JP2006104278A - Resin composition containing inorganic fine particle - Google Patents

Resin composition containing inorganic fine particle Download PDF

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JP2006104278A
JP2006104278A JP2004291088A JP2004291088A JP2006104278A JP 2006104278 A JP2006104278 A JP 2006104278A JP 2004291088 A JP2004291088 A JP 2004291088A JP 2004291088 A JP2004291088 A JP 2004291088A JP 2006104278 A JP2006104278 A JP 2006104278A
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resin composition
propylene polymer
inorganic fine
fine particles
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JP4661155B2 (en
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Hiroshi Nozawa
博 野澤
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Sumitomo Chemical Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which contains a propylene polymer resin and inorganic fine particles and is excellent in dispersibility of the inorganic fine particles. <P>SOLUTION: The resin composition is obtained by melt kneading (A) 80-99 pts.wt. propylene polymer resin having a melt tension ratio at 190°C of ≥1.6 and (B) 1-20 pts.wt. inorganic fine particles against 100 pts.wt. total weight of (A) the propylene polymer resin and (B) the inorganic fine particles. A film made of a thermoplastic resin composition containing the resin composition and a thermoplastic resin (other than the resin composition) is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、プロピレン重合体樹脂と無機微粒子とを含有する樹脂組成物に関するものである。さらに詳しくは、無機微粒子の分散性に優れる樹脂組成物に関するものである。   The present invention relates to a resin composition containing a propylene polymer resin and inorganic fine particles. More specifically, the present invention relates to a resin composition excellent in dispersibility of inorganic fine particles.

従来から、熱可塑性樹脂を用いて得られるフィルムやシートには、ブロッキングを防止するために無機微粒子が用いられている。
例えば、特開平8−92424号公報には、平均粒子径が50〜500μで100μ以下の微粒子の割合が10重量%以上のオレフィン重合体粒子に無機系微粉末3.0〜25.0重量%を配合し、溶融混練したポリオレフィンフィルム用マスターバッチであって、アンチブロッキング剤の分散性が良好でフィルムの外観、透明性、耐ブロッキング性、耐傷付き性の良好なポリオレフィンフィルム用マスターバッチが記載されている。
Conventionally, inorganic fine particles have been used in films and sheets obtained using thermoplastic resins in order to prevent blocking.
For example, JP-A-8-92424 discloses an inorganic fine powder of 3.0 to 25.0% by weight to olefin polymer particles having an average particle diameter of 50 to 500 μm and a proportion of fine particles of 100 μm or less of 10% by weight or more. A masterbatch for polyolefin film, which is a melt-kneaded polyolefin film masterbatch, which has good anti-blocking agent dispersibility and good film appearance, transparency, blocking resistance and scratch resistance, is described. ing.

さらに、特開2003−170420号公報には、混合割合が特定の範囲である熱可塑性樹脂と無機微粒子を、特定の混合温度で混合した後、溶融混練する樹脂組成物の製造方法であって、無機微粒子の濃度が高く、無機微粒子の分散性に優れる樹脂組成物の製造方法が記載されている。   Furthermore, JP-A-2003-170420 discloses a method for producing a resin composition in which a thermoplastic resin having a mixing ratio in a specific range and inorganic fine particles are mixed at a specific mixing temperature and then melt-kneaded. A method for producing a resin composition having a high concentration of inorganic fine particles and excellent dispersibility of the inorganic fine particles is described.

さらに、特開2003−171565号公報には、重量平均粒子径が特定の範囲であり、粒子径が特定の範囲である粒子の割合が特定の範囲である熱可塑性樹脂と無機微粒子を含む樹脂組成物であって、粉体としての取り扱いが容易で、無機微粒子の分散性に優れる樹脂組成物が記載されている。   Furthermore, JP-A No. 2003-171565 discloses a resin composition containing a thermoplastic resin and inorganic fine particles in which the weight average particle diameter is in a specific range and the ratio of the particles having a specific particle diameter is in a specific range. A resin composition that is easy to handle as a powder and excellent in dispersibility of inorganic fine particles is described.

特開平8−92424号公報JP-A-8-92424 特開2003−170420号公報JP 2003-170420 A 特開2003−171565号公報JP 2003-171565 A

しかし、上記公報等に記載されている樹脂組成物においても、無機微粒子の分散性については、改良が望まれていた。
かかる状況の下、本発明の目的は、プロピレン重合体樹脂と無機微粒子とを含有し、無機微粒子の分散性に優れる樹脂組成物を提供することにある。
However, even in the resin composition described in the above publications and the like, it has been desired to improve the dispersibility of the inorganic fine particles.
Under such circumstances, an object of the present invention is to provide a resin composition containing a propylene polymer resin and inorganic fine particles and having excellent dispersibility of the inorganic fine particles.

