JP5751539B2 - Transparent polypropylene resin composition for injection molding and molded article - Google Patents

Transparent polypropylene resin composition for injection molding and molded article Download PDF

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JP5751539B2
JP5751539B2 JP2010279656A JP2010279656A JP5751539B2 JP 5751539 B2 JP5751539 B2 JP 5751539B2 JP 2010279656 A JP2010279656 A JP 2010279656A JP 2010279656 A JP2010279656 A JP 2010279656A JP 5751539 B2 JP5751539 B2 JP 5751539B2
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resin composition
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ethylene
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JP2012126829A (en
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中島　武
武 中島
四十四 菅野
四十四 菅野
信幸 鶴見
信幸 鶴見
和彦 坂井
和彦 坂井
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SunAllomer Ltd
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Priority to TW100146706A priority patent/TW201231538A/en
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    • 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
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • 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
    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding 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
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

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  • Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

本発明は、射出成形に適したポリプロピレン樹脂組成物に関する。その樹脂組成物を射出成形して得た成形品に関する。   The present invention relates to a polypropylene resin composition suitable for injection molding. The present invention relates to a molded product obtained by injection molding the resin composition.

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、衣装ケースや食品容器のコンテナ類などにも広く使用されている。
衣装ケースやコンテナ類においては収納物を視認可能にするために、透明性が求められる。また、輸送中や使用時の破損を防止するために、高い耐衝撃強度が求められる。さらに、ヒンジ部を有する場合には、折り曲げた際の耐白化性が求められる。また、衣装ケースやコンテナ類は射出成形によって成形されるので、射出成形性も求められる。
従来、透明性が求められる成形品においては、特許文献１に記載されているような、エチレン・プロピレンのランダム共重合体を主成分として含有する樹脂組成物が用いられていた。また、高い耐衝撃強度が求められる成形品においては、特許文献２，３に記載されているような、ブロックポリプロピレンを主成分として含有する樹脂組成物が用いられていた。 Polypropylene resin compositions containing polypropylene as a main component are inexpensive and have excellent mechanical properties, and thus are used in various applications and widely used in clothing cases and food container containers.
In costume cases and containers, transparency is required to make the stored items visible. Also, high impact strength is required to prevent damage during transportation and use. Furthermore, when it has a hinge part, the whitening resistance at the time of bending is calculated | required. In addition, since costume cases and containers are formed by injection molding, injection moldability is also required.
Conventionally, in a molded product requiring transparency, a resin composition containing a random copolymer of ethylene / propylene as a main component as described in Patent Document 1 has been used. Further, in a molded product requiring high impact strength, a resin composition containing block polypropylene as a main component as described in Patent Documents 2 and 3 has been used.

特表２００８−５４０７５６号公報Special table 2008-540756 gazette 特開平７−３０８７号公報JP 7-3087 A 特開平９−３１２６４号公報JP-A-9-31264

しかしながら、特許文献１に記載の樹脂組成物から得られた成形品は、耐衝撃強度、特に低温での耐衝撃強度が不充分になることがあった。特許文献２，３に記載の樹脂組成物から得られた成形品は、透明性および耐白化性が不充分になることがあった。
本発明は、透明性、耐白化性および低温衝撃強度に優れた射出成形用ポリプロピレン樹脂組成物および成形品を提供することを目的とする。 However, the molded product obtained from the resin composition described in Patent Document 1 may have insufficient impact strength, particularly impact strength at low temperatures. The molded products obtained from the resin compositions described in Patent Documents 2 and 3 may have insufficient transparency and whitening resistance.
An object of this invention is to provide the polypropylene resin composition for injection molding excellent in transparency, whitening resistance, and low temperature impact strength, and a molded article.

