JP4908300B2 - Photochromic laminate - Google Patents
Photochromic laminate Download PDFInfo
- Publication number
- JP4908300B2 JP4908300B2 JP2007111095A JP2007111095A JP4908300B2 JP 4908300 B2 JP4908300 B2 JP 4908300B2 JP 2007111095 A JP2007111095 A JP 2007111095A JP 2007111095 A JP2007111095 A JP 2007111095A JP 4908300 B2 JP4908300 B2 JP 4908300B2
- Authority
- JP
- Japan
- Prior art keywords
- photochromic
- parts
- methyl
- laminate
- hexafluorocyclopentene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000009835 boiling Methods 0.000 claims description 6
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- DYZAFEDVNIEMEL-UHFFFAOYSA-N 3-[2-(2,4-dimethyl-5-phenylthiophen-3-yl)-3,3,4,4,5,5-hexafluorocyclopenten-1-yl]-2,4-dimethyl-5-phenylthiophene Chemical compound CC=1SC(C=2C=CC=CC=2)=C(C)C=1C(C(C(F)(F)C1(F)F)(F)F)=C1C(C=1C)=C(C)SC=1C1=CC=CC=C1 DYZAFEDVNIEMEL-UHFFFAOYSA-N 0.000 description 1
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- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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Description
本発明はフォトクロミック積層体に関する。更に詳細には、変色感度、耐光堅牢性及び発色濃度を向上させたジアリールエテン系フォトクロミック材料を用いたフォトクロミック積層体に関する。 The present invention relates to a photochromic laminate. More specifically, the present invention relates to a photochromic laminate using a diarylethene photochromic material with improved color change sensitivity, light fastness and color density.
従来、ジアリールエテン系フォトクロミック化合物を含む材料としては、ジアリールエテン系フォトクロミック化合物をスチレン樹脂又は芳香族化合物に溶解、固着させたもの(例えば、特許文献1参照)、ジアリールエテン系フォトクロミック化合物をマイクロカプセルに内包させたもの(例えば、特許文献2参照)、ジアリールエテン系フォトクロミック化合物と光安定剤を併用したもの(例えば特許文献3)が開示されている。
しかしながら、ジアリールエテン系フォトクロミック化合物をスチレン樹脂に溶解させると、該樹脂が固体であるためフォトクロミック化合物が変色し難くなり、よって、変色感度が損なわれる虞がある。また、トルエン等の芳香族化合物に溶解させると、該芳香族化合物は沸点が低いため蒸発を生じ易く、よって、安定性に欠けると共に組成変化を起こし、一部は溶出して種々の機能に影響を及ぼす虞がある。
また、ジアリールエテン系フォトクロミック化合物をマイクロカプセルに内包する試みは、酸素や水分への影響を低減させる点で効果が認められるが、内包物には依然として樹脂等のバインダーを併用していることから、該樹脂によって変色感度、耐光性、着色時の濃度が不十分であった。
更に、ジアリールエテン系フォトクロミック化合物と種々の光安定剤を併用する試みは、光安定剤の種類によっては逆に光劣化を促進させる傾向があった。
前述したように、従来のジアリールエテン系フォトクロミック化合物を含む材料は種々の不具合を生じ易く、実用性を損なうものであり、支持体上に前記材料を含む光変色層を設けた積層体も同様の不具合を有するものであった。
However, when the diarylethene-based photochromic compound is dissolved in the styrene resin, the photochromic compound is difficult to be discolored because the resin is solid, and there is a possibility that the discoloration sensitivity may be impaired. In addition, when dissolved in an aromatic compound such as toluene, the aromatic compound has a low boiling point and thus tends to evaporate. Therefore, it lacks stability and causes a composition change, and a part of the aromatic compound is eluted to affect various functions. There is a risk of affecting.
In addition, an attempt to encapsulate a diarylethene photochromic compound in a microcapsule is effective in reducing the influence on oxygen and moisture, but the inclusion still contains a binder such as a resin, Resin discoloration sensitivity, light resistance, and concentration during coloring were insufficient.
Furthermore, attempts to use diarylethene-based photochromic compounds in combination with various light stabilizers tend to promote light degradation depending on the type of light stabilizer.
As described above, the material containing the conventional diarylethene-based photochromic compound is liable to cause various problems and impairs practicality, and the laminate having the photochromic layer containing the material on the support has the same problem. It was what had.
発明者らはジアリールエテン系フォトクロミック化合物を溶解する樹脂の種類により発色時の色濃度や発色時の色調が損なわれたり、或いは、フォトクロミック化合物の構造変化によって生じる発消色機能を阻害する固体樹脂に該化合物を溶解して変色感度が損なわれることのない、種々の用途に利用可能な構成を検討した結果、支持体上に、特定の芳香族化合物又はエステル化合物中にジアリールエテン系フォトクロミック化合物を溶解したフォトクロミック材料を含む光変色層を設けることによって、発色時に良好な色調を呈し、しかも、発色時の色濃度が濃いと共に、変色感度に優れたフォトクロミック積層体が得られることを見出した。
即ち、本発明は、支持体上に、ジアリールエテン系フォトクロミック化合物と、融点或いは軟化点が40℃以下であり、且つ、沸点が200℃以上であり、重量平均分子量200乃至6000のスチレン系オリゴマーとをカプセルに内包してなるフォトクロミック顔料を含む光変色層を積層してなるフォトクロミック積層体、或いは、支持体上に、ジアリールエテン系フォトクロミック化合物と、融点或いは軟化点が40℃以下であり、且つ、沸点が200℃以上であり、重量平均分子量200乃至6000のスチレン系オリゴマーとを樹脂粒子中に分散してなるフォトクロミック顔料を含む光変色層を積層してなるフォトクロミック積層体を要件とする。
更には、一般式(A)で示されるフェノール系化合物を含んでなること等を要件とする。
That is, the present invention provides a diarylethene photochromic compound and a styrene oligomer having a melting point or softening point of 40 ° C. or lower and a boiling point of 200 ° C. or higher and a weight average molecular weight of 200 to 6000 on a support. A photochromic laminate obtained by laminating a photochromic pigment containing a photochromic pigment encapsulated in a capsule, or a diarylethene-based photochromic compound on a support and a melting point or softening point of 40 ° C. or lower, and a boiling point A requirement is a photochromic laminate obtained by laminating a photochromic layer containing a photochromic pigment obtained by dispersing a styrene oligomer having a weight average molecular weight of 200 to 6000 in a resin particle at 200 ° C. or higher.
Furthermore, the requirement such that comprising a phenolic compound shown by a general formula (A).
本発明は、ジアリールエテン系フォトクロミック化合物による良好な色調を呈すると共に発色時の色濃度が濃く、しかも、変色感度に優れた実用性を満たすフォトクロミック積層体を提供できる。 INDUSTRIAL APPLICABILITY The present invention can provide a photochromic laminate that exhibits good color tone due to a diarylethene photochromic compound, has a high color density at the time of color development, and satisfies practicality with excellent color change sensitivity.
前記ジアリールエテン系フォトクロミック化合物を以下に例示するが、本発明に用いられるジアリールエテン系フォトクロミック化合物はこれらに限定されるものではない。
ジアリールエテン系フォトクロミック化合物の基本骨格としては一般式(1)で示される化合物が挙げられる。
Examples of the basic skeleton of the diarylethene photochromic compound include compounds represented by the general formula (1).
