm thick plate-shaped test piece. Using this test piece, the surface impact strength was measured with a surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation) in an environment of −20 ° C.
Further, the test piece was impacted in the same manner as the measurement of the surface impact strength except that the temperature was 0 ° C., and the whitening resistance was evaluated according to the following criteria.
○: Whitening was not observed.
X: Whitening was observed.
［曲げ弾性率］
　ＩＳＯ１７８に従って測定した。 [Bending elastic modulus]
Measured according to ISO178.
［薄肉成形性］
　各樹脂組成物を成形温度２３０℃、射出速度２００ｍｍ／秒で射出成形して、厚さ０．５ｍｍで開口部分にフランジ部を有する有底円筒状の成形品を作製した。その成形の際の、ショートショットの有無、金型からの取り出しの際の座屈の有無、フランジ部のヒケの有無を目視により観察し、以下の基準で評価した。
・ショートショットの有無
　○：ショートショットは生じなかった。
　△：ショートショットが時々生じることもあったが、実用上問題ない程度。
　×：ショートショットが生じた。
・座屈の有無
　○：取り出し時に座屈は生じなかった。
　△：取り出し時に座屈が時々生じることもあったが、実用上問題ない程度。
　×：取り出し時に座屈が生じた。
・ヒケの有無
　○：フランジ部にヒケは生じなかった。
　△：フランジ部に小さなヒケが生じたが、実用上問題ない程度。
　×：フランジ部に大きなヒケが生じた。 [Thin formability]
Each resin composition was injection-molded at a molding temperature of 230 ° C. and an injection speed of 200 mm / second to produce a bottomed cylindrical molded product having a thickness of 0.5 mm and a flange portion at the opening. During the molding, the presence or absence of short shots, the presence or absence of buckling during removal from the mold, and the presence or absence of sink marks in the flange were visually observed and evaluated according to the following criteria.
-Presence / absence of short shot ○: No short shot occurred.
Δ: Although short shots sometimes occur, there is no practical problem.
X: A short shot occurred.
-Presence / absence of buckling ○: No buckling occurred during removal.
(Triangle | delta): Although buckling sometimes arises at the time of taking out, it is a grade which is satisfactory practically.
X: Buckling occurred during removal.
-Presence or absence of sink marks ○: No sink marks were generated on the flange.
Δ: Small sink marks are formed in the flange portion, but there is no practical problem.
X: A large sink occurred in the flange portion.
　実施例１～８の樹脂組成物は、透明性、耐白化性、低温衝撃強度および薄肉成形性のいずれにも優れていた。
　ゴム成分がエチレン・プロピレン共重合体の比較例１の樹脂組成物は、生産が困難であった。
　ゴム成分がエチレン・プロピレン共重合体である上にエチレン・プロピレン共重合体のエチレン単位が３５％であった比較例２の樹脂組成物は、重合によるプロピレン系樹脂材料の製造が困難であった上に、透明性、耐白化性が低かった。
　ゴム成分がエチレン・プロピレン共重合体である上にエチレン・プロピレン共重合体の含有量を１８％、エチレン・プロピレン共重合体のエチレン単位を３２％とした比較例３の樹脂組成物は、透明性、耐白化性、低温衝撃強度が低かった。
　ゴム成分がエチレン・プロピレン共重合体である上にエチレン・プロピレン共重合体の含有量を２０％、エチレン・プロピレン共重合体のエチレン単位が４０％とした比較例４の樹脂組成物は、透明性、耐白化性、低温衝撃強度が低かった。
　エチレン単位が２．２％のエチレン・１－ブテン共重合体を含む比較例５の樹脂組成物は、生産性が低かった上に、剛性、薄肉成形性が低かった。
　エチレン・１－ブテン共重合体のエチレン単位を９０％とした比較例６の樹脂組成物は、低温衝撃強度が低かった。
　エチレン・１－ブテン共重合体のエチレン単位を７０％とした比較例７の樹脂組成物は、重合によるプロピレン系樹脂材料の製造が困難であった。
　エチレン・１－ブテン共重合体の含有量を２０％とした比較例８の樹脂組成物は、低温衝撃強度が低かった。
　エチレン・１－ブテン共重合体の含有量を３５％とした比較例９の樹脂組成物は、製造が困難であった。
　極限粘度が１．４ｄｌ／ｇであった比較例１０の樹脂組成物は、重合によるプロピレン系樹脂材料の製造が困難であった上に、透明性、耐白化性が低かった。
　極限粘度が０．７ｄｌ／ｇであった比較例１１の樹脂組成物は、重合によるプロピレン系樹脂材料の製造が困難であった。
　ＭＦＲが７５ｇ／１０分であった比較例１２の樹脂組成物は、重合によるプロピレン系樹脂材料の製造が困難であった上に、低温衝撃強度が低かった。
　ＭＦＲが２０ｇ／１０分であった比較例１３の樹脂組成物は、薄肉成形性が低かった。
　透明化核剤を含まなかった比較例１４の樹脂組成物は、透明性、薄肉成形性が低かった。
　ポリプロピレンとエチレン・１－ブテン共重合体とをコンパウンドにより混合した比較例１５の樹脂組成物は、生産性が低かった上に、低温衝撃強度、薄肉成形性が低かった。
　高密度ポリエチレンを用いた比較例１６の樹脂組成物は、透明性、薄肉成形性が低かった。 The resin compositions of Examples 1 to 8 were excellent in transparency, whitening resistance, low-temperature impact strength, and thin-wall moldability.
