JP2006117820A - Colorant composition for printing and its molding - Google Patents
Colorant composition for printing and its molding Download PDFInfo
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- JP2006117820A JP2006117820A JP2004307816A JP2004307816A JP2006117820A JP 2006117820 A JP2006117820 A JP 2006117820A JP 2004307816 A JP2004307816 A JP 2004307816A JP 2004307816 A JP2004307816 A JP 2004307816A JP 2006117820 A JP2006117820 A JP 2006117820A
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本発明は、ポリオレフィン系樹脂成形品における印刷、接着等の二次加工性能が改良された着色剤組成物に関する。 The present invention relates to a colorant composition having improved secondary processing performance such as printing and adhesion in a polyolefin resin molded article.
熱可塑性樹脂、特にポリオレフィン系樹脂は、加工性、耐薬品性、機械的強度などの物性が優れており、フィルム類、シート類、ボトルやコンテナ等の容器類、家電、自動車等の工業部品等の成形材料として広く使用されている。また着色の自由度も優れているため、ドライカラー・ペーストカラー・マスターバッチ等の着色剤により着色され、さらに意匠性・識別のための印刷・塗装が施され市場に提供されている。 Thermoplastic resins, especially polyolefin resins, have excellent physical properties such as processability, chemical resistance, and mechanical strength. Films, sheets, containers such as bottles and containers, industrial parts such as home appliances and automobiles, etc. It is widely used as a molding material. In addition, since the degree of freedom in coloring is excellent, it is colored with a colorant such as dry color, paste color, masterbatch, etc., and further printed / painted for design and identification, and is provided to the market.
しかしポリオレフィン系樹脂は表面極性が低く、印刷適性、塗装性及び接着性等の二次加工性が悪い。よってこの二次加工性を向上させるために熱処理、プラズマ処理、コロナ処理等の様々な表面処理が試みられている。 However, polyolefin resins have low surface polarity and poor secondary processability such as printability, paintability and adhesion. Therefore, various surface treatments such as heat treatment, plasma treatment, and corona treatment have been attempted in order to improve the secondary workability.
また、成形品の基材樹脂に水酸基を有する脂肪酸又はその誘導体を含有させて表面改質させる方法（特許文献１）や、不飽和カルボン酸を含有する方法（特許文献２）が開示されている。また、１分子内に１個以上の反応性官能基と３個以上のカチオン性基を有した樹脂改質剤を熱可塑性樹脂に配合する技術（特許文献３）も開示されている。しかしながらいずれも充分な二次加工性が得られなかった。 Moreover, the method (patent document 1) which makes the base resin of a molded article contain the fatty acid which has a hydroxyl group, or its derivative (s), and the method (patent document 2) which contains unsaturated carboxylic acid is disclosed. . Also disclosed is a technique (Patent Document 3) in which a resin modifier having one or more reactive functional groups and three or more cationic groups in one molecule is added to a thermoplastic resin. However, in all cases, sufficient secondary processability was not obtained.
一方、熱可塑性樹脂成形品は着色剤により着色されていることが多い。意匠性や外観を損なわないため、着色剤には顔料の分散性が要求される。なかでも二酸化チタンは凝集しやすいため、無機及び有機の表面処理をして分散性を向上させている。
しかし有機表面処理により二酸化チタンの分散性が向上する一方、上記の印刷適性が悪化するという相反する問題があった。
However, while the dispersibility of titanium dioxide is improved by the organic surface treatment, there is a conflicting problem that the printability is deteriorated.
本発明の目的は、ポリオレフィン系樹脂の特性を実質的に損なうことなく、顔料分散性に優れ、かつ成形品における印刷適性などの二次加工性が良好な着色剤を提供することである。 An object of the present invention is to provide a colorant that has excellent pigment dispersibility and good secondary processability such as printability in a molded product without substantially impairing the properties of the polyolefin-based resin.
本発明は、上記目的を達成するために鋭意研究を重ねた結果、以下の発明に到達した。
すなわち第１の発明は、ポリオレフィン系樹脂（Ａ）と、水酸基を有する脂肪酸金属塩（Ｂ）０．２〜５重量％と、有機表面処理剤で処理された二酸化チタン（Ｄ）とを含有する印刷用着色剤組成物である。
The present invention has reached the following invention as a result of intensive studies to achieve the above object.
