JP2019131708A - Polypropylene resin composition - Google Patents
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本発明は、剛性及び耐傷付き性に優れるポリプロピレン樹脂組成物に関する。 The present invention relates to a polypropylene resin composition having excellent rigidity and scratch resistance.
自動車のグローブボックス等の車両用部品には、ポリプロピレン樹脂組成物から射出成形や押出成形等により成形されたポリプロピレン樹脂成形体が多用されている。車両用部品として使用されるポリプロピレン樹脂成形体には、剛性が求められている。 For parts for vehicles such as a glove box of an automobile, a polypropylene resin molded body molded from a polypropylene resin composition by injection molding or extrusion molding is often used. The polypropylene resin molded body used as a vehicle component is required to have rigidity.
従来、ポリプロピレン樹脂成形体の剛性を向上させるため、タルクを添加することが行われている。特に、十分な剛性を得るために、タルクの添加量を２０重量％以上にしたタルク強化ポリプロピレン樹脂組成物が、車両用部品の成形に使用されている。 Conventionally, talc has been added to improve the rigidity of a polypropylene resin molded body. In particular, in order to obtain sufficient rigidity, a talc-reinforced polypropylene resin composition in which the amount of talc added is 20% by weight or more is used for molding vehicle parts.
しかし、タルクが２０重量％以上添加されたタルク強化ポリプロピレン樹脂組成物から成形されたポリプロピレン成形体は、タルク自体の色が白く、かつ含まれるタルクの量が多いため、表面が傷付いた際に、露出したタルクで傷の内部が白く見えることで、表面の傷が一層目立つようになる。 However, a polypropylene molded body molded from a talc-reinforced polypropylene resin composition containing 20% by weight or more of talc has a white talc color and a large amount of talc. The exposed talc makes the inside of the wound appear white, making the surface scratch more noticeable.
また、タルク強化ポリプロピレン樹脂組成物は、タルクを２０重量％以上添加したことにより比重が１．０５以上になり、軽量化が求められる車両用部品においては、好ましいものではなかった。 Further, the talc-reinforced polypropylene resin composition has a specific gravity of 1.05 or more due to the addition of 20% by weight or more of talc, which is not preferable for vehicle parts that are required to be lighter.
本発明は前記の点に鑑みなされたものであって、剛性、耐傷付き性及び軽量性に優れるポリプロピレン樹脂組成物の提供を目的とする。 This invention is made | formed in view of the said point, Comprising: It aims at provision of the polypropylene resin composition excellent in rigidity, scratch resistance, and lightweight property.
請求項１の発明は、ポリプロピレン樹脂組成物中に、有機変性クレーを３〜３０重量％含み、タルクを含まないことを特徴とするポリプロピレン樹脂組成物に係る。 The invention of claim 1 relates to a polypropylene resin composition comprising 3 to 30% by weight of organically modified clay and no talc in the polypropylene resin composition.
請求項２の発明は、請求項１において、前記ポリプロピレン樹脂組成物中に、酸変性ポリプロピレンを含むことを特徴とする。 The invention of claim 2 is characterized in that, in claim 1, acid-modified polypropylene is contained in the polypropylene resin composition.
請求項３の発明は、請求項１または２において、前記ポリプロピレン樹脂組成物の比重が１．０４以下であることを特徴とする。 The invention of claim 3 is characterized in that, in claim 1 or 2, the specific gravity of the polypropylene resin composition is 1.04 or less.
本発明によれば、ポリプロピレン樹脂組成物中に有機変性クレーを３〜３０重量％含み、タルクを含まないため、剛性及び耐傷付き性に優れ、比重が１．０５未満のポリプロピレン樹脂組成物が得られる。また、ポリプロピレン樹脂組成物中に酸変性ポリプロピレンを含むことにより、さらに剛性を大にすることができる。 According to the present invention, since the polypropylene resin composition contains 3 to 30% by weight of the organically modified clay and does not contain talc, a polypropylene resin composition having excellent rigidity and scratch resistance and a specific gravity of less than 1.05 is obtained. It is done. Moreover, rigidity can be further increased by including acid-modified polypropylene in the polypropylene resin composition.
