JP2006225529A - Manufacturing method of polyolefin aqueous dispersion system and additive for coating agent containing polyolefin aqueous dispersion system obtained therewith - Google Patents
Manufacturing method of polyolefin aqueous dispersion system and additive for coating agent containing polyolefin aqueous dispersion system obtained therewith Download PDFInfo
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本発明はポリオレフィン水性分散系の製造方法及びその方法で得られたポリオレフィン水性分散系の用途に関し、より詳しくは、粗大粒子を含み、かつ密度が０.９９ｇ／ｃｍ3以下のポリオレフィンの水性分散系から粗大粒子が除去されたポリオレフィン水性分散系を製造する方法、及びその方法で得られるポリオレフィンの水性分散系を含むコーティング剤用添加剤に関する。 The present invention relates to a method for producing an aqueous polyolefin dispersion and uses of the aqueous polyolefin dispersion obtained by the method, and more specifically, an aqueous polyolefin dispersion containing coarse particles and having a density of 0.99 g / cm 3 or less. The present invention relates to a method for producing an aqueous polyolefin dispersion from which coarse particles have been removed, and an additive for a coating agent comprising the aqueous polyolefin dispersion obtained by the method.
ポリオレフィン水性分散系はコーティング材料耐摩剤として使用しており、近年ではこれらの分野では光沢性や透明性などの意匠性が求められている。例えば、数平均分子量１０，０００以下のポリオレフィン水性分散系は耐摩剤、離型剤、潤滑剤等として使用されているが、粒子径１.５μｍ以上の粒子を含むと光沢が悪化し造膜性や透明性を損なうなどの課題があった。しかしながら、粒子径１.５〜１０μｍの粗大粒子は、従来の濾紙やメッシュを用いて濾過する方法では除去は困難であった。 Polyolefin aqueous dispersions are used as antiwear agents for coating materials, and in recent years, design properties such as glossiness and transparency are required in these fields. For example, an aqueous polyolefin dispersion having a number average molecular weight of 10,000 or less is used as an anti-wear agent, a release agent, a lubricant, etc., but if it contains particles having a particle size of 1.5 μm or more, the gloss deteriorates and the film forming property is increased. And problems such as loss of transparency. However, it has been difficult to remove coarse particles having a particle diameter of 1.5 to 10 μm by a conventional filtering method using filter paper or mesh.
粗大粒子を除去する方法としては、従来より、遠心分離を用いる方法が提案されている（特許文献１，２，３）。これらの方法は、何れもタンパク質、水系顔料、シリカ粒子などの水よりも密度の高い物質を除去する方法であって、遠心分離後の上澄み液を回収することで粗大粒子を除去している。しかしながら、水より密度の低いポリオレフィンの粗大粒子を除去する方法は報告されていない。 As a method for removing coarse particles, methods using centrifugation have been proposed (Patent Documents 1, 2, and 3). Each of these methods is a method for removing a substance having a higher density than water, such as protein, water-based pigment, silica particles, and the like, and removing coarse particles by collecting the supernatant after centrifugation. However, a method for removing coarse polyolefin particles having a density lower than that of water has not been reported.
一般に、粒子径の異なる粗大粒子の除去方法としては、沈降法、濾過法、遠心分離法の慣性の原理に基づく方法が有る。これらの方法の中で、沈降法では、密度が０.９９ｇ／ｃｍ3以下のポリオレフィンの水性分散系から粒子径１.５μｍ以上の粒子の分離を行う場合、数か月単位の時間がかかる。また、濾過法で行う場合は、使用した濾過やフィルターの目詰まりが起こり効率的でない。遠心分離法については、水性分散系から密度が０.９９ｇ／ｃｍ3以下の粒子を除去する方法は知られていない。しかしながら、遠心分離法は、一般的に、数十秒で分離可能であり、時間当りの処理量も多く有効であることから、水性分散系から密度が０.９９ｇ／ｃｍ3以下の粒子を除去すること可能であれば、非常に有用な粒子調製方法である。 In general, as a method for removing coarse particles having different particle diameters, there are methods based on the principle of inertia of sedimentation, filtration, and centrifugation. Among these methods, in the sedimentation method, when separating particles having a particle diameter of 1.5 μm or more from an aqueous dispersion of polyolefin having a density of 0.99 g / cm 3 or less, it takes several months. Moreover, when performing by a filtration method, the used filtration and the filter are clogged, and it is not efficient. As for the centrifugal separation method, there is no known method for removing particles having a density of 0.99 g / cm 3 or less from an aqueous dispersion. However, since the centrifugal separation method can generally be separated in several tens of seconds and has a large throughput per hour, it is effective to remove particles having a density of 0.99 g / cm 3 or less from the aqueous dispersion. If possible, it is a very useful particle preparation method.