That is, the first invention contains a polyolefin resin (A), a fatty acid metal salt (B) having a hydroxyl group of 0.2 to 5% by weight, and titanium dioxide (D) treated with an organic surface treatment agent. It is a colorant composition for printing.
第２の発明は、有機表面処理剤がポリオール系有機表面処理剤である第１の発明に記載の印刷用着色剤組成物である。 2nd invention is the coloring agent composition for printing as described in 1st invention whose organic surface treating agent is a polyol type organic surface treating agent.
また、本発明の第３の発明は、ポリオレフィン系樹脂（Ａ）と、脂肪酸金属塩（Ｃ）０．２〜５重量％と、ポリオール系有機表面処理剤で処理された二酸化チタン（Ｅ）とを含有する印刷用着色剤組成物である。 The third invention of the present invention is a polyolefin resin (A), a fatty acid metal salt (C) 0.2 to 5% by weight, and titanium dioxide (E) treated with a polyol organic surface treatment agent. Is a printing colorant composition containing
第４の発明は、第１〜第３の発明いずれかに記載の着色剤組成物を用いて得られる印刷用樹脂成形品である。 The fourth invention is a resin molded article for printing obtained using the colorant composition according to any one of the first to third inventions.
本発明の印刷用着色剤組成物は、ポリオレフィン系樹脂（Ａ）と、水酸基を有する脂肪酸金属塩（Ｂ）０．２〜５重量％と、有機表面処理剤で処理された二酸化チタン（Ｄ）とを含有するので、二酸化チタンの分散性が良好である。また、これを用いて得られる成形品はポリオレフィン系基材樹脂の加工特性を損なう事がなく、長期にわたり親水性を保持し、良好な印刷適性を有する。 The printing colorant composition of the present invention comprises a polyolefin resin (A), a fatty acid metal salt having a hydroxyl group (B) 0.2 to 5% by weight, and titanium dioxide (D) treated with an organic surface treatment agent. Therefore, the dispersibility of titanium dioxide is good. In addition, a molded product obtained by using this does not impair the processing characteristics of the polyolefin base resin, retains hydrophilicity for a long time, and has good printability.
上記印刷用着色剤組成物は、有機表面処理剤がポリオール系有機表面処理剤なので、これを用いて得られる成形品は、さらに長期にわたり親水性を保持し、良好な印刷適性を有する。 In the colorant composition for printing, since the organic surface treatment agent is a polyol-based organic surface treatment agent, a molded product obtained using the organic surface treatment agent retains hydrophilicity for a longer period and has good printability.
本発明の印刷用着色剤組成物は、ポリオレフィン系樹脂（Ａ）と、脂肪酸金属塩（Ｃ）０．２〜５重量％と、ポリオール系有機表面処理剤で処理された二酸化チタン（Ｅ）とを含有するので、二酸化チタンの分散性が良好である。また、これを用いて得られる成形品はポリオレフィン系基材樹脂の加工特性を損なう事がなく、長期にわたり親水性を保持し、良好な印刷適性を有する。 The printing colorant composition of the present invention comprises a polyolefin resin (A), a fatty acid metal salt (C) 0.2 to 5% by weight, and titanium dioxide (E) treated with a polyol organic surface treatment agent. Therefore, the dispersibility of titanium dioxide is good. In addition, a molded product obtained by using this does not impair the processing characteristics of the polyolefin base resin, retains hydrophilicity for a long time, and has good printability.
本発明の印刷用樹脂成形品は、上記いずれかの着色剤組成物を用いて得られるので、二酸化チタンの分散性が良好であると共に印刷適性も良好である。 Since the resin molded article for printing of the present invention is obtained using any one of the above colorant compositions, the dispersibility of titanium dioxide is good and the printability is also good.