前記一般式(1)で示される化合物を、一般式(2)又は(3)で具体的に例示する。
更に、別のジアリールエテン系フォトクロミック化合物の基本骨格としては一般式(4)で示される化合物が挙げられる。
前記一般式(4)で示される化合物を、一般式(5)及び(6)で具体的に例示する。
前記した一般式(1)乃至(6)で示される化合物中のB基とC基は、同一或いは異なっていてもよく、次の構造式で示される基を例示できる。
前記B基及びC基について更に具体的には、
前記一般式(2)又は(3)で示される化合物を更に詳しく説明すると、
マレイン酸無水物系化合物としては、
3,4−ビス(1,2−ジメチル−3−インドリル)フラン−2,5−ジオン、
3,4−ジ(2−メチル−3−ベンゾチオフェン)フラン−2,5−ジオン等があげられる。
シクロペンテン系化合物としては、
1−(1,2−ジメチルインドリル)−2−(2−シアノ−3,5−ジメチル−4−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(1,2−ジメチル−3−インドリル)−2−(3−シアノ−2,5−ジメチル−4−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(1,2,−ジメチル−3−インドリル)−2−(2−メチル−3−ベンゾチエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(4−メトキシフェニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(2−(4−メトキシフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(2−(4−シアノフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−(2−(2−キノリル)−1−エテニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−(2−(4−ピリジル)−1−エテニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−(2−(1−ナフチル)−1−エテニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−4−オクチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(2−(4−t−ブチルフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−(2−(2−ベンゾチアジル)−1−エテニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−2−(5−(4−(4−ジメチルアミノフェニル)−1,3−ブタジエニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(4−(4−メトキシフェニル)−1,3−ブタジエニル)−2−メチル−3−ベンゾチエニル)−2−(5−(4−(4−メトキシフェニル)−1,3−ブタジチエニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(6−(4−(4−メトキシフェニル)−1,3−ブタジエニル)−2−メチル−3−ベンゾチエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(6−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(2−(4−ジメチルアミノフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−2−(5−(2−(4−シアノフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−2−(5−(2−(4−シアノフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−2−(5−(2−(4−メトキシフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(4−(4−メトキシフェニル)−1,3−ブタジエニル)−2−メチル−3−ベンゾチエニル)−2−(5−(2−(4−メトキシフェニル)−1−エテニル)−2,4−ジメチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(6−(2−(4−メトキシフェニル)−1−エテニル)−2−メチル−3−ベンゾチエニル)−2−(2,4−ジメチル−(5−(4−(4−メトキシフェニル)−1,3−ブタジエニル))−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(1,2−ジメチル−3−インドリル)−2−(2−シアノ−3−メトキシ−5−メチルチエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン
1,2−ビス(2−メチル−5−フェニル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−フェニル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2−フェニル−5−メチル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2−メチルベンゾチオフェン−3−イル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(3−メチルベンゾチオフェン−2−イル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(3−メチル−2−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2−メチル−6−ニトロ−3−ベンゾチエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−2−チエニル)−2−(2−メチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(5−(4−メチルフェニル)−2−メチル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2,4−ジメチル−5−フェニル−3−チエニル)−2−(2−メチル−5−フェニル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1,2−ビス(2,4−ジメチル−5−(4−メトキシフェニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−5−(4−メチルフェニル)−3−チエニル)−2−(2,4−ジメチル−5−(4−メチルフェニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−5−(4−メトキシフェニル)−3−チエニル)−2−(2,4−ジメチル−5−(4−メトキシフェニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−2−チエニル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチルベンゾチオフェン−2−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチルベンゾチオフェン−3−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−5−メチル−ベンゾチオフェン−3−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−5−フェニル−ベンゾチオフェン−3−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−5−メチル−ベンゾチオフェン−2−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−5−フェニル−ベンゾチオフェン−2−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−6−メチル−ベンゾチオフェン−2−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(3−メチル−6−フェニル−ベンゾチオフェン−2−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−6−メチル−ベンゾチオフェン−3−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン、
1−(2−メチル−6−フェニル−ベンゾチオフェン−3−イル)−2−(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン等が挙げられる。
The compound represented by the general formula (2) or (3) will be described in more detail.
As maleic anhydride compounds,
3,4-bis (1,2-dimethyl-3-indolyl) furan-2,5-dione,
Examples include 3,4-di (2-methyl-3-benzothiophene) furan-2,5-dione.
As cyclopentene compounds,
1- (1,2-dimethylindolyl) -2- (2-cyano-3,5-dimethyl-4-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (1,2-dimethyl-3-indolyl) -2- (3-cyano-2,5-dimethyl-4-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (1,2, -dimethyl-3-indolyl) -2- (2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (5- (4-methoxyphenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (5- (2- (4-methoxyphenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (5- (2- (4-cyanophenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2,4-dimethyl-5- (2- (2-quinolyl) -1-ethenyl) -3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2,4-dimethyl-5- (2- (4-pyridyl) -1-ethenyl) -3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2,4-dimethyl-5- (2- (1-naphthyl) -1-ethenyl) -3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (5- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-4-octyl-3-thienyl) -3,3,4,4,5,5-hexafluoro Cyclopentene,
1,2-bis (5- (2- (4-t-butylphenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluoro Cyclopentene,
1,2-bis (2,4-dimethyl-5- (2- (2-benzothiazyl) -1-ethenyl) -3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (4- (4-dimethylaminophenyl) -1,3- Butadienyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2- (5- (4- (4-methoxyphenyl) -1,3 -Butadithienyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1,2-bis (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (2- (4-Dimethylaminophenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-cyanophenyl) -1-ethenyl) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-cyanophenyl) -1-ethenyl)- 2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-methoxyphenyl) -1-ethenyl)- 2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (4- (4-methoxyphenyl) -1,3-butadienyl) -2-methyl-3-benzothienyl) -2- (5- (2- (4-methoxyphenyl) -1-ethenyl ) -2,4-dimethyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (6- (2- (4-methoxyphenyl) -1-ethenyl) -2-methyl-3-benzothienyl) -2- (2,4-dimethyl- (5- (4- (4-methoxyphenyl) ) -1,3-butadienyl))-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (1,2-Dimethyl-3-indolyl) -2- (2-cyano-3-methoxy-5-methylthienyl) -3,3,4,4,5,5-hexafluorocyclopentene 1,2- Bis (2-methyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2,4-dimethyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2-phenyl-5-methyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methylbenzothiophen-3-yl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (3-methylbenzothiophen-2-yl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (3-methyl-2-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2-methyl-6-nitro-3-benzothienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (3-methyl-2-thienyl) -2- (2-methyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (5- (4-methylphenyl) -2-methyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (2,4-dimethyl-5-phenyl-3-thienyl) -2- (2-methyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1,2-bis (2,4-dimethyl-5- (4-methoxyphenyl) -3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5- (4-methylphenyl) -3-thienyl) -2- (2,4-dimethyl-5- (4-methylphenyl) -3-thienyl) -3,3,4, 4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5- (4-methoxyphenyl) -3-thienyl) -2- (2,4-dimethyl-5- (4-methoxyphenyl) -3-thienyl) -3,3,4 4,5,5-hexafluorocyclopentene,
1- (3-methyl-2-thienyl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (3-methylbenzothiophen-2-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (2-methylbenzothiophen-3-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene,
1- (2-Methyl-5-methyl-benzothiophen-3-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (2-Methyl-5-phenyl-benzothiophen-3-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (3-Methyl-5-methyl-benzothiophen-2-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (3-Methyl-5-phenyl-benzothiophen-2-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (3-Methyl-6-methyl-benzothiophen-2-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (3-Methyl-6-phenyl-benzothiophen-2-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (2-Methyl-6-methyl-benzothiophen-3-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene ,
1- (2-Methyl-6-phenyl-benzothiophen-3-yl) -2- (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene Etc.
前記一般式(5)又は(6)で示される化合物を更に詳しく説明すると、
マレイン酸系化合物としては、2,3−ジ(2−メチルベンゾチエニル)−マレイン酸ジメチル等が挙げられる。
ジシアノエチレン系化合物としては、1,2−ビス(2,3,5−トリメチル−4−チエニル)−1,2−ジシアノエチレン、1,2−ビス(2−メチル−3−ベンゾチエニル)−1,2−ジシアノエチレン等が挙げられる。
The compound represented by the general formula (5) or (6) will be described in more detail.
Examples of maleic acid compounds include 2,3-di (2-methylbenzothienyl) -dimethyl maleate.
Examples of the dicyanoethylene compound include 1,2-bis (2,3,5-trimethyl-4-thienyl) -1,2-dicyanoethylene and 1,2-bis (2-methyl-3-benzothienyl) -1. , 2-dicyanoethylene and the like.