本発明の課題は、粗大粒子を含み、かつ密度が０.９９ｇ／ｃｍ3以下のポリオレフィンの水性分散系から粗大粒子が除去されたポリオレフィン水性分散系を製造する方法、及び耐摩性、離型性、潤滑性に優れ、さらに、造膜性に優れるとともに、光沢や透明性を維持するコーティング剤用添加剤を提供することにある。 An object of the present invention is to provide a method for producing an aqueous polyolefin dispersion in which coarse particles are removed from an aqueous dispersion of polyolefin containing coarse particles and having a density of 0.99 g / cm 3 or less, and abrasion resistance and releasability. An object of the present invention is to provide an additive for a coating agent that is excellent in lubricity, further excellent in film-forming properties, and maintains gloss and transparency.
本発明者らは前記課題を解決するために鋭意検討した結果、粗大粒子を含み、かつ密度が０.９９ｇ／ｃｍ3以下のポリオレフィンの水性分散系を遠心分離することにより、粗大粒子が密度の低い軽液側より除去され、粒子径の小さい粒子が密度の高い重液側より回収できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have determined that the coarse particles have a density by centrifuging an aqueous dispersion of polyolefin containing coarse particles and having a density of 0.99 g / cm 3 or less. The present invention was completed by finding that particles having a small particle diameter removed from the low light liquid side can be recovered from the heavy liquid side having a high density.
すなわち、本発明は、
粗大粒子を含み、かつ密度が０.９９ｇ／ｃｍ3以下のポリオレフィンの水性分散系から粗大粒子が除去されたポリオレフィン水性分散系を製造する方法であって、遠心分離法により粗大粒子を含む液を密度の低い軽液側より除去し、粒子径の小さい粒子を含む液を密度の高い重液側より回収する、粗大粒子が除去されたポリオレフィン水性分散系の製造方法、
並びに、
前記の方法で得られるポリオレフィンの水性分散系を含むコーティング剤用添加剤
である。
That is, the present invention
A method for producing an aqueous polyolefin dispersion in which coarse particles are removed from an aqueous dispersion of polyolefin having coarse particles and a density of 0.99 g / cm 3 or less, wherein a liquid containing coarse particles is obtained by centrifugal separation. A method for producing an aqueous polyolefin dispersion from which coarse particles have been removed, wherein a liquid containing particles having a small particle diameter is removed from a light liquid side having a low density and recovered from a heavy liquid side having a high density.
And
An additive for a coating agent comprising an aqueous dispersion of polyolefin obtained by the above method.
本発明のポリオレフィン水性分散系の製造方法においては、水よりも密度の低い０.９９ｇ／ｃｍ3以下のポリオレフィン水性分散系は遠心分離により、粒子径の大きい粒子は優先的に上澄み液である軽液側に分離され、粒子径の小さい粒子は重液側に分離されずに残る。上記原理を利用して回収した軽液は、粒子径１.５μｍ以上の粗大粒子が除去されており、その含有量は０.０１％以下に調整される。本ポリオレフィン水性分散系をコーティング材料の添加剤として使用した場合、粗大粒子が造膜性、透明性・光沢性に優れた皮膜を形成する。さらに、数平均分子量１０，０００以下であり結晶化度が２０％以上であるポリオレフィン水性分散系を添加剤として使用した場合、耐摩性、離型性、潤滑性に優れ、かつ透明性・光沢性に優れる。 In the method for producing an aqueous polyolefin dispersion of the present invention, an aqueous polyolefin dispersion having a density of 0.99 g / cm 3 or less, which is lower than that of water, is obtained by centrifugation, and particles having a large particle size are preferentially a supernatant. Particles that are separated to the liquid side and have a small particle diameter remain without being separated to the heavy liquid side. In the light liquid recovered using the above principle, coarse particles having a particle diameter of 1.5 μm or more are removed, and the content thereof is adjusted to 0.01% or less. When this polyolefin aqueous dispersion is used as an additive for a coating material, coarse particles form a film excellent in film forming property, transparency and glossiness. Further, when an aqueous polyolefin dispersion having a number average molecular weight of 10,000 or less and a crystallinity of 20% or more is used as an additive, it is excellent in abrasion resistance, releasability and lubricity, and is transparent and glossy. Excellent.