本発明におけるポリプロピレン樹脂組成物は、ポリプロピレン樹脂と、有機変性クレーとを含み、さらに好ましくは酸変性ポリプロピレンを含み、タルクを含まない配合からなる。ポリプロピレン樹脂組成物の比重は、１．０５未満が好ましい。 The polypropylene resin composition in the present invention contains a polypropylene resin and an organically modified clay, more preferably contains an acid-modified polypropylene and does not contain talc. The specific gravity of the polypropylene resin composition is preferably less than 1.05.
ポリプロピレン樹脂としては、プロピレン単独重合体、プロピレンを主体とする共重合体（例えばプロピレン−エチレン共重合体、プロピレン−α−オレフィン共重合体）、又はこれらの混合物を挙げることができる。 Examples of the polypropylene resin include a propylene homopolymer, a copolymer mainly composed of propylene (for example, propylene-ethylene copolymer, propylene-α-olefin copolymer), or a mixture thereof.
有機変性クレーとしては、セピオライトなどの鎖状粘土鉱物、パリゴスカイトなどの長繊維状粘土鉱物、サポナイト、ヘクトライトなどの板状・層状粘土鉱物を有機処理したものが用いられる。例えば、第四級アルキルアンモニウム塩で変性（表面処理）された粘土鉱物混合物を挙げる。入手可能な有機変性クレーとして、例えば、ＢＹＫ Ｃｈｅｍｉｅ ＧｍｂＨ社のＧａｒａｍｉｔｅ（登録商標）１９５８、１２１０、７３０５を挙げる。 As the organically modified clay, chain-treated clay minerals such as sepiolite, long fiber clay minerals such as palygoskite, and plate / layered clay minerals such as saponite and hectorite are organically treated. An example is a clay mineral mixture modified (surface treatment) with a quaternary alkyl ammonium salt. Examples of the organically modified clay that can be obtained include Garamite (registered trademark) 1958, 1210, and 7305 manufactured by BYK Chemie GmbH.
有機変性クレーの含有量は、少なすぎると効果が小になり、一方、多すぎるとポリプロピレン樹脂組成物の比重が大になるため、ポリプロピレン樹脂組成物中に３〜３０重量％が好ましく、より好ましくは４〜２０重量％である。タルクに代えて有機変性クレーをポリプロピレン樹脂組成物に含有させたことにより、有機変性クレーの少ない含有量で剛性及び耐傷付き性を高めることができ、ポリプロピレン樹脂組成物の比重を１．０５未満にできる。さらに、有機変性クレーの含有量をポリプロピレン樹脂組成物中に４〜１５重量％とすれば、ポリプロピレン樹脂組成物の比重を１．０未満にできる点でより好ましい。 If the content of the organically modified clay is too small, the effect becomes small. On the other hand, if the content is too large, the specific gravity of the polypropylene resin composition becomes large. Therefore, the content in the polypropylene resin composition is preferably 3 to 30% by weight, more preferably. Is 4 to 20% by weight. By including an organically modified clay in the polypropylene resin composition instead of talc, rigidity and scratch resistance can be increased with a small content of the organically modified clay, and the specific gravity of the polypropylene resin composition is less than 1.05. it can. Furthermore, if the content of the organically modified clay is 4 to 15% by weight in the polypropylene resin composition, it is more preferable because the specific gravity of the polypropylene resin composition can be less than 1.0.
酸変性ポリプロピレンとしては、制限されることなく使用できる。酸変性ポリプロピレンは、ポリプロピレンを、不飽和カルボン酸またはその誘導体でグラフト共重合して変性したものである。不飽和カルボン酸としては、マレイン酸、フマル酸、イタコン酸、アクリル酸などを挙げることができる。不飽和カルボン酸の誘導体としては、無水マレイン酸、無水イタコン酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸エチル、マレイン酸モノエチルエステル等を挙げることができる。 The acid-modified polypropylene can be used without limitation. The acid-modified polypropylene is obtained by graft-copolymerizing polypropylene with an unsaturated carboxylic acid or a derivative thereof. Examples of the unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, acrylic acid and the like. Examples of the unsaturated carboxylic acid derivative include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and monoethyl maleate.