前記ジアリールエテン系フォトクロミック化合物は、沸点が200℃以上であり、重量平均分子量200乃至6000のスチレン系オリゴマーに溶解して用いられる。
前記スチレン系オリゴマーは、好ましくは200乃至4000のスチレン系オリゴマーである。
スチレン系オリゴマーの重量平均分子量が200未満の場合、含有モノマーが多くなり、安定性に欠けるため耐光性向上効果を発現し難くなる。
また、重量平均分子量が6000を越えると、軟化点が高くなり、光照射により色残りが発生し易く、且つ、発色濃度が低くなり、変色感度は鈍くなる傾向にある。
前記スチレン系オリゴマーを以下に例示するが、本発明に用いられるスチレン系オリゴマーはこれらに限定されるものではない。
なお、重量平均分子量は、GPC法(ゲル浸透クロマトグラフ法)により測定する。
前記スチレン系オリゴマーとしては、低分子量ポリスチレン、スチレン−α−メチルスチレン系共重合体、α−メチルスチレン重合体、α−メチルスチレンとビニルトルエンの共重合体等が挙げられる。
スチレン−α−メチルスチレン系共重合体としては、理化ハーキュレス(株)製、商品名:ピコラスチックA5(重量平均分子量317)、ピコラスチックA25(重量平均分子量348)等が用いられる。
α−メチルスチレン重合体としては、理化ハーキュレス(株)製、商品名:クリスタレックス3025等が用いられる。
前記スチレン系オリゴマーは単独で用いてもよいし、2種類以上を併用して用いることもできる。
The diarylethene photochromic compound is used by dissolving in a styrene oligomer having a boiling point of 200 ° C. or higher and a weight average molecular weight of 200 to 6000 .
The styrenic oligomer is preferably a 200-4000 styrenic oligomer.
When the weight average molecular weight of the styrene-based oligomer is less than 200, the amount of the monomer is increased and the stability is insufficient, so that it is difficult to exhibit the effect of improving light resistance.
On the other hand, when the weight average molecular weight exceeds 6000, the softening point becomes high, color residue is likely to occur due to light irradiation, the color density is lowered, and the color change sensitivity tends to be dull.
Illustrate the styrene oligomer to, styrene oligomer used in the present invention is not limited thereto.
The weight average molecular weight is measured by GPC method (gel permeation chromatography).
Examples of the styrene oligomer include low molecular weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, α-methylstyrene and vinyltoluene copolymer , and the like .
As the styrene-α-methylstyrene-based copolymer, Rika Hercules Co., Ltd., trade names: picolastic A5 (weight average molecular weight 317), picolastic A25 (weight average molecular weight 348) and the like are used.
As the α-methylstyrene polymer, Rika Hercules Co., Ltd., trade name: Crystallex 3025 or the like is used.
The styrene oligomers may be used alone or in combination of two or more.
前記フォトクロミック化合物とスチレン系オリゴマーの重量比は、1:1〜1:10000であることが好ましく、より好ましくは1:5〜1:500である。
前記重量比を満たすことによって、耐光性向上効果に優れ、且つ、フォトクロミック化合物は十分な発色濃度を示すことができる。
The weight ratio of the photochromic compound to the styrene oligomer is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 500.
By satisfying the weight ratio, the effect of improving the light resistance is excellent, and the photochromic compound can exhibit a sufficient color density.
前記フォトクロミック化合物とスチレン系オリゴマーは、マイクロカプセルに内包させてフォトクロミック顔料(可逆光変色性微小カプセル顔料)を形成したり、熱可塑性又は熱硬化性樹脂中に分散してフォトクロミック顔料(可逆光変色性樹脂粒子)を形成する。
なお、前記マイクロカプセルは、平均粒子径0.5〜50μm、好ましくは1〜30μm、より好ましくは、1〜10μmの範囲が実用性を満たす。
前記マイクロカプセルの平均粒子径が50μmを越えると、インキ、塗料等の液状組成物への適用に際して、分散安定性に欠ける。
一方、平均粒子径が0.5μm未満では、高濃度の発色性を示し難くなる。
フォトクロミック顔料は、液状組成物中に0.5〜70重量%、好ましくは1〜50重量%の範囲で含有させることができ、視覚効果を満たす。
0.5重量%未満では、低発色濃度であり、光変色による視覚効果を十分に発現でき難い。一方、70重量%以上添加しても含有量に相応する発色濃度が得られ難い。
ここで、非光変色性染料又は顔料を含有して有色(1)から有色(2)へと色変化させることができる。
前記フォトクロミック顔料の発色性を効果的に発現させて高視覚濃度の積層体を形成させるためには、液状組成物のビヒクルは下記測定方法による350nm〜400nmの波長域における乾燥塗膜の光反射率が20%以上であることが好ましく、また、エマルジョン型バインダーを適用した、バインダー自体が溶剤に非溶解状態にある系では反射率30%以上であることが好ましく、バインダーがビヒクルに溶解状態にある系では反射率40%以上であることが好ましい。
測定方法は、ビヒクルを、白色合成紙(白色顔料がブレンドされたポリオレフィン系合成紙)上にバーコーターを使用して約50nmの厚みに塗布し、常温で乾燥して乾燥塗膜を形成して測定試料とし、前記白色合成紙を比較対照試料として、分光光度計〔(株)日立製作所製、自記分光光度計U−3210型〕を使用して、350nm〜400nmの波長域の反射率を測定して求める。
ビヒクルの光反射率が20%未満では、フォトクロミック化合物に対する紫外線の照射効果の有効な発現を阻害し、本来のフォトクロミック化合物の発色濃度を有効に発現させて視覚させる効果に乏しい。
従って、ビヒクルを構成するバインダー樹脂や各種添加物は、紫外線吸収性のないもの、或いは、紫外線吸収性を有するとしても、前記照射効果を阻害しない程度のものが適用される。
なお、紫外線吸収剤等の光安定剤についても、前記照射効果を阻害しない程度であればビヒクル中に添加することができる。
前記マイクロカプセル化は、従来より公知のイソシアネート系の界面重合法、メラミン−ホルマリン系等のin Situ重合法、液中硬化被覆法、水溶液からの相分離法、有機溶媒からの相分離法、融解分散冷却法、気中懸濁被覆法、スプレードライング法等があり、用途に応じて適宜選択される。更に微小カプセルの表面には、目的に応じて更に二次的な樹脂皮膜を設けて耐久性を付与させたり、表面特性を改質させて実用に供することもできる。
The photochromic compound and styrene oligomer are encapsulated in microcapsules to form a photochromic pigment (reversible photochromic microcapsule pigment), or dispersed in a thermoplastic or thermosetting resin to produce a photochromic pigment (reversible photochromic property). Resin particles).
The microcapsules satisfy practicality in the range of an average particle size of 0.5 to 50 μm, preferably 1 to 30 μm, more preferably 1 to 10 μm.
When the average particle size of the microcapsules exceeds 50 μm, the dispersion stability is insufficient when applied to liquid compositions such as inks and paints.
On the other hand, when the average particle size is less than 0.5 μm, it is difficult to exhibit high density color developability.
The photochromic pigment can be contained in the liquid composition in the range of 0.5 to 70% by weight, preferably 1 to 50% by weight, and satisfies the visual effect.
If it is less than 0.5% by weight, the color density is low, and it is difficult to fully develop the visual effect due to photodiscoloration. On the other hand, even when added in an amount of 70% by weight or more, it is difficult to obtain a color density corresponding to the content.
Here, the color can be changed from colored (1) to colored (2) by containing a non-photochromic dye or pigment.
In order to effectively develop the color developability of the photochromic pigment to form a laminate having a high visual density, the vehicle of the liquid composition has a light reflectance of a dry coating film in a wavelength range of 350 nm to 400 nm according to the following measurement method. Is preferably 20% or more, and in a system in which an emulsion type binder is applied and the binder itself is in an insoluble state in the solvent, the reflectance is preferably 30% or more, and the binder is in a dissolved state in the vehicle. In the system, the reflectance is preferably 40% or more.
The measurement method is to apply a vehicle on white synthetic paper (polyolefin synthetic paper blended with white pigment) to a thickness of about 50 nm using a bar coater, and dry at room temperature to form a dry coating film. Using a spectrophotometer (manufactured by Hitachi, Ltd., self-recording spectrophotometer U-3210 type) as a measurement sample and using the white synthetic paper as a comparative control sample, the reflectance in the wavelength range of 350 nm to 400 nm is measured. And ask.
