JP3698640B2 - 2- (2'-Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole type II crystal modification, process for its preparation, and composition containing it - Google Patents

Description

【０００９】
本発明の第２は、請求項１記載の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールII型結晶変態を含有し、パウダーテストによる圧縮度が３５以下である２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール組成物に関する。なお、本明細書の記載における２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール組成物とは、化合物としては１種類であるが、いろいろの結晶変態を含んでいるという点で化合物の末尾に組成物を付加したものである。
【００１０】
本発明の第３は、請求項１記載の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールII型結晶変態を２０％以上含有する２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール組成物に関する。
【００１１】
本発明の第４は、請求項１記載の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールII型結晶変態を含有するか、または請求項２あるいは３記載の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール組成物を含有することを特徴とする紫外線吸収剤に関する。
【００１２】
本発明の第５は、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールを無溶媒または難溶性溶媒の存在下、晶析またはフレーク化するに当り、結晶を溶解または融解させないように７０〜７９℃の範囲で加熱処理することを特徴とする請求項１記載の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールII型結晶変態の製造方法に関する。
【００１３】
本発明者らは、市販品の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールＩ型結晶変態の流動性を評価するために、先ず、パウダーテストによる圧縮度を測定した。その圧縮度は４０〜４３の範囲にあり、平均が４２であった。通常、パウダーテストによる圧縮度は、粉体の流動性と最も関係が深い因子として知られており、その測定値が小さいほど流動性が良いとされており、圧縮度が４０以上の粉体は、流動性が悪いとされている。このことから、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール市販品（Ｉ型結晶変態）の流動性が悪いことは明らかである。
【００１４】
そこで、本発明者らは、この結果をもとに研究を重ね、流動性のよい粉体を得るため、種々検討した結果、晶析またはフレーク化する時、結晶を溶解または融解させないように適当な条件で熱処理して得られたフレーク状結晶または組成物（粉体）は、圧縮度が３５以下、通常３０付近を示す、市販品より明らかに圧縮度が小さく流動性が良い粉体が得られることを見出した。圧縮度の測定は〔００２５〕〜〔００２８〕に記載した。
【００１５】
このような晶析条件の違いから、同一化合物であっても、物性が変わることは良く知られているが、全ての化合物に当てはまるわけではない。例えば、本発明の化合物と類似化合物である２−（２′−ヒドロキシ−５′−メチルフェニル）ベンゾトリアゾールについて本発明と同様の要領で行っても本発明のような結晶変態を得られない。すなわち、本発明における現象は、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールの特有の性質である。また、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールに関しては、今まで結晶の分析に関する知見が全くなく、本発明の結果は容易に見出せるものではない。
【００１６】
さらに、本発明者らは、得られた粉体の特徴を更に明確にするため、Ｃｕ−Ｋα線による粉末Ｘ線回折分析を行った。その結果、既知の結晶変態である市販品は、回折角（２θ±０．１°）５．５°、１０．４°、１１．０°、１４．３°、１６．５°、１７．８°、１８．８°に強いピークを有するＩ型（図２参照）であるのに対し、本発明で得られた流動性のよい粉体は、回折角（２θ±０．１°）５．６°、７．３°、９．４°、１０．５°、１３．０°、１３．７°、１６．０°、１６．４°、１８．３°、１８．７°に強いピークを有する（明らかなピークの保存が認められる）新規な結晶変態のII型であることを見出した。また、Ｉ型は、７９〜８２℃の融点を有するのに対し、II型は、８６〜８８℃の融点を有する知見も得た。
【００１７】