以下に、本発明について詳細に説明する。 The present invention is described in detail below.
本発明における粒子径とは粒子の直径のことをいい、動的光散乱式粒子径分布測定装置やマイクロトラック粒度分布測定装置を使用して測定することができる。 The particle diameter in the present invention refers to the particle diameter, and can be measured using a dynamic light scattering particle size distribution measuring device or a microtrack particle size distribution measuring device.
本発明におけるポリオレフィン水性分散系の製造方法は、ポリオレフィン水性分散系を回転体内に供給して遠心力で分離し、分離した液体を連続的に排出する遠心分離機において、粒子径１.５μm以上の粗大粒子を密度の低い軽液側より除去し、密度の高い重液側より連続的に回収する、遠心分離機による粗大粒子を除去する方法である。密度の低い軽液側と密度の高い重液側の排出比率は５０／５０〜１０／９０であると粒子径１.５μｍ以上の粗大粒子が効率よく除去され、回収率も高い。さらに、高効率で粗大粒子を分級するには回転数が３０００ｒｐｍ以上であることが望ましい。また、分散系の滞留時間は１０秒以上であることが粗大粒子の除去効率を高める点で望ましい。また、分散効率を高める上で分散系の粘度は１００ｃｐｓ以下であることが望ましく、５０ｃｐｓ以下であることが更に望ましい。 In the method for producing a polyolefin aqueous dispersion in the present invention, a polyolefin aqueous dispersion is supplied into a rotating body, separated by centrifugal force, and the separated liquid is continuously discharged. In this method, coarse particles are removed from the light liquid side having a low density and continuously collected from the heavy liquid side having a high density, and the coarse particles are removed by a centrifugal separator. When the discharge ratio between the light liquid side with low density and the heavy liquid side with high density is 50/50 to 10/90, coarse particles having a particle diameter of 1.5 μm or more are efficiently removed, and the recovery rate is also high. Furthermore, in order to classify coarse particles with high efficiency, it is desirable that the rotational speed is 3000 rpm or more. Further, the residence time of the dispersion system is preferably 10 seconds or more from the viewpoint of increasing the removal efficiency of coarse particles. In order to increase the dispersion efficiency, the viscosity of the dispersion system is desirably 100 cps or less, and more desirably 50 cps or less.
遠心分離法に用いる遠心分離機は特に限定されるものではないが、中でも回転体内に多数の分離板を積層した分離板群を装着し、分離板群の大きい沈降面積を利用して微粒子などを効率よく分離することができる分離板型遠心分離機が望ましい。 The centrifuge used for the centrifugal separation method is not particularly limited, but in particular, a separation plate group in which a large number of separation plates are stacked in a rotating body is mounted, and particulates etc. are collected using the large sedimentation area of the separation plate group. A separation plate type centrifuge capable of efficient separation is desirable.