好ましい酸変性ポリプロピレンとして、マレイン酸変性ポリプロピレンを挙げることができる。マレイン酸変性ポリプロピレンの含有量は、多すぎると高温時の変色や、流動性の著しい低下の原因となるため、ポリプロピレン樹脂組成物中に０〜３０重量％が好ましく、より好ましくは、５〜２０重量％である。マレイン酸変性ポリプロピレンの含有量を５〜２０重量％とすることで、引張強度および弾性率を高めることができる。 A preferred acid-modified polypropylene is maleic acid-modified polypropylene. If the content of maleic acid-modified polypropylene is too large, it causes discoloration at high temperatures and a significant decrease in fluidity. Therefore, 0 to 30% by weight is preferable in the polypropylene resin composition, and more preferably 5 to 20%. % By weight. By setting the content of maleic acid-modified polypropylene to 5 to 20% by weight, the tensile strength and elastic modulus can be increased.
ポリプロピレン樹脂組成物は、押出成形機などでペレット化され、作製されたペレットを用いて周知のプラスチック成形方法、例えば押出成形、射出成形、ブロー成形、ホットプレスなどによってポリプロピレン樹脂成形体が製造される。ポリプロピレン樹脂成形体としては、自動車のグローブボックス等の車両用内装部品が特に好適である。 The polypropylene resin composition is pelletized by an extrusion molding machine or the like, and a polypropylene resin molded body is produced by a known plastic molding method, for example, extrusion molding, injection molding, blow molding, hot pressing, etc., using the prepared pellets. . As the polypropylene resin molded body, interior parts for vehicles such as an automobile glove box are particularly suitable.
以下の原料成分を用い、図１の表に示す配合からなるポリプロピレン樹脂組成物のペレットを押出成形機で作製し、射出成形により、ＩＳＯ多目的試験片および１００×２００×２ｍｍの板状のポリプロピレン樹脂成形体を作成した。 Using the following raw material components, pellets of a polypropylene resin composition having the composition shown in the table of FIG. 1 were produced with an extrusion molding machine, and then ISO multipurpose test pieces and a plate-like polypropylene resin of 100 × 200 × 2 mm were formed by injection molding. A molded body was prepared.
ポリプロピレン：品名；ノバテックＰＰ ＢＣ０５ＧＳ、日本ポリプロ社製
酸変性ポリプロピレン：マレイン酸変性ポリプロピレン、品名；ユーメックス１００１、三洋化成社製
タルク：品名；ＳＫ−７８００、海城社製
有機変性クレー：品名；Ｇａｒａｍｉｔｅ（登録商標）１９５８、ＢＹＫ Ｃｈｅｍｉｅ ＧｍｂＨ社製
Polypropylene: Product name; Novatec PP BC05GS, manufactured by Nippon Polypro Co., Ltd. Acid-modified polypropylene: Maleic acid-modified polypropylene, Product name: Umex 1001, Sanyo Chemical Co., Ltd. Talc: Product name; SK-7800, Kaijo Co., Ltd. Organic modified clay: Product name; (Registered trademark) 1958, manufactured by BYK Chemie GmbH
実施例及び比較例のポリプロピレン樹脂成形体に対して、引張試験（ＩＳＯ ５２７準拠）、弾性率試験（ＩＳＯ ５２７準拠）、耐傷付き性試験（引掻き試験）を行った。引張試験で用いた試験片は、ＩＳＯ多目的試験片形状である。弾性率試験は、剛性を判断するために行い、用いた試験片はＩＳＯ多目的試験片形状である。 A tensile test (based on ISO 527), an elastic modulus test (based on ISO 527), and a scratch resistance test (scratch test) were performed on the polypropylene resin molded bodies of Examples and Comparative Examples. The test piece used in the tensile test has an ISO multipurpose test piece shape. The elastic modulus test is performed to determine the rigidity, and the test piece used is an ISO multipurpose test piece shape.