本発明の射出成形用透明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結晶化核剤を含有する射出成形用透明ポリプロピレン樹脂組成物であって、該射出成形用透明ポリプロピレン樹脂組成物におけるキシレン可溶分の、１３５℃のテトラヒドロナフタレン中での極限粘度が０．８〜１．４ｄｌ／ｇ、ＪＩＳ Ｋ ７２１０に準拠し、該射出成形用透明ポリプロピレン樹脂組成物の、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５〜１５ｇ／１０分、該射出成形用透明ポリプロピレン樹脂組成物の、ＪＩＳ Ｋ ７１０５に従い、１ｍｍ厚の試験片で測定したヘイズが９〜１６％であり、前記プロピレン系樹脂材料は、チーグラー・ナッタ触媒を用いて重合されたものであり、且つ、エチレン単位が２．０〜４．０質量％のエチレン・プロピレン共重合体の存在下、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、射出成形用透明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１０〜２０質量％であり、結晶化核剤の含有量が、プロピレン系樹脂材料１００質量部に対して０．０１〜０．５質量部であることを特徴とする。
本発明の成形品は、上記射出成形用透明ポリプロピレン樹脂組成物を射出成形したものである。 Transparent polypropylene resin composition for injection molding of the present invention is a propylene-based resin material and a crystallization nucleating agent for injection molding a transparent polypropylene resin composition containing xylene soluble in the molding transparent polypropylene resin composition exits the injection The intrinsic viscosity in tetrahydronaphthalene at 135 ° C. is 0.8 to 1.4 dl / g, according to JIS K 7210, and the transparent polypropylene resin composition for injection molding has a temperature of 230 ° C. and a load of 21.6 N. According to JIS K 7105, the haze measured by a 1 mm-thick test piece of the transparent polypropylene resin composition for injection molding is 9 to 16%. The propylene-based resin material is polymerized using a Ziegler-Natta catalyst, and the ethylene unit is 2.0 to A transparent polypropylene resin composition for injection molding is obtained by polymerizing an ethylene / 1-butene copolymer having an ethylene unit of 74 to 86% by mass in the presence of 4.0% by mass of an ethylene / propylene copolymer. Ri content of the ethylene-1-butene copolymer is 10 to 20% by mass when taken as 100% by mass, the content of the crystallization nucleating agent, with respect to 100 parts by weight of propylene-based resin material 0.01 It is -0.5 mass part, It is characterized by the above-mentioned .
The molded product of the present invention is obtained by injection molding the transparent polypropylene resin composition for injection molding.

本発明の射出成形用ポリプロピレン樹脂組成物は、透明性、耐白化性および低温衝撃強度に優れ、射出成形に適している。   The polypropylene resin composition for injection molding of the present invention is excellent in transparency, whitening resistance and low temperature impact strength, and is suitable for injection molding.

本発明の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結晶化核剤を含有する。
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０．８〜１．４ｄｌ／ｇであり、０．８〜１．２ｄｌ／ｇであることが好ましい。該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。樹脂組成物のキシレン可溶分の極限粘度はエチレン・１−ブテン共重合体の粘度に大きく依存するが、極限粘度を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５〜１５ｇ／１０分であり、８〜１２ｇ／１０分であることが好ましい。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。該樹脂組成物のＭＦＲが前記下限値未満であると、射出成形性が低くなり、前記上限値を超えると、低温衝撃強度が低くなる。 The polypropylene resin composition for injection molding of the present invention (hereinafter abbreviated as “resin composition”) contains a propylene-based resin material and a crystallization nucleating agent.
In the resin composition of the present invention, the intrinsic viscosity in tetrahydronaphthalene at 135 ° C. of the xylene-soluble component is 0.8 to 1.4 dl / g and 0.8 to 1.2 dl / g. Is preferred. 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 xylene-soluble component of the resin composition largely depends on the viscosity of the ethylene / 1-butene copolymer, it is difficult to produce a propylene-based resin material for making the intrinsic viscosity less than the lower limit.
Moreover, the melt flow rate (MFR) of a resin composition is 5-15 g / 10min, and it is preferable that it is 8-12 g / 10min. 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 injection moldability is lowered, and when the upper limit is exceeded, 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-based resin material is a reaction blend type polypropylene obtained by polymerizing an ethylene / 1-butene copolymer in the presence of an ethylene / propylene copolymer 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, the productivity is increased and the dispersibility is increased, 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、エチレン−プロピレン共重合体を重合し、得られたエチレン−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、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、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、ＭＦＲ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, in the first stage polymerization reactor, the ethylene-propylene copolymer is polymerized, and the obtained ethylene-propylene copolymer is supplied to the second stage polymerization reactor and the second stage polymerization reactor. A propylene-based resin material can be obtained by polymerizing an ethylene / 1-butene copolymer. In this method, an ethylene-propylene copolymer and a produced ethylene / 1-butene copolymer are mixed in a second stage polymerization reactor.
The multi-stage polymerization is not limited to the above method, and the ethylene-propylene copolymer may be polymerized in a plurality of polymerization reactors, or the ethylene / 1-butene copolymer is polymerized in a plurality of polymerization reactors. May be.
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 MFR as needed.

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２．０〜４．０質量％であり、３．０〜４．０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、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透明性と低温衝撃強度が低下することがある。   The ethylene unit content in the ethylene / propylene copolymer is 2.0 to 4.0% by mass, and more preferably 3.0 to 4.0% by mass. If the ethylene unit content in the ethylene / propylene copolymer exceeds the upper limit, the production of the propylene-based resin material tends to be difficult, and if it is less than the lower limit, the transparency of the resulting resin composition and Low temperature impact strength may be reduced.

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％であり、７９〜８４質量％であることが好ましい。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、透明性が低下することがある。   The ethylene unit content in the ethylene / 1-butene copolymer is 74 to 86% by mass, and preferably 79 to 84% 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 The production tends to be difficult, and the rigidity and transparency of the resin composition may be lowered.