本発明におけるポリオレフィンとは例えば、エチレン、プロピレン、1−ブテン、3−メチル−1−ブテン、4−メチル−1−ペンテン、3−メチル−1−ペンテン、1−ヘプテン、1−ヘキセン、1−オクテン、1−デセン、1−ドデセン等のα−オレフィン；ブタジエン、エチリデンノルボルネン、ジシクロペンタジエン、１，５−ヘキサジエン等の共役ジエン、非共役ジエンが挙げられ、さらに、スチレン、酢酸ビニル、ビニルアルコールなどの単量体を単独又は２種以上組み合わせて重合することができる重合物である。具体的にはポリエチレン、ポリプロピレン、ポリブテン、エチレン・プロピレン共重合体、エチレン・酢酸ビニル共重合体、エチレン・エチルアクリレート共重合体、エチレン・ビニルアルコール共重合体、エチレン・スチレン共重合体などが挙げられる。 Examples of the polyolefin in the present invention include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1- Α-olefins such as octene, 1-decene, 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, non-conjugated dienes, and styrene, vinyl acetate, vinyl alcohol It is a polymer which can superpose | polymerize monomer, such as these individually or in combination of 2 or more types. Specific examples include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, and ethylene / styrene copolymer. It is done.
さらに上記重合物にエチレン性不飽和単量体がグラフトしたり、酸素または酸素含有ガスを用いて溶融状態で酸化したり、ハロゲン化アルカリ金属を用いてハロゲン化することで得られる変性物も含まれる。 Also included are modified products obtained by grafting ethylenically unsaturated monomers onto the above polymer, oxidizing in the molten state using oxygen or an oxygen-containing gas, or halogenating using an alkali metal halide. It is.
本発明における粗大粒子を含むポリオレフィン水性分散系とは通常、粒子径１０ｎｍ〜１０μｍの粒子が水に分散した組成物のことである。ポリオレフィン水性分散系の製造方法としては特に限定されるものではないが、各種の乳化方法を利用することが望ましい。具体的に例えばポリオレフィン及び界面活性剤又はカルボキシル基を有する重合体を溶剤に溶解後高圧ホモジナイザー、高圧ホモミキサー等により乳化後溶剤を除去する方法、オレフィン系重合体を溶融状態にして高圧ホモジナイザー、高圧ホモミキサー、押出混練機により乳化する方法、α−オレフィン及び（メタ）アクリル酸の共重合体及びカリウム、ナトリウム、アンモニウムなどのアルカリ物質をオートクレーブ中で乳化する方法、その他機械的に粉砕する方法、高圧で噴射粉砕する方法、細孔より噴霧させる方法などが挙げられる。 The polyolefin aqueous dispersion containing coarse particles in the present invention is usually a composition in which particles having a particle diameter of 10 nm to 10 μm are dispersed in water. The method for producing the aqueous polyolefin dispersion is not particularly limited, but it is desirable to use various emulsification methods. Specifically, for example, a method in which a polyolefin and a surfactant or a polymer having a carboxyl group are dissolved in a solvent and then emulsified with a high-pressure homogenizer, a high-pressure homomixer or the like, and the solvent is removed after being emulsified. A method of emulsifying with a homomixer, an extrusion kneader, a method of emulsifying a copolymer of α-olefin and (meth) acrylic acid and an alkaline substance such as potassium, sodium, ammonium, etc. in an autoclave, other methods of mechanically pulverizing, Examples thereof include a method of spraying and pulverizing at a high pressure and a method of spraying from fine pores.
本発明により粗大粒子を除去したポリオレフィン水性分散系は各種コーティング剤の添加剤として用いる事ができるか、本分散系を添加剤の耐摩擦性、離型性、潤滑性を発揮するにはポリオレフィンの数平均分子量は６００〜１０,０００であることが望ましい。ポリオレフィンの数平均分子量（Ｍｎ）とはゲル浸透クロマトグラフィー（ＧＰＣ）により測定することで求められる数平均分子量のことをいう。 The polyolefin aqueous dispersion from which coarse particles have been removed according to the present invention can be used as an additive for various coating agents, or the polyolefin can be used for exhibiting the friction resistance, releasability and lubricity of the additive. The number average molecular weight is desirably 600 to 10,000. The number average molecular weight (Mn) of a polyolefin means the number average molecular weight calculated | required by measuring by gel permeation chromatography (GPC).