耐傷付き性試験の方法は、エリクセン社製引掻き硬度計(先端径０．７５ｍｍ)を用いて、荷重１０Ｎ、５０ｍｍ／ｓの速度で５０ｍｍの直線に引掻き、目視にて傷の程度及び白化の有無を確認した（ｎ＝３）。 The scratch resistance test was conducted using an Ericksen scratch hardness tester (tip diameter: 0.75 mm), scratching on a 50 mm straight line at a load of 10 N and a speed of 50 mm / s, and the degree of scratches and the presence or absence of whitening. Was confirmed (n = 3).
引張試験の評価は、最大点応力の値が２０Ｍｐａ未満「×」、２０〜３０ＭＰａ未満「〇」、３０ＭＰａ以上「◎」とした。
弾性率試験の評価は、弾性率が２０００ＭＰａ未満「×」、２０００〜２４００ＭＰａ未満「〇」、２５００ＭＰａ以上「◎」とした。
耐傷付き性の評価は、明らかに白化が見られるもの「×」、白化がみられないものの、傷が少しあるもの「〇」、白化が見られず、傷も目立っていないもの「◎」とした。
In the evaluation of the tensile test, the maximum point stress value was less than 20 MPa, “x”, less than 20-30 MPa “◯”, and 30 MPa or more “◎”.
In the evaluation of the elastic modulus test, the elastic modulus was “x” less than 2000 MPa, “◯” less than 2000-2400 MPa, “◎”, 2500 MPa or more.
Scratch resistance was evaluated as “x” where whitening was clearly observed, “0” where whitening was not observed, but with slight scratches, and “◎” where whitening was not observed and scratches were not noticeable. .
また、総合評価は、各評価の最も悪い評価を総合評価とした。すなわち、各評価に１つでも「×」がある場合に総合評価「×」、各評価に「×」が無く、「△」が１つでもある場合に総合評価「△」、各評価に「×」及び「△」が無く、「〇」のみまたは「〇」と「◎」の場合に総合評価「〇」、各評価が「◎」のみの場合に総合評価「◎」とした。 Moreover, comprehensive evaluation made the worst evaluation of each evaluation the comprehensive evaluation. That is, if there is at least one “×” in each evaluation, the overall evaluation is “×”. If there is no “×” in each evaluation and there is even one “Δ”, the overall evaluation is “△”. When there was no “x” and “△” and only “◯” or “◯” and “◎”, the overall evaluation was “◯”, and when each evaluation was “◎” only, the overall evaluation was “◎”.
実施例１は、ポリプロピレン９５重量部と有機変性クレー５重量部（５重量％）からなる例である。実施例１は、比重０．９３、引張試験の最大点応力２３．０ＭＰａ、評価「〇」、弾性率２０００ＭＰａ、評価「〇」、耐傷付き性の評価「〇」であり、総合評価「〇」であった。 Example 1 is an example composed of 95 parts by weight of polypropylene and 5 parts by weight (5% by weight) of organically modified clay. Example 1 has a specific gravity of 0.93, a tensile stress maximum point stress of 23.0 MPa, an evaluation of “◯”, an elastic modulus of 2000 MPa, an evaluation of “◯”, and an evaluation of scratch resistance of “◯”. Met.
実施例２は、ポリプロピレン９０重量部と有機変性クレー１０重量部（１０重量％）からなる例である。実施例２は、比重０．９５、引張試験の最大点応力２５．０ＭＰａ、評価「〇」、弾性率２６００ＭＰａ、評価「◎」、耐傷付き性の評価「〇」であり、総合評価「〇」であった。 Example 2 is an example composed of 90 parts by weight of polypropylene and 10 parts by weight (10% by weight) of organically modified clay. Example 2 has a specific gravity of 0.95, a maximum point stress of 25.0 MPa in a tensile test, an evaluation of “◯”, an elastic modulus of 2600 MPa, an evaluation of “◎”, and an evaluation of scratch resistance of “◯”. Met.
