JP2006089590A - Pigment-dispersing resin and color masterbatch using the same - Google Patents
Pigment-dispersing resin and color masterbatch using the same Download PDFInfo
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本発明は、高速型混合機を用いて、ポリオレフィン樹脂を層流状態にして高速攪拌処理することにより得られる顔料分散樹脂、及び、該顔料分散樹脂に顔料を配合して得られるカラ−マスタ−バッチに関するものである。 The present invention relates to a pigment dispersion resin obtained by high-speed stirring treatment in a laminar flow state of a polyolefin resin using a high-speed mixer, and a color master obtained by blending a pigment into the pigment dispersion resin. It relates to batches.
従来よりポリオレフィン樹脂用着色剤として、有機顔料や無機顔料等の単独使用では、それ自体は微粒子であるが包装、運搬、貯蔵の際に凝集を生じ易く巨大な粒子に成長し易いという性質があり、一旦凝集が起こると通常の着色されるべきポリオレフィン樹脂とのブレンド工程で攪拌では、この凝集はほぐれない。
従って、ポリオレフィン樹脂中への顔料分散性が悪く、着色成形品はカラ−スペック、カラ−ストリ−ク等を生じて、品質が不安定となって好ましくない。
Conventionally, the use of organic pigments and inorganic pigments alone as a polyolefin resin colorant is a fine particle, but it tends to agglomerate during packaging, transportation, and storage, and it tends to grow into large particles. Once agglomeration occurs, this agglomeration is not loosened by stirring in the usual blending process with the polyolefin resin to be colored.
Therefore, the dispersibility of the pigment in the polyolefin resin is poor, and the colored molded product produces color specs, color streaks, etc., and the quality becomes unstable, which is not preferable.
そこで、有機顔料や無機顔料等の性質を考慮しポリオレフィン樹脂用着色剤としては、一般にドライカラ−、カラ−マスタバッチ等の形態で製造・使用されている。
ドライカラ−は、顔料にステアリン酸カルシウムやステアリン酸亜鉛等の金属石鹸等を混合機を用い、配合処理した粉末状着色剤であり、製造が容易な樹脂用着色剤として使用されている。
しかし、ドライカラ−は、製品として包装の仕方、包装品の貯蔵状態、貯蔵期間、季節等によって影響を受け凝集を生じ易く巨大な粒子に成長し易いという性質があり、これを防ぐことは困難なことである。
In view of the properties of organic pigments, inorganic pigments, and the like, the polyolefin resin colorant is generally produced and used in the form of a dry color, a color masterbatch or the like.
Dry color is a powdered colorant obtained by blending a pigment with a metal soap such as calcium stearate or zinc stearate using a mixer, and is used as a resin colorant that can be easily produced.
However, dry color is affected by the way of packaging, the storage state of the packaged product, the storage period, the season, etc., and has a property that it tends to agglomerate and grow into huge particles, and it is difficult to prevent this. That is.
更に、ドライカラ−を使用したポリオレフィン樹脂の着色成形では、ドライカラ−自体が飛散性大であって作業性が悪く取扱も容易でない。また、ポリオレフィン樹脂の着色成形では、被着色樹脂に均一に混合することが困難であり、顔料の分散不良が起こり着色むらを生じ易いという欠点がある。
そして具体的には、樹脂の着色成形の際に、混合機・成形機周辺の汚れ、作業者の汚れ、粉塵の吸い込みが問題となり、労働安全衛生上からも成形の際には細心の注意をもって作業を行うことが必要になっている。
Furthermore, in the coloring molding of polyolefin resin using a dry color, the dry color itself has a high scattering property, and workability is poor and handling is not easy. Further, in the coloring molding of polyolefin resin, it is difficult to uniformly mix with the resin to be colored, and there is a disadvantage that poor dispersion of the pigment occurs and color unevenness is likely to occur.
Specifically, when molding colored resin, dirt around the mixer / molding machine, dirt on the operator, and inhalation of dust become a problem. From the viewpoint of occupational safety and hygiene, careful attention should be paid during molding. It is necessary to do work.
一方、従来品のマスタ−バッチでは、顔料分散性を付与するためエチレンビスアマイド、ポリエチレンワックス、ポリプロピレンワックス等低分子量樹脂ワックス類を分散剤として、顔料粉末と配合して製造されている。
該マスタ−バッチを製造する際には、顔料粉末と上記の分散剤を、ロ−ル、ニ−ダ−、押出機等の高剪断力により混練して顔料の分散を図っているが、一旦乾燥した顔料粉末は粗大な二次凝集粒子として存在し易く、これら粗大粒子を改めて微細な粒子にして分散することは非常に困難である。しかも、有機顔料の場合には、吸油量が大であるため更に高濃度微分散が困難である。
On the other hand, conventional master batches are manufactured by blending with pigment powder using low molecular weight resin waxes such as ethylene bisamide, polyethylene wax and polypropylene wax as dispersants to impart pigment dispersibility.
In the production of the master batch, the pigment powder and the above dispersant are kneaded with a high shear force such as a roll, a kneader, an extruder, etc. to disperse the pigment. The dried pigment powder tends to exist as coarse secondary agglomerated particles, and it is very difficult to disperse these coarse particles into fine particles. In addition, in the case of organic pigments, the oil absorption is large, so that it is difficult to finely disperse at a high concentration.
しかも、上記の製造法で得られたポリオレフィン樹脂用マスタ−バッチでは、ポリオレフィン樹脂の着色成形で１０数ミクロン径で高速紡糸したり、フィルム化するなど高度な顔料分散性が求められる場合には、顔料分散不良による糸切れ、溶融紡糸機のフィルタ−の目詰まり、フイルムでの成形不良を起こし易い欠点がある。
そこで、近年、エチレンビスアマイド、ポリエチレンワックス、ポリプロピレンワックス等低分子量樹脂ワックスに代えて、分散剤として水を使用し、装置としてニ−ダや押出機を用いて所謂フラッシング法によるマスターバッチの製造法、即ち担体樹脂と粉末顔料を加熱混練する際に水を加えることにより、粉末顔料の凝集体に水分が浸透・破壊して得られる顔料合成時に近い粒径の顔料を担体樹脂中に配合した、分散性の良好な着色剤が得られるフラッシング法によるマスタ−バッチが盛ん商品化されている。
Moreover, in the polyolefin resin master batch obtained by the production method described above, when high pigment dispersibility is required such as high-speed spinning with a diameter of 10 or more microns by coloring molding of polyolefin resin, or forming into a film, There are drawbacks that yarn breakage due to poor pigment dispersion, clogging of a filter of a melt spinning machine, and molding failure in a film are likely to occur.
Therefore, in recent years, in place of low molecular weight resin waxes such as ethylene bisamide, polyethylene wax, polypropylene wax, etc., water is used as a dispersant, and a masterbatch production method by a so-called flushing method using a kneader or an extruder as a device. That is, by adding water when kneading the carrier resin and the powder pigment by heating, a pigment having a particle size close to that at the time of pigment synthesis obtained by allowing water to permeate and break into the aggregate of the powder pigment was blended in the carrier resin. Master batches by the flushing method that can obtain a colorant with good dispersibility are widely commercialized.