本発明者らは鋭意検討の結果、本発明が、上記の課題を解決できることを見出し、本発明を完成させるに至った。
すなわち、本発明は、
190℃におけるメルトテンション比が1.6以上であるプロピレン重合体樹脂(A)と無機微粒子(B)とを溶融混練して得られる樹脂組成物であって、前記プロピレン重合体樹脂(A)と前記無機微粒子(B)の重量の合計100重量部に対して、前記プロピレン重合体樹脂(A)80〜99重量部と前記無機微粒子(B)1〜20重量部とを溶融混練して得られる樹脂組成物、および、前記樹脂組成物と熱可塑性樹脂(但し、前記樹脂組成物を除く)を含有する熱可塑性樹脂組成物からなるフィルムに係るものである。
As a result of intensive studies, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.
That is, the present invention
A resin composition obtained by melt-kneading a propylene polymer resin (A) having a melt tension ratio at 190 ° C. of 1.6 or more and inorganic fine particles (B), the propylene polymer resin (A) and Obtained by melt-kneading 80 to 99 parts by weight of the propylene polymer resin (A) and 1 to 20 parts by weight of the inorganic fine particles (B) with respect to a total of 100 parts by weight of the inorganic fine particles (B). The present invention relates to a resin composition and a film made of a thermoplastic resin composition containing the resin composition and a thermoplastic resin (excluding the resin composition).

本発明によれば、プロピレン重合体樹脂と無機微粒子とを含有し、無機微粒子の分散性に優れる樹脂組成物、および、前記樹脂組成物と熱可塑性樹脂(但し、前記樹脂組成物を除く)を含有する熱可塑性樹脂組成物からなるフィルムを得ることができる。   According to the present invention, a resin composition containing a propylene polymer resin and inorganic fine particles and having excellent dispersibility of the inorganic fine particles, and the resin composition and the thermoplastic resin (however, excluding the resin composition) A film made of the thermoplastic resin composition contained can be obtained.

本発明で用いられるプロピレン重合体樹脂(A)は、プロピレンを主成分とする単量体を重合して得られる重合体であり、プロピレン単独重合体、プロピレン−エチレン共重合体、プロピレンと炭素原子数4〜12のα−オレフィンの共重合体、プロピレンとエチレンと炭素原子数4〜12のα−オレフィンの三元共重合体等が挙げられる。これらの重合体は単独で用いてもよく、少なくとも2種を併用しても良い。   The propylene polymer resin (A) used in the present invention is a polymer obtained by polymerizing a monomer mainly composed of propylene, and is a propylene homopolymer, a propylene-ethylene copolymer, propylene and a carbon atom. Examples thereof include copolymers of α-olefins of 4 to 12 and terpolymers of propylene, ethylene and α-olefins of 4 to 12 carbon atoms. These polymers may be used alone or in combination of at least two kinds.

プロピレン−エチレン共重合体におけるエチレン含量は、プロピレン−エチレン共重合体の全重量を100重量%として、当該全重量に対して0.1重量%〜10重量%のものを用いることができる。   The ethylene content in the propylene-ethylene copolymer may be 0.1 wt% to 10 wt% with respect to 100 wt% of the total weight of the propylene-ethylene copolymer.

プロピレンと炭素原子数4〜12のα−オレフィンの共重合体において、炭素原子数4〜12のα−オレフィンとしては、例えば、ブテン−1、ヘキセン−1、オクテン−1等が挙げられ、α−オレフィン含量は、プロピレンと炭素原子数4〜12のα−オレフィンの共重合体の全重量を100重量%として、当該全重量に対して0.1重量%〜30重量%が挙げられる。プロピレンと炭素原子数4〜12のα−オレフィンの共重合体としては、例えばプロピレン−ブテン−1共重合体、プロピレン−ヘキセン−1共重合体等が挙げられる。   In the copolymer of propylene and an α-olefin having 4 to 12 carbon atoms, examples of the α-olefin having 4 to 12 carbon atoms include butene-1, hexene-1, octene-1, and the like. -The olefin content may be 0.1 wt% to 30 wt% based on the total weight of the copolymer of propylene and the α-olefin copolymer having 4 to 12 carbon atoms as 100 wt%. Examples of the copolymer of propylene and an α-olefin having 4 to 12 carbon atoms include propylene-butene-1 copolymer and propylene-hexene-1 copolymer.

プロピレンとエチレンと炭素原子数4〜12のα−オレフィンの三元共重合体において、エチレン含量は、三元共重合体の全重量を100重量%として、当該全重量に対して0.1重量%〜10重量%のものを用いることができる。炭素原子数4〜12のα−オレフィンとしては、例えば、ブテン−1、ヘキセン−1、オクテン−1等が挙げられ、α−オレフィン含量は、三元共重合体の全重量に対して0.1重量%〜30重量%が挙げられる。プロピレンとエチレンと炭素原子数4〜12のα−オレフィンの三元共重合体としては、例えば、プロピレン−エチレン−ブテン−1共重合体、プロピレン−エチレン−ヘキセン−1共重合体等が挙げられる。   In the terpolymer of propylene, ethylene, and an α-olefin having 4 to 12 carbon atoms, the ethylene content is 0.1% by weight based on the total weight of the terpolymer as 100% by weight. % To 10% by weight can be used. Examples of the α-olefin having 4 to 12 carbon atoms include butene-1, hexene-1, octene-1, and the like, and the α-olefin content is 0. 0 relative to the total weight of the terpolymer. 1 wt% to 30 wt% is mentioned. Examples of the terpolymer of propylene, ethylene, and α-olefin having 4 to 12 carbon atoms include propylene-ethylene-butene-1 copolymer and propylene-ethylene-hexene-1 copolymer. .