When the light reflectance of the vehicle is less than 20%, the effective expression of the ultraviolet irradiation effect on the photochromic compound is inhibited, and the effect of visualizing the developed color density of the original photochromic compound is poor.
Therefore, the binder resin and various additives constituting the vehicle are those that do not absorb ultraviolet rays, or those that do not inhibit the irradiation effect even if they have ultraviolet absorbing properties.
Note that a light stabilizer such as an ultraviolet absorber can also be added to the vehicle as long as the irradiation effect is not impaired.
The microencapsulation includes conventionally known isocyanate-based interfacial polymerization methods, in-situ polymerization methods such as melamine-formalin, in-liquid curing coating methods, phase separation methods from aqueous solutions, phase separation methods from organic solvents, melting There are a dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Further, a secondary resin film may be provided on the surface of the microcapsules according to the purpose to impart durability, or the surface characteristics may be modified for practical use.
本発明においては、前記フォトクロミック化合物と、スチレン系オリゴマーと共に一般式(A)で示されるフェノール系化合物を含有させることができ、発色濃度が更に濃くなり、また、耐光性が更に向上する効果を有する。
なお、一般式(A)のR’、R’’はそれぞれ水素原子、直鎖又は分枝を有する炭素数1乃至4の炭化水素基から選ばれ、R’’’は直鎖又は分枝を有する炭化水素基である。
前記フェノール系化合物としては、4,4′−ジヒドロキシジフェニルスルフォン、2,2′−ビス(4−ヒドロキシフェニル)プロパン、ビス(4−ヒドロキシフェニル)メタン、1,1′−ビス(4−ヒドロキシフェニル)デカン、1,1′−ビス(4−ヒドロキシフェニル)デカン、1,1′−ビス(4−ヒドロキシフェニル)−2−メチルプロパン、4,4′−(2−エチルヘキサン−1,1−ジイル)ジフェノール、4,4′−(1−メチルエチリデン)−ビス(2−メチル−フェノール)、2,2′−メチレンビス(4−メチルフェノール)、2,2′,6,6′−テトラメチル−4,4′−メチレンジフェノール、ペンタエリスリトールテトラキス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕、チオジエチレンビス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕、オクタデシル−3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、N,N′−ヘキサン−1,6−ジイルビス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニルプロピオナミド〕、ジエチル〔〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル〕メチル〕ホスフォネート、3,3′,3″,5,5′,5″−ヘキサ−tert−ブチル−a,a′,a″−(メシチレン−2,4,6−トリイル)トリ−p−クレゾール、4,6−ビス(オクチルチオメチル)−o−クレゾール、エチレンビス(オキシエチレン)ビス〔3−(5−tert−ブチル−4−ヒドロキシ−m−トリル)プロピオネート〕、ヘキサメチレンビス〔3−(3,5―ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕、1,3,5−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−1,3,5−トリアジン−2,4,6−(1H,3H,5H)−トリオン、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)〔〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル〕メチル〕ブチルマロネート等を例示できる。
In the present invention, the photochromic compound and the phenol compound represented by the general formula (A) can be contained together with the styrene oligomer , and the color density is further increased and the light resistance is further improved. .
In the general formula (A), R ′ and R ″ are each selected from a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R ′ ″ is a linear or branched group. It is a hydrocarbon group.
Examples of the phenol compound include 4,4′-dihydroxydiphenyl sulfone, 2,2′-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, and 1,1′-bis (4-hydroxyphenyl). ) Decane, 1,1'-bis (4-hydroxyphenyl) decane, 1,1'-bis (4-hydroxyphenyl) -2-methylpropane, 4,4 '-(2-ethylhexane-1,1- Diyl) diphenol, 4,4 '-(1-methylethylidene) -bis (2-methyl-phenol), 2,2'-methylenebis (4-methylphenol), 2,2', 6,6'-tetra Methyl-4,4'-methylenediphenol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione ), Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide], diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl ) Tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydro Cym-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Examples include [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate.
本発明においては、前記フォトクロミック顔料をビヒクル中に分散して、塗料や印刷インキ等の液状組成物を調製し、従来より公知の方法、例えば、スクリーン印刷、オフセット印刷、グラビヤ印刷、コーター、タンポ印刷、転写等の印刷手段、刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装、等の手段により、紙、合成紙、糸、布帛、植毛或いは起毛布、不織布、合成皮革、レザー、プラスチック、ガラス、陶磁器、木材、石材、金属等の支持体上に光変色層を形成してフォトクロミック積層体を得る。
なお、前記光変色層は、液状組成物中の溶剤が揮発してそれ以外の化合物により形成される層であり、前記フォトクロミック顔料は樹脂に分散状態に固着されてなる。
前記積層体の形態としては、光変色層が支持体表面に層状に固着された形態、支持体内部にフォトクロミック材料が含浸固着され、表面に一部を露出させた形態を含み、プラスチック等の非浸透性基材からなる各種造形物、繊維及び紙製加工体等を例示でき、具体例としては、被服、履物、貴金属、照明器具、玩具、造花、文房具、日用品、台所用品、化粧用具、運動用具、書籍等の印刷物、乗物、機械、屋内装飾品、医療品等が挙げられる。
また、熱可塑性樹脂や熱硬化性樹脂中に前記フォトクロミック材料をブレンドした成形用樹脂組成物により成形した成形物を支持体上に貼着して積層体を形成してもよい。
In the present invention, the photochromic pigment is dispersed in a vehicle to prepare a liquid composition such as paint or printing ink, and conventionally known methods such as screen printing, offset printing, gravure printing, coater, tampo printing. , Printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, paper, synthetic paper, thread, fabric, flocked or brushed fabric, non-woven fabric A photochromic laminate is obtained by forming a photochromic layer on a support such as synthetic leather, leather, plastic, glass, ceramics, wood, stone, or metal.
In addition, the said photochromic layer is a layer formed by the compound in which the solvent in a liquid composition volatilizes, and the said photochromic pigment adheres to a resin in the dispersion state.
Forms of the laminate include a form in which the photochromic layer is fixed in a layered manner on the surface of the support, a form in which the photochromic material is impregnated and fixed inside the support, and a part of the surface is exposed, and a non-plastic or the like is included. Examples of various shaped articles made of permeable base materials, fibers and paper processed bodies, etc., include clothes, footwear, precious metals, lighting equipment, toys, artificial flowers, stationery, daily necessities, kitchen utensils, cosmetics, exercise Examples include tools, printed materials such as books, vehicles, machines, interior decorations, and medical products.
Further, a laminate may be formed by sticking a molded product formed by a molding resin composition obtained by blending the photochromic material into a thermoplastic resin or a thermosetting resin on a support.
更に、前記積層体の光変色層上には、光安定剤を含む層を積層することによって耐光性を向上させたり、或いは、トップコート層を設けて耐久性を向上させることもできる。 Furthermore, it is possible to improve light resistance by laminating a layer containing a light stabilizer on the photochromic layer of the laminate, or to improve durability by providing a topcoat layer.
以下に実施例を示すが、本発明はこれらに限定されるものではない。
なお、実施例中の部は、質量部を示す。
実施例1
フォトクロミック顔料の調製
ジアリールエテン系フォトクロミック化合物A(1,2−ビス(2−メチル−5−フェニル−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン)1部、スチレン−α−メチルスチレン共重合体(重量平均分子量317、商品名:ピコラスティックA5)50部を内包物として混合した後、膜材として芳香族イソシアネートプレポリマー20部、酢酸エチル20部からなる溶液に前記内包物を混入し、15%ゼラチン水溶液100重量部に投入して微小滴になるように攪拌し、70℃で1時間反応を行った。
次いで、液温を90℃に保って3時間攪拌を続け、マイクロカプセル分散液を調整した後、遠心分離法によりマイクロカプセル形態のフォトクロミック顔料を得た。
Examples are shown below, but the present invention is not limited thereto.
In addition, the part in an Example shows a mass part.
Example 1
Preparation of photochromic pigment 1 part of diarylethene photochromic compound A (1,2-bis (2-methyl-5-phenyl-3-thienyl) -3,3,4,4,5,5-hexafluorocyclopentene), styrene- After mixing 50 parts of an α-methylstyrene copolymer (weight average molecular weight 317, trade name: pico-stick A5) as an inclusion, a solution comprising 20 parts of an aromatic isocyanate prepolymer and 20 parts of ethyl acetate as a film material was added to the solution. The inclusions were mixed, put into 100 parts by weight of a 15% gelatin aqueous solution, stirred to form fine droplets, and reacted at 70 ° C. for 1 hour.