この様にして得られるフラッシング法のマスタ−バッチでは、被着色樹脂を用いて着色成形の際の操作性が容易であり、顔料分散性の優れた成形品が製造可能であり、市場での技術信頼度が最も優れた着色剤としての地位が確立されている。
しかし、フラッシング法マスタ−バッチの製造は、他の着色剤の製造工程に比べ、製造ライン及び作業が複雑であり、製造コストも著しく高価になっている。
In the master batch of the flushing method thus obtained, the operability at the time of color molding using the resin to be colored is easy, and a molded product having excellent pigment dispersibility can be produced. The position as the colorant with the highest reliability has been established.
However, in the production of the flushing method master batch, the production line and operation are complicated, and the production cost is remarkably high as compared with the production process of other colorants.
また、フラッシング法マスタ−バッチの製造は、製造ライン及び製造作業が複雑であるため、顔料品種の交換や色替えに変更することに多くの時間を要し、生産ラインの変更は容易でない欠点がある。
即ち、フラッシング法によるマスタ−バッチの製造では、混練→練肉→賦形工程と製造ラインが複雑で、それぞれで熱履歴をうけることが多く、担体樹脂自体も熱劣化を生じ易く、着色に際して被着色樹脂の物性を低下させる欠点もある。
In addition, the production of the flushing master batch is complicated in production line and production work, so it takes a lot of time to change the color of the pigment and change the color, and it is not easy to change the production line. is there.
That is, in the production of a master batch by the flushing method, the kneading → knitted meat → forming process and the production line are complicated, and each is often subjected to a thermal history. There is also a drawback of reducing the physical properties of the colored resin.
上記の非特許文献１では、マスタ−バッチが、ドライカラ−に比較し顔料分散性に優れていることが記載されている。
特許文献１では、マスタ−バッチとして使用する分散剤として、エチレンビスアマイド、ポリエチレンワックス又はポリプロピレンワックス等低分子量樹脂ワックス類を使用する方法が記載されている。
特許文献２では、分散剤に水を主成分とするフラッシング法によるマスタ−バッチの製法が記載されており、分散剤に水を使用して得られるマスタ−バッチが、顔料分散性が非常に良好であると述べられている。
In said nonpatent literature 1, it is described that a master batch is excellent in pigment dispersibility compared with a dry color.
Patent Document 1 describes a method of using low molecular weight resin waxes such as ethylene bisamide, polyethylene wax or polypropylene wax as a dispersant used as a master batch.
Patent Document 2 describes a method of producing a master batch by a flushing method in which water is the main component of the dispersant, and the master batch obtained using water as the dispersant has very good pigment dispersibility. It is stated that.
しかし、特許文献２にも記載の通り、フラッシング法によるマスタバッチの製法では、製造に高度な技術を持つた混練技術が必要で製造方法も複雑となっており、このため顔料銘柄や色替えの交換に多くの時間を要し、カラーマスタ−バッチ製品の迅速な生産には、不向きな製法である。
そこで本発明者らは、ドライカラ−を製造の際に使用する混合機の攪拌条件を鋭意検討して従来品のフラッシング法によるカラーマスタ−バッチと同等の顔料分散性に富み、しかも、ドライカラ−の製造法と同様な簡便な生産方法で、ポリオレフィン樹脂用カラーマスターバッチを製造することを検討したのである。
However, as described in Patent Document 2, the master batch production method by the flushing method requires a kneading technique with advanced technology and the production method is complicated. It takes a lot of time for replacement, and is not suitable for rapid production of color master-batch products.
Therefore, the present inventors have intensively studied the stirring conditions of the mixer used in the production of the dry color, and are rich in pigment dispersibility equivalent to the color master batch by the conventional flushing method. We studied the production of a color masterbatch for polyolefin resin by a simple production method similar to the production method.
しかし、従来より、ドライカラーの混合（配合）では、縦型円筒形の混合機として最も汎用な混合機であるヘンシェル型ミキサ−が一般に使用されているが、同装置による混合攪拌では、非特許文献２に記載の通り、混合物が（イ）容器側面に沿い一定周速度で攪拌されながら容器内側面に沿い持ち上げられた後に、（ロ）容器側面上部まで持ち上げられた混合物は、上部より容器底面に落下するというサイクルによる混合操作が連続して行われている。 However, the Henschel mixer, which is the most general-purpose mixer as a vertical cylindrical mixer, is generally used for dry color mixing (compounding). As described in Document 2, after the mixture was lifted along the inner surface of the container while being stirred at a constant circumferential speed along the side surface of the container, (b) The mixing operation by the cycle of falling to the top is continuously performed.
即ち、ヘンシェルミキサ−の混合操作では、混合速度が異なる（イ）及び（ロ）の２種類から構成されており、乱流を繰り返すことにより混合が行われている。
この事実は、非特許文献２でも、最上段の攪拌羽根より上面では攪拌により作り出された空気流のために混合物が浮遊した状態になり、均一分散性が困難となっていると、記載されている。
That is, the mixing operation of the Henschel mixer is composed of two types (a) and (b) with different mixing speeds, and mixing is performed by repeating turbulent flow.
This fact is also described in Non-Patent Document 2, where the mixture floats due to the air flow created by stirring above the uppermost stirring blade, making uniform dispersion difficult. Yes.
以上の通り、従来は、いずれも上記各種分散剤を交換することで優れた着色剤の製造を検討していたが、上記に示す様な各種の欠点があり好ましく無かった。
そこで本発明者は、今回、カラ−マスタ−バッチを製造の際に、顔料に配合するポリオレフィン樹脂（担体樹脂）について改質を試みることで、上記引例に示す各種の欠点を解消した着色剤の開発を検討したのである。
そこで、層流状攪拌が可能な高速型混合機を用いて、上記のポリオレフィン樹脂について攪拌処理を行った処、該樹脂は顔料との配合が容易であり、上記の各種分散剤を使用せずに、顔料の着色性に優れ、機械的物等に良好なカラーマスターバッチが容易に得られることを知見し、本発明品を完成したのである。
As described above, conventionally, the production of an excellent colorant has been studied by exchanging the above-mentioned various dispersants. However, there are various disadvantages as described above, which are not preferable.
Therefore, the present inventor has attempted to modify the polyolefin resin (carrier resin) to be blended with the pigment at the time of manufacturing the color master batch, and thereby the colorant that has solved the various drawbacks shown in the above reference. Development was considered.
Therefore, when the polyolefin resin is stirred using a high-speed mixer capable of laminar flow stirring, the resin can be easily blended with a pigment, and the above various dispersants are not used. In addition, the inventors have found that a color master batch excellent in pigment coloration and good in mechanical materials can be easily obtained, and completed the product of the present invention.