好ましい実施の形態を挙げて本発明を更に詳細に説明する。
＜ポリオレフィン系樹脂（Ａ）＞
本発明の着色剤組成物におけるベース樹脂として、または成形品における基材樹脂（被着色樹脂または希釈樹脂）としてポリオレフィン系樹脂（Ａ）が使用される。従来各種の樹脂成形品の製造に使用されている公知のポリオレフィン系樹脂はいずれも使用することができる。
The present invention will be described in more detail with reference to preferred embodiments.
<Polyolefin resin (A)>
The polyolefin resin (A) is used as the base resin in the colorant composition of the present invention or as a base resin (colored resin or diluted resin) in a molded product. Any known polyolefin resin that has been conventionally used in the production of various resin molded products can be used.
具体的には高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、ポリ−３−メチルペンテン等のα−オレフィン重合体、エチレン−酢酸ビニル共重合体、エチレン−プロピレン共重合体、プロピレン−１−ペンテン共重合体、プロピレン−１−へキセン共重合体等のプロピレンと他のα−オレフィン等とのランダムまたはブロック共重合体、１−ブテン等他のα−オレフィンの単独重合体または相互共重合体およびこれらの混合物等が挙げられる。 Specifically, α-olefin polymers such as high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, poly-3-methylpentene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, Random or block copolymers of propylene such as propylene-1-pentene copolymer and propylene-1-hexene copolymer and other α-olefins, and homopolymers of other α-olefins such as 1-butene Or a mutual copolymer, these mixtures, etc. are mentioned.
＜水酸基を有する脂肪酸金属塩（Ｂ）＞
本発明の着色剤組成物で使用される水酸基を有する脂肪酸金属塩（Ｂ）の例としては、１２−ヒドロキシステアリン酸のマグネシウム、リチウム、ナトリウム、カリウム、カルシウム、亜鉛等の金属塩が挙げられる。特に１２−ヒドロキシステアリン酸マグネシウムが好ましい。
本発明の着色剤組成物における水酸基を有する脂肪酸金属塩（Ｂ）は０．２〜５重量％の範囲で配合される。更に０．５〜３重量％が好ましく、０．５〜２重量％が最も好ましい。
０．２重量％未満では顔料の分散性が低下し、成形品中に顔料の凝集が発生することにより外観を損ねる。また、５重量％を超えても印刷適性に問題はないもののブルーミングが発生し、加工性に支障をきたすおそれがある。
<Fatty acid metal salt having a hydroxyl group (B)>
Examples of the fatty acid metal salt (B) having a hydroxyl group used in the colorant composition of the present invention include metal salts of 12-hydroxystearic acid such as magnesium, lithium, sodium, potassium, calcium, and zinc. In particular, 12-hydroxy magnesium stearate is preferable.
The fatty acid metal salt (B) having a hydroxyl group in the colorant composition of the present invention is blended in the range of 0.2 to 5% by weight. Furthermore, 0.5 to 3% by weight is preferable, and 0.5 to 2% by weight is most preferable.
If it is less than 0.2% by weight, the dispersibility of the pigment is lowered, and the appearance of the pigment is impaired due to the aggregation of the pigment in the molded product. Even if it exceeds 5% by weight, there is no problem in printability, but blooming may occur, which may hinder workability.
＜脂肪酸金属塩（Ｃ）＞
本発明の着色剤組成物で使用される脂肪酸金属塩（Ｃ）の例としては、ステアリン酸のマグネシウム、リチウム、ナトリウム、カリウム、カルシウム、亜鉛等の金属塩が挙げられる。特にステアリン酸マグネシウムが好ましい。
本発明の着色剤組成物における脂肪酸金属塩（Ｃ）は０．２〜５重量％の範囲で配合される。更に０．５〜３重量％が好ましく、０．５〜２重量％が最も好ましい。
０．２重量％未満では顔料の分散性が低下し、成形品中に顔料の凝集が発生することにより外観を損ねる。また、５重量％を超えても印刷適性に問題はないもののブルーミングが発生し、加工性に支障をきたすおそれがある。
<Fatty acid metal salt (C)>
Examples of the fatty acid metal salt (C) used in the colorant composition of the present invention include metal salts of magnesium stearate such as magnesium, lithium, sodium, potassium, calcium, and zinc. In particular, magnesium stearate is preferable.