さらに本発明者らは、本発明のII型の結晶変態と流動性について研究を重ねたところ、II型の結晶変態またはＩ型結晶変態とII型の結晶変態の混合物（II型が２０重量％以上）は、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールを無溶媒または難溶解性溶媒の存在下で、晶析またはフレーク化するに当り溶融又は溶解させないように適当な条件すなわち７０〜７９℃、好ましくは７６〜７９℃で熱処理することにより簡便に得ることができることも分った。なお、加熱処理の条件によってはII型結晶変態の他に従来型のＩ型結晶変態を含有することがある。例えば、７９℃で１時間程度加熱処理するとＩ型結晶変態とII型結晶変態の混合物を得ることができる。
【００１８】
II型を得るために使用する難溶性溶媒としては、水およびメタノール、エタノール、イソプロピルアルコール、ｎ−プロパノール、イソブタノール、ｎ−ブタノール、シクロヘキサノール、エチレングリコール、プロピレングリコールなどのアルコール類、ジオキサン、テトラヒドロフラン、ジブチルエーテル、エチルイソアミルエーテル、エチルフェニルエーテルなどのエーテル類、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカン、３−エチルヘキサン、シクロヘキサン、メチルシクロヘキサン、トルエン、エチルベンゼン、クメン、ｏ−シメン、ｐ−シメン、ｍ−シメン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、ｔ−ブチルベンゼン、１−ブチル−４−メチルベンゼン、１−ブチル−２−メチルベンゼン、１，２，３−トリメチルベンゼン、１，２，４−トリメチルベンゼン、１，３，５−トリメチルベンゼン、１，２，４，５−テトラメチルベンゼンなどの炭化水素類、酢酸エチル、酢酸ブチル、プロピオン酸エチルなどのカルボン酸エステル類、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、クロロホルム、塩化メチレン、四塩化炭素、１，２−ジクロロエタン、クロロベンゼン、ｏ−ジクロロベンゼンなどの有機ハロゲン化物、ホルムアミド、アセトアミド、キノリン、トリエチルアミン、ｎ−ブチルアミン、２−メチルピロリドンなどの含窒素化合物類を用いることができ、１種類あるいは混合溶媒で用いることができる。
【００１９】
溶媒の使用量および混合割合は、結晶が溶解せずにスラリー状態であること以外は、特に制限されるものではないが、当然、収率は、溶解度に大きく影響される。
【００２０】
また、得られた結晶は、市販品の結晶変態であるＩ型と比べ、圧縮度が小さく、流動性が良いこと、さらに、II型とＩ型の混合物を晶析および／または別々製造したII型とＩ型をブレンドして用いることができ、その混合割合は、II型が２０％以上、好ましくは４０％以上、更に好ましくは５０％以上含有する組成物であれば、依然として流動性が良いことを見出し問題を解決するに至った。II型とＩ型の混合割合は、それぞれ単独の結晶変態でのＤＳＣ測定による融解熱量比より検量線を作成し決定した。
【００２１】
すなわち、本発明によれば、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールを無溶媒または難溶性溶媒の存在下、７０〜７９℃、好ましくは、７６℃〜７９℃の範囲で加熱撹拌することで、Ｃｕ−Ｋα線による粉末Ｘ線回折分析において、回折角（２θ±０．１°）５．６°、７．３°、９．４°、１０．５°、１３．０°、１３．７°、１６．０°、１６．４°、１８．３°、１８．７°に強いピークを有するII型およびII型とＩ型の混合物が粉体またはフレーク状結晶として得ることができる。
【００２２】
【実施例】
以下に本発明を実施例によって説明するが、本発明はこれらにより何ら限定されるものではない。
【００２３】
ＤＳＣ測定は、ＴＡインスツルメント２９２０型ＤＳＣを用いて、試料量を１〜３ｍｇ、炉内雰囲気を窒素気流５０ｍｌ／ｍｉｎ昇温速度を２．０℃／ｍｉｎの条件で行った。
【００２４】
Ｃｕ−Ｋα線による粉末Ｘ線回折分析は、マックサイエンス製ＴＦＤ−１８ｋｗを用いて、対陰極Ｃｕ−Ｋα（１．５４０５Å）、４０ｋＶ−５０ｍＡ、走査速度２．０００°／ｍｉｎの条件で行った。また、粉末Ｘ線回折分析による回折角（２θ）は同一結晶型のものであれば、±０．１°程度の誤差で一致するものであるので、結晶変態の違いを明確に示すものであり、回折線の相対強度は、測定試料の粒径により、強度比が変化することがある。
【００２５】
パウダーテストは、ホソカワミクロンパウダーテスターＴＹＰＥ−Ｅを使用し、見掛比重の測定に、直径５ｃｍの１００ｃｃ円柱容器を使用した。
【００２６】
ゆるめ見掛比重の測定操作は、容器に粉体を山盛りになるまで静かに充填し、容器面より上にある余分な粉体をすり切って重量を測定した。ゆるめ見掛比重は、このときの粉体の重量（ｇ）÷１００で求めた。
【００２７】
かため見掛比重は、ゆるめ見掛比重のときと同様に粉体を充填し、タッピングを１８０回行った後、容器面より上にある余分な粉体をすり切って重量を測定した。かため見掛比重は、このときの粉体の重量（ｇ）÷１００で求めた。
【００２８】