即ち、請求項１では、ポリオレフィン樹脂を、攪拌羽根先端部と攪拌槽内壁面との間隙が３〜３０ｍｍであり、且つ、回転する攪拌羽根の先端速度が２０〜６０ｍ／ｓｅｃを有する高速型混合機を用い、前記ポリオレフィン樹脂軟化点以下の温度で層流状の攪拌処理を行って得られる赤外線吸収スペクトルのピ−ク（全内部反射法＝ＡＴＲ法）が１５８０〜１６８０ｃｍ−１に存在することを特徴とする顔料分散樹脂を開発したのである。 That is, in claim 1, the polyolefin resin is mixed at high speed with a gap between the tip of the stirring blade and the inner wall surface of the stirring tank of 3 to 30 mm, and the tip speed of the rotating stirring blade is 20 to 60 m / sec. The infrared absorption spectrum peak (total internal reflection method = ATR method) obtained by performing laminar stirring at a temperature below the polyolefin resin softening point is 1580 to 1680 cm −1. We have developed a pigment-dispersed resin characterized by this.
本発明の顔料分散樹脂は、実施例にも記載の通り赤外線吸収スペクトル測定結果、特徴あるピ−クが１５８０〜１６８０ｃｍ−１に確認される樹脂である。
該顔料分散樹脂は、各実施例にも記載の通り分散剤を全く使用せず、本発明の顔料分散樹脂に顔料を直接配合することが可能な担体樹脂が発明したのである。
The pigment dispersion resin of the present invention is a resin in which a characteristic peak is confirmed at 1580 to 1680 cm −1 as a result of infrared absorption spectrum measurement as described in Examples.
As described in each example, the pigment dispersion resin does not use a dispersant at all, and the carrier resin capable of directly blending the pigment with the pigment dispersion resin of the present invention has been invented.
本発明で使用するポリオレフィン樹脂としては、従来より汎用の樹脂を使用して良く、具体的には、低密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン等のポリエチレン樹脂、ポリプリプロピレン単独重合体、エチレン−プロピレン共重合体、エチレン−α−オレフィン共重合体、エチレン酢酸ビニル共重合体、エチレン−酢酸ビニル共重合体、エチレン−メタクリル酸共重合体、エチレン−メタクリル酸エステル共重合体等が挙げられる。尚、使用するポリオレフィンの平均粒径は、本発明のより優れた効果を発揮する顔料分散樹脂を得るためには、５０μｍ〜４ｍｍが好ましい。 As the polyolefin resin used in the present invention, a conventionally used resin may be used. Specifically, a polyethylene resin such as low density polyethylene, high density polyethylene, linear low density polyethylene, etc. Polymer, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, etc. Is mentioned. The average particle size of the polyolefin used is preferably 50 μm to 4 mm in order to obtain a pigment-dispersed resin that exhibits the better effect of the present invention.
本発明で使用の高速型混合機は、攪拌羽根と攪拌槽との間隔が３〜３０ｍｍで、且つ、回転する攪拌羽根の先端速度が２０〜６０ ｍ／ｓｅｃを有し、一定方向へ層流状の周速度を発揮するものとして、数種類の混合機が挙げられるが、最も汎用な装置として米国特許３２６６７３８号に基づくもので米国 DRAISWERKE社製のモデルＧシリ−ズ装置、同モデルGＳシリ−ズ装置が挙げられる。
これらの混合機（装置）は、いずれも攪拌軸及び円筒形の槽を基盤に対して横向きに設置した所謂横型ミキサ−であり、層流状（一定スピ−ド）の周速度が容易に得られる。
The high-speed mixer used in the present invention has a gap between the stirring blade and the stirring tank of 3 to 30 mm, and the rotating stirring blade has a tip speed of 20 to 60 m / sec. There are several types of mixers that exhibit a peripheral speed, but the most versatile device is based on US Pat. No. 3,266,738, which is a model G series device manufactured by DRAISWERKE, USA, and the same model GS series. Apparatus.
Each of these mixers (equipment) is a so-called horizontal mixer in which a stirring shaft and a cylindrical tank are installed sideways with respect to the base, and a laminar flow (constant speed) peripheral speed can be easily obtained. It is done.
尚、攪拌軸及び円筒形の槽が基盤（地面）に対し縦型である縦型ミキサ−の場合でも、２０〜６０ｍ／ｓｅｃの周速度が得られ層流状攪拌処理が可能となる様に設計されたものであれば良く、例えば、ヘンシェルミキサ−の様な筒形槽が縦型に設置された場合でも、円筒槽の内側面のみに沿って一定方向への層流攪拌ができれば、本発明の顔料分散樹脂は、容易に得られるものである。 Even in the case of a vertical mixer in which the stirring shaft and the cylindrical tank are vertical to the base (ground), a peripheral speed of 20 to 60 m / sec can be obtained and laminar stirring can be performed. For example, even if a cylindrical tank such as a Henschel mixer is installed vertically, if the laminar flow stirring can be performed in a certain direction along only the inner surface of the cylindrical tank, The pigment dispersion resin of the invention can be easily obtained.
本発明で使用の混合機は、攪拌羽根先端部と円筒状壁面との間隔が３〜３０ｍｍの間隔であり、攪拌羽根は、複数段から構成されものが好ましい。該間隔が３ｍｍより狭いと攪拌処理の際に、ポリオレフィン樹脂に溶融塊状化を生じることが有り好ましくない。また、３０ｍｍより広いと攪拌処理が十分に行われず、本発明の顔料分散樹脂は得られない。
また、攪拌羽根の先端速度は２０〜６０ｍ／ｓｅｃが好ましく、２０ｍ／ｓｅｃより遅いと攪拌処理による応力が不十分で１５８０〜１６８０ｃｍ−１での赤外線吸収スペクトルが現れず本発明の顔料分散樹脂が得られない、また６０ｍ／ｓｅｃより速いとオレフィン樹脂が劣化し好ましくない。
In the mixer used in the present invention, the distance between the tip of the stirring blade and the cylindrical wall surface is 3 to 30 mm, and the stirring blade is preferably composed of a plurality of stages. If the distance is smaller than 3 mm, the polyolefin resin may be melted and agglomerated during the stirring process, which is not preferable. On the other hand, when the width is larger than 30 mm, the stirring treatment is not sufficiently performed and the pigment dispersion resin of the present invention cannot be obtained.
Further, the tip speed of the stirring blade is preferably 20 to 60 m / sec, and if it is slower than 20 m / sec, the stress due to the stirring treatment is insufficient and the infrared absorption spectrum at 1580 to 1680 cm −1 does not appear and the pigment dispersion resin of the present invention is used. If it is not obtained or faster than 60 m / sec, the olefin resin is deteriorated, which is not preferable.
請求項２において使用のポリエチレン系樹脂には、低密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、及び、これらポリエチレンの共重合体樹脂等が挙げられ、請求項１記載の赤外線吸収スペクトルのピ−クが１６００ｃｍ−１付近に存在することを特徴とするポリエチレン系樹脂を用い得られる顔料分散樹脂である。 Examples of the polyethylene-based resin used in claim 2 include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and copolymer resins of these polyethylenes. This is a pigment-dispersed resin obtained by using a polyethylene-based resin characterized by having a peak in the vicinity of 1600 cm −1 .