粗大粒子調整工程により粗大粒子を除去したポリオレフィン水性分散系は各種・コーティング剤の添加剤として用いられ、本分散系を添加剤の耐摩擦性、離型性、潤滑性を発揮するにはポリオレフィンの結晶化度が２０％以上であることが望ましい。結晶化度とは、Ｘ線回折装置により測定することで求められる結晶化度のことをいう。 Aqueous polyolefin dispersions from which coarse particles have been removed by the coarse particle adjustment step are used as additives for various coating agents, and this dispersion can be used to demonstrate the friction resistance, mold release and lubricity of additives. It is desirable that the crystallinity is 20% or more. The crystallinity refers to the crystallinity determined by measuring with an X-ray diffractometer.
本発明におけるコーティング剤とはスプレー、カーテン、フローコーター、ロールコーター、グラビアコーター、刷毛塗り、浸漬等の各種方法にて、樹脂、金属、紙、木材、繊維、皮革、ガラス、ゴムなどに塗工することにより積層体を構成する。具体的には、オーバープリントワニス、保護コート剤などが挙げられるが、一般的に透明性が高く、高光沢であることが望まれている。粒子径１.５μm以上の粗大粒子を除去したポリオレフィン水性分散系を用いると、高光沢でかつ透明性に優れる点で望ましい。 The coating agent in the present invention is applied to resin, metal, paper, wood, fiber, leather, glass, rubber, etc. by various methods such as spray, curtain, flow coater, roll coater, gravure coater, brush coating, and dipping. By doing so, a laminated body is constituted. Specifically, an overprint varnish, a protective coating agent, and the like can be mentioned. Generally, high transparency and high gloss are desired. Use of an aqueous polyolefin dispersion from which coarse particles having a particle diameter of 1.5 μm or more are removed is desirable because of high gloss and excellent transparency.
［実施例］
以下、実施例により本発明を更に詳しく説明するが、本発明はこれら実施例に限られるものではない。尚、実施例及び比較例における「部」、「％」は、特に断りのない限り質量基準である。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.
以下に本発明で用いた分析方法および物性測定方法を記す。
１．粗大粒子含有量（％）
マイクロトラックＵＰＡ（ＨＯＮＥＹＷＥＬＬ社製）にて、粒子径を測定し、粒子径が１.４９９μｍ〜７０４.０μｍまでの累積頻度を求めた。
２．数平均分子量
数平均分子量（Ｍn）は以下のようにして測定した。分離カラムとして、ＴＳＫ ＧＮＨ ＨＴであり、カラムサイズは直径７．５ｍｍ、長さ３００ｍｍのものを使用した。カラム温度は１４０℃とし、移動相にはオルトジクロルベンゼン(和光純薬)及び酸化防止剤としてＢＨＴ(武田薬品)０．０２５％を用い、１．０ｍｌ／分で移動させた。試料濃度は０．１％とし、試料注入量は５００マイクロリットルとした。検出器として示差屈折計を用いた。標準ポリスチレンは東ソー社製を用いた。
３．結晶化度
ポリオレフィン水性分散系を乾燥後（厚さ１mm）のスペーサを用いて、２００℃でホットプレスした直後、２０℃冷却プレスで１００kg／cm2 の荷重下に５分間冷却した後１週間後、Ｘ線回折装置（ＲＩＮＴ２５００ リガク社製）により測定した。
４．光沢度
有効成分１０％のポリオレフィン水性分散系１０部及びアクリルエマルション（Ｊｏｎｃｒｙｌ７７ ジョンソンポリマー社製）６５部、アクリル水溶液（Ｊｏｎｃｒｙｌ６０ ジョンソンポリマー社製）３０部を混合し、コーティング組成物を調整した。本組成物を隠ペイ率試験紙に膜厚が５μｍとなるように塗工し、２５℃にて２４時間乾燥した。その後、光沢度計（VG１０ 日本電色工業製）にて６０℃の反射率を観測した。
The analysis method and physical property measurement method used in the present invention are described below.
1. Coarse particle content (%)
The particle diameter was measured with Microtrac UPA (manufactured by HONEYWELL), and the cumulative frequency from 1.499 μm to 704.0 μm was determined.
2. Number average molecular weight The number average molecular weight (Mn) was measured as follows. The separation column was TSK GNH HT, and the column size was 7.5 mm in diameter and 300 mm in length. The column temperature was 140 ° C., orthodichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase and 0.025% BHT (Takeda Pharmaceutical) was used as the antioxidant, and the mobile phase was moved at 1.0 ml / min. The sample concentration was 0.1% and the sample injection volume was 500 microliters. A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation.