また、圧縮度は、ゆるめ見掛比重をＡ、かため見掛比重をＰとし、下記式より算出した。
【数１】
圧縮度＝１００（Ｐ−Ａ）／Ｐ
【００２９】
実施例１
１０００ｍｌ四つロフラスコに２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール−Ｎ−オキシド３３０ｇ（０．８９８ｍｏｌ）、５％パラジウムカーボン３．０ｇ、トルエン：２−プロパノール：水（容量比１０：２：１の割合に混合）６００ｍｌ、及びシュウ酸２水和物１０ｇ（０．０８ｍｏｌ）を入れ３０〜４０℃で攪拌しながら水素を吹き込んだ。吸収された水素量を補いながら、１５時間反応を行った。反応終了後、水素添加触媒をろ別し〔ろ液の一部をＨＰＬＣにより定量した所、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールの生成率は９９．０％であった。〕、溶媒層の残留酸性物質を水洗浄により除去した後、溶媒等を留去し、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールの粗製物を固形物として得た。晶析溶媒として、トルエン１０ｍｌ、メタノール３００ｍｌ、水４５０ｍｌを加え、７７〜７９℃で２時間撹拌した。固形物は、完全に溶解することなく、スラリーの状態であった。室温に冷却後、ろ過し、３０５．０ｇ（収率９７．０％）の収量で白色結晶性粉末の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールを得た。得られた結晶のＣｕ−Ｋα線による粉末Ｘ線回折分析の結果は、図１に示すとおり回折角（２θ±０．１°）５．６°、７．３°、９．４°、１０．５°、１３．０°、１３．７°、１６．０°、１６．４°、１８．３°、１８．７°に強いピークを有するII型であった。また、ＤＳＣ分析の結果は、８７℃に１本の吸熱ピークを示した。さらに、得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３０】
実施例２
５００ｍｌ四つ口フラスコに２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール５０．０ｇを仕込み、７７〜７９℃で２４時間撹拌した。粉末は、淡黄色から白色に変化した。室温に冷却し、白色粉末を得た。得られた結晶のＤＳＣ分析の結果は、８７℃に１本の吸熱ピークを示した。また、Ｃｕ−Ｋα線による粉末Ｘ線回折分析の結果は、図１に示す通り、回折角（２θ±０．１°）５．６°、７．３°、９．４°、１０．５°、１３．０°、１３．７°、１６．０°、１６．４°、１８．３°、１８．７°に強いピークを有するII型であった。さらに、得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３１】
実施例３
５００ｍｌ四つ口フラスコに２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール５０．０ｇ、４０％メタノール水溶液４００ｍｌを仕込み、７９℃で１０時間撹拌した。室温に冷却した後、ろ別、乾燥し、白色結晶４９．９ｇを得た。得られた結晶のＤＳＣ分析の結果は、８７℃に１本の吸熱ピークを示した。また、Ｃｕ−Ｋα線による粉末Ｘ線回折分析の結果は、図１に示す通り、回折角（２θ±０．１°）５．６°、７．３°、９．４°、１０．５°、１３．０°、１３．７°、１６．０°、１６．４°、１８．３°、１８．７°に強いピークを有するII型であった。さらに、得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３２】
実施例４
５００ｍｌ四つ口フラスコに２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾール５０．０ｇ、４０％メタノール水溶液４００ｍｌを仕込み、７０〜７５℃で２時間撹拌した。室温に冷却した後、ろ別、乾燥し、白色結晶４９．９ｇを得た。図３に示した通り、Ｃｕ−Ｋα線による粉末Ｘ線回折分析の結果から、得られた結晶は、明らかにI型とII型の混合物であることを示した。また、得られた結晶の混合割合をＤＳＣ測定により、求めた結果、I型（８１℃）とII型（８７℃）は、重量比で３０（I型）：７０（II型）であった。そのＤＳＣ測定結果を図４に示した。
さらに、得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３３】
実施例５
II 型２５ｇと後述の比較例１で得られたＩ型７５ｇを混合した。得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３４】
比較例１
実施例４と同様に反応を行い、（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールの粗製物を固形物として得た。晶析溶媒として、トルエン５０ｍｌ、メタノール５００ｍｌを加え、７０℃で溶解後、再結晶を行い、３０３．０ｇ（収率９６．０％）の微黄色結晶性粉末の２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）ベンゾトリアゾールを得た。Ｃｕ−Ｋα線による粉末Ｘ線回折分析の結果は、図２に示す通り、回折角（２θ±０．１°）５．５°、１０．４°、１１．０°、１４．３°、１６．５°、１７．８°、１８．８°に強いピークを有する市販品と同じＩ型であった。さらに、得られた結晶について、パウダーテスターをもちいて、圧縮度を測定した結果を表１に示した。