請求項３において使用のポリプロピレン系樹脂には、ポリプリプロピレン単独重合体、エチレン−プロピレン共重合体、エチレン−α−オレフィン共重合体等が挙げられ、請求項１記載の赤外線吸収スペクトルのピ−クが、１６５０ｃｍ−１付近に存在することを特徴とするポリプロピレ系樹脂を用い得られる顔料分散樹脂樹脂である。 Polypropylene homopolymers, ethylene-propylene copolymers, ethylene-α-olefin copolymers, etc. may be mentioned as the polypropylene resin used in claim 3, and the infrared absorption spectrum peak of claim 1 may be mentioned. Is a pigment-dispersed resin resin obtained by using a polypropylene resin characterized by being present in the vicinity of 1650 cm −1 .
本願発明の請求項１で得られた顔料分散樹脂について、該顔料分散樹脂を錠剤プレス機で薄膜化し、樹脂の二重結合に基づく吸収帯（例：ポリエチレン１６００ｃｍ−１、ポリプロピレン１６５０ｃｍ−１）をキイ−バンドとし、使用する樹脂の標準バンド（例：ポリエチレン１３６７ｃｍ−１、ポリプロピレン１１６７ｃｍ−１等）との強度比を算出すると、請求項２では０．１〜２が、請求項３では０．１〜２の数値が示されている。
請求項２及び３で得られる顔料分散樹脂は、従来、顔料との均一配合が容易でないポリオレフィン樹脂についても、実施例にも記載の通り分散剤を配合せず、顔料を直接に配合してカラ−マスタ−バッチが容易に製造可能である。
About the pigment dispersion resin obtained in claim 1 of the present invention, the pigment dispersion resin is made into a thin film by a tablet press and an absorption band (eg, polyethylene 1600 cm −1 , polypropylene 1650 cm −1 ) based on the double bond of the resin is formed. When a strength ratio with a standard band of a resin to be used (eg, polyethylene 1367 cm −1 , polypropylene 1167 cm −1, etc.) is calculated as a key band, 0.1 to 2 in claim 2, and 0.2 in claim 3. Numerical values of 1-2 are shown.
The pigment-dispersed resins obtained in claims 2 and 3 are conventionally used for polyolefin resins that are not easily blended uniformly with pigments, as described in the examples. -Master batches can be easily manufactured.
請求項４は、請求項１〜３記載の顔料分散樹脂に対し顔料を加えた混合物を、汎用の方法で押出機を用い溶融混練して、容易に得られるカラ−マスタ−バッチである。
本発明でのカラ−マスタ−バッチの製造では、従来から使用の添加剤としての分散剤を全く使用せずに、本発明の顔料分散樹脂を担体樹脂に代え顔料を直接配合することで、従来品のカラ−マスタ−バッチに全く分散性の劣らぬ優秀なカラ−マスタ−バッチが容易に得られるものである。
即ち、本発明のカラ−マスタ−バッチは、従来から分散剤として使用のエチレンビスアマイドや、ポリエチレンワックス、ポリプロピレンワックス等低分子量樹脂ワックス等の分散剤を全く配合せず、又、水を用いたフラッシング法で得られるカラ−マスタ−バッチに劣らぬ顔料分散性を提供するものである。
A fourth aspect of the present invention is a color master batch which can be easily obtained by melt-kneading a mixture obtained by adding a pigment to the pigment-dispersed resin according to any one of the first to third aspects using an extruder using a general-purpose method.
In the production of the color master batch according to the present invention, the pigment dispersion resin of the present invention is replaced with a carrier resin and the pigment is directly blended without using any dispersant as a conventionally used additive. An excellent color master batch having no dispersibility at all can be easily obtained.
That is, the color master batch of the present invention does not contain any dispersant such as ethylene bisamide, low molecular weight resin wax such as polyethylene wax and polypropylene wax, which has been conventionally used as a dispersant, and uses water. The pigment dispersibility is not inferior to the color master batch obtained by the flushing method.
本発明のカラーマスターバッチは、着色成形品の製造でも長時間操業しても何ら物性変化を生じない耐熱性に良好なカラ−マスタ−バッチを提供するものであり、上記の特徴を生かして各種成形品の用途に使用可能であり、紡糸やフィルム成形品として最適である。
本発明のカラ−マスタ−バッチは、従来から使用の各種分散剤使用した場合に発生する耐熱性や耐候性等の低下の心配も全く心配の必要がない。
The color master batch of the present invention provides a color master batch having good heat resistance that does not cause any change in physical properties even when a colored molded article is manufactured or operated for a long time. It can be used for molded products, and is ideal for spinning and film moldings.
In the color master batch of the present invention, there is no need to worry at all about the deterioration of heat resistance, weather resistance, etc. that occurs when various conventional dispersants are used.
本発明で使用の顔料は、従来より汎用されている有機顔料及び無機顔料であれば良く、フタロシアニン系、アゾ系、縮合アゾ系、アントラキノン系、キナクリドン系、インジゴ系、ペリレン系等有機顔料、及び酸化チタン、カ−ボンブラック、弁柄、群青等無機顔料が挙げられる。尚、使用する顔料の平均粒径は、従来からポリオレフィン樹脂の着色の際に汎用されているものを使用するれば良い。 The pigments used in the present invention may be organic pigments and inorganic pigments that have been widely used conventionally, such as phthalocyanine-based, azo-based, condensed azo-based, anthraquinone-based, quinacridone-based, indigo-based, and perylene-based organic pigments, and Inorganic pigments such as titanium oxide, carbon black, petiole, ultramarine blue and the like can be mentioned. In addition, what is necessary is just to use the average particle diameter of the pigment to be used conventionally when coloring polyolefin resin.
請求項５は、請求項４に記載の顔料分散樹脂が、ポリエチレン系樹脂を使用したものであるカラ−マスタ−バッチである。
本発明のカラ−マスタ−バッチは、従来より使用されている用途、例えばフイルム成形、ブロ−成形等に何ら問題なく、容易に使用できるものである。
請求項６は、請求項４に記載の顔料分散樹脂が、ポリプロピレン系樹脂を用い得られたものを使用のカラ−マスタ−バッチである。
本発明のカラ−マスタ−バッチは、従来より使用されている用途、例えばフイルム成形、ブロ−成形等に何ら問題なく、容易に使用できるものである。
A fifth aspect of the present invention is a color master batch in which the pigment-dispersed resin according to the fourth aspect uses a polyethylene resin.
The color master batch of the present invention can be easily used without any problem for conventional applications such as film molding and blow molding.
A sixth aspect of the present invention is a color master batch in which the pigment dispersion resin according to the fourth aspect is obtained by using a polypropylene-based resin.
The color master batch of the present invention can be easily used without any problem for conventional applications such as film molding and blow molding.