実施例３は、ポリプロピレン８５重量部と有機変性クレー１５重量部（１５重量％）からなる例である。実施例３は、比重１．００、引張試験の最大点応力２６．０ＭＰａ、評価「〇」、弾性率２８００ＭＰａ、評価「◎」、耐傷付き性の評価「〇」であり、総合評価「〇」であった。 Example 3 is an example composed of 85 parts by weight of polypropylene and 15 parts by weight (15% by weight) of organically modified clay. Example 3 has a specific gravity of 1.00, a maximum point stress of 26.0 MPa in the tensile test, an evaluation “◯”, an elastic modulus of 2800 MPa, an evaluation “」 ”, an evaluation of scratch resistance“ ◯ ”, and a comprehensive evaluation“ O ”. Met.
実施例４は、ポリプロピレン８０重量部と有機変性クレー２０重量部（２０重量％）からなる例である。実施例４は、比重１．０４、引張試験の最大点応力２７．０ＭＰａ、評価「〇」、弾性率３０００ＭＰａ、評価「◎」、耐傷付き性の評価「〇」であり、総合評価「〇」であった。 Example 4 is an example comprising 80 parts by weight of polypropylene and 20 parts by weight (20% by weight) of organically modified clay. Example 4 has a specific gravity of 1.04, a maximum stress of 27.0 MPa in tensile test, an evaluation “◯”, an elastic modulus of 3000 MPa, an evaluation “「 ”, an evaluation of scratch resistance“ ◯ ”, and a comprehensive evaluation“ O ”. Met.
実施例５は、ポリプロピレン７０重量部、酸変性ポリプロピレン２０重量部、有機変性クレー１０重量部（１０重量％）からなる例である。実施例５は、比重０．９６、引張試験の最大点応力４１．０ＭＰａ、評価「◎」、弾性率３２００ＭＰａ、評価「◎」、耐傷付き性の評価「◎」であり、総合評価「◎」であった。 Example 5 is an example comprising 70 parts by weight of polypropylene, 20 parts by weight of acid-modified polypropylene, and 10 parts by weight (10% by weight) of organically modified clay. Example 5 has a specific gravity of 0.96, a tensile stress maximum point stress of 41.0 MPa, an evaluation of “」 ”, an elastic modulus of 3200 MPa, an evaluation of“ ◎ ”, and an evaluation of scratch resistance of“ ◎ ”, and an overall evaluation of“ ◎ ”. Met.
実施例６は、ポリプロピレン８５重量部、酸変性ポリプロピレン１０重量部、有機変性クレー５重量部（５重量％）の例である。実施例６は、比重０．９３、引張試験の最大点応力２４．０ＭＰａ、評価「〇」、弾性率２５００ＭＰａ、評価「◎」、耐傷付き性の評価「◎」であり、総合評価「〇」であった。 Example 6 is an example of 85 parts by weight of polypropylene, 10 parts by weight of acid-modified polypropylene, and 5 parts by weight (5% by weight) of organic-modified clay. Example 6 has a specific gravity of 0.93, a maximum point stress of 24.0 MPa in the tensile test, an evaluation of “◯”, an elastic modulus of 2500 MPa, an evaluation of “◎”, and an evaluation of scratch resistance of “◎”. Met.
実施例７は、ポリプロピレン９０重量部、酸変性ポリプロピレン６重量部、有機変性クレー４重量部（４重量％）からなる例である。実施例７は、比重０．９３、引張試験の最大点応力２２．０ＭＰａ、評価「〇」、弾性率２１００ＭＰａ、評価「〇」、耐傷付き性の評価「〇」であり、総合評価「〇」であった。 Example 7 is an example comprising 90 parts by weight of polypropylene, 6 parts by weight of acid-modified polypropylene, and 4 parts by weight (4% by weight) of organically modified clay. Example 7 has a specific gravity of 0.93, a tensile stress maximum point stress of 22.0 MPa, an evaluation of “◯”, an elastic modulus of 2100 MPa, an evaluation of “◯”, and an evaluation of scratch resistance of “◯”. Met.