【００３５】
【表１】

【００３６】
【発明の効果】
実施例とその表１に示したように、本発明によって、II型の結晶変態およびII型の結晶変態を２０％以上含有する組成物は、見掛比重が大きく、圧縮度が小さい結晶として得ることができ、市販品より、流動性が良く、粉体の取り扱いに有利なことは、明らかである。
【図面の簡単な説明】
【図１】図１は、実施例１、２および３で得た本発明の新規な結晶変態であるII型のＸ線回折パターンである。
【図２】図２は、市販品の既知の結晶変態であるＩ型のＸ線回折パターンである。
【図３】図３は、実施例４で得たＩ型とII型の混合物のＸ線回折パターンである。
【図４】図４は、実施例４で得たＩ型とII型の混合物のＤＳＣチャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole having a novel type II crystal modification, a process for producing the same, a composition containing the same, and an ultraviolet ray using the same It relates to an absorbent.
[0002]
[Prior art]
In recent years, the demand for additives such as flame retardants, antioxidants, and UV absorbers has increased with the increasing use of polymer products such as various plastics, synthetic rubbers, nylon fibers, and resin paints. In particular, the use of UV absorbers is an important issue in order to prevent degradation of polymer products such as cracking and discoloration due to ultraviolet rays, while the differentiation and high added value of polymer products are advancing. A stable supply of the agent is required.
[0003]
2- (2′-Hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole is generally used as an ultraviolet absorber for plastics, paints, oils, fibers, etc., and is manufactured by Tinuvin 328K (Ciba Specialty) Name), Seasorb 704 (trade name of Sipro Kasei Co., Ltd.), and KEMISORB 74 (trade name of Chemipro Kasei Co., Ltd.) are commercially available in powder form.
[0004]
Properties of 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole commercially available product (known crystal modification type I, Fig. 2 is its X-ray diffraction pattern) Is a fine powder with a small bulk specific gravity, and there is a problem in workability that powder scattering and partial aggregation occur during handling such as drying, packing process, weighing at the time of use, and preparation. Further, at the time of transportation and storage, depending on the storage conditions, local solidification occurs and the fluidity of the powder deteriorates. Therefore, it is desired to provide a powder with good fluidity that does not affect the workability when handling the powder.