以上の通り、請求項４〜６記載のカラ−マスタ−バッチは、従来から分散剤として使用のエチレンビスアマイドや、ポリエチレンワックス、ポリプロピレンワックス等低分子量樹脂ワックス等の分散剤を全く配合せず、又、水を用いたフラッシング法で得られるカラ−マスタ−バッチに劣らぬ顔料分散性を提供するものである。
本発明のカラーマスターバッチは、着色成形品の製造でも長時間操業しても何ら物性変化を生じない耐熱性に良好な製品を提供するものであり、本発明品は、上記の特徴を生かして各種成形品の用途に使用可能であり、特に紡糸やフィルム成形品として最適である。
本発明のカラ−マスタ−バッチは、従来から使用の各種分散剤を使用の場合に発生する耐熱性や耐候性等の低下の心配も全く心配の必要がない。
As described above, the color master batch according to claims 4 to 6 does not contain a dispersant such as ethylene bisamide, a low molecular weight resin wax such as polyethylene wax and polypropylene wax, which has been conventionally used as a dispersant, Further, the present invention provides pigment dispersibility comparable to that of a color master batch obtained by a flushing method using water.
The color masterbatch of the present invention provides a product having good heat resistance that does not cause any change in physical properties even when a colored molded product is manufactured or operated for a long time. The product of the present invention takes advantage of the above characteristics. It can be used for various molded products, and is particularly suitable for spinning and film moldings.
In the color master batch of the present invention, there is no need to worry at all about the deterioration of heat resistance, weather resistance and the like that occurs when various dispersants conventionally used are used.
本発明で得られる請求項４〜６記載のカラーマスターバッチは、紡糸やフイルムの製造でも、長時間操業でも何ら支障を生じない作業性に富んだ製品を提供するものである。
本発明で得られるカラーマスターバッチは、単品のポリエチレン樹脂と同様に紡糸やフイルムの製造でも、長時間操業でも何ら支障を生じない作業性に富んでおり、しかも、顔料分散性に富んだ製品を提供するものである。
The color masterbatch according to claims 4 to 6 obtained by the present invention provides a product with high workability that does not cause any trouble even in the production of spinning and film or in the operation for a long time.
The color masterbatch obtained in the present invention has a workability that does not cause any troubles even in the production of spinning and film as well as the long-time operation, as in the case of a single polyethylene resin. It is to provide.
本発明のカラーマスターバッチを使用して得られる成形品は、特許文献２記載のフラッシング法マスターバッチに全く劣らぬ顔料分散性、着色力等を発揮する製品を提供するものであり、非常に優れた製品を提供するものである。
本発明のカラーマスターバッチには、その特徴を損なわない程度で各種添加剤、例えば酸化防止剤、紫外線吸収剤等安定剤を配合しても良い。また、剛性、耐熱性等を向上するために必要に応じて、シリカ、炭酸カルシウム、ベントナイト、酸化亜鉛、マイカ、金属水酸化物等を配合しても良い。
The molded product obtained by using the color masterbatch of the present invention provides a product that exhibits pigment dispersibility, coloring power, etc., which is not inferior to the flushing method masterbatch described in Patent Document 2, and is extremely excellent. Product.
Various additives such as antioxidants and stabilizers such as ultraviolet absorbers may be blended in the color masterbatch of the present invention to the extent that the characteristics are not impaired. Further, silica, calcium carbonate, bentonite, zinc oxide, mica, metal hydroxide, and the like may be blended as necessary to improve rigidity, heat resistance, and the like.
以上の通り、本発明の顔料分散樹脂は、高速型混合機を用いて一定層流状態で攪拌処理するのみで、下記実施例１〜１０についての測定結果表１にも記載の通り、顔料との配合が容易な顔料分散樹脂を提供するものである。
更に、得られたカラーマスターバッチは、物性が優れており、従来のフラッシング法で得られるマスタ−バッチに匹敵する顔料分散性に富んだ着色剤が容易に得られる技術を確立したのである。
しかも、本発明の製造操作は、従来から行われているフラッシング法に比較し非常に簡便であり、小ロット製造が容易であり、カラーマスターバッチ製造の合理化に大いに貢献するものである。
As described above, the pigment-dispersed resin of the present invention is only stirred in a constant laminar flow state using a high-speed mixer, and as described in the measurement results for the following Examples 1 to 10, as shown in Table 1, It is intended to provide a pigment-dispersed resin that can be easily blended with
Furthermore, the obtained color masterbatch has excellent physical properties, and has established a technique for easily obtaining a colorant rich in pigment dispersibility comparable to a masterbatch obtained by a conventional flushing method.
In addition, the production operation of the present invention is very simple compared with the conventional flushing method, facilitates the production of small lots, and greatly contributes to the rationalization of color master batch production.
そして、本発明のカラーマスターバッチを用いて、容器やフィルム成形品を製造した場合にも、顔料分散性に富み、引張り強度等が優れた各種製品が容易に得られるものである。
更に、本発明のカラーマスターバッチは、フラッシング法マスタ−バッチの重要な用途である、紡糸や高級フィルムの用途に使用可能なな樹脂用着色剤を提供するものである。
And even when a container or a film molded product is manufactured using the color master batch of the present invention, various products having excellent pigment dispersibility and excellent tensile strength can be easily obtained.
Furthermore, the color masterbatch of the present invention provides a resin colorant that can be used for spinning and high-grade film applications, which are important uses of the flushing method masterbatch.
本発明では、ポリオレフィン樹脂を、攪拌羽根先端部と攪拌槽内壁面との間隔が３〜３０ｍｍであり、高速型混合機攪拌羽根先端の周速度を２０〜６０ｍ／ｓｅｃとして層流状態で攪拌処理することで、赤外線吸収スペクトルのピ−クが１５８０〜１６８０ｃｍ−１に存在することを特徴とする顔料分散樹脂の製造を確立したのである。
しかも、該顔料分散樹脂を担体樹脂に用い顔料を配合したカラ−マスタ−バッチの製造は、汎用の押出機を用い容易に製造可能である。
以下に実施例及び比較例を記載する。尚、重量部は部と記載する。
In the present invention, the polyolefin resin is stirred in a laminar flow state with a gap between the tip of the stirring blade and the inner wall surface of the stirring tank of 3 to 30 mm and a peripheral speed of the tip of the high-speed mixer stirring blade set to 20 to 60 m / sec. As a result, the manufacture of a pigment-dispersed resin characterized by the presence of a peak in the infrared absorption spectrum at 1580 to 1680 cm −1 was established.
Moreover, a color master batch in which the pigment dispersion resin is used as a carrier resin and a pigment is blended can be easily manufactured using a general-purpose extruder.
Examples and comparative examples are described below. In addition, a weight part is described as a part.