本発明で用いられるプロピレン重合体樹脂(A)は、190℃におけるメルトテンション比が1.6以上である。フィルムの外観を良好なものにするという観点から、好ましくは、1.6以上3.0以下である。より好ましくは1.8以上3.0以下である。1.6未満であると無機微粒子の分散性が不十分なことがある。   The propylene polymer resin (A) used in the present invention has a melt tension ratio at 190 ° C. of 1.6 or more. From the viewpoint of improving the appearance of the film, it is preferably 1.6 or more and 3.0 or less. More preferably, it is 1.8 or more and 3.0 or less. If it is less than 1.6, the dispersibility of the inorganic fine particles may be insufficient.

本発明で用いられるプロピレン重合体樹脂(A)のメルトテンション比とは、下記の調整条件で調整されるメルトテンション測定用ペレットを用いて、東洋精機社製溶融張力測定機によって、下記の測定条件で測定されるメルトテンションについて、下記の式から算出されるものである。   The melt tension ratio of the propylene polymer resin (A) used in the present invention is the following measurement conditions using a melt tension measuring machine manufactured by Toyo Seiki Co., Ltd. using pellets for melt tension measurement adjusted under the following adjustment conditions. Is calculated from the following equation.

〔メルトテンション測定用ペレットの調整条件〕
プロピレン重合体100重量部に、ステアリン酸カルシウム0.05重量部、酸化防止剤イルガノックス1010(チバ・スペシャリティ・ケミカル社製)0.2重量部、酸化防止剤スミライザーGP(住友化学工業株式会社製)0.1重量部を加え、40mm単軸押出機で230℃で溶融混練することによりペレットを得る。
[Conditions for melt tension measurement pellets]
100 parts by weight of propylene polymer, 0.05 parts by weight of calcium stearate, 0.2 parts by weight of antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals), antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by weight is added and pellets are obtained by melting and kneading at 230 ° C. with a 40 mm single screw extruder.

〔メルトテンションの測定条件〕
上記で調整されたペレットのメルトテンションを東洋精機社製溶融張力測定機を用いて、下記条件で測定する。
内径9.55mmのシリンダに、長さ8.00mm、内径2.10mmのオリフィスを取り付ける。シリンダにプロピレン重合体樹脂を充填し、ピストンを挿入して190℃で5分間予熱し十分に融解させる。5.7mm/分の速度でピストンを降下させ、オリフィスからの樹脂を滑車を通して所定の速度で引き取り、滑車とつりあう荷重の重さ(g)をロードセルで測定しメルトテンションとする。
[Melt tension measurement conditions]
The melt tension of the pellets adjusted as described above is measured under the following conditions using a melt tension measuring machine manufactured by Toyo Seiki Co., Ltd.
An orifice having a length of 8.00 mm and an inner diameter of 2.10 mm is attached to a cylinder having an inner diameter of 9.55 mm. Fill the cylinder with propylene polymer resin, insert the piston and preheat at 190 ° C. for 5 minutes to melt sufficiently. The piston is lowered at a speed of 5.7 mm / min, the resin from the orifice is taken through the pulley at a predetermined speed, and the weight (g) of the load that balances with the pulley is measured with a load cell to obtain the melt tension.

〔メルトテンション比〕
メルトテンション比は以下の式で計算する。
メルトテンション比=(引き取り速度28.3m/分のメルトテンション(g))/(引き取り速度3.2m/分のメルトテンション(g))
[Melt tension ratio]
The melt tension ratio is calculated by the following formula.
Melt tension ratio = (Melt tension (g) of take-up speed 28.3 m / min) / (Melt tension (g) of take-up speed 3.2 m / min)

プロピレン重合体樹脂(A)は、チーグラー・ナッタ触媒や、メタロセン触媒などを用いて、原料となるプロピレンやエチレンを重合させる事によって得られる。プロピレン重合体樹脂(A)の製造は、ヘキサン、ヘプタン、トルエン、キシレンなどの不活性溶剤中で行う方法や、液状のプロピレンやエチレン中で重合を行う方法、または気体となったプロピレンやエチレン中に触媒を添加し、気相状態で製造する方法、またはこれらの組み合わせによる方法によって行うことができる。   The propylene polymer resin (A) is obtained by polymerizing propylene and ethylene as raw materials using a Ziegler-Natta catalyst, a metallocene catalyst, or the like. The production of the propylene polymer resin (A) is carried out in an inert solvent such as hexane, heptane, toluene, xylene, a method in which polymerization is carried out in liquid propylene or ethylene, or a gas in propylene or ethylene. The method can be carried out by a method in which a catalyst is added to the catalyst and produced in a gas phase, or a combination thereof.

プロピレン重合体樹脂(A)として、好ましくは、極限粘度が5dL/g以上の結晶性プロピレン重合体部分(a)を製造する工程および極限粘度が3dL/g未満の結晶性プロピレン重合体部分(b)を製造する工程を含む重合方法により得られるプロピレン重合体(C)である。   The propylene polymer resin (A) is preferably a step of producing a crystalline propylene polymer portion (a) having an intrinsic viscosity of 5 dL / g or more and a crystalline propylene polymer portion (b) having an intrinsic viscosity of less than 3 dL / g. ) Is a propylene polymer (C) obtained by a polymerization method including a step of producing.