比較例１は、実施例４における有機変性クレー２０重量部に代えてタルク２０重量部を添加した例であり、ポリプロピレン８０重量部とタルク２０重量部とからなり、酸変性ポリプロピレン及び有機変性クレーを含まない例である。比較例１は、比重１．０５、引張試験の最大点応力２２．０ＭＰａ、評価「〇」、弾性率２２００ＭＰａ、評価「〇」、耐傷付き性の評価「×」であり、総合評価「×」であった。タルクを含む比較例１は、有機変性クレーを含む実施例４と比べて比重が大、弾性率（剛性）が小、さらに耐傷付き性が悪いものであった。 Comparative Example 1 is an example in which 20 parts by weight of talc was added instead of 20 parts by weight of the organically modified clay in Example 4, and consisted of 80 parts by weight of polypropylene and 20 parts by weight of talc. It is an example that does not include. Comparative Example 1 has a specific gravity of 1.05, a maximum point stress of 22.0 MPa in a tensile test, an evaluation “◯”, an elastic modulus of 2200 MPa, an evaluation “◯”, and an evaluation of scratch resistance “×”, and an overall evaluation “×”. Met. In Comparative Example 1 containing talc, the specific gravity was large, the elastic modulus (rigidity) was small, and the scratch resistance was poor compared to Example 4 containing organically modified clay.
比較例２は、ポリプロピレン９２．５重量部、酸変性ポリプロピレン５重量部、有機変性クレー２．５重量部（２．５重量％）からなる例である。比較例２は、比重０．９２、引張試験の最大点応力１８．５ＭＰａ、評価「×」、弾性率１７５０ＭＰａ、評価「×」、耐傷付き性の評価「〇」であり、総合評価「×」であった。比較例２は、有機変性クレーの量が、本発明における有機変性クレーの下限である３重量％よりも少ない２．５重量％であるため、引張試験の最大点応力及び弾性率(剛性)の何れも実施例１〜７と比べて悪くなった。 Comparative Example 2 is an example comprising 92.5 parts by weight of polypropylene, 5 parts by weight of acid-modified polypropylene, and 2.5 parts by weight (2.5% by weight) of organic-modified clay. Comparative Example 2 has a specific gravity of 0.92, a maximum point stress of 18.5 MPa in the tensile test, an evaluation “×”, an elastic modulus of 1750 MPa, an evaluation “×”, and an evaluation of scratch resistance “◯”, and a comprehensive evaluation “×”. Met. In Comparative Example 2, the amount of the organically modified clay is 2.5% by weight, which is lower than 3% by weight which is the lower limit of the organically modified clay in the present invention. Therefore, the maximum point stress and elastic modulus (rigidity) of the tensile test are All became worse compared with Examples 1-7.
このように、本発明のポリプロピレン樹脂組成物は、ポリプロピレン樹脂組成物中に、有機変性クレーを３〜３０重量％含み、タルクを含まないため、剛性及、耐傷付き性及び軽量性に優れ、車両用部品としてのポリプロピレン樹脂成形体に好適な素材である。 Thus, since the polypropylene resin composition of the present invention contains 3 to 30% by weight of the organically modified clay and does not contain talc in the polypropylene resin composition, it is excellent in rigidity, scratch resistance, and light weight. It is a material suitable for a polypropylene resin molded body as a part for use.
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| JP2002167484A (en) * | 2000-12-04 | 2002-06-11 | Japan Polychem Corp | Polypropylene based resin composition and production method therefor |
| JP2003253126A (en) * | 2002-01-08 | 2003-09-10 | Idemitsu Petrochem Co Ltd | Thermoplastic resin composition |
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