実施例１
MFR７．２ｇ／１０分（JIS-K-7210に準拠）、軟化点100.2℃（JIS-K-7206に準拠）の低密度ポリエチレンペレット（三井化学社製商品：M11P、３ｍｍ径ペレット）を、攪拌羽根の先端部と攪拌槽内面の間隔を１０ｍｍに調節した容量５リットルの横型高速型混合機（米国DRAISWERKE社製：G5シリ−ズ）の高速型混合機ホッパー口より投入して、回転羽根の先端速度を３０ｍ／secとして、９０℃以下で５分間攪拌し、層流状攪拌処理を行って、本発明の顔料分散樹脂を製造した。
Example 1
MFR 7.2g / 10 min (conforming to JIS-K-7210), softening point 100.2 ° C (conforming to JIS-K-7206), low density polyethylene pellets (Mitsui Chemicals product: M11P, 3 mm diameter pellets) It is inserted from the high-speed mixer hopper port of a 5 liter horizontal high-speed mixer (made by DRAISWERKE USA: G5 series) with the distance between the tip of the blade and the inner surface of the stirring tank adjusted to 10 mm. The pigment dispersion resin of the present invention was produced by stirring at a tip speed of 30 m / sec for 5 minutes at 90 ° C. or less and performing laminar stirring.
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。そして、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前２．４に比較して３．２と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . . And the difference with 3.2 was compared with the process which calculated the intensity ratio with 1367cm < -1 > which is a polyethylene standard band, compared with 2.4 before processing.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded using a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
該カラーマスターバッチのペレットを試料として、次に示す（ａ）グリッド個数の測定及び（ｂ）昇圧試験の測定を行い、その結果を表１に記載した。
実施例１で得られた本発明のカラーマスターバッチについて、（ａ）及び（ｂ）ともに優れた数値を示しており、カラーマスターバッチとして優れていることを証明している。又、比較例４の従来法フラッシング法と変わらぬ着色剤（マスタ−バッチ）が容易に得られる事実を証明している。
Using the pellets of the color masterbatch as a sample, the following (a) measurement of the number of grids and (b) measurement of the pressurization test were performed, and the results are shown in Table 1.
About the color masterbatch of this invention obtained in Example 1, (a) and (b) have shown the outstanding numerical value, and have proved that it is excellent as a color masterbatch. Further, it is proved that the colorant (master batch) which is the same as the conventional flushing method of Comparative Example 4 can be easily obtained.
（ａ）グリッド個数の測定
試料について厚さ30μｍのインフレションフイルムを作成し、容積10ｃｃ中のフィルムに存在する０．１ｍｍ２以上のグリット個数を測定する。
その結果について、次の基準で顔料分散性の評価を行った。
○‥‥‥１０個／ｃｍ３未満であり、あらゆる用途に使用可能である
△‥‥‥１０個／ｃｍ３〜５０個／ｃｍ３未満であり、分散性が若干劣りフイルムなどの 薄物には不適当である。
×‥‥‥５０個／ｃｍ３以上であり、使用不可能
(A) Measurement of the number of grids An inflation film having a thickness of 30 μm is prepared for a sample, and the number of grids of 0.1 mm 2 or more present in a film having a volume of 10 cc is measured.
The results were evaluated for pigment dispersibility according to the following criteria.
○ ............ Less than 10 pieces / cm 3 , which can be used for any application △ ............ 10 pieces / cm 3 to less than 50 pieces / cm 3 , slightly dispersible and thin film such as film Inappropriate.
× ·········· 50 / cm 3 or more
（ｂ）昇圧試験の測定
スクリュ−径１５ｍｍ単軸押出機の先端に325メッシュの金網を装着し、試料１kgを
押出し、金網の目詰まり状態をダイス部での圧力上昇値（ＭＰａ）を測定する。
尚、実施例２〜９及び比較例１〜６についても、同様に（ａ）と（ｂ）を測定して、その結果を表１に記載する。
(B) Measurement of pressurization test
Attach a 325 mesh wire mesh to the tip of a single screw extruder with a screw diameter of 15 mm, extrude a 1 kg sample, and measure the clogged state of the wire mesh to measure the pressure rise (MPa) at the die.
In addition, also about Examples 2-9 and Comparative Examples 1-6, (a) and (b) are measured similarly, and the result is described in Table 1.
実施例２
MFR１．０ｇ／１０分、軟化点１３５℃の高密度ポリエチレンペレット（KEIYOポリエチレン社製商品：E8082、２ｍｍ径ペレット）を、攪拌羽根の先端部と攪拌槽内面の間隔を１０ｍｍに調節した容量５リットルの横型高速型混合機（米国DRAISWERKE社製：G5シリ−ズ）の高速型混合機ホッパー口より投入して、回転羽根の先端速度を３０ｍ／secとして、９５℃以下で５分間攪拌し、層流状攪拌処理を行って、本発明の顔料分散樹脂を製造した。
Example 2
Capacity 5 with MFR 1.0 g / 10 min, high density polyethylene pellets with softening point of 135 ° C. (KEIYO polyethylene product: E8082, 2 mm diameter pellets) with the distance between the tip of the stirring blade and the inner surface of the stirring tank adjusted to 10 mm A liter horizontal high-speed mixer (made by US DRAISWERKE: G5 series) was introduced from the high-speed mixer hopper port, the tip speed of the rotary blade was 30 m / sec, and the mixture was stirred at 95 ° C. or less for 5 minutes. The pigment dispersion resin of this invention was manufactured by performing the laminar flow stirring process.
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認され、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前1.24に比較して2.07と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
The pigment-dispersed resin was thinned with a press machine, and a peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 after measuring the change in the infrared spectrum before and after the treatment of the present invention. When the strength ratio with 1367 cm −1 , which is a standard band of polyethylene, was calculated, a difference of 2.07 was recognized compared to 1.24 before treatment.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded using a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例３
攪拌羽根が上下２段からなり攪拌羽根の先端部と攪拌槽内面の間隔を５ｍｍに調節しており、下段攪拌羽が底部材に平行に取り付けられた容量１リットル縦型円筒槽である攪拌羽根が２段からなる実験用高速型混合機（以後ラボミキサ−と省略）を用い、周速度26ｍ／secに調節一定層流で５分間攪拌処理した以外は実施例１同様にして、顔料分散樹脂を得た。
本発明の顔料分散樹脂１００重量部に、顔料としてキナクリドン（C．I．Pigment Red）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 3
The stirring blade is a two-stage upper and lower stirring blade, and the distance between the tip of the stirring blade and the inner surface of the stirring tank is adjusted to 5 mm, and the lower stirring blade is a 1 liter vertical cylindrical tank attached in parallel to the bottom member. Pigment-dispersed resin in the same manner as in Example 1, except that a high-speed experimental mixer (hereinafter abbreviated as “lab mixer”) having two stages of blades was used for stirring for 5 minutes with a constant laminar flow adjusted to a peripheral speed of 26 m / sec. Got.
A mixture obtained by adding 40 parts by weight of quinacridone (CI Pigment Red) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention is melt-kneaded using a single screw extruder of L / D = 37, and the present invention. Color master batches were manufactured and pelletized.
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。
そして、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前２．４に比較して２．９と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . .
And when the intensity ratio with 1367 cm −1 , which is a polyethylene standard band, was calculated, a difference of 2.9 was recognized compared to 2.4 before the treatment.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded in a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例４
実施例３で使用の高速型混合機の周速度を４０ｍ／ｓｅｃとした以外は、実施例１同様にして、本発明の顔料分散樹脂を製造した。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。そして、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前２．４に比較して３．２と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 4
A pigment-dispersed resin of the present invention was produced in the same manner as in Example 1 except that the peripheral speed of the high-speed mixer used in Example 3 was 40 m / sec.
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . . And the difference with 3.2 was compared with the process which calculated the intensity ratio with 1367cm < -1 > which is a polyethylene standard band, compared with 2.4 before processing.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded using a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例５
実施例３で使用の高速型混合機の周速度を５０ｍ／ｓｅｃとした以外は、実施例３同様にして、本発明の顔料分散樹脂を得た。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。そして、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前２．４に比較し３．８と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 5
A pigment-dispersed resin of the present invention was obtained in the same manner as in Example 3 except that the peripheral speed of the high-speed mixer used in Example 3 was changed to 50 m / sec.
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . . And the process which calculated intensity ratio with 1367cm < -1 > which is a polyethylene standard band compared with 2.4 before a process, and the difference with 3.8 was recognized.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded using a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例６
実施例３で使用の高速型混合機の攪拌羽根の先端部と攪拌槽内面の間隔を１０ｍｍに調節して、実施例１で使用のポリエチレンをMFR７．２ｇ／１０分、軟化点１００．２℃の低密度ポリエチレンに代える以外は、実施例３と同様にして、本発明の顔料分散樹脂を得た。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にナチュラルのポリエチレン樹脂には見られぬピ−クが確認された。そして、ポリエチレンの標準バンドである１３６７ｃｍ−１との強度比を算出した処、処理前２．４に比較し２．８と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 6
The distance between the tip of the stirring blade of the high-speed mixer used in Example 3 and the inner surface of the stirring tank was adjusted to 10 mm, and the polyethylene used in Example 1 was MFR 7.2 g / 10 min and the softening point 100.2. A pigment-dispersed resin of the present invention was obtained in the same manner as in Example 3 except that the low-density polyethylene at 0 ° C. was used.
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . .
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. A peak that was not found in a natural polyethylene resin was confirmed in the vicinity of 1600 cm −1 . . And the process which calculated intensity ratio with 1367cm < -1 > which is a polyethylene standard band compared with 2.4 before a process, and the difference with 2.8 was recognized.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded in a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例７
実施例３において使用のポリプロピレンをMFR２５ｇ／１０分、軟化点１５５．９℃のポリプロピレン（日本ポリプロ社製MA03 平均粒径３ｍｍ）に代える以外は、実施例３と同様に攪拌処理し、本発明の顔料分散樹脂を製造した。
Example 7
The same procedure as in Example 3 was followed except that the polypropylene used in Example 3 was replaced with polypropylene having an MFR of 25 g / 10 min and a softening point of 155.9 ° C. (MA03 average particle size of 3 mm manufactured by Nippon Polypro Co., Ltd.). A pigment dispersion resin was produced.
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６５０ｃｍ−１付近にナチュラルのポリプロピレン樹脂には見られぬピ−クが確認され、ポリプロピレンの標準バンドである１１６７ｃｍ−１との強度比を算出した処、処理前１．１に比較して１．６と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用いて溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
The pigment-dispersed resin was thinned with a press, and after measuring the change in the infrared spectrum before and after the treatment of the present invention, a peak not found in the natural polypropylene resin was confirmed near 1650 cm −1 . When the strength ratio with 1167 cm −1 , which is a standard band of polypropylene, was calculated, a difference of 1.6 was recognized compared to 1.1 before the treatment.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (C.I. Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melted using a single screw extruder of L / D = 37. By kneading, the color master batch of the present invention was manufactured and pelletized.
実施例８
実施例３において使用のポリプロピレンをランダム共重合体ポリプロピレン（三井化学社製品：Ｆ３２９Ｄ、平均粒径０．５ｍｍ）に代える以外は、実施例３と同様に攪拌処理し、本発明の顔料分散樹脂を得た。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６００ｃｍ−１付近にポリプロピレン樹脂には見られぬピ−クが確認された。そして、ポリプロピレンの標準バンドである１１６７ｃｍ−１との強度比を算出した処、処理前０．３２に比較して０．４８と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 8
Except for replacing the polypropylene used in Example 3 with a random copolymer polypropylene (Mitsui Chemicals product: F329D, average particle size: 0.5 mm), stirring treatment was carried out in the same manner as in Example 3 to obtain the pigment-dispersed resin of the present invention. Obtained.
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention, and a peak not found in the polypropylene resin was confirmed in the vicinity of 1600 cm −1 . And when the intensity ratio with 1167 cm −1 , which is a standard band of polypropylene, was calculated, a difference of 0.48 was recognized compared to 0.32 before the treatment.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded in a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
実施例９
実施例３において使用のポリプロピレンをブロック共重合体ポリプロピレン（三井化学社製品：Ｊ７０４）に代える以外は、実施例３と同様に攪拌処理し、本発明の顔料分散樹脂を得た。
該顔料分散樹脂についてプレス機で薄膜化し、本発明の処理前と処理後について赤外線スペクトルの変化について測定した処、１６５０ｃｍ−１付近にポリプロピレン樹脂には見られぬピ−クが確認された。そして、ポリプロピレンの標準バンド１１６７ｃｍ−１との強度比を算出した処、処理前に０．２６比較して０．３３と違いが認められた。
本発明の顔料分散樹脂１００重量部に、顔料としてフタロシアニンブル−（C．I．Pigment Blue 15:1）４０重量部を加えた混合物を、Ｌ／Ｄ＝３７の単軸押出機を用い溶融混練して、本発明のカラ−マスタ−バッチを製造し、ペレット化した。
Example 9
The pigment dispersion resin of the present invention was obtained by stirring in the same manner as in Example 3 except that the polypropylene used in Example 3 was replaced with block copolymer polypropylene (product of Mitsui Chemicals, Inc .: J704).
The pigment-dispersed resin was thinned with a press and measured for changes in the infrared spectrum before and after the treatment of the present invention. As a result, a peak not found in the polypropylene resin was confirmed in the vicinity of 1650 cm −1 . And when the strength ratio with the standard band of 1167 cm −1 of polypropylene was calculated, a difference of 0.33 was recognized compared with 0.26 before treatment.
A mixture obtained by adding 40 parts by weight of phthalocyanine blue (CI Pigment Blue 15: 1) as a pigment to 100 parts by weight of the pigment dispersion resin of the present invention was melt kneaded using a single screw extruder of L / D = 37. The color master batch of the present invention was manufactured and pelletized.
比較例１
実施例１における攪拌羽根の先端部と攪拌槽内面の間隔を２ｍｍに調節した以外は、実施例１と同様に攪拌処理を試みた。
しかし、攪拌処理の際に攪拌槽内の温度が上昇しポリエチレンが塊状化し得られた樹脂には、１６００ｃｍ−１のピ−クが現れず、顔料との混練を試みたがマスタ−バッチとしての満足する顔料分散効果が示されなかった。
Comparative Example 1
The stirring treatment was tried in the same manner as in Example 1 except that the distance between the tip of the stirring blade and the inner surface of the stirring tank in Example 1 was adjusted to 2 mm.