該プロピレン重合体(C)に含有される結晶性プロピレン重合体部分(a)の割合として、好ましくは0.05〜35重量%であり(但し、プロピレン重合体(C)の全重量を100重量%とする)、該プロピレン重合体(C)の極限粘度として、好ましくは3dL/g未満である。   The proportion of the crystalline propylene polymer portion (a) contained in the propylene polymer (C) is preferably 0.05 to 35% by weight (provided that the total weight of the propylene polymer (C) is 100% by weight) %), And the intrinsic viscosity of the propylene polymer (C) is preferably less than 3 dL / g.

結晶性プロピレン重合体部分(a)の極限粘度として、無機微粒子の分散性に優れるという本発明の効果が大きいという観点から、さらに好ましくは、7dL/g以上である。   The intrinsic viscosity of the crystalline propylene polymer portion (a) is more preferably 7 dL / g or more from the viewpoint that the effect of the present invention that the inorganic fine particles are excellent in dispersibility is great.

また、プロピレン重合体(C)の極限粘度として、加工機の負荷を少なくするという観点や、フィルムの外観を良好なものにするという観点から、さらに好ましくは、2dL/g以下である。   Further, the intrinsic viscosity of the propylene polymer (C) is more preferably 2 dL / g or less from the viewpoint of reducing the load on the processing machine and improving the appearance of the film.

本発明で用いられる無機微粒子(B)は、具体的には、二酸化ケイ素、アルミノシリケート、タルク等のケイ酸マグネシウム、カオリン等のケイ酸アルミニウム、ホウ酸アルミニウム、炭酸カルシウム等が挙げられる。この中でも、無機微粒子の分散性に優れるという本発明の効果が大きいという観点から、好ましくは二酸化ケイ素である。   Specific examples of the inorganic fine particles (B) used in the present invention include magnesium silicate such as silicon dioxide, aluminosilicate, and talc, aluminum silicate such as kaolin, aluminum borate, and calcium carbonate. Among these, silicon dioxide is preferred from the viewpoint that the effect of the present invention, which is excellent in dispersibility of inorganic fine particles, is great.

本発明で用いられる無機微粒子(B)の平均粒子径や見掛け比重は、フィルムの外観、耐ブロッキング性や耐傷つき性を良好にするという観点から、平均粒子径として、好ましくは1〜10μmであり、見掛け比重として、好ましくは0.1〜1g/ccである。   The average particle diameter and apparent specific gravity of the inorganic fine particles (B) used in the present invention are preferably 1 to 10 μm as the average particle diameter from the viewpoint of improving the appearance of the film, blocking resistance and scratch resistance. The apparent specific gravity is preferably 0.1 to 1 g / cc.

本発明の樹脂組成物に含有されるプロピレン重合体樹脂(A)と無機微粒子(B)の含有量は、プロピレン重合体樹脂(A)と無機微粒子(B)の重量の合計100重量部に対して、プロピレン重合体樹脂(A)の含有量が80〜99重量部であり、無機微粒子(B)の含有量が1〜20重量部である。好ましくは、プロピレン重合体樹脂(A)の含有量が90〜98重量部であり、無機微粒子(B)の含有量が2〜10重量部である。
プロピレン重合体樹脂(A)の含有量が80重量部未満の場合(即ち、無機微粒子(B)の含有量が20重量部を超えた場合)、無機微粒子(B)の分散性が不充分なことがある。また、プロピレン重合体樹脂(A)の含有量が99重量部を超えた場合(即ち、無機微粒子(B)の含有量が1重量部未満の場合)、フィルムなどの製品に用いる場合に大量に添加しなければ耐ブロッキング性が改良されず、製品としての価値が低いものとなることがある。
The content of the propylene polymer resin (A) and the inorganic fine particles (B) contained in the resin composition of the present invention is 100 parts by weight in total of the weight of the propylene polymer resin (A) and the inorganic fine particles (B). The content of the propylene polymer resin (A) is 80 to 99 parts by weight, and the content of the inorganic fine particles (B) is 1 to 20 parts by weight. Preferably, the content of the propylene polymer resin (A) is 90 to 98 parts by weight, and the content of the inorganic fine particles (B) is 2 to 10 parts by weight.
When the content of the propylene polymer resin (A) is less than 80 parts by weight (that is, when the content of the inorganic fine particles (B) exceeds 20 parts by weight), the dispersibility of the inorganic fine particles (B) is insufficient. Sometimes. In addition, when the content of the propylene polymer resin (A) exceeds 99 parts by weight (that is, when the content of the inorganic fine particles (B) is less than 1 part by weight), a large amount is used for products such as films. If not added, the blocking resistance is not improved, and the product value may be low.

