JPH01500276A - Irreversible photochromism display - Google Patents

Irreversible photochromism display

Info

Publication number
JPH01500276A
JPH01500276A JP62503843A JP50384387A JPH01500276A JP H01500276 A JPH01500276 A JP H01500276A JP 62503843 A JP62503843 A JP 62503843A JP 50384387 A JP50384387 A JP 50384387A JP H01500276 A JPH01500276 A JP H01500276A
Authority
JP
Japan
Prior art keywords
light
composition according
dhq
support
sensitive
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.)
Pending
Application number
JP62503843A
Other languages
Japanese (ja)
Inventor
トランデル　クライブ
ブリトル　ジャック
Original Assignee
ジーイーシィ―マルコニー　リミテッド
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ジーイーシィ―マルコニー　リミテッド filed Critical ジーイーシィ―マルコニー　リミテッド
Publication of JPH01500276A publication Critical patent/JPH01500276A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 不可逆性フォトクロミズム表示 本発明は、Ｕ、Ｖ、成分を有する光に露出することにより着色状態まで不可逆的 に変換されるフォトクロミズムインキ組成物に関するものである。[Detailed description of the invention] Irreversible photochromism display The present invention is capable of irreversibly changing to a colored state by exposure to light having U, V, components. The present invention relates to a photochromic ink composition that is converted into a photochromic ink composition.

１．２−ジヒドロキノリン（ＤＨＱ）は、酸の存在下でＵ、Ｖ、光に露出すると 不可逆的に着色する。１，２−ジヒドロキノリンにおけるＮ−水素が電子吸引基 （たとえばアセチル基）により置換されると、これら化合物は中性条件下で着色 する。1.2-Dihydroquinoline (DHQ) when exposed to U, V, light in the presence of acid Colors irreversibly. N-hydrogen in 1,2-dihydroquinoline is an electron-withdrawing group (e.g. an acetyl group), these compounds become colored under neutral conditions. do.

本発明は、実用目的で１，２−ジヒドロキノリンのこの性質を使用する。The present invention uses this property of 1,2-dihydroquinoline for practical purposes.

本発明の一面によれば、重合体溶液中における１、２〜ジヒドロキノリンの溶液 からなるフォトクロミズムインキ組成物が提供され、ジヒドロキノリンは紫外光 に対し感受性であり或いは感受性となる。According to one aspect of the invention, a solution of 1,2-dihydroquinoline in a polymer solution A photochromic ink composition is provided, wherein the dihydroquinoline is treated with ultraviolet light. be sensitive to or become sensitive to.

ＤＨＱはインキ組成物中に酸を含ませて感受性にすることができる。適する酸の 例はトリクロル酢酸である。同様なＣｊＫａ値を有する他の酸も適している。DHQ can be made sensitive by including an acid in the ink composition. of suitable acids An example is trichloroacetic acid. Other acids with similar CjKa values are also suitable.

或いは、窒素原子が電子吸引置換基を有覆るＤＨＱも選択することができ、この 場合には化合物は中性および酸性の条件下でＵ、Ｖ、感受性である。Alternatively, DHQ in which the nitrogen atom is covered with an electron-withdrawing substituent can also be selected; In some cases, the compound is U, V sensitive under neutral and acidic conditions.

本発明に使用しうるＤ　ＨＱの特定例は、一般式（■）：［式中、Ｒは水素また はアルキル基もしくは電子吸引基であり、かつ Ｒ１は独立してアルキル基から選択されるコによって示される。Specific examples of D HQ that can be used in the present invention include the general formula (■): [wherein R is hydrogen or is an alkyl group or an electron-withdrawing group, and R1 is represented by groups independently selected from alkyl groups.

ＲおよびＲ１により示されるアルキル基は好ましくは（ＩＣ級アルキル基（すな わち５個までの炭素原子を右する）、たとえばメチル、エチルもしくはプロピＪ ｌ／２３である３、他の置（■（ベンゼン環における置換Ｕをも含む）を４１覆 るＤ　ＨＱも使用しうるが、これら化合物の吸収スペクトルは特定置換基の導入 により移動することがある。The alkyl group represented by R and R1 is preferably an IC class alkyl group (such as i.e. up to 5 carbon atoms), e.g. methyl, ethyl or propylene 3, which is l/23, and other positions (■ (including the substituted U in the benzene ring) are 41 DHQ can also be used, but the absorption spectra of these compounds depend on the introduction of specific substituents. It may move due to

このインキ組成物は、たとえばトルエンもしくは″ｔ：シレンのようなりＨＱが 可溶性となる溶剤を用いて「１合体溶液を生成することにより製逸することがで きる。適する重合体は、望ましくはＵ、Ｖ、光を強力には吸収せずかつ溶剤がｈ 工介した際に支持体上に無色の柔軟性被覆を形成せねばならない。This ink composition may be made of HQ such as toluene or "t:silene". By using a solvent that makes it soluble, it is possible to Wear. Suitable polymers desirably do not strongly absorb U, V, light and are solvent free. A colorless, flexible coating must be formed on the support during engineering.