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１０〜２０質量％であり、１２〜１６質量％であることが好ましい。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、剛性が低下する傾向にあり、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 10 to 20% by mass, preferably 12 to 16% by mass, based on 100% by mass of the resin composition. If the content of the ethylene / 1-butene copolymer exceeds the upper limit, the rigidity tends to decrease, and if it is less than the lower limit, the low-temperature impact strength of the resulting resin composition tends to decrease. .

（結晶化核剤）
結晶化核剤は、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や剛性を向上させるものである。結晶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。 (Crystal nucleating agent)
The crystallization nucleating agent promotes the formation of polypropylene crystal nuclei and improves the transparency and rigidity of the resulting resin composition. By including a crystallization nucleating agent, the haze value (JIS K 7105, 1 mm thickness) can be easily reduced to 30% or less.

結晶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、結晶化核剤として、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 crystallization 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, and 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 crystallization nucleating agent.

結晶化核剤の含有量は、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より好ましい。ただし、結晶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。結晶化核剤の含有量が前記下限値以上であれば、該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 crystallization nucleating agent is preferably 0.01 to 0.5 parts by mass, more 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 crystallization nucleating agent is a triaminobenzene derivative, the amount is preferably 0.01 to 0.02 parts by mass. If the content of the crystallization nucleating agent is not less than the lower limit, the molded product obtained from the resin composition can be made more transparent, and if it is not more than the upper limit, odor can be suppressed.

（他の重合体）
該樹脂組成物には、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結晶化核剤と、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 crystallization nucleating agent, and, if necessary, other polymers and additives, 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、射出成形により成形品に加工される。
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 molded product by injection molding.
The conditions at the time of 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１〜４，６〜１０、比較例１〜１０）
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１〜３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１〜３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１〜３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部に結晶化核剤（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 4 , 6 to 10, Comparative Examples 1 to 10)
Using a polymerization apparatus equipped with all four-stage polymerization reactors in series, the ethylene / propylene copolymer was polymerized in the two-stage polymerization reactor in the first stage, and these were fed to the two-stage polymerization reactor in the second stage. An ethylene / 1-butene copolymer (indicated as “C2C4” in Tables 1 to 3) or an ethylene / propylene copolymer (indicated as “C2C3” in Tables 1 to 3) in a stage polymerization reactor. .) Was polymerized. At that time, the propylene-based resin materials shown in Tables 1 to 3 were 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 resin material, 0.2 part of a crystallization nucleating agent (Mirken 3988 Millard 3988) was blended and melt kneaded at 230 ° C. using an extruder to obtain a resin composition.

（比較例１１）
エチレン・プロピレンランダム共重合体にゴム成分を配合した樹脂組成物（サンアロマー社製ＰＭ６３３Ｖ）を用いた。 (Comparative Example 11)
A resin composition (PM633V manufactured by Sun Allomer Co., Ltd.) in which a rubber component was blended with an ethylene / propylene random copolymer was used.

Figure 0005751539
Figure 0005751539

Figure 0005751539
Figure 0005751539

Figure 0005751539
Figure 0005751539

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, and impact resistance at low temperature of each resin composition were evaluated as follows. The evaluation results are shown in Tables 1-3.

［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 with a haze measuring device (HM-150 model 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、２ｍｍ厚の板状の試験片を作製した。この試験片を用い、０℃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、各樹脂組成物を成形温度２３０℃で射出成形して、有底半球状の容器を作製した。この容器を、０℃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）により破壊させた。その際の割れの状況を目視により観察して、以下の基準で評価した。
○：割れずに潰れ、破片が生じない。
×：割れて破片が生じた。
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 2 mm thick plate-like 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 0 ° C.
Each resin composition was injection molded at a molding temperature of 230 ° C. to prepare a bottomed hemispherical container. The container was broken with a surface impact strength measuring device (Hydroshot manufactured by Shimadzu Corporation) in an environment of 0 ° C. The state of cracking at that time was visually observed and evaluated according to the following criteria.
◯: Crush without breaking and no debris.
X: Broken and fragmented.
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］
ＪＩＳ Ｋ６７５８に従って測定した。 [Bending elastic modulus]
It measured according to JIS K6758.