Next, stirring was continued for 3 hours while maintaining the liquid temperature at 90 ° C. to prepare a microcapsule dispersion, and a microcapsule-type photochromic pigment was obtained by a centrifugal separation method.
以下の表1に実施例1乃至10、比較例1乃至8のフォトクロミック顔料の組成を示す。表中の括弧内の数字は重量部を示す。
なお、表中の材料について以下に示す。
ジアリールエテン系フォトクロミック化合物B:1,2−ビス(5−メチル−2−フェニル−4−チアゾイル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン(ピンク色)、
ジアリールエテン系フォトクロミック化合物C:1−(2,4−ジメチル−5−(4−メチル−フェニル)−3−チエニル)−2−(2−メチル−5−(4−メチル−フェニル)−3−チエニル)−3,3,4,4,5,5−ヘキサフルオロシクロペンテン(青色)、
イルガノックス1035(商品名):チオジエチレンビス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕、
イルガノックス259(商品名):ヘキサメチレンビス〔3−(3,5−−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート〕、
イルガノックス3114(商品名):1,3,5−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−1,3,5−トリアジン−2,4,6(1H,3H,5H)−トリオン、
イルガノックス1520(商品名):4,6−ビス(オクチルチオメチル)−o−クレゾールであり、
イルガノックス1222(商品名):ジエチル〔〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル〕メチル〕ホスフォネート、
ピコラスティックA75(商品名):軟化点が75℃のスチレン−α−メチルスチレン共重合体、
実施例2乃至8、比較例5乃至8は表中の組成を内包液として、実施例1と同様の方法によりマイクロカプセル形態のフォトクロミック顔料を作製した。
実施例9については、表中の実施例9の組成を内包液として混合した後、エチレン−無水マレイン酸共重合体(米国モンサント化学社製、商品名:EMA−31、分子量75000〜90000)の10%水溶液100部に、尿素10部、レゾルシン1部、水55部を添加し、水酸化ナトリウムの20%水溶液を添加してpHを3.5に調整した後、前記内包液を攪拌しながら投入し、油滴の平均粒子径が約3μmになるまで乳化した。
次に、前記溶液に37%ホルムアルデヒド水溶液25部を加え、温度を65℃に調整したまま2時間放置した後、遠心分離法によりマイクロカプセル形態のフォトクロミック顔料を得た。
実施例10については、表中の実施例10の組成物を内包液として、スチレン樹脂15部、トルエン40部からなる混合溶液に前記内包液を混入し、10%ポリビニルアルコール水溶液100重量部に投入して微小滴になるように攪拌し、70℃で1時間反応を行った。次いで、液温を90℃に保って10時間攪拌を続け、微小樹脂粒子分散液を調整した後、遠心分離法により樹脂粒子形態のフォトクロミック顔料を得た。
Table 1 below shows the compositions of the photochromic pigments of Examples 1 to 10 and Comparative Examples 1 to 8. The numbers in parentheses in the table indicate parts by weight.
In addition, it shows below about the material in a table | surface.
Diarylethene-based photochromic compound B: 1,2-bis (5-methyl-2-phenyl-4-thiazoyl) -3,3,4,4,5,5-hexafluorocyclopentene (pink),
Diarylethene-based photochromic compound C: 1- (2,4-dimethyl-5- (4-methyl-phenyl) -3-thienyl) -2- (2-methyl-5- (4-methyl-phenyl) -3-thienyl ) -3,3,4,4,5,5-hexafluorocyclopentene (blue),
Irganox 1035 (trade name): thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Irganox 259 (trade name): hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Irganox 3114 (trade name): 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione,
Irganox 1520 (trade name): 4,6-bis (octylthiomethyl) -o-cresol,
Irganox 1222 (trade name): diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate,
Picola stick A75 (trade name): styrene-α-methylstyrene copolymer having a softening point of 75 ° C.,
In Examples 2 to 8 and Comparative Examples 5 to 8 , microcapsule-type photochromic pigments were produced in the same manner as in Example 1, using the composition in the table as the inclusion liquid.
For Example 9, it was mixed with the composition of Example 9 in the table as containing solution, ethylene - maleic anhydride copolymer (Monsanto Chemical Co., Ltd., trade name: EMA-31, molecular weight 75,000 to 90,000) of To 100 parts of a 10% aqueous solution, 10 parts of urea, 1 part of resorcin, and 55 parts of water are added, and a 20% aqueous solution of sodium hydroxide is added to adjust the pH to 3.5, and then the inclusion liquid is stirred. The resulting mixture was emulsified until the average particle size of the oil droplets was about 3 μm.
Next, 25 parts of a 37% formaldehyde aqueous solution was added to the solution, and the mixture was allowed to stand for 2 hours while adjusting the temperature to 65 ° C., and then a photochromic pigment in the form of microcapsules was obtained by a centrifugal separation method.
For Examples 10, the composition of Example 10 in the table as containing solution, 15 parts of styrene resin, mixed with the encapsulated liquid into a mixed solution consisting of 40 parts of toluene, poured into 10% aqueous solution of polyvinyl alcohol 100 parts by weight The mixture was stirred to form fine droplets and reacted at 70 ° C. for 1 hour. Next, stirring was continued for 10 hours while maintaining the liquid temperature at 90 ° C. to prepare a fine resin particle dispersion, and then a photochromic pigment in the form of resin particles was obtained by centrifugation.
フォトクロミック積層体の作製
前記実施例1乃至10のフォトクロミック顔料40部、アクリル系樹脂エマルジョン60部、粘度調整剤2部、消泡剤1部を均一に分散、混合しインキを調製し、スクリーン印刷により支持体(白色合成紙)に印刷してフォロクロミック積層体1乃至10を作製した。
Preparation of a photochromic laminate 40 parts of the photochromic pigment of Examples 1 to 10 , 60 parts of an acrylic resin emulsion, 2 parts of a viscosity modifier, and 1 part of an antifoaming agent are uniformly dispersed and mixed to prepare an ink, and screen printing is performed. Phorochromic laminates 1 to 10 were produced by printing on a support (white synthetic paper).
フォトクロミック積層体11(比較例1)
比較例1のフォトクロミック顔料101部をバーコーターにて支持体(白色合成紙上)にウェット膜が厚み90μmになるように塗工した後、乾燥させてフォトクロミック積層体を得た。
Photochromic laminate 11 (Comparative Example 1)
101 parts of the photochromic pigment of Comparative Example 1 was coated on a support (on white synthetic paper) with a bar coater so that the wet film had a thickness of 90 μm, and then dried to obtain a photochromic laminate.
フォトクロミック積層体12(比較例2)
比較例2のフォトクロミック顔料101部、シリコーン系樹脂添加剤1部を均一に分散した後、スクリーン印刷により、支持体(白色合成紙上)上に印刷してフォトクロミック積層体を得た。
Photochromic laminate 12 (Comparative Example 2)
101 parts of the photochromic pigment of Comparative Example 2 and 1 part of the silicone resin additive were uniformly dispersed, and then printed on a support (on white synthetic paper) by screen printing to obtain a photochromic laminate.
フォトクロミック積層体13(比較例3)
比較例3の組成101部、シリコーン系樹脂添加剤1部を均一に分散した後、スクリーン印刷により、支持体(白色合成紙上)上に印刷してフォトクロミック積層体を得た。
Photochromic laminate 13 (Comparative Example 3)
101 parts of the composition of Comparative Example 3 and 1 part of the silicone resin additive were uniformly dispersed, and then printed on a support (on white synthetic paper) by screen printing to obtain a photochromic laminate.
フォトクロミック積層体14(比較例4)
比較例4の組成101部、シリコーン系樹脂添加剤1部を均一に分散した後、スクリーン印刷により、支持体(白色合成紙上)上に印刷してフォトクロミック積層体を得た。
Photochromic laminate 14 (Comparative Example 4)
101 parts of the composition of Comparative Example 4 and 1 part of the silicone resin additive were uniformly dispersed, and then printed on a support (on white synthetic paper) by screen printing to obtain a photochromic laminate.