本発明の樹脂組成物の製造方法は、プロピレン重合体樹脂(A)と無機微粒子(B)とを溶融混練する方法である。
溶融混練に用いられる装置としては、例えば、一軸の溶融押出機、二軸以上の多軸の溶融押出機、バンバリーミキサー等が挙げられ、好ましくは二軸以上の多軸押出機である。
溶融混練方法に関しては熱可塑性樹脂の融点以上の温度で溶融混練する方法であれば良く、例えば、以下の方法が挙げられる。
(1)タンブラーミキサー、スーパーミキサー、ヘンシェルミキサー、スクリューブレンダー、リボンブレンダー等などの公知の混合装置を用いて予備混合した後、上記溶融混練に用いられる装置を用いて溶融混練する方法。
(2)上記溶融混練に用いられる装置にプロピレン重合体樹脂(A)と、無機微粒子(B)を単位時間あたり一定の量比で同時に投入して溶融混練する方法。
(3)上記溶融混練に用いられる装置を用いて、あらかじめプロピレン重合体樹脂(A)のみを溶融させ、その状態に無機微粒子(B)を投入する方法。
The method for producing a resin composition of the present invention is a method in which a propylene polymer resin (A) and inorganic fine particles (B) are melt-kneaded.
Examples of the apparatus used for melt kneading include a uniaxial melt extruder, a biaxial or higher multiaxial melt extruder, and a Banbury mixer, and a biaxial or higher multiaxial extruder is preferable.
Any melt kneading method may be used as long as it is a melt kneading method at a temperature equal to or higher than the melting point of the thermoplastic resin. Examples thereof include the following methods.
(1) A method of pre-mixing using a known mixing device such as a tumbler mixer, super mixer, Henschel mixer, screw blender, ribbon blender or the like and then melt-kneading using the device used for the melt kneading.
(2) A method in which the propylene polymer resin (A) and the inorganic fine particles (B) are simultaneously charged at a constant quantity ratio per unit time into the apparatus used for the melt kneading.
(3) A method in which only the propylene polymer resin (A) is melted in advance using the apparatus used for the melt kneading, and the inorganic fine particles (B) are put into the state.

本発明の樹脂組成物には、必要な場合には、金属石けん、塩素補足剤、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、滑剤、難燃剤、核剤、顔料などの添加剤を加えてもよい。   If necessary, the resin composition of the present invention includes addition of metal soap, chlorine scavenger, antioxidant, ultraviolet absorber, light stabilizer, antistatic agent, lubricant, flame retardant, nucleating agent, pigment, etc. An agent may be added.

本発明の樹脂組成物は、押出成形、射出成形、発泡成形、中空成形等の幅広い用途に好適に用いることができる。中でも押出成形に、好適に用いられる。
本発明の樹脂組成物と熱可塑性樹脂(但し、前記の本発明の樹脂組成物を除く)とを含有する熱可塑性樹脂組成物も、押出成形、射出成形、発泡成形、中空成形等の幅広い用途に好適に用いることができる。
特に、本発明の樹脂組成物と熱可塑性樹脂(但し、前記の本発明の樹脂組成物を除く)とを含有する熱可塑性樹脂組成物は、押出成形に好適に用いられ、無機微粒子の分散が良好なフィルムが得られる。この場合、前記熱可塑性樹脂組成物としては、前記熱可塑性樹脂組成物の重量の合計100重量部に対して、本発明の樹脂組成物0.1〜30重量部と、前記熱可塑性樹脂(但し、前記の本発明の樹脂組成物を除く)70〜99.9重量部とを含有する熱可塑性樹脂組成物が好ましい。
そして、前記熱可塑性樹脂組成物を混合し、押出成形することによって、特に無機微粒子の分散が良好なフィルムが効率的に得られる。
また、前記熱可塑性樹脂組成物に含有される上記の熱可塑性樹脂(但し、前記の本発明の樹脂組成物を除く)として、無機微粒子の分散性に優れるという本発明の効果が大きいという観点から、無機微粒子を含まない熱可塑性樹脂、または、無機微粒子の含有量が1重量%以下である熱可塑性樹脂が好ましい。
The resin composition of the present invention can be suitably used for a wide range of applications such as extrusion molding, injection molding, foam molding, and hollow molding. Among these, it is suitably used for extrusion molding.
The thermoplastic resin composition containing the resin composition of the present invention and a thermoplastic resin (excluding the above-described resin composition of the present invention) is also widely used for extrusion molding, injection molding, foam molding, hollow molding and the like. Can be suitably used.
In particular, a thermoplastic resin composition containing the resin composition of the present invention and a thermoplastic resin (excluding the above-described resin composition of the present invention) is suitably used for extrusion molding, and dispersion of inorganic fine particles is achieved. A good film is obtained. In this case, the thermoplastic resin composition includes 0.1 to 30 parts by weight of the resin composition of the present invention and 100 parts by weight of the thermoplastic resin (provided that the total weight of the thermoplastic resin composition is 100 parts by weight). And a thermoplastic resin composition containing 70 to 99.9 parts by weight (excluding the resin composition of the present invention).
And the film with especially favorable dispersion | distribution of an inorganic fine particle is efficiently obtained by mixing the said thermoplastic resin composition and extrusion-molding.
In addition, as the above-described thermoplastic resin (excluding the above-described resin composition of the present invention) contained in the thermoplastic resin composition, from the viewpoint that the effect of the present invention is excellent in dispersibility of inorganic fine particles. A thermoplastic resin containing no inorganic fine particles or a thermoplastic resin having an inorganic fine particle content of 1% by weight or less is preferred.

以下、本発明について、実施例および比較例を用いて説明する。なお、発明の詳細な説明および実施例および比較例における各項目の測定値は、下記の方法で測定した。   Hereinafter, the present invention will be described using examples and comparative examples. The detailed description of the invention and the measured values of each item in the examples and comparative examples were measured by the following methods.

(1)MFR(単位:g/10分)
JIS K7210に準拠し、温度230℃、荷重2.16kgfで測定した。
(1) MFR (unit: g / 10 minutes)
According to JIS K7210, the temperature was 230 ° C. and the load was 2.16 kgf.