[0005]
JP-A-2-134370 discloses a method for producing 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole in the presence of a platinum catalyst and an organic amine. In the method of catalytic hydrogenation, JP-A-7-228576, JP-A-7-228577 and JP-A-8-217762, a hydrogenation catalyst in which o-nitroazobenzenes are poisoned with a sulfur compound and basicity are disclosed. JP-A-2000-154180 discloses a method of reducing 2-phenylbenzotriazole-N-oxides with a hydrogenation catalyst and hydrogen in the presence of an acidic substance. However, there is no description about the crystal modification of the product.
[0006]
Usually, a compound having a plurality of crystal modifications has different properties depending on the crystal modification, and even if it is the same compound, it is known that its functionality and physical properties are different. For example, JP-A-6-128195 and JP-A-6-72960 disclose differences in bulk specific gravity, particle size distribution, and fluidity of the powder for each crystal modification in the same compound. Obtaining knowledge of crystal transformation in this way is important for improving the added value and quality of products. The X-ray diffraction method and the melting point measurement are practical methods for analyzing substances from the viewpoint of crystals, and are used in many fields such as distinction of crystal transformation and development of functional new materials.
[0007]
[Problems to be solved by the invention]
It is an object of the present invention to provide a type II crystal modification of 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, which is easy to handle such as workability during use and has good fluidity, and a process for producing the same Another object of the present invention is to provide a composition containing the same and an ultraviolet absorber using them.
[0008]
[Means for Solving the Problems]
In the first aspect of the present invention, in powder X-ray diffraction analysis using Cu-Kα rays, diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, 9.4 °, 10.5 °, 13 2- (2′-hydroxy-3) represented by the following formula (1) showing diffraction peaks at 0.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 ° and 18.7 °. The present invention relates to a ', 5'-di-t-amylphenyl) benzotriazole crystal modification (this crystal modification may be hereinafter referred to as type II).
[Chemical formula 2]

[0009]
A second aspect of the present invention contains the 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1, and has a degree of compression by powder test of 35. The following relates to a 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole composition. Incidentally, the 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole composition in the description of the present specification is one kind of compound, but various crystal modifications. The composition is added to the end of the compound in that it contains it .
[0010]
According to a third aspect of the present invention, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1 containing 20% or more of 2- (2' -Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole composition.
[0011]
A fourth aspect of the present invention contains the 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1, or the claim 2 or 3 The present invention relates to an ultraviolet absorber comprising the described 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole composition.
[0012]
The fifth aspect of the present invention is to crystallize or flake 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole in the absence of a solvent or a hardly soluble solvent . The 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzoate according to claim 1, which is heat-treated in the range of 70 to 79 ° C so as not to dissolve or melt the crystals. The present invention relates to a method for producing a triazole type II crystal modification.
[0013]
In order to evaluate the fluidity of the commercially available 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole type I crystal modification, the inventors first performed a powder test. The degree of compression was measured. The degree of compression was in the range of 40 to 43, with an average of 42. Usually, the compressibility by the powder test is known as the factor most closely related to the fluidity of the powder. The smaller the measured value, the better the fluidity. It is said that the fluidity is bad. From this, it is clear that the flowability of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole commercial product (type I crystal modification) is poor.
[0014]
Therefore, the present inventors have conducted research based on this result, and obtained various fluids to obtain a powder with good fluidity. As a result of various studies, the inventors of the present invention are suitable not to dissolve or melt crystals when crystallizing or flaking. The flaky crystals or composition (powder) obtained by heat treatment under various conditions gives a powder with a compressibility of 35 or less and usually around 30, which is clearly less compressible than commercial products and has good fluidity. I found out that The measurement of the degree of compression was described in [0025] to [0028].
[0015]
It is well known that the physical properties change even with the same compound due to the difference in crystallization conditions, but this does not apply to all compounds. For example, even if 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, which is a similar compound to the compound of the present invention, is carried out in the same manner as in the present invention, the crystal modification as in the present invention cannot be obtained. That is, the phenomenon in the present invention is a characteristic property of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole. Further, regarding 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, there is no knowledge about the analysis of crystals so far, and the results of the present invention cannot be easily found. .