実施例１〜４，６〜１０の樹脂組成物は、透明性、耐白化性および低温衝撃強度のいずれにも優れていた。
極限粘度が０．７ｄｌ／ｇであった比較例１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。
極限粘度が１．７ｄｌ／ｇであった比較例２の樹脂組成物は、耐白化性が低かった。
エチレン単位が４．２％のエチレン・１−ブテン共重合体を含む比較例３の樹脂組成物は、重合によるプロピレン系樹脂材料の連続的な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９％とした比較例４の樹脂組成物は、低温衝撃強度が低かった。
ＭＦＲが２０ｇ／１０分であった比較例５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８８％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７２％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連続的な製造が困難であった。
結晶化核剤を含まない比較例８の樹脂組成物は、透明性および剛性が低かった。
ゴム成分がエチレン・プロピレン共重合体の比較例９，１０の樹脂組成物は、耐白化性が低かった。
エチレン・プロピレンランダム共重合体にゴム成分を配合した比較例１１の樹脂組成物は、低温衝撃強度が低かった。
The resin compositions of Examples 1 to 4, 6 to 10 were excellent in transparency, whitening resistance, and low temperature impact strength.
In the resin composition of Comparative Example 1 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 2 having an intrinsic viscosity of 1.7 dl / g had low whitening resistance.
In the resin composition of Comparative Example 3 containing an ethylene / 1-butene copolymer having 4.2% ethylene units, it was difficult to continuously produce a propylene-based resin material by polymerization.
The resin composition of Comparative Example 4 in which the ethylene / 1-butene copolymer content was 9% had low low-temperature impact strength.
The resin composition of Comparative Example 5 having an MFR of 20 g / 10 min had low low temperature impact strength.
The resin composition of Comparative Example 6 in which the ethylene unit of the ethylene / 1-butene copolymer was 88% 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 72%, it was difficult to continuously produce a propylene-based resin material by polymerization.
The resin composition of Comparative Example 8 that did not contain a crystallization nucleating agent had low transparency and rigidity.
The resin compositions of Comparative Examples 9 and 10 in which the rubber component was an ethylene / propylene copolymer had low whitening resistance.
The resin composition of Comparative Example 11 in which a rubber component was blended with an ethylene / propylene random copolymer had low low-temperature impact strength.

本発明の射出成形用ポリプロピレン樹脂組成物は、透明衣装ケース、食品用容器、化粧品容器など各種包装容器やヒンジ付きの容器蓋などに好適に利用できる。   The polypropylene resin composition for injection molding of the present invention can be suitably used for various packaging containers such as transparent costume cases, food containers, cosmetic containers, and container covers with hinges.

Claims (2)

プロピレン系樹脂材料および結晶化核剤を含有する射出成形用透明ポリプロピレン樹脂組成物であって、
該射出成形用透明ポリプロピレン樹脂組成物におけるキシレン可溶分の、１３５℃のテトラヒドロナフタレン中での極限粘度が０．８〜１．４ｄｌ／ｇ、ＪＩＳ Ｋ ７２１０に準拠し、該射出成形用透明ポリプロピレン樹脂組成物の、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５〜１５ｇ／１０分、該射出成形用透明ポリプロピレン樹脂組成物の、ＪＩＳ Ｋ ７１０５に従い、１ｍｍ厚の試験片で測定したヘイズが９〜１６％であり、
前記プロピレン系樹脂材料は、チーグラー・ナッタ触媒を用いて重合されたものであり、且つ、エチレン単位が２．０〜４．０質量％のエチレン・プロピレン共重合体の存在下、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、
射出成形用透明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１０〜２０質量％であり、
結晶化核剤の含有量が、プロピレン系樹脂材料１００質量部に対して０．０１〜０．５質量部であることを特徴とする射出成形用透明ポリプロピレン樹脂組成物。 A transparent polypropylene resin composition for injection molding containing a propylene-based resin material and a crystallization nucleating agent,
The intrinsic viscosity of the xylene-soluble component in the transparent polypropylene resin composition for injection molding is 0.8 to 1.4 dl / g in tetrahydronaphthalene at 135 ° C., according to JIS K 7210, and the transparent polypropylene for injection molding A test piece having a melt flow rate of 5 to 15 g / 10 min measured under conditions of a temperature of 230 ° C. and a load of 21.6 N of the resin composition, and a 1 mm thick test piece of the transparent polypropylene resin composition for injection molding according to JIS K 7105 The haze measured by is 9 to 16%,
The propylene-based resin material is polymerized using a Ziegler-Natta catalyst and has an ethylene unit of 74 in the presence of an ethylene / propylene copolymer having an ethylene unit of 2.0 to 4.0% by mass. -86 mass% of ethylene / 1-butene copolymer is polymerized,
Ri content of the ethylene-1-butene copolymer is 10 to 20% by mass when the injection molding transparent polypropylene resin composition was 100% by mass,
The transparent polypropylene resin composition for injection molding , wherein the content of the crystallization nucleating agent is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the propylene-based resin material . 請求項１に記載の射出成形用透明ポリプロピレン樹脂組成物を射出成形した成形品。 A molded article obtained by injection molding the transparent polypropylene resin composition for injection molding according to claim 1 .
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