フォトクロミック積層体15乃至18の作製
前記比較例5乃至8のフォトクロミック顔料40部、アクリル系樹脂エマルジョン60部、粘度調整剤2部、消泡剤1部を均一に分散、混合しインキを調製し、スクリーン印刷により支持体(白色合成紙上)上に印刷してフォトクロミック積層体15乃至18を作製した。
Preparation of photochromic laminates 15 to 18 40 parts of the photochromic pigment of Comparative Examples 5 to 8, 60 parts of an acrylic resin emulsion, 2 parts of a viscosity modifier, and 1 part of an antifoaming agent are uniformly dispersed and mixed to prepare an ink. Photochromic laminates 15 to 18 were produced by printing on a support (on white synthetic paper) by screen printing.
初期発色濃度試験
前記各フォトクロミック積層体を光源〔東芝ライテック(株)製、電球形蛍光ランプ、商品名:ネオボール5ブラックライトEFD15BLB〕から10cm離して1分間光照射した後、色差計〔東京電色(株)製、TC−3600)にて、明度値(Y値から換算)を測定した。
なお、明度値は数字が大きい程、色濃度が低く、小さい程、色濃度が高い。
耐光性試験
各フォトクロミック積層体に卓上型耐光性試験機(ヘレウス社製、SUNTEST CPS)を用いて照度140000luxにて1時間、2時間、3時間、4時間、5時間、光照射した後、前記色差計にて、明度値を測定した。
Initial Color Density Test Each photochromic laminate was irradiated with light for 10 minutes from a light source (manufactured by Toshiba Lighting & Technology Co., Ltd., bulb-type fluorescent lamp, product name: Neoball 5 Black Light EFD15BLB), and then color difference meter [Tokyo Denshoku The brightness value (converted from the Y value) was measured with TC-3600 manufactured by Co., Ltd.
The lightness value has a higher color density as the number is larger and lower as the color value is smaller.
Light resistance test Each photochromic laminate was irradiated with light for 1 hour, 2 hours, 3 hours, 4 hours, 5 hours at an illuminance of 140000 lux using a tabletop light resistance tester (manufactured by Heraeus, SUNTEST CPS). The brightness value was measured with a color difference meter.
以下の表に各フォトクロミック積層体の初期発色濃度、及び、耐光性試験結果を示す。
なお、表中の耐光性試験の評価に関する記号は以下のとおりである。
◎:初期と比較して100〜80%の色濃度を保持している。
○:初期と比較して80〜60%の色濃度を保持している。
△:初期と比較して60〜40%の色濃度を保持している。
▲:初期と比較して40〜20%の色濃度を保持している。
×:初期と比較して20〜0%の色濃度を保持している。
The symbols related to the evaluation of the light resistance test in the table are as follows.
(Double-circle): The color density of 100 to 80% is hold | maintained compared with the initial stage.
A: The color density of 80 to 60% is maintained compared to the initial value.
(Triangle | delta): The color density of 60 to 40% is hold | maintained compared with the initial stage.
(Triangle | delta): The color density of 40 to 20% is hold | maintained compared with the initial stage.
X: The color density of 20 to 0% is maintained as compared with the initial value.
発色感度試験
東芝ライテック(株)製、電球形蛍光ランプ、商品名:ネオボール5ブラックライトEFD15BLBを用いて、530μW/cm2の強度の位置にフォトクロミック積層体を置き、時間毎に発色濃度を東京電飾社製MODEL TC−3600にてY値を測定し、明度値に変換した。
消色感度試験
紫外線照射により完全発色させたフォトクロミック積層体を色差計(東京電飾社製、MODEL TC−3600)に設置されたランプ(東芝ネオハロゲンミニJ12V2020W−AXS)にて4600Luxの条件下で照射して時間毎に消色濃度を東京電飾社製MODEL TC−3600にてY値を測定し、明度値に変換した。
Color-sensitivity test TOSHIBA LIGHTING Co., Ltd., light bulb-type fluorescent lamp, product name: Neoball 5 Black Light EFD15BLB is used to place a photochromic laminate at an intensity of 530 μW / cm 2 , and the color density is changed every time by TEPCO The Y value was measured with a decorative model MODEL TC-3600 and converted to a brightness value.
Decolorization sensitivity test A photochromic laminate that was completely colored by ultraviolet irradiation was placed on a color difference meter (Model Den TC-3600, manufactured by Tokyo Electric Decoration Co., Ltd.) under the condition of 4600 Lux under the condition of Toshiba Neohalogen Mini J12V2020W-AXS. The Y value was measured with MODEL TC-3600 manufactured by Tokyo Denka Co., Ltd. and converted to a lightness value every time after irradiation.
以下の表に各フォトクロミック積層体の発色感度試験、及び、消色感度試験結果を示す。
なお、試験はフォトクロミック積層体1、1−1、2、2−1、15、16、18を用いた。
フォトクロミック積層体1−1については、実施例1のフォトクロミック顔料40部、アクリル系樹脂エマルジョン60部、粘度調整剤2部、消泡剤1部を均一に分散、混合しインキを調製し、スクリーン印刷により支持体(白色ケント紙)に印刷して作製した。
フォトクロミック積層体2−1については、実施例2のフォトクロミック顔料40部、アクリル系樹脂エマルジョン60部、粘度調整剤2部、消泡剤1部を均一に分散、混合しインキを調製し、スクリーン印刷により支持体(白色ケント紙)に印刷して作製した。
The table below shows the color development sensitivity test and decolorization sensitivity test results of each photochromic laminate.
In addition, the test used the photochromic laminated body 1,1-1,2,2-1,15,16,18.
For the photochromic laminate 1-1, 40 parts of the photochromic pigment of Example 1, 60 parts of the acrylic resin emulsion, 2 parts of the viscosity modifier, and 1 part of the antifoaming agent are uniformly dispersed and mixed to prepare ink, and screen printing is performed. And printed on a support (white Kent paper).
For the photochromic laminate 2-1, 40 parts of the photochromic pigment of Example 2, 60 parts of the acrylic resin emulsion, 2 parts of the viscosity modifier, and 1 part of the antifoaming agent are uniformly dispersed and mixed to prepare ink, and screen printing is performed. And printed on a support (white Kent paper).
応用例1
フォトクロミック積層体の作製
実施例2のフォトクロミック顔料10部を、アクリル樹脂(ロームアンドハース社製、商品名:パラロイドB−72)の15%キシレン溶液に均一に分散し、更にキシレン及びメチルイソブチルケトンを用いて希釈して液状組成物(塗料)を得た。
前記塗料を用いて支持体として白色の軟質塩化ビニル製シート(厚さ200μm)上にスプレーガンにて塗装し、フォトクロミック積層体を得た。
前記積層体に太陽光を照射するとピンク色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記ピンク色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色からピンク色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 1
Preparation of photochromic laminate 10 parts of the photochromic pigment of Example 2 were uniformly dispersed in a 15% xylene solution of acrylic resin (Rohm and Haas, trade name: Paraloid B-72), and further xylene and methyl isobutyl ketone were added. A liquid composition (paint) was obtained by diluting with use.
Using the coating material, a white soft vinyl chloride sheet (thickness: 200 μm) was coated as a support with a spray gun to obtain a photochromic laminate.
When the laminated body was irradiated with sunlight, it turned pink, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the pink laminate is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case, and other light ( Since visible light was irradiated, the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it is taken out from the case and irradiated with sunlight, it changes from white to pink due to the ultraviolet light contained in the sunlight, and this state is maintained without discoloring outdoors, indoors, or in dark places. did.
This color change could be repeated.
応用例2
フォトクロミック積層体の作製
実施例4のフォトクロミック顔料30重量部を、アクリル酸エステル樹脂エマルジョン45.0部、消泡剤1.0部、希釈水23.0部からなるビヒクル中に均一分散し、180メッシュスクリーンでろ過してフォトクロミック液状組成物(スプレー塗料)を得た。
前記スプレー塗料をスプレーガン(口径0.6mm)に充填して白色布帛(支持体)の全面に塗装を施した後、乾燥させて光変色層を形成してフォトクロミック積層体(フォトクロミック布帛)を得た。
前記布帛を縫製して、人形用の水着を作製した。
前記積層体に太陽光を照射すると青色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記青色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色から青色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 2
Production of Photochromic Laminate 30 parts by weight of the photochromic pigment of Example 4 is uniformly dispersed in a vehicle comprising 45.0 parts of an acrylic ester resin emulsion, 1.0 part of an antifoaming agent, and 23.0 parts of diluted water, 180 It filtered with the mesh screen and obtained the photochromic liquid composition (spray paint).