Production of the resin composition of Comparative Example 1 in which the rubber component was an ethylene / propylene copolymer was difficult.
In the resin composition of Comparative Example 2 in which the rubber component was an ethylene / propylene copolymer and the ethylene unit of the ethylene / propylene copolymer was 35%, it was difficult to produce a propylene-based resin material by polymerization. Moreover, transparency and whitening resistance were low.
The resin composition of Comparative Example 3 in which the rubber component is an ethylene / propylene copolymer, the ethylene / propylene copolymer content is 18%, and the ethylene unit of the ethylene / propylene copolymer is 32% is transparent. , Whitening resistance and low temperature impact strength were low.
The resin composition of Comparative Example 4 in which the rubber component is an ethylene / propylene copolymer, the ethylene / propylene copolymer content is 20%, and the ethylene unit of the ethylene / propylene copolymer is 40% is transparent. , Whitening resistance and low temperature impact strength were low.
The resin composition of Comparative Example 5 containing an ethylene / 1-butene copolymer having an ethylene unit of 2.2% had low productivity and low rigidity and thin-wall moldability.
The resin composition of Comparative Example 6 in which the ethylene unit of the ethylene / 1-butene copolymer was 90% had low low-temperature impact strength.
In the resin composition of Comparative Example 7 in which the ethylene unit of the ethylene / 1-butene copolymer was 70%, it was difficult to produce a propylene-based resin material by polymerization.
The resin composition of Comparative Example 8 in which the ethylene / 1-butene copolymer content was 20% had low low-temperature impact strength.
The resin composition of Comparative Example 9 in which the ethylene / 1-butene copolymer content was 35% was difficult to produce.
In the resin composition of Comparative Example 10 having an intrinsic viscosity of 1.4 dl / g, it was difficult to produce a propylene-based resin material by polymerization, and transparency and whitening resistance were low.
In the resin composition of Comparative Example 11 having an intrinsic viscosity of 0.7 dl / g, it was difficult to produce a propylene-based resin material by polymerization.
The resin composition of Comparative Example 12 having an MFR of 75 g / 10 min was difficult to produce a propylene-based resin material by polymerization and had low low-temperature impact strength.
The resin composition of Comparative Example 13 having an MFR of 20 g / 10 min had low thin moldability.
The resin composition of Comparative Example 14 that did not contain a clearing nucleating agent had low transparency and thin-wall moldability.
The resin composition of Comparative Example 15 in which polypropylene and ethylene / 1-butene copolymer were mixed by a compound had low productivity, low temperature impact strength, and low formability.
The resin composition of Comparative Example 16 using high-density polyethylene had low transparency and thin wall moldability.
　本発明の薄肉射出成形用ポリプロピレン樹脂組成物は、食品用容器、化粧品容器など各種包装容器、ボトル類の蓋などに好適に利用できる。 The polypropylene resin composition for thin-wall injection molding of the present invention can be suitably used for various packaging containers such as food containers and cosmetic containers, and bottle lids.

Claims (4)

  1. 　プロピレン系樹脂材料および透明化核剤を含有する薄肉射出成形用ポリプロピレン樹脂組成物であって、
    　キシレン可溶分の、１３５℃のテトラヒドロナフタレン中での極限粘度が０．９～１．３ｄｌ／ｇであり、ＪＩＳ　Ｋ　７２１０に準拠し、温度２３０℃、荷重２１．６Ｎの条件で測定したメルトフローレートが３０～７０ｇ／１０分であり、
    　前記プロピレン系樹脂材料は、エチレン単位が１．２質量％以下のエチレン・プロピレン共重合体またはホモポリプロピレンの存在下、エチレン単位が７４～８６質量％のエチレン・１－ブテン共重合体を重合させたものであり、
    　薄肉射出成形用ポリプロピレン樹脂組成物を１００質量％とした際のエチレン・１－ブテン共重合体の含有量が２２～３２質量％である薄肉射出成形用ポリプロピレン樹脂組成物。     A polypropylene resin composition for thin-walled injection molding containing a propylene-based resin material and a clearing nucleating agent,
    Melt of xylene soluble in tetrahydronaphthalene at 135 ° C of 0.9 to 1.3 dl / g, measured in accordance with JIS K 7210 at a temperature of 230 ° C and a load of 21.6 N The flow rate is 30-70 g / 10 min,
    The propylene-based resin material is obtained by polymerizing an ethylene / 1-butene copolymer having an ethylene unit of 74 to 86% by mass in the presence of an ethylene / propylene copolymer or homopolypropylene having an ethylene unit of 1.2% by mass or less. And
    A polypropylene resin composition for thin-wall injection molding, wherein the content of the ethylene / 1-butene copolymer is 22 to 32 mass% when the polypropylene resin composition for thin-wall injection molding is 100 mass%.
  2. 　透明化核剤の含有量が、プロピレン系樹脂材料１００質量部に対して０．０１～０．５質量部である請求項１に記載の薄肉射出成形用ポリプロピレン樹脂組成物。 The polypropylene resin composition for thin-wall injection molding according to claim 1, wherein the content of the clearing nucleating agent is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the propylene-based resin material.
  3. 　請求項１または２に記載の薄肉射出成形用ポリプロピレン樹脂組成物を射出成形した成形品。 A molded product obtained by injection molding the polypropylene resin composition for thin-wall injection molding according to claim 1 or 2.
  4. 　請求項３に記載の成形品を備えた容器。 A container provided with the molded product according to claim 3.
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