However, in the resin in which the temperature in the stirring tank rose during the stirring process and the polyethylene was agglomerated, no peak of 1600 cm −1 appeared, and kneading with the pigment was attempted. A satisfactory pigment dispersion effect was not shown.
比較例２
実施例１における攪拌羽根の先端部と攪拌槽内面の間隔を３５ｍｍに調節した以外は、実施例１と同様に攪拌処理を試みた。
しかし、ポリエチレンは塊状化は見られなかったが得られた樹脂には、１６００ｃｍ−１のピ−クが現れず、顔料との混練を試みたがマスタ−バッチとしての満足する顔料分散効果が示されなかった。
Comparative Example 2
Stirring was performed in the same manner as in Example 1 except that the distance between the tip of the stirring blade and the inner surface of the stirring tank in Example 1 was adjusted to 35 mm.
However, polyethylene did not show agglomeration, but no peak of 1600 cm −1 appeared in the obtained resin, and although kneading with a pigment was attempted, a satisfactory pigment dispersion effect as a master batch was shown. Was not.
比較例３
実施例１における周速度を１７ｍ／ｓｅｃとする以外は、実施例１と同様に攪拌処理を試みた。
しかし、ポリエチレンは塊状化は見られなかったが得られた樹脂には、１６００ｃｍ−１のピ−クが現れず、顔料との混練を試みたがマスタ−バッチとしての満足する顔料分散効果が示されなかった。
Comparative Example 3
Stirring was attempted in the same manner as in Example 1 except that the peripheral speed in Example 1 was 17 m / sec.
However, polyethylene did not show agglomeration, but no peak of 1600 cm −1 appeared in the obtained resin, and although kneading with a pigment was attempted, a satisfactory pigment dispersion effect as a master batch was shown. Was not.
比較例４
実施例１における周速度を６３ｍ／ｓｅｃとする以外は、実施例１と同様に攪拌処理を試みた。
しかし、攪拌処理の際に攪拌槽内の温度が上昇しポリエチレンが塊状化し得られた樹脂には、１６００ｃｍ−１のピ−クが現れず、顔料との混練を試みたがマスタ−バッチとしての満足する顔料分散効果が示されなかった。
Comparative Example 4
Stirring was attempted in the same manner as in Example 1 except that the peripheral speed in Example 1 was 63 m / sec.
However, in the resin in which the temperature in the stirring tank rose during the stirring process and the polyethylene was agglomerated, no peak of 1600 cm −1 appeared, and kneading with the pigment was attempted. A satisfactory pigment dispersion effect was not shown.
比較例５
ACポリエチレン6A（アライドケミカル＆ダイコ−ポレション社製）１００部、フタロシアニンブル−（CIピグメントブル−15:1）１０部、及び蒸留水５０部をニ−ダ−に仕込み加熱混練した後、水分を蒸発させて得られた混合物を３本ロ−ルを用い混練して、フラッシング法によるカラ−マスタ−バッチを得た。
比較例６
比較例４で使用のACポリエチレン6A及びフタロシアニンブル−を予備溶融混練した後に、３本ロ−ルを用いて加熱混練してカラ−マスタ−バッチを得た。
Comparative Example 5
After 100 parts of AC polyethylene 6A (made by Allied Chemical & Dyco-Polysion Co., Ltd.), 10 parts of phthalocyanine blue (CI Pigment Bull-15: 1), and 50 parts of distilled water were charged into a kneader and heated and kneaded, The mixture obtained by evaporation was kneaded using three rolls to obtain a color master batch by the flushing method.
Comparative Example 6
The AC polyethylene 6A and phthalocyanine blue used in Comparative Example 4 were premelted and kneaded, and then heated and kneaded using three rolls to obtain a color master batch.
以上の通り、本発明の顔料分散樹脂は、実施例１〜１０でも記載の通り簡便な装置で容易に製造され、しかも、得られた本発明の顔料分散樹脂を用いたカラ−マスタ−バッチは、フラッシング法で得られる着色剤と変わらぬ品質の優れた製品が容易に得られるものである。 As described above, the pigment dispersion resin of the present invention is easily produced by a simple apparatus as described in Examples 1 to 10, and the obtained color master batch using the pigment dispersion resin of the present invention is A product excellent in quality that is the same as the colorant obtained by the flushing method can be easily obtained.
Claims (6)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117809A (en) * | 2004-10-22 | 2006-05-11 | Tokyo Printing Ink Mfg Co Ltd | Pigment dispersing resin and color masterbatch using the same |
| JP2007302824A (en) * | 2006-05-12 | 2007-11-22 | Tokyo Printing Ink Mfg Co Ltd | Method of conglobation for resin particle |
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| JP2006117809A (en) * | 2004-10-22 | 2006-05-11 | Tokyo Printing Ink Mfg Co Ltd | Pigment dispersing resin and color masterbatch using the same |
| JP2006160976A (en) * | 2004-12-10 | 2006-06-22 | Tokyo Printing Ink Mfg Co Ltd | Resin for mixing pigments and color master batch using the resin |
-
2004
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| JPS48101482A (en) * | 1972-04-03 | 1973-12-20 | ||
| JPS5496597A (en) * | 1977-12-29 | 1979-07-31 | Bayer Ag | Preparation of polymer containing hydroperoxide group |
| JPH026506A (en) * | 1988-06-27 | 1990-01-10 | Mitsui Petrochem Ind Ltd | Oxide of ethylene copolymer wax and use thereof |
| JPH02173005A (en) * | 1988-11-12 | 1990-07-04 | Basf Ag | Manufacture of ethylene polymer |
| JPH03167204A (en) * | 1989-11-27 | 1991-07-19 | Mitsui Petrochem Ind Ltd | Production of acid group-containing polyolefin wax |
| JPH04304205A (en) * | 1991-04-02 | 1992-10-27 | Mitsui Petrochem Ind Ltd | Production of thermal decomposition wax |
| JPH07233275A (en) * | 1994-02-25 | 1995-09-05 | Toyo Ink Mfg Co Ltd | Production of resin composition for coloring, and resin composition for coloring |
| JP2006117809A (en) * | 2004-10-22 | 2006-05-11 | Tokyo Printing Ink Mfg Co Ltd | Pigment dispersing resin and color masterbatch using the same |
| JP2006160976A (en) * | 2004-12-10 | 2006-06-22 | Tokyo Printing Ink Mfg Co Ltd | Resin for mixing pigments and color master batch using the resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006117809A (en) * | 2004-10-22 | 2006-05-11 | Tokyo Printing Ink Mfg Co Ltd | Pigment dispersing resin and color masterbatch using the same |
| JP2007302824A (en) * | 2006-05-12 | 2007-11-22 | Tokyo Printing Ink Mfg Co Ltd | Method of conglobation for resin particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4758628B2 (en) | 2011-08-31 |
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