[0016]
Furthermore, in order to further clarify the characteristics of the obtained powder, the present inventors performed powder X-ray diffraction analysis using Cu—Kα rays. As a result, commercially available products having known crystal modifications have diffraction angles (2θ ± 0.1 °) of 5.5 °, 10.4 °, 11.0 °, 14.3 °, 16.5 °, 17. Whereas it is type I having strong peaks at 8 ° and 18.8 ° (see FIG. 2), the powder having good fluidity obtained by the present invention has a diffraction angle (2θ ± 0.1 °) of 5 Strong against .6 °, 7.3 °, 9.4 °, 10.5 °, 13.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 °, 18.7 ° It was found to be a novel crystal modification type II having a peak (a clear peak preservation was observed). In addition, it was found that type I has a melting point of 79 to 82 ° C, whereas type II has a melting point of 86 to 88 ° C.
[0017]
Furthermore, the present inventors conducted research on the type II crystal modification and fluidity of the present invention, and as a result, the type II crystal modification or a mixture of the type I crystal modification and the type II crystal modification (II type is 20% by weight). The above is a method for melting or crystallization of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole in the absence of a solvent or in the presence of a hardly soluble solvent. It has also been found that it can be easily obtained by heat treatment under suitable conditions, that is, 70 to 79 ° C., preferably 76 to 79 ° C. so as not to dissolve. Depending on the conditions of the heat treatment, a conventional type I crystal modification may be contained in addition to the type II crystal modification. For example, when heat treatment is performed at 79 ° C. for about 1 hour, a mixture of type I crystal modification and type II crystal modification can be obtained.
[0018]
As the poorly soluble solvent used for obtaining type II, water and alcohols such as methanol, ethanol, isopropyl alcohol, n-propanol, isobutanol, n-butanol, cyclohexanol, ethylene glycol, propylene glycol, dioxane, tetrahydrofuran , Ethers such as dibutyl ether, ethyl isoamyl ether, ethyl phenyl ether, n-pentane, n-hexane, n-heptane, n-octane, n-decane, 3-ethylhexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, Cumene, o-cymene, p-cymene, m-cymene, o-xylene, m-xylene, p-xylene, t-butylbenzene, 1-butyl-4-methylbenzene, 1-butyl-2-methylbenzene Hydrocarbons such as 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,4,5-tetramethylbenzene, ethyl acetate, butyl acetate, Carboxylic acid esters such as ethyl propionate, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, organic halides such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene, formamide , Acetamide, quinoline, triethylamine, n-butylamine, 2-methylpyrrolidone and other nitrogen-containing compounds can be used, and one kind or a mixed solvent can be used.
[0019]
The amount of the solvent used and the mixing ratio are not particularly limited except that the crystals are not dissolved but are in a slurry state, but the yield is naturally greatly influenced by the solubility.
[0020]
In addition, the obtained crystal has a smaller degree of compression and better fluidity than the commercially available type I, which is a crystal modification, and further, a mixture of type II and type I is crystallized and / or separately produced II A mold and an I-type can be blended and used, and if the mixing ratio of the type II is 20% or more, preferably 40% or more, more preferably 50% or more, the fluidity is still good. I found out that the problem was solved. The mixing ratio of type II and type I was determined by preparing a calibration curve from the heat of fusion ratio by DSC measurement in each single crystal transformation.
[0021]
That is, according to the present invention, 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole is formed at 70 to 79 ° C. in the absence of a solvent or a hardly soluble solvent, preferably, By heating and stirring in the range of 76 ° C to 79 ° C, in powder X-ray diffraction analysis using Cu-Kα rays, diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, and 9.4 ° Type II and mixtures of Type II and Type I with strong peaks at 10.5 °, 13.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 °, 18.7 ° Can be obtained as powder or flaky crystals.
[0022]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[0023]
The DSC measurement was performed using a TA instrument 2920 type DSC under the conditions of a sample amount of 1 to 3 mg and a furnace atmosphere with a nitrogen air flow of 50 ml / min and a heating rate of 2.0 ° C./min.