(2)メルトテンション(単位:g)
メルトテンション測定用ペレットは以下の条件で調整した。
プロピレン重合体100重量部に、ステアリン酸カルシウム0.05重量部、酸化防止剤イルガノックス1010(チバ・スペシャリティ・ケミカル社製)0.2重量部、酸化防止剤スミライザーGP(住友化学工業株式会社製)0.1重量部を加え、40mm単軸押出機で230℃で溶融混練することによりペレットを得た。
このペレットのメルトテンションを東洋精機社製溶融張力測定機を用いて、下記条件で測定した。
内径9.55mmのシリンダに、長さ8.00mm、内径2.10mmのオリフィスを取り付けた。シリンダにプロピレン重合体樹脂を充填し、ピストンを挿入して190℃で5分間予熱し十分に融解させた。5.7mm/分の速度でピストンを降下させ、オリフィスからの樹脂を滑車を通して所定の速度で引き取り、滑車とつりあう荷重の重さ(g)をロードセルで測定しメルトテンションとした。
メルトテンション比は以下の式で計算した。
メルトテンション比=(引き取り速度28.3m/分のメルトテンション(g))/(引き取り速度3.2m/分のメルトテンション(g))
(2) Melt tension (unit: g)
The pellet for melt tension measurement was adjusted under the following conditions.
100 parts by weight of propylene polymer, 0.05 parts by weight of calcium stearate, 0.2 parts by weight of antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals), antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) Pellets were obtained by adding 0.1 parts by weight and melt kneading at 230 ° C. with a 40 mm single screw extruder.
The melt tension of the pellet was measured under the following conditions using a melt tension measuring machine manufactured by Toyo Seiki Co., Ltd.
An orifice having a length of 8.00 mm and an inner diameter of 2.10 mm was attached to a cylinder having an inner diameter of 9.55 mm. The cylinder was filled with propylene polymer resin, the piston was inserted, and preheated at 190 ° C. for 5 minutes to be sufficiently melted. The piston was lowered at a speed of 5.7 mm / min, the resin from the orifice was taken through the pulley at a predetermined speed, and the weight (g) of the load balanced with the pulley was measured with a load cell to obtain the melt tension.
The melt tension ratio was calculated by the following formula.
Melt tension ratio = (Melt tension (g) of take-up speed 28.3 m / min) / (Melt tension (g) of take-up speed 3.2 m / min)

(3)プロピレン重合体(C)に含有される結晶性プロピレン重合体部分(a)の割合
重合時の物質収支から求めた。
(3) Proportion of crystalline propylene polymer portion (a) contained in propylene polymer (C) The proportion was determined from the material balance during polymerization.

(4)極限粘度(単位:dL/g)
ウベローデ型粘度計を用いて135℃テトラリン中で測定を行った。なお、プロピレン重合体(C)にのうち、結晶性プロピレン重合体部分(b)の極限粘度は、成分(a)および全体のプロピレン系重合体の極限粘度より以下の計算式より求めた。
[η]b=([η]C×100−[η]a× Wa)/Wb
[η]C:結晶性プロピレン系重合体全体(C)の極限粘度
[η]a:成分(a)の極限粘度
Wa:成分(a)の含量(重量%)
Wb:成分(b)の含量(重量%)
(4) Intrinsic viscosity (unit: dL / g)
The measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer. In the propylene polymer (C), the intrinsic viscosity of the crystalline propylene polymer portion (b) was determined from the following formula using the intrinsic viscosity of the component (a) and the entire propylene polymer.
[η] b = ([η] C × 100− [η] a × Wa) / Wb
[η] C: Intrinsic viscosity of the entire crystalline propylene polymer (C)
[η] a: Intrinsic viscosity of component (a) Wa: Content of component (a) (% by weight)
Wb: Content of component (b) (% by weight)

(5)エチレン含量(単位:重量%)
高分子ハンドブック(1995年、紀伊国屋書店発行)の616ページに記載されている方法により求めた。
(5) Ethylene content (unit:% by weight)
It was determined by the method described on page 616 of the Polymer Handbook (1995, published by Kinokuniya Shoten).

(6)フィルム外観
フィルムを5枚重ねたものについて200cm2あたり、目視により確認できるフィッシュアイの個数を計測した。20個以上のものを「不良」、20個以下の物を「良好」とした。
(6) Film appearance The number of fish eyes that can be confirmed by visual observation was measured per 200 cm 2 of a stack of five films. 20 or more were rated as “bad” and 20 or less were rated as “good”.

(8)透明性(ヘイズ、単位:%)
JIS K7105に従い測定した。この値が小さいほど、透明性が良好であり無機微粒子が微分散していると判断される。
(8) Transparency (haze, unit:%)
It measured according to JIS K7105. It is judged that the smaller this value, the better the transparency and the finely dispersed inorganic fine particles.

(9)透明性(LSI、単位:%)
株式会社東洋精機製作所社製視覚透明度試験機(LIGHT SCATTERING METER)を用いて、フィルムの透過光のうち、−1.2°〜−0.4°、0.4°〜1.2°の散乱光を求めた。この値が小さいほど、透明性が良好であり無機微粒子が微分散していると判断される。
(9) Transparency (LSI, unit:%)
Using a visual transparency tester (LIGHT SCATTERING METER) manufactured by Toyo Seiki Seisakusho Co., Ltd., scattering of −1.2 ° to −0.4 ° and 0.4 ° to 1.2 ° in the transmitted light of the film Sought light. It is judged that the smaller this value, the better the transparency and the finely dispersed inorganic fine particles.