The spray paint is filled in a spray gun (diameter 0.6 mm), the entire surface of the white fabric (support) is coated, and then dried to form a photochromic layer to obtain a photochromic laminate (photochromic fabric). It was.
The fabric was sewed to prepare a swimsuit for a doll.
When the laminate was irradiated with sunlight, it turned blue, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the blue laminate is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case and other light (visible) is visible. Light), the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it was taken out from the case and irradiated with sunlight, it changed from white to blue by the ultraviolet light contained in the sunlight, and this state was maintained without discoloring outdoors, indoors, or in dark places. .
This color change could be repeated.
応用例3
フォトクロミック積層体の作製
実施例10のフォトクロミック顔料35重量部、及び、青色顔料1重量部を、軟質エポキシ樹脂45.0部、低粘度エポキシ樹脂20.0部、ヒンダードアミン系光安定剤6.0部、揺変性付与剤2.0部、消泡剤0.3部からなるビヒクル中に均一に分散混合した後、常温硬化型の脂肪族ポリアミン40.0部を均一に攪拌混合してフォトクロミック液状組成物(軟質エポキシインキ)を得た。
前記インキを白色ミニチュアハウス成形物の屋根(支持体)に刷毛を用いて塗装し、70℃で1時間加温硬化させて光変色層を形成し、フォトクロミック積層体(フォトクロミックミニチュアハウス)を得た。
前記積層体に太陽光を照射すると紫色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記紫色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して青色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって青色から紫色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 3
Production of Photochromic Laminate 35 parts by weight of the photochromic pigment of Example 10 and 1 part by weight of the blue pigment were mixed with 45.0 parts of a soft epoxy resin, 20.0 parts of a low viscosity epoxy resin, and 6.0 parts of a hindered amine light stabilizer. Then, after uniformly dispersing and mixing in a vehicle composed of 2.0 parts of thixotropic agent and 0.3 part of antifoaming agent, 40.0 parts of room temperature curing type aliphatic polyamine is uniformly stirred and mixed to produce a photochromic liquid composition. A product (soft epoxy ink) was obtained.
The ink was applied to the roof (support) of a white miniature house molding with a brush and heated and cured at 70 ° C. for 1 hour to form a photochromic layer to obtain a photochromic laminate (photochromic miniature house). .
When the laminate was irradiated with sunlight, it turned purple, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the purple laminate is accommodated in a colorless and transparent polyester resin case having ultraviolet absorption ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case and other light (visible) is visible. Light), the color gradually changed to blue, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it is taken out from the case and irradiated with sunlight, it changes from blue to purple due to the ultraviolet light contained in the sunlight, and this state is maintained without discoloring in any place, outdoors, indoors, and dark places. .
This color change could be repeated.
応用例4
フォトクロミック積層体の作製
実施例4のフォトクロミック顔料20.0部、及び、実施例10のフォトクロミック顔料20.0部を、硬質液状エポキシ樹脂60.0部、ヒンダードアミン系光安定剤2.0部、揺変性付与剤2.0部、消泡剤0.5部からなるビヒクル中に均一に分散混合した後、常温硬化型の脂肪族ポリアミン35.0部を添加し、均一に分散混合してフォトクロミック液状組成物(エポキシインキ)を得た。
前記インキを白色マグカップ(支持体)の表面にスクリーン印刷にて丸形状に印刷し、70℃で1時間加温硬化させて光変色層を形成し、フォトクロミック積層体(フォトクロミックマグカップ)を得た。
前記積層体に太陽光を照射すると紫色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記紫色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色から紫色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 4
Preparation of Photochromic Laminate 20.0 parts of the photochromic pigment of Example 4 and 20.0 parts of the photochromic pigment of Example 10 were mixed with 60.0 parts of a hard liquid epoxy resin, 2.0 parts of a hindered amine light stabilizer, After uniformly dispersing and mixing in a vehicle composed of 2.0 parts of a modification imparting agent and 0.5 part of an antifoaming agent, 35.0 parts of a room temperature curing type aliphatic polyamine is added and uniformly dispersed and mixed to form a photochromic liquid. A composition (epoxy ink) was obtained.
The ink was printed in a round shape on the surface of a white mug (support) by screen printing and heated and cured at 70 ° C. for 1 hour to form a photochromic layer to obtain a photochromic laminate (photochromic mug).
When the laminate was irradiated with sunlight, it turned purple, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the purple laminate is accommodated in a colorless and transparent polyester resin case having ultraviolet absorption ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case and other light (visible) is visible. Light), the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it was taken out from the case and irradiated with sunlight, it changed from white to purple by the ultraviolet light contained in the sunlight, and this state was maintained without discoloring in any place, outdoors, indoors, and dark places. .
This color change could be repeated.
応用例5
フォトクロミック積層体の作製
実施例10のフォトクロミック顔料40.0部を、エチレン酢酸ビニル共重合樹脂エマルジョン58.0部、消泡剤3.0部、増粘剤(アルギン酸ナトリウム)1.0部、レベリング剤3.0部、防腐剤1.0部からなるビヒクル中に均一に混合してフォトクロミック液状組成物(スクリーンインキ)を得た。
白色合成紙(支持体)上に前記スクリーンインキを用いて桃の図柄の光変色層を形成してフォトクロミック積層体(フォトクロミック印刷物)を得た。
前記積層体に太陽光を照射するとピンク色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記ピンク色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色からピンク色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 5
Production of Photochromic Laminate 40.0 parts of the photochromic pigment of Example 10 were mixed with 58.0 parts of an ethylene vinyl acetate copolymer resin emulsion, 3.0 parts of an antifoaming agent, 1.0 part of a thickener (sodium alginate), and leveling. A photochromic liquid composition (screen ink) was obtained by uniformly mixing in a vehicle comprising 3.0 parts of an agent and 1.0 part of a preservative.
A photochromic layer (photochromic printed matter) was obtained by forming a photochromic layer having a peach pattern on the white synthetic paper (support) using the screen ink.
When the laminated body was irradiated with sunlight, it turned pink, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the pink laminate is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case, and other light ( Since visible light was irradiated, the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it is taken out from the case and irradiated with sunlight, it changes from white to pink due to the ultraviolet light contained in the sunlight, and this state is maintained without discoloring outdoors, indoors, or in dark places. did.
This color change could be repeated.
応用例6
フォトクロミック積層体の作製
実施例4のフォトクロミック顔料30.0部を、アクリル酸エステル樹脂エマルジョン80.0部、水分散ヒンダードアミン系光安定剤1.5部からなるビヒクル中に均一に分散してフォトクロミック液状組成物(水性コーティング溶液)を得た。
フォトクロミック積層体の作製
前記コーティング溶液中に、70mmの長さにカットした7デニールのポリアクリロニトリル原綿100.0重量部を浸漬させた後、遠心分離により余分なコーティング溶液を除去して90℃で10分間乾燥させてフォトクロミック積層体(フォトクロミックポリアクリロニトリル原綿)を得た。
前記原綿をカードにかけてスライバーにした後、ハイパイル編み機で製編しシャーリング加工してパイル長20mmのフォトクロミックハイパイル生地を得た。
前記積層体に太陽光を照射すると青色になり、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記青色の積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色から青色に変化し、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 6
Preparation of Photochromic Laminate 30.0 parts of the photochromic pigment of Example 4 was uniformly dispersed in a vehicle composed of 80.0 parts of an acrylic ester resin emulsion and 1.5 parts of a water-dispersed hindered amine light stabilizer to produce a photochromic liquid. A composition (aqueous coating solution) was obtained.
Preparation of Photochromic Laminate 100.0 parts by weight of 7 denier polyacrylonitrile raw cotton cut to a length of 70 mm was immersed in the coating solution, and then the excess coating solution was removed by centrifugation to remove the coating solution at 90 ° C. It was made to dry for minutes and the photochromic laminated body (photochromic polyacrylonitrile raw cotton) was obtained.