重合体溶液中にはＵ、Ｖ、光を照射した際にン；色変化を（［せしめるのに充分 なりＨＱを溶解させる。When irradiated with U, V, or light in the polymer solution, there are enough Dissolve HQ.

一般に、単合体溶液中約０．２〜２％のＤＨＱ溌ＩｆｆがＱ（適である。必要に 応じ、ＤＨＱを添加する前に酸を重合体溶液中に分散させる。酸の必要量はその 強度に依存するが、トリクロル酢酸の場合には約１〜２％で充分である。Generally, about 0.2-2% DHQ Iff in the monomer solution is suitable for If necessary, disperse the acid into the polymer solution before adding the DHQ. The amount of acid required is Depending on the strength, about 1-2% is sufficient in the case of trichloroacetic acid.

本発明のＤ　Ｉ−Ｉ　Ｑ含有インキの乾燥被覆は、一般にＵ、Ｖ。Dry coatings of DI-IQ-containing inks of the present invention are generally U,V.

成分を含む光を照射すると黄緑色まで強力に着色する。この着色変化は永久的で ある。When irradiated with light containing ingredients, it is strongly colored to yellow-green. This color change is permanent be.

〕ｔトクロミズムインキの重要な実用的用途は、たとえば安全性または確認の目 的に対する支持体の表示である。たとえば、インキを支持体上にスクリーン印刷 しかつ乾燥さゼて、目に見えない潜在画像を形成することができる。Ｕ、Ｖ、光 を照射すると、印刷された表示は直ちに可視的となり、したがって商品または書 類が標準物であるかどうかを点検するのに使用することができる。この表示は、 ラベルを含め全ゆる支持体に印刷することができる。] Important practical uses of tochromistic inks include, for example, safety or identification purposes. This is an indication of the support relative to the target. For example, screen printing ink onto a substrate And when dried, it can form an invisible latent image. U, V, light When illuminated, the printed markings become immediately visible and therefore It can be used to check whether a class is standard. This display is It can be printed on any substrate, including labels.

本発明によるインキの他の用途は、湿式用像工程を必要とせずに支持体上に画像 を形成するリトグラフ法を与えることである。すなわち、インキの層をたとえば スクリーン印刷により支持体上に被覆し、かつ乾燥させることができる。次いで 、画像を被覆支持体上に写真形成させることができ、その際この層をネガティブ もしくはステンシルを介しＵ、Ｖ、光に露出する。Another use of the ink according to the invention is to form images on a support without the need for a wet imaging step. The purpose is to provide a lithographic method for forming . That is, if the ink layer is It can be coated onto a support by screen printing and dried. then , an image can be photoformed onto a coated support, with this layer being a negative Or exposed to U, V, light through a stencil.

さらに、フォトクロミズムインキの層で被覆された支持体は、適当な波長のレー ザーを用いる書込み用の感光層とり、で使用することもできる。Furthermore, the support coated with a layer of photochromic ink can be exposed to a laser beam of a suitable wavelength. It can also be used to prepare a photosensitive layer for writing using a laser.

本発明のインキは主として３００〜３８０ｎｍ波長で放出するＵ、Ｖ、光源と共 に使用することを目的とするが、これらはさらに認めうるＵ、、Ｖ、成分を含む 幅広バンドの光源、たとえば未濾光の写真フラッシュガンもしくは強力日光にも 感受性である。これら組成物にＵ、Ｖ、光を照射するこの用途の例は、Ｕ、Ｖ、 成分を含む光源に露出することを包含する。The ink of the present invention is mainly used in combination with U, V, and light sources emitting at wavelengths of 300 to 380 nm. Intended for use in Also suitable for wide band light sources, such as unfiltered photographic flashguns or strong sunlight. Sensitivity. An example of this application is to irradiate these compositions with U, V, light. exposure to a light source containing the component.

以下、実施例により本発明をさらに説明する。The present invention will be further explained below with reference to Examples.

実施例　１ １．２−ジヒドロ−２，２，４−トリメチルキノリン（５０ｍｇ＞をポリメチル メタクリレート（ｐｍｍａ）（１ｇ）とトルエン（３ｇ）との溶液に溶解させ、 かつトリクロル酢酸（４０ｍｇ＞を添加した。得られた溶液をガラス板上に注ぎ かつ乾燥させて、無色の重合体フィルムを形成させた。このフィルムに紫外光（ ３６６ｎｍ）を照射して、６７０ｎｍで生ずる最大吸収を持った黄緑色まで着色 変化さ１．２−ジヒドロ−２，２，４−トリメチル−Ｎ−アセチルキノリン（１ ０ｍｑ＞をｐｍｍａ（１Ｃ］）およびトルエン（３ｑ）の溶液に溶解させた。得 られた溶液をガラス板上に注ぎかつ乾燥させて、無色の重合体フィルムを形成さ せた。Example 1 1,2-dihydro-2,2,4-trimethylquinoline (>50 mg) in polymethyl Dissolved in a solution of methacrylate (pmma) (1 g) and toluene (3 g), and trichloroacetic acid (>40 mg) was added. The resulting solution was poured onto a glass plate. and dried to form a colorless polymer film. This film is exposed to ultraviolet light ( 366nm) to color it to yellow-green with maximum absorption occurring at 670nm. 1,2-dihydro-2,2,4-trimethyl-N-acetylquinoline (1 0 mq> was dissolved in a solution of pmma (1C) and toluene (3q). profit The solution is poured onto a glass plate and dried to form a colorless polymeric film. I set it.