(実施例1)
〔プロピレン重合体樹脂(A)の製造〕
チーグラー・ナッタ型触媒を用いて第1工程で極限粘度が8dL/gのプロピレン単独重合体部分(a)を製造した(極限粘度は重合槽からの抜き取り物を測定することによって求めた)後、触媒を失活させずに、触媒と第一の成分を第2工程へ移し、第2工程で極限粘度が1.3dL/gである成分であるプロピレン単独重合体部分(b)を製造した。最終的に得られた重合体(C)の極限粘度は1.9dL/gであり、重合体(C)に占める極限粘度が8dL/gのプロピレン単独重合体部分(a)は10重量%であった。
このプロピレン重合体樹脂のメルトテンション比は2.2、MFRは13g/10分であった。
(Example 1)
[Production of propylene polymer resin (A)]
After producing a propylene homopolymer portion (a) having an intrinsic viscosity of 8 dL / g in the first step using a Ziegler-Natta type catalyst (the intrinsic viscosity was determined by measuring an extract from the polymerization tank), Without deactivating the catalyst, the catalyst and the first component were transferred to the second step, and a propylene homopolymer portion (b), which was a component having an intrinsic viscosity of 1.3 dL / g, was produced in the second step. The intrinsic viscosity of the finally obtained polymer (C) is 1.9 dL / g, and the propylene homopolymer part (a) having an intrinsic viscosity of 8 dL / g in the polymer (C) is 10% by weight. there were.
The propylene polymer resin had a melt tension ratio of 2.2 and an MFR of 13 g / 10 min.

〔樹脂組成物の製造およびフィルム製膜〕
プロピレン重合体樹脂(A)100重量部を、20Lヘンシェルミキサー(川田製作所製)内で80℃まで予熱し、無機微粒子としてサイリシア420(富士シリシア化学製、平均粒子径3μm、見掛け比重0.2g/cc)2.3重量部、酸化防止剤イルガノックス1010(チバ・スペシャリティ・ケミカル社製)0.05重量部、イルガフォス168(チバ・スペシャリティ・ケミカル社製)0.50重量部を加え、535rpm、80℃で3分間混合した。(なお、プロピレン重合体樹脂(A)が100重量部であり、無機微粒子であるサイリシア420が2.3重量部であることから、プロピレン重合体樹脂(A)とサイリシア420の合計100重量部に対するプロピレン重合体樹脂(A)の含有量は、97.8重量部であり、サイリシア420の含有量は、2.2重量部である。)
この混合物をΦ30mm二軸混練機(TEX30:日鋼製作所製)で230℃で20Kg/時で混練し樹脂組成物を得た。製造時の粉体の取り扱い性は良好であった。
この組成物6重量部に、無機微粒子を含まないプロピレン−エチレン−ブテン−1共重合体(MFR=7)94重量部を加え、250℃でTダイを用いた厚さ30μmのフィルムを製膜した。得られたフィルムの外観は良好であり、ヘイズは1.2%、LSIは2.4%であった。
[Production of resin composition and film formation]
100 parts by weight of the propylene polymer resin (A) is preheated to 80 ° C. in a 20 L Henschel mixer (manufactured by Kawada Seisakusho), and as inorganic fine particles, Silysia 420 (manufactured by Fuji Silysia Chemical, average particle diameter of 3 μm, apparent specific gravity 0.2 g / cc) 2.3 parts by weight, 0.05 parts by weight of antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals), 0.50 part by weight of Irgaphos 168 (manufactured by Ciba Specialty Chemicals), and 535 rpm, Mix for 3 minutes at 80 ° C. (Note that since propylene polymer resin (A) is 100 parts by weight and silicia 420 as inorganic fine particles is 2.3 parts by weight, the total amount of propylene polymer resin (A) and silicia 420 is 100 parts by weight. (The content of the propylene polymer resin (A) is 97.8 parts by weight, and the content of the silicia 420 is 2.2 parts by weight.)
This mixture was kneaded at 230 ° C. at 20 Kg / hour with a Φ30 mm biaxial kneader (TEX30: manufactured by Nikko Seisakusho) to obtain a resin composition. The handleability of the powder during production was good.
94 parts by weight of propylene-ethylene-butene-1 copolymer (MFR = 7) containing no inorganic fine particles was added to 6 parts by weight of this composition, and a film having a thickness of 30 μm was formed using a T-die at 250 ° C. did. The appearance of the obtained film was good, the haze was 1.2%, and the LSI was 2.4%.

(比較例1)
〔プロピレン重合体樹脂(A)の製造〕
チーグラー・ナッタ型触媒を用いて極限粘度が1.7dL/gのエチレン−プロピレン共重合体(エチレン含量=4重量%)を製造した。
このプロピレン重合体樹脂のメルトテンション比は1.1、MFRは6g/10分であった。
〔樹脂組成物の製造およびフィルム製膜〕
実施例1と同様に行った。得られたフィルムの外観は不良であり、ヘイズは1.4%、LSIは3.8%であった。
(Comparative Example 1)
[Production of propylene polymer resin (A)]
An ethylene-propylene copolymer (ethylene content = 4% by weight) having an intrinsic viscosity of 1.7 dL / g was produced using a Ziegler-Natta type catalyst.
The propylene polymer resin had a melt tension ratio of 1.1 and an MFR of 6 g / 10 min.
[Production of resin composition and film formation]
The same operation as in Example 1 was performed. The appearance of the obtained film was poor, haze was 1.4%, and LSI was 3.8%.