3. Crystallinity Immediately after hot drying at 200 ° C. using a spacer after drying the aqueous polyolefin dispersion (thickness 1 mm), after cooling for 5 minutes under a load of 100 kg / cm 2 with a 20 ° C. cooling press, one week later And an X-ray diffractometer (RINT2500 manufactured by Rigaku Corporation).
4). Glossiness 10 parts of an aqueous polyolefin dispersion containing 10% active ingredient, 65 parts of an acrylic emulsion (manufactured by Joncryl 77 Johnson Polymer) and 30 parts of an aqueous acrylic solution (manufactured by Joncryl 60 Johnson Polymer) were mixed to prepare a coating composition. This composition was coated on a hidden pay rate test paper so as to have a film thickness of 5 μm, and dried at 25 ° C. for 24 hours. Thereafter, the reflectance at 60 ° C. was observed with a gloss meter (VG10, Nippon Denshoku Industries Co., Ltd.).
粗大粒子を２.５％含むポリオレフィン水性分散系（ケミパールＷ４００５ 三井化学社製）を１５％に希釈し、ディスク型遠心分離機（ＬＡＰＸ２０２Ｂ アルファラバル社製）を用いて回転数１０，０００ｒｐｍにて軽液側／重液側＝３０／７０の比率で排出し、重液側を分取し、粗大粒子を除去したポリオレフィン水性分散系1を得た。得たポリオレフィン水性分散系の有効成分は１０％であり、粗大粒子含有量、数平均分子量（Ｍn）、結晶化度、光沢度を測定した。測定結果を表1に示す。 A polyolefin aqueous dispersion containing 2.5% coarse particles (Chemipearl W4005, Mitsui Chemicals) is diluted to 15% and lightly rotated at 10,000 rpm using a disk-type centrifuge (LAPX202B Alfa Laval). The liquid side / heavy liquid side was discharged at a ratio of 30/70, the heavy liquid side was separated, and a polyolefin aqueous dispersion 1 from which coarse particles were removed was obtained. The active component of the obtained aqueous polyolefin dispersion was 10%, and the coarse particle content, number average molecular weight (Mn), crystallinity, and gloss were measured. Table 1 shows the measurement results.
粗大粒子を４．１％含むポリオレフィン水性分散系（ケミパールＷ９００ 三井化学社製）を１５％に希釈し、ディスク型遠心分離機（ＬＡＰＸ２０２Ｂ アルファラバル社製）を用いて回転数１０，０００ｒｐｍにて軽液側／重液側＝３０／７０の比率で排出し、重液側を分取し、粗大粒子を除去したポリオレフィン水性分散系２を得た。得たポリオレフィン水性分散系の有効成分は１０％であり、粗大粒子含有量、数平均分子量（Ｍn）、結晶化度、光沢度を測定した。測定結果を表1に示す。 A polyolefin aqueous dispersion containing 4.1% coarse particles (Chemipearl W900, Mitsui Chemicals) is diluted to 15% and lightly rotated at 10,000 rpm using a disk-type centrifuge (LAPX202B Alfa Laval). It discharged | emitted by the ratio of the liquid side / heavy liquid side = 30/70, the heavy liquid side was fractionated, and the polyolefin aqueous dispersion 2 which removed the coarse particle was obtained. The active component of the obtained aqueous polyolefin dispersion was 10%, and the coarse particle content, number average molecular weight (Mn), crystallinity, and gloss were measured. Table 1 shows the measurement results.