The raw cotton was carded into a sliver, then knitted with a high pile knitting machine and sheared to obtain a photochromic high pile fabric having a pile length of 20 mm.
When the laminate was irradiated with sunlight, it turned blue, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the blue laminate is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case and other light (visible) is visible. Light), the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place.
After that, when it was taken out from the case and irradiated with sunlight, it changed from white to blue by the ultraviolet light contained in the sunlight, and this state was maintained without discoloring outdoors, indoors, or in dark places. .
This color change could be repeated.
応用例7
フォトクロミック積層体の作製
実施例4のフォトクロミック顔料15.0重量部を、アクリル樹脂(50%)を含むキシレン溶液25.0重量部、シクロヘキサノン10.0重量部、イソシアネート系硬化剤5.0重量部、消泡剤1.0重量部からなるビヒクル中に均一に混合してフォトクロミック液状組成物(タンポ印刷インキ)を得た。
白色の筒型ABS製成形体(支持体)上に前記タンポ印刷インキを用いて「ABC」の文字を印刷し、次に、その上からアクリル系樹脂(50%)を含むキシレン溶液25.0重量部、メチルイソブチルケトン30.0重量部、キシレン10.0重量部、イソシアネート系硬化剤5.0重量部からなる透明インキ(乾燥塗装膜での400nmの光透過率80%)をスプレー塗装し、50℃で加温、硬化を行って光変色層を形成してフォトクロミック積層体(フォトクロミック成形体)を得た。
前記積層体に太陽光を照射すると青色の「ABC」の文字が現れ、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記青色文字が現れた積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂製ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれかの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって白色から青色の「ABC」の文字が現れ、この状態は屋外、屋内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 7
Production of Photochromic Laminate 15.0 parts by weight of the photochromic pigment of Example 4 is 25.0 parts by weight of a xylene solution containing an acrylic resin (50%), 10.0 parts by weight of cyclohexanone, and 5.0 parts by weight of an isocyanate curing agent. The mixture was uniformly mixed in a vehicle composed of 1.0 part by weight of an antifoaming agent to obtain a photochromic liquid composition (tampo printing ink).
The letter “ABC” is printed on the white cylindrical ABS molded body (support) using the tampo printing ink, and then a xylene solution 25.0 containing acrylic resin (50%) is formed thereon. Spray coating with clear ink (light transmittance of 400 nm at dry coating film 80%) consisting of 3 parts by weight, 30.0 parts by weight of methyl isobutyl ketone, 10.0 parts by weight of xylene and 5.0 parts by weight of isocyanate curing agent. The photochromic layer was formed by heating and curing at 50 ° C. to obtain a photochromic laminate (photochromic molded product).
When the laminated body was irradiated with sunlight, blue letters “ABC” appeared, and this state was not erased even in a dark place and was not erased in a normal use state.
Next, when the laminated body in which the blue characters appear is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case, Since light (visible light) was irradiated, the color gradually changed to white, and this state was maintained without being discolored even when left in a room or in a dark place. .
After that, when it is taken out from the case and irradiated with sunlight, the letters "ABC" from white to blue appear by the ultraviolet light contained in the sunlight, and this state does not change color in any place, outdoors, indoors, and dark places. That state was maintained.
This color change could be repeated.
応用例8
フォトクロミック積層体の作製
実施例10のフォトクロミック顔料40.0部を、エチレン酢酸ビニル共重合樹脂エマルジョン58.0部、消泡剤3.0部、増粘剤(アルギン酸ナトリウム)1.0部、レベリング剤3.0部、防腐剤1.0部からなるビヒクル中に均一に混合してフォトクロミック液状組成物1(スクリーンインキ1)を得た。
実施例4のフォトクロミック顔料40.0部を、エチレン酢酸ビニル共重合樹脂エマルジョン58.0部、消泡剤3.0部、増粘剤(アルギン酸ナトリウム)1.0部、レベリング剤3.0部、防腐剤1.0部からなるビヒクル中に均一に混合してフォトクロミック液状組成物2(スクリーンインキ2)を得た。
実施例1のフォトクロミック顔料20.0部、実施例2のフォトクロミック顔料20.0部を、エチレン酢酸ビニル共重合樹脂エマルジョン58.0部、消泡剤3.0部、増粘剤(アルギン酸ナトリウム)1.0部、レベリング剤3.0部、防腐剤1.0部からなるビヒクル中に均一に混合してフォトクロミック液状組成物3(スクリーンインキ3)を得た。
白色合成紙上に、前記スクリーンインキ1を用いて「1」の数字(光変色層)をスクリーン印刷により形成した。次いで、前記白色合成紙上の「1」の数字の近傍に前記スクリーンインキ2を用いて「2」の数字(光変色層)と、スクリーンインキ3を用いて「3」の数字(光変色層)をスクリーン印刷により形成してフォトクロミック積層体(フォトクロミック印刷物)を得た。
前記積層体は太陽光に曝露する前は白色であったが、太陽光を照射すると青色の「1」の数字、ピンク色の「2」の数字、紫色の「3」の数字が現れ、この状態は暗所でも消色することなく、通常の使用状態では消色しなかった。
次に前記数字が現れた積層体を、紫外線吸収能を有する無色透明のポリエステル樹脂性ケースに収容して太陽光を照射すると、太陽光に含まれる紫外光はケースにより遮断され、それ以外の光(可視光)が照射されるため、徐々に変色して白色になり、この状態は、室内、暗所のいずれの場所で放置しても変色することなく、その状態を維持していた。
その後、ケースから取り出して太陽光を照射すると太陽光に含まれる紫外光によって、白色から青色の「1」の数字、ピンク色の「2」の数字、紫色の「3」の数字が現れ、この状態は屋外、室内、暗所のいずれの場所でも変色することなく、その状態を維持した。
この色変化は繰り返し行うことができた。
Application example 8
Production of Photochromic Laminate 40.0 parts of the photochromic pigment of Example 10 were mixed with 58.0 parts of an ethylene vinyl acetate copolymer resin emulsion, 3.0 parts of an antifoaming agent, 1.0 part of a thickener (sodium alginate), and leveling. A photochromic liquid composition 1 (screen ink 1) was obtained by uniformly mixing in a vehicle comprising 3.0 parts of an agent and 1.0 part of a preservative.
40.0 parts of the photochromic pigment of Example 4 is 58.0 parts of an ethylene vinyl acetate copolymer resin emulsion, 3.0 parts of an antifoaming agent, 1.0 part of a thickener (sodium alginate), and 3.0 parts of a leveling agent. A photochromic liquid composition 2 (screen ink 2) was obtained by uniformly mixing in a vehicle comprising 1.0 part of a preservative.
20.0 parts of the photochromic pigment of Example 1, 20.0 parts of the photochromic pigment of Example 2, 58.0 parts of ethylene vinyl acetate copolymer resin emulsion, 3.0 parts of antifoaming agent, thickener (sodium alginate) A photochromic liquid composition 3 (screen ink 3) was obtained by uniformly mixing in a vehicle comprising 1.0 part, 3.0 parts of a leveling agent and 1.0 part of a preservative.
On the white synthetic paper, the number “1” (photochromic layer) was formed by screen printing using the screen ink 1. Next, in the vicinity of the number “1” on the white synthetic paper, the number “2” (photochromic layer) using the screen ink 2 and the number “3” (photochromic layer) using the screen ink 3 Was formed by screen printing to obtain a photochromic laminate (photochromic printed matter).
The laminate was white before exposure to sunlight, but when exposed to sunlight, blue numbers “1”, pink numbers “2” and purple numbers “3” appear. The condition was not erased even in a dark place and was not erased under normal use conditions.
Next, when the laminate on which the numbers appear is housed in a colorless and transparent polyester resin case having ultraviolet absorbing ability and irradiated with sunlight, the ultraviolet light contained in the sunlight is blocked by the case, and the other light Since (visible light) was irradiated, the color gradually changed to white, and this state was maintained without being discolored even if left in a room or a dark place.
After that, when it is taken out from the case and irradiated with sunlight, the ultraviolet light contained in the sunlight will cause white to blue numbers “1”, pink numbers “2” and purple numbers “3”. The state was maintained without discoloring outdoors, indoors, or in dark places.
This color change could be repeated.
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