The fatty acid metal salt (C) in the colorant composition of the present invention is blended in the range of 0.2 to 5% by weight. Furthermore, 0.5 to 3% by weight is preferable, and 0.5 to 2% by weight is most preferable.
If it is less than 0.2% by weight, the dispersibility of the pigment is lowered, and the appearance of the pigment is impaired due to the aggregation of the pigment in the molded product. Even if it exceeds 5% by weight, there is no problem in printability, but blooming may occur, which may hinder workability.
＜二酸化チタン＞
本発明で使用される二酸化チタンは塩素法、硫酸法いずれの製法で得られるもので良い。また、ルチル型、アナターゼ型いずれの結晶構造でも良いが、耐候性の観点からルチル型が好ましい。二酸化チタンの平均粒径は、一般に入手できる範囲（０．１〜０．４μｍ）のものであれば使用できるが、着色力の観点から０．２〜０．３μｍが好ましい。
<Titanium dioxide>
The titanium dioxide used in the present invention may be obtained by any of the chlorine method and the sulfuric acid method. Moreover, although a rutile type or anatase type crystal structure may be used, a rutile type is preferable from the viewpoint of weather resistance. The average particle diameter of titanium dioxide can be used as long as it is in a generally available range (0.1 to 0.4 μm), but is preferably 0.2 to 0.3 μm from the viewpoint of coloring power.
二酸化チタンは、その表面をアルミナ処理、シリカ処理等の金属酸化物で無機処理されていることが好ましい。特にアルミナ処理の後、シリカ処理されたものが好ましい。さらに必要に応じてチタン化合物、ジルコニウム（Ｚｒ）、亜鉛、マグネシウム等の金属化合物、カルシウム化合物、リン化合物等を任意の量で処理することもできる。無機処理は公知の方法で行うことが出来る。
二酸化チタン１００重量部に対して無機表面処理剤０．２〜１０重量部で表面処理することが好ましい。０．２重量部未満では耐候性等の耐性が低下し、１０重量部を超えると白色顔料としての着色力が著しく低下する場合がある。
The surface of titanium dioxide is preferably inorganic-treated with a metal oxide such as alumina treatment or silica treatment. In particular, those treated with silica after alumina treatment are preferred. Furthermore, a titanium compound, a metal compound such as zirconium (Zr), zinc, and magnesium, a calcium compound, a phosphorus compound, and the like can be treated in any amount as necessary. The inorganic treatment can be performed by a known method.
The surface treatment is preferably performed with 0.2 to 10 parts by weight of an inorganic surface treatment agent with respect to 100 parts by weight of titanium dioxide. If it is less than 0.2 parts by weight, resistance such as weather resistance is lowered, and if it exceeds 10 parts by weight, the coloring power as a white pigment may be remarkably lowered.
また、本発明で用いられる二酸化チタンは分散性向上のため、その表面を有機表面処理剤によって処理されることが必要である。
有機表面処理剤としてはトリメチロールプロパン等のポリオール系、ジメチルポリシロキサン、メチル水素ポリシロキサン、アルコキシシラン類等のシリコン系、トリエタノールアミンの有機酸塩などのアルカノールアミン系が例示できる。
Further, the titanium dioxide used in the present invention needs to have its surface treated with an organic surface treatment agent in order to improve dispersibility.
Examples of the organic surface treatment agent include polyols such as trimethylolpropane, silicons such as dimethylpolysiloxane, methylhydrogen polysiloxane, and alkoxysilanes, and alkanolamines such as organic acid salts of triethanolamine.
本発明の着色剤組成物において、有機表面処理剤で処理された二酸化チタン（Ｄ）は、いずれの有機表面処理剤でも用いることができる。コロナ処理後数週間経過しても濡れ性が良好な点でポリオール系が好ましく、特に分子内に２〜４個の水酸基を有し炭素数１０個以下の炭化水素化合物が好ましい。例えばトリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール等が挙げられる。 In the colorant composition of the present invention, any organic surface treating agent can be used as the titanium dioxide (D) treated with the organic surface treating agent. Polyols are preferred in terms of good wettability even after several weeks after corona treatment, and hydrocarbon compounds having 2 to 4 hydroxyl groups in the molecule and having 10 or less carbon atoms are particularly preferred. For example, trimethylolethane, trimethylolpropane, pentaerythritol and the like can be mentioned.