(比較例2)
〔プロピレン重合体樹脂(A)の製造〕
チーグラー・ナッタ型触媒を用いて極限粘度が1.3dL/gのエチレン−プロピレン共重合体(エチレン含量=4重量%)を製造した。
このプロピレン重合体樹脂のメルトテンション比は1.2、MFRは26g/10分であった。
〔樹脂組成物の製造およびフィルム製膜〕
実施例1と同様に行った。得られたフィルムの外観は良好であり、ヘイズは1.5%、LSIは3.9%であった。
(Comparative Example 2)
[Production of propylene polymer resin (A)]
An ethylene-propylene copolymer (ethylene content = 4% by weight) having an intrinsic viscosity of 1.3 dL / g was produced using a Ziegler-Natta type catalyst.
This propylene polymer resin had a melt tension ratio of 1.2 and an MFR of 26 g / 10 min.
[Production of resin composition and film formation]
The same operation as in Example 1 was performed. The appearance of the obtained film was good, the haze was 1.5%, and the LSI was 3.9%.

本発明の要件を満足する実施例は、フィルムの外観が良好であり、ヘイズ、LSI等の透明性に優れていることから、無機微粒子の分散性に優れていることが分かる。
これに対して、本発明の要件を満足しない比較例1はフィルム外観及び透明性に劣り、比較例2も透明性に劣ることから、無機微粒子の分散性が不充分であることが分かる。
It can be seen that Examples satisfying the requirements of the present invention are excellent in dispersibility of inorganic fine particles since the film has good appearance and excellent transparency such as haze and LSI.
In contrast, Comparative Example 1 that does not satisfy the requirements of the present invention is inferior in film appearance and transparency, and Comparative Example 2 is also inferior in transparency, indicating that the dispersibility of the inorganic fine particles is insufficient.

Claims (4)

190℃におけるメルトテンション比が1.6以上であるプロピレン重合体樹脂(A)と無機微粒子(B)とを溶融混練して得られる樹脂組成物であって、前記プロピレン重合体樹脂(A)と前記無機微粒子(B)の重量の合計100重量部に対して、前記プロピレン重合体樹脂(A)80〜99重量部と前記無機微粒子(B)1〜20重量部とを溶融混練して得られる樹脂組成物。   A resin composition obtained by melt-kneading a propylene polymer resin (A) having a melt tension ratio at 190 ° C. of 1.6 or more and inorganic fine particles (B), the propylene polymer resin (A) and Obtained by melt-kneading 80 to 99 parts by weight of the propylene polymer resin (A) and 1 to 20 parts by weight of the inorganic fine particles (B) with respect to a total of 100 parts by weight of the inorganic fine particles (B). Resin composition. 無機微粒子が二酸化ケイ素である請求項1記載の樹脂組成物。   The resin composition according to claim 1, wherein the inorganic fine particles are silicon dioxide. プロピレン重合体樹脂(A)が、極限粘度が5dL/g以上の結晶性プロピレン重合体部分(a)を製造する工程および極限粘度が3dL/g未満の結晶性プロピレン重合体部分(b)を製造する工程を含む重合方法により得られるプロピレン重合体(C)であって、該プロピレン重合体(C)に含有される結晶性プロピレン重合体部分(a)の割合が0.05〜35重量%であり(但し、プロピレン重合体(C)の全重量を100重量%とする)、該プロピレン重合体(C)の極限粘度が3dL/g未満である請求項1記載の樹脂組成物。   Propylene polymer resin (A) produces a crystalline propylene polymer part (a) having an intrinsic viscosity of 5 dL / g or more and a crystalline propylene polymer part (b) having an intrinsic viscosity of less than 3 dL / g A propylene polymer (C) obtained by a polymerization method including a step of: a proportion of the crystalline propylene polymer portion (a) contained in the propylene polymer (C) is 0.05 to 35% by weight Yes (provided that the total weight of the propylene polymer (C) is 100% by weight), and the intrinsic viscosity of the propylene polymer (C) is less than 3 dL / g. 請求項1から3のいずれかに記載の樹脂組成物と熱可塑性樹脂(但し、請求項1から3のいずれかに記載の樹脂組成物を除く)とを含有する熱可塑性樹脂組成物からなるフィルムであって、前記熱可塑性樹脂組成物の重量の合計100重量部に対して、請求項1から3のいずれかに記載の樹脂組成物が0.1〜30重量部であり、前記熱可塑性樹脂が70〜99.9重量部である熱可塑性樹脂組成物からなるフィルム。   A film comprising a thermoplastic resin composition comprising the resin composition according to any one of claims 1 to 3 and a thermoplastic resin (excluding the resin composition according to any one of claims 1 to 3). The resin composition according to any one of claims 1 to 3 is 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the thermoplastic resin composition, and the thermoplastic resin Is a film comprising a thermoplastic resin composition having a weight of 70 to 99.9 parts by weight.
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JP2008260847A (en) * 2007-04-12 2008-10-30 Sumitomo Chemical Co Ltd Polypropylenic resin composition and film thereof

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