[0024]
Powder X-ray diffraction analysis using Cu-Kα rays was performed using TFD-18 kw manufactured by Mac Science under the conditions of counter-cathode Cu-Kα (1.5405 mm), 40 kV-50 mA, and scanning speed of 2.000 ° / min. . Moreover, if the diffraction angle (2θ) by powder X-ray diffraction analysis is of the same crystal type, it matches with an error of about ± 0.1 °, and thus clearly shows the difference in crystal transformation. The relative intensity of diffraction lines may vary in intensity ratio depending on the particle size of the measurement sample.
[0025]
In the powder test, Hosokawa Micron Powder Tester TYPE-E was used, and a 100 cc cylindrical container having a diameter of 5 cm was used for measuring the apparent specific gravity.
[0026]
In the measurement operation of the loose apparent specific gravity, the container was gently filled with the powder until it piled up, and the excess powder above the container surface was scraped off and the weight was measured. The loose apparent specific gravity was determined by the weight of the powder at this time (g) / 100.
[0027]
For the apparent specific gravity, the powder was filled in the same manner as in the case of the loose apparent specific gravity, tapping was performed 180 times, and then the excess powder above the container surface was ground to measure the weight. The apparent specific gravity was determined by the weight of the powder at this time (g) / 100.
[0028]
The degree of compression was calculated from the following equation, with the loose apparent specific gravity being A and the apparent specific gravity being P.
[Expression 1]
Compressibility = 100 (P−A) / P
[0029]
Example 1
In a 1000 ml four-flask flask, 330 g (0.898 mol) of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole-N-oxide, 3.0 g of 5% palladium carbon, toluene: 2 -600 ml of propanol: water (mixed at a volume ratio of 10: 2: 1) and 10 g (0.08 mol) of oxalic acid dihydrate were added, and hydrogen was blown into the mixture while stirring at 30 to 40 ° C. The reaction was carried out for 15 hours while supplementing the amount of absorbed hydrogen. After completion of the reaction, the hydrogenation catalyst was removed by filtration [a part of the filtrate was quantified by HPLC, and the yield of 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole] Was 99.0%. ] After removing the residual acidic substance in the solvent layer by washing with water, the solvent and the like were distilled off to obtain a crude product of 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole. Obtained as a solid. As a crystallization solvent, 10 ml of toluene, 300 ml of methanol and 450 ml of water were added and stirred at 77 to 79 ° C. for 2 hours. The solid was in a slurry state without completely dissolving. After cooling to room temperature, it was filtered and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole was obtained as white crystalline powder in a yield of 305.0 g (97.0% yield). Got. The results of powder X-ray diffraction analysis of the obtained crystals by Cu—Kα rays are as shown in FIG. 1, with diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, 9.4 °, 10 ° It was a type II having strong peaks at .5 °, 13.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 ° and 18.7 °. Moreover, the result of DSC analysis showed one endothermic peak at 87 ° C. Furthermore, Table 1 shows the results of measuring the degree of compression of the obtained crystals using a powder tester.
[0030]
Example 2
A 500 ml four-necked flask was charged with 50.0 g of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole and stirred at 77 to 79 ° C. for 24 hours. The powder changed from pale yellow to white. Cooled to room temperature to give a white powder. The results of DSC analysis of the obtained crystal showed one endothermic peak at 87 ° C. The results of powder X-ray diffraction analysis using Cu-Kα rays are as shown in FIG. 1, and diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, 9.4 °, 10.5 It was a type II having strong peaks at °, 13.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 ° and 18.7 °. Furthermore, Table 1 shows the results of measuring the degree of compression of the obtained crystals using a powder tester.
[0031]
Example 3
A 500 ml four-necked flask was charged with 50.0 g of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole and 400 ml of 40% aqueous methanol solution, and stirred at 79 ° C. for 10 hours. After cooling to room temperature, it was filtered and dried to obtain 49.9 g of white crystals. The results of DSC analysis of the obtained crystal showed one endothermic peak at 87 ° C. The results of powder X-ray diffraction analysis using Cu-Kα rays are as shown in FIG. 1, and diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, 9.4 °, 10.5 It was a type II having strong peaks at °, 13.0 °, 13.7 °, 16.0 °, 16.4 °, 18.3 ° and 18.7 °. Furthermore, Table 1 shows the results of measuring the degree of compression of the obtained crystals using a powder tester.