粗大粒子を２.５％含むポリオレフィン水性分散系（ケミパールＷ４００５ 三井化学社製）を１５％に希釈し、ディスク型遠心分離機（ＬＡＰＸ２０２Ｂ アルファラバル社製）を用いて回転数１０，０００ｒｐｍにて軽液側／重液側＝７０／３０の比率で排出し、重液側を分取し、粗大粒子を除去したポリオレフィン水性分散系３を得た。得たポリオレフィン水性分散系の有効成分は１０％であり、粗大粒子含有量、数平均分子量（Ｍn）、結晶化度、光沢度を測定した。測定結果を表1に示す。 A polyolefin aqueous dispersion containing 2.5% coarse particles (Chemipearl W4005, Mitsui Chemicals) is diluted to 15% and lightly rotated at 10,000 rpm using a disk-type centrifuge (LAPX202B Alfa Laval). It discharged | emitted by the ratio of the liquid side / heavy liquid side = 70/30, the heavy liquid side was fractionated, and the polyolefin aqueous dispersion 3 which removed the coarse particle was obtained. The active component of the obtained aqueous polyolefin dispersion was 10%, and the coarse particle content, number average molecular weight (Mn), crystallinity, and gloss were measured. Table 1 shows the measurement results.
［比較例１］
粗大粒子を２．５％含むポリオレフィン水性分散系（ケミパールＷ４００５ 三井化学社製）を１０％に希釈し、メンブランフィルター（ＴＳＴＰ０２５ ミリポア社製）を用いて除去を試みたが、フィルターが詰り連続的に回収できなかった。
[Comparative Example 1]
Polyolefin aqueous dispersion containing 2.5% coarse particles (Chemipearl W4005, Mitsui Chemicals) was diluted to 10%, and removal was attempted using a membrane filter (TSTP025 Millipore). It could not be recovered.
○ 光沢度８５％以上 ○ Glossiness 85% or more
本発明のポリオレフィン水性分散系の製造方法によれば、水よりも密度の低い０.９９ｇ／ｃｍ3以下のポリオレフィン水性分散系は遠心分離法により、粒子径の大きい粒子は優先的に上澄み液である軽液側に分離され、粒子径の小さい粒子は重液側に分離されずに残る。 According to the method for producing a polyolefin aqueous dispersion of the present invention, a polyolefin aqueous dispersion having a density lower than that of water of 0.99 g / cm 3 or less is obtained by centrifugal separation, and particles having a large particle size are preferentially obtained as a supernatant. Particles with a small particle size separated on the light liquid side remain without being separated on the heavy liquid side.
従って、上記原理を利用して回収した重液は、粒子径１.５μｍ以上の粗大粒子が除去されており、その含有量は通常０.０１％以下に調整される。 Therefore, the heavy liquid recovered using the above principle has coarse particles having a particle diameter of 1.5 μm or more removed, and the content thereof is usually adjusted to 0.01% or less.
本発明の方法により得られるポリオレフィン水性分散系をコーティング材料の添加剤として使用した場合、造膜性、透明性・光沢性に優れた皮膜を形成する。さらに、数平均分子量１０，０００以下であり結晶化度が２０％以上であるポリオレフィン水性分散系を添加剤として使用した場合、耐摩性、離型性、潤滑性に優れ、かつ透明性・光沢性に優れる。 When the polyolefin aqueous dispersion obtained by the method of the present invention is used as an additive for a coating material, a film excellent in film forming property, transparency and glossiness is formed. Further, when an aqueous polyolefin dispersion having a number average molecular weight of 10,000 or less and a crystallinity of 20% or more is used as an additive, it is excellent in abrasion resistance, releasability and lubricity, and is transparent and glossy. Excellent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07155510A (en) * | 1993-10-13 | 1995-06-20 | Fine Kurei:Kk | Method for classifying suspended particles |
| JP2000219749A (en) * | 1999-01-29 | 2000-08-08 | Dainippon Ink & Chem Inc | Aqueous pigment dispersion and aqueous recording liquid |
| JP2003335905A (en) * | 2002-05-22 | 2003-11-28 | Unitika Ltd | Aqueous dispersion, method for producing the same and ultraviolet light-shading film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07155510A (en) * | 1993-10-13 | 1995-06-20 | Fine Kurei:Kk | Method for classifying suspended particles |
| JP2000219749A (en) * | 1999-01-29 | 2000-08-08 | Dainippon Ink & Chem Inc | Aqueous pigment dispersion and aqueous recording liquid |
| JP2003335905A (en) * | 2002-05-22 | 2003-11-28 | Unitika Ltd | Aqueous dispersion, method for producing the same and ultraviolet light-shading film |
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