しかし、本発明の着色剤組成物において脂肪酸金属塩（Ｃ）を用いる場合は、ポリオール系有機表面処理剤で処理された二酸化チタン（Ｅ）を用いることが必要である。 However, when the fatty acid metal salt (C) is used in the colorant composition of the present invention, it is necessary to use titanium dioxide (E) treated with a polyol organic surface treating agent.
二酸化チタン１００重量部に対して有機表面処理剤０．１〜１重量部で表面処理することが好ましい。０．１重量部未満では十分な顔料分散性が得られず、１重量部を超えると有機処理剤がブリードし、成形品等の外観を損ねる場合がある。 The surface treatment is preferably performed with 0.1 to 1 part by weight of an organic surface treatment agent with respect to 100 parts by weight of titanium dioxide. If the amount is less than 0.1 part by weight, sufficient pigment dispersibility cannot be obtained. If the amount exceeds 1 part by weight, the organic treatment agent may bleed and the appearance of a molded product or the like may be impaired.
＜その他の成分＞
本発明の着色剤組成物及び成形品においては、必要に応じて二酸化チタン以外の顔料及び添加剤を配合することができる。例えばアゾ系、アンスラキノン系、フタロシアニン系、キナクリドン系、イソインドリノン系、ジオキサジン系、ペリレン系、キノフタロン系、ペリレン系等の有機顔料や、チタンイエロー、群青、コバルトブルー、酸化鉄や複合系酸化物等の無機顔料が挙げられる。また、酸化防止剤、紫外線吸収剤、安定剤、帯電防止剤、カップリング剤、造核剤、難燃剤、改質剤、界面活性剤等が挙げられる。これらは２種以上を併用することができる。
<Other ingredients>
In the colorant composition and molded article of the present invention, pigments and additives other than titanium dioxide can be blended as necessary. For example, organic pigments such as azo, anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxazine, perylene, quinophthalone, and perylene, titanium yellow, ultramarine, cobalt blue, iron oxide and complex oxides And inorganic pigments. Moreover, antioxidants, ultraviolet absorbers, stabilizers, antistatic agents, coupling agents, nucleating agents, flame retardants, modifiers, surfactants and the like can be mentioned. Two or more of these can be used in combination.
＜印刷用着色剤組成物＞
本発明の印刷用着色剤組成物はポリオレフィン系樹脂（Ａ）と、水酸基を有する脂肪酸金属塩（Ｂ）と、有機表面処理剤で処理された二酸化チタン（Ｄ）、またはポリオレフィン系樹脂（Ａ）と、脂肪酸金属塩（Ｃ）と、ポリオール系有機表面処理剤で処理された二酸化チタン（Ｅ）とを、公知の方法で混練装置で溶融混合して製造することができる。
<Colorant composition for printing>
The printing colorant composition of the present invention comprises a polyolefin resin (A), a fatty acid metal salt having a hydroxyl group (B), titanium dioxide (D) treated with an organic surface treatment agent, or a polyolefin resin (A). And a fatty acid metal salt (C) and titanium dioxide (E) treated with a polyol-based organic surface treating agent can be produced by melting and mixing with a kneading apparatus by a known method.
本発明の印刷用着色剤組成物における、二酸化チタン（Ｄ）または（Ｅ）の配合量は５〜７０重量％が好ましい。マスターバッチとして用いる場合は６０〜７０重量％が好ましい。混練装置の例として単軸押出機、二軸押出機、バンバリーミキサー、ニーダー、ロール等が挙げられる。 The blending amount of titanium dioxide (D) or (E) in the printing colorant composition of the present invention is preferably 5 to 70% by weight. When using as a masterbatch, 60 to 70 weight% is preferable. Examples of the kneading apparatus include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a roll.
＜印刷用成形品＞
本発明の印刷用成形品は、上記着色剤組成物と基材樹脂とを適当な割合で配合し、フィルム等に公知の方法で成形して得られる。印刷適性向上のため、成形品には必要に応じて熱処理、プラズマ処理、コロナ処理等の表面処理を行うことが好ましい。前記表面処理を行うと、濡れ性の効果を更に持続できる。
<Molded product for printing>
The molded article for printing of the present invention is obtained by blending the colorant composition and the base resin in an appropriate ratio and molding the film or the like by a known method. In order to improve printability, the molded article is preferably subjected to surface treatment such as heat treatment, plasma treatment or corona treatment as necessary. When the surface treatment is performed, the wettability effect can be further maintained.
以下、本発明について具体的に実施例をもって説明するが、本発明はこれらの実施例に限定されず幅広い応用範囲を持つものである。なお以下の記載において「部」は「重量部」を、「％」は「重量％」をそれぞれ表す。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples and has a wide range of applications. In the following description, “part” represents “part by weight” and “%” represents “% by weight”.
＜二酸化チタンの無機表面処理＞
平均粒子径０．２５μｍのルチル型二酸化チタンを、公知の方法でアルミナ処理した後シリカ処理し、無機表面処理した二酸化チタンｄを得た。
＜二酸化チタンの有機表面処理＞
（１）二酸化チタンａ
無機表面処理二酸化チタンｄ １００部をヘンシェルミキサー中で攪拌しながら、トリメチロールプロパン（ポリオール系）０．５部添加して１０分間攪拌し、有機表面処理された二酸化チタンａを得た。
（２）二酸化チタンｂ
二酸化チタンｄ １００部を、ヘンシェルミキサー中で攪拌しながら、ジメチルポリシロキサン（シリコン系）を０．５部添加して１０分間攪拌し、有機表面処理された二酸化チタンｂを得た。
（３）二酸化チタンｃ
二酸化チタンｄ １００部を、ヘンシェルミキサー中で攪拌しながら、トリエタノールアミン（アルカノールアミン系）を０．５部添加して１０分間攪拌し、有機表面処理された二酸化チタンｃを得た。
二酸化チタンについて表１に示す。
<Inorganic surface treatment of titanium dioxide>
Rutile titanium dioxide having an average particle size of 0.25 μm was treated with alumina by a known method and then silica-treated to obtain an inorganic surface-treated titanium dioxide d.
<Organic surface treatment of titanium dioxide>
(1) Titanium dioxide a
While stirring 100 parts of inorganic surface-treated titanium dioxide d in a Henschel mixer, 0.5 part of trimethylolpropane (polyol system) was added and stirred for 10 minutes to obtain organic surface-treated titanium dioxide a.
(2) Titanium dioxide b
While stirring 100 parts of titanium dioxide d in a Henschel mixer, 0.5 part of dimethylpolysiloxane (silicon-based) was added and stirred for 10 minutes to obtain an organic surface-treated titanium dioxide b.
(3) Titanium dioxide c
While stirring 100 parts of titanium dioxide d in a Henschel mixer, 0.5 part of triethanolamine (alkanolamine type) was added and stirred for 10 minutes to obtain an organic surface-treated titanium dioxide c.
It shows in Table 1 about titanium dioxide.
[実施例１]
ポリオレフィン系樹脂（Ａ） ３４．３％
（低密度ポリエチレン 比重０．９２、ＭＦＲ７．０ｇ／１０ｍｉｎ）
二酸化チタン（Ｄ） ６０．０％
（二酸化チタンａ ポリオール表面処理）
黄色酸化鉄 ５．０％
水酸基を有する脂肪酸金属塩（Ｂ） ０．５％
（１２−ヒドロキシステアリン酸マグネシウム）
酸化防止剤（フェノール／リン系） ０．２％
上記配合比率で混合後、二軸押出機にて温度１８０℃で溶融混練し、ペレット状の着色剤組成物を製造した。表２に示す。
[Example 1]
Polyolefin resin (A) 34.3%
(Low density polyethylene, specific gravity 0.92, MFR 7.0 g / 10 min)
Titanium dioxide (D) 60.0%
(Titanium dioxide a polyol surface treatment)
Yellow iron oxide 5.0%
Fatty acid metal salt having a hydroxyl group (B) 0.5%
(12-hydroxy magnesium stearate)
Antioxidant (phenol / phosphorus) 0.2%
After mixing at the above blending ratio, the mixture was melt kneaded at a temperature of 180 ° C. with a twin-screw extruder to produce a pellet-like colorant composition. It shows in Table 2.
[実施例２〜４、比較例１〜６]
表２に記載の配合割合で、実施例１と同様に着色剤組成物を製造した。
[Examples 2 to 4, Comparative Examples 1 to 6]
A colorant composition was produced in the same manner as in Example 1 at the blending ratio shown in Table 2.
＜評価試験＞
試験用フィルムの作成
基材樹脂（低密度ポリエチレン 比重０．９２４ ＭＦＲ３．０ｇ／１０ｍｉｎ）１００部に対して上記で得られた着色剤組成物１５部を配合し、ラボプラストミル（東洋精機社製）にてＴダイを用い厚さ７０μｍのフィルム成形品を成形した。
<Evaluation test>
Preparation of test film 15 parts of the colorant composition obtained above is blended with 100 parts of base resin (low density polyethylene, specific gravity 0.924 MFR 3.0 g / 10 min), and Laboplast mill (manufactured by Toyo Seiki Co., Ltd.). ) To form a 70 μm-thick film molded product using a T-die.
（１）成形品における顔料分散性
上記Ｔダイ成形により得られたフィルムを目視観察し、フィルム０．６５ｍ２における顔料凝集体（フィルムブツ）個数をカウントした。○を合格とした。
○：５０個未満
△：５０個以上、１００個未満
×：１００個以上
(1) Pigment dispersibility in molded article The film obtained by the above T-die molding was visually observed, and the number of pigment aggregates (film spots) in the film 0.65 m 2 was counted. ○ was accepted.
○: Less than 50 Δ: 50 or more, less than 100 ×: 100 or more
（２）成形品における濡れ性
上記Ｔダイ成形により得られたフィルム表面に、処理エネルギー０．５Ｋｗ、ライン速度３０ｍ／ｍｉｎの条件でコロナ処理した後、２３±２℃湿度５０±５％の恒温恒湿室に６時間静置し、温湿度の平衡状態に達したものについて濡れ性を評価した。
濡れ張力試験はＪＩＳ Ｋ６７６８に準じて下記の方法にて評価した。
(2) Wettability in molded product The film surface obtained by the above T-die molding was subjected to corona treatment under the conditions of treatment energy of 0.5 Kw and line speed of 30 m / min, and then a constant temperature of 23 ± 2 ° C. and humidity of 50 ± 5%. The sample was allowed to stand in a constant humidity chamber for 6 hours, and the wettability of the sample that reached an equilibrium state of temperature and humidity was evaluated.
The wetting tension test was evaluated by the following method according to JIS K6768.
液滴がたれない程度にたっぷり標準液に浸した綿棒を、コロナ処理フィルムの表面に水平に当て、一方向に移動しながら標準液を塗布した。約０．５秒間で塗布が完了するようにした。塗布される液膜の幅はできるだけ広くなるようにし、塗布面積が約６ｃｍ２になるようにした。
塗布した後、液膜が破れず２秒以上塗布された状態を保っている場合を濡れていると判定した。
初期、及び塗布後１週間経過の濡れ指数が、４１ｄｙｎ（４．１×１０−４Ｎ）以上保持しているものを合格とした。
A cotton swab soaked in the standard solution so as not to drip was applied horizontally to the surface of the corona-treated film, and the standard solution was applied while moving in one direction. Application was completed in about 0.5 seconds. The width of the liquid film to be applied was made as wide as possible so that the application area was about 6 cm 2 .
After the application, the liquid film was not torn and the case where it was applied for 2 seconds or more was determined to be wet.
A sample having an initial wetting index of 41 dyn (4.1 × 10 −4 N) or more after 1 week after application was regarded as acceptable.
（３）着色剤組成物における顔料分散性
ラボプラストミル（東洋精機製）５０ｒｐｍ、温度３００℃、フィルター目開き１０μｍの条件で、高密度ポリエチレン（比重０．９６、ＭＦＲ０．４ｇ／１０ｍｉｎ）を通過させ、圧力が一定になったときの樹脂圧力（Ｐ１）を測定した。その後、着色剤組成物を６００ｇ通過させ、次いで前記の高密度ポリエチレンを通過させ、圧力が一定になったときの樹脂圧力（Ｐ２）を測定した。
Ｐ２からＰ１を減じた値を樹脂圧力差（ΔＰ）として分散性の指数とした。ΔＰが小さいほど顔料の分散性が良好であるといえる。
尚、比較例５及び６で得られた着色剤組成物は、着色剤組成物通過中にフィルター目詰まりを起こしたため実験中止とした。
以上の評価結果を表３に示す。
(3) Pigment dispersibility in the colorant composition Laboplast mill (manufactured by Toyo Seiki) passes through high-density polyethylene (specific gravity 0.96, MFR 0.4 g / 10 min) under the conditions of 50 rpm, temperature 300 ° C., and filter opening 10 μm. The resin pressure (P1) when the pressure became constant was measured. Thereafter, 600 g of the colorant composition was passed, and then the high-density polyethylene was passed, and the resin pressure (P2) when the pressure became constant was measured.
A value obtained by subtracting P1 from P2 was taken as a resin pressure difference (ΔP) and used as an index of dispersibility. It can be said that the smaller the ΔP, the better the dispersibility of the pigment.
Note that the colorant compositions obtained in Comparative Examples 5 and 6 were stopped because the filter was clogged while passing through the colorant composition.
The above evaluation results are shown in Table 3.
本発明の成形品は塗装性及び接着性等にも優れるので、これらの用途への展開も可能である。また、着色剤の分散性が良好なため、着色の自由度が高く意匠性や外観に優れた成形品を提供できる。 Since the molded article of the present invention is excellent in paintability and adhesiveness, it can be developed for these uses. In addition, since the dispersibility of the colorant is good, it is possible to provide a molded product having a high degree of freedom in coloring and excellent design and appearance.
Claims (4)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161654A (en) * | 2008-01-07 | 2009-07-23 | Pilot Corporation | Aqueous ink composition for ballpoint pen |
| JP2010150408A (en) * | 2008-12-25 | 2010-07-08 | Sumika Color Kk | Thermoplastic resin composition and sheet with white surface coated therewith |
| JP2011094035A (en) * | 2009-10-29 | 2011-05-12 | Kureha Corp | Polyvinylidene chloride resin composition, method for producing the same, and molded product formed from the resin composition |
| JP2013181123A (en) * | 2012-03-02 | 2013-09-12 | Dainippon Printing Co Ltd | Resin composition for reflector, resin frame for reflector, reflector, semiconductor light emitting device and molding method |
| JP2018178468A (en) * | 2017-04-10 | 2018-11-15 | 凸版印刷株式会社 | Foam wallpaper original fabric and foam wallpaper |
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| JP2010150408A (en) * | 2008-12-25 | 2010-07-08 | Sumika Color Kk | Thermoplastic resin composition and sheet with white surface coated therewith |
| JP2011094035A (en) * | 2009-10-29 | 2011-05-12 | Kureha Corp | Polyvinylidene chloride resin composition, method for producing the same, and molded product formed from the resin composition |
| JP2013181123A (en) * | 2012-03-02 | 2013-09-12 | Dainippon Printing Co Ltd | Resin composition for reflector, resin frame for reflector, reflector, semiconductor light emitting device and molding method |
| JP2018178468A (en) * | 2017-04-10 | 2018-11-15 | 凸版印刷株式会社 | Foam wallpaper original fabric and foam wallpaper |
| JP7069560B2 (en) | 2017-04-10 | 2022-05-18 | 凸版印刷株式会社 | Raw fabric and foam wallpaper for foam wallpaper |
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