このフィルムに紫外光を照射して、４１０ｎｍで生ずる最大吸収を持った黄色ま で着色変化させた。This film was irradiated with ultraviolet light to produce a yellow color with maximum absorption occurring at 410 nm. The coloring was changed.

国際調査報告international search report

Claims (8)

【特許請求の範囲】[Claims] １．重合体溶液中の１，２−ジヒドロキノリン（ＤＨＱ）の溶液からなり、ジヒ ドロキノリンが紫外光に対し感受性または感受性となることを特徴とするフォト クロミズムインキ組成物。1. Consists of a solution of 1,2-dihydroquinoline (DHQ) in a polymer solution; A photo characterized in that droquinoline is sensitive or sensitive to ultraviolet light. Chromism ink composition. ２．酸を含ませてＵ．Ｖ．光に対し感受性にしてなる請求の範囲第１項記載の組 成物。2. Add acid to U. V. The set according to claim 1, which is made sensitive to light. A product. ３．ＤＨＱにおける窒素原子が電子吸引性置換基を有して、組成物を∪．Ｖ．感 受性にしてなる請求の範囲第１項記載の組成物。3. The nitrogen atom in DHQ has an electron-withdrawing substituent to make the composition ∪. V. Feeling 2. The composition according to claim 1, wherein the composition is made of a phosphatide. ４．電子吸引基がＮ−アセチル基である請求の範囲第３項記載の組成物。4. 4. The composition according to claim 3, wherein the electron-withdrawing group is an N-acetyl group. ５．ＤＨＱが重合体溶液に対し約０．２〜２重量％の量で存在する請求の範囲第 １項〜第４項のいずれか一項に記載の組成物。5. Claim No. 1, wherein the DHQ is present in an amount of about 0.2 to 2% by weight of the polymer solution. The composition according to any one of items 1 to 4. ６．請求の範囲第１項〜第５項のいずれか一項に記載のインキ組成物で表示を支 持体上に印刷しかつこのインキを乾燥させることにより、Ｕ．Ｖ．光を支持体に 照射して可視的にしうる潜在表示を形成することを特徴とする支持体に対する安 全性表示または確認表示の形成方法。6. Display is supported by the ink composition according to any one of claims 1 to 5. By printing on the carrier and drying the ink, the U. V. Light as a support Safety for a support characterized in that it forms a latent display that can be made visible by irradiation. How to form a full gender or confirmation label. ７．請求の範囲第１項〜第６項のいずれか一項に記載の組成物の乾燥被覆を支持 体上に形成すると共に、この乾燥被覆をステンシルもしくはネガティブを介しＵ ．Ｖ．光に露出して画像を形成させることを特徴とする支持体上への画像の形成 方法。7. Supporting dry coating of the composition according to any one of claims 1 to 6 This dry coating is applied to the body using a stencil or negative. ．． V. Formation of an image on a support characterized by exposure to light to form an image Method. ８．潜在的な確認表示もしくは安全性表示が印刷されており、この表示が請求の 範囲第６項記載の方法により形成されていることを特徴とする支持体。8. A potential confirmation or safety label is printed and this label is included in the claim. A support formed by the method according to item 6.
JP62503843A 1986-06-27 1987-06-25 Irreversible photochromism display Pending JPH01500276A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8615706A GB8615706D0 (en) 1986-06-27 1986-06-27 Irreversible photochromic markings
GB8615706 1986-06-27

Publications (1)

Publication Number Publication Date
JPH01500276A true JPH01500276A (en) 1989-02-02

Family

ID=10600187

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62503843A Pending JPH01500276A (en) 1986-06-27 1987-06-25 Irreversible photochromism display

Country Status (5)

Country Link
US (1) US4812171A (en)
EP (1) EP0272298B1 (en)
JP (1) JPH01500276A (en)
GB (2) GB8615706D0 (en)
WO (1) WO1988000223A1 (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8703400D0 (en) * 1987-02-13 1987-03-18 Courtaulds Plc Security marking
GB2214191B (en) * 1988-01-12 1990-10-31 Sicpa Holding Sa Reversibly photochromic printing inks
GB8903300D0 (en) * 1989-02-14 1989-04-05 Rue Company The Plc De Ink composition
GB9014339D0 (en) * 1990-06-27 1990-08-15 Cleary Michael Improvements in or relating to security of articles or premises
US5383959A (en) * 1993-02-22 1995-01-24 Xytronyx, Inc. Reversible inks
US5699182A (en) * 1995-05-25 1997-12-16 Xytronyx, Inc. Light fatigue resistant photochromic formulations
GB2318356B (en) * 1996-10-16 1999-03-10 Willett Int Ltd Composition and method
US6259506B1 (en) 1997-02-18 2001-07-10 Spectra Science Corporation Field activated security articles including polymer dispersed