[0032]
Example 4
A 500 ml four-necked flask was charged with 50.0 g of 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole and 400 ml of 40% aqueous methanol solution, and stirred at 70 to 75 ° C. for 2 hours. . After cooling to room temperature, it was filtered and dried to obtain 49.9 g of white crystals. As shown in FIG. 3, from the result of powder X-ray diffraction analysis using Cu—Kα ray, the obtained crystal was clearly a mixture of type I and type II. Further, the mixing ratio of the obtained crystals was determined by DSC measurement. As a result, type I (81 ° C.) and type II (87 ° C.) were 30 (I type): 70 (II type) in weight ratio. . The DSC measurement result is shown in FIG.
Furthermore, Table 1 shows the results of measuring the degree of compression of the obtained crystals using a powder tester.
[0033]
Example 5
25 g of type II and 75 g of type I obtained in Comparative Example 1 described later were mixed. Table 1 shows the results of measuring the compression degree of the obtained crystals using a powder tester.
[0034]
Comparative Example 1
The reaction was carried out in the same manner as in Example 4 to obtain a crude product of (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole as a solid. As a crystallization solvent, 50 ml of toluene and 500 ml of methanol were added and dissolved at 70 ° C., followed by recrystallization, and 303.0 g (yield 96.0%) of 2- (2′-hydroxy-) as a slightly yellow crystalline powder. 3 ', 5'-di-t-amylphenyl) benzotriazole was obtained. As shown in FIG. 2, the results of powder X-ray diffraction analysis using Cu-Kα rays are as follows. Diffraction angles (2θ ± 0.1 °) 5.5 °, 10.4 °, 11.0 °, 14.3 °, It was the same type I as a commercial product having strong peaks at 16.5 °, 17.8 °, and 18.8 °. Furthermore, Table 1 shows the results of measuring the degree of compression of the obtained crystals using a powder tester.
[0035]
[Table 1]

[0036]
【The invention's effect】
As shown in the Examples and Table 1, according to the present invention, a composition containing 20% or more of the II type crystal modification and the II type crystal modification is obtained as a crystal having a large apparent specific gravity and a small degree of compression. It is clear that it has better flowability than commercial products and is advantageous for handling powder.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction pattern of type II which is a novel crystal modification of the present invention obtained in Examples 1, 2 and 3. FIG.
FIG. 2 is an X-ray diffraction pattern of type I, which is a known crystal modification of a commercially available product.
FIG. 3 is an X-ray diffraction pattern of a mixture of type I and type II obtained in Example 4.
4 is a DSC chart of a mixture of type I and type II obtained in Example 4. FIG.

Claims (5)

In powder X-ray diffraction analysis by Cu-Kα ray, diffraction angles (2θ ± 0.1 °) of 5.6 °, 7.3 °, 9.4 °, 10.5 °, 13.0 °, 13.7 2- (2'-hydroxy-3 ', 5'-di-) represented by the following formula (1) showing diffraction peaks at °, 16.0 °, 16.4 °, 18.3 ° and 18.7 °. t-Amylphenyl) benzotriazole crystal modification (this crystal modification may hereinafter be referred to as type II).

  A 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1, which has a degree of compression by powder test of 35 or less. '-Hydroxy-3', 5'-di-t-amylphenyl) benzotriazole composition.   2- (2'-hydroxy-3 ', 5 containing 20% or more of the 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1. '-Di-t-amylphenyl) benzotriazole composition.   The 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1 or the 2- (2' An ultraviolet absorber comprising a -hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole composition. When 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole is crystallized or flaked in the absence of a solvent or a poorly soluble solvent , the crystal should not be dissolved or melted. The production of 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole type II crystal modification according to claim 1, wherein the heat treatment is carried out at 70 to 79 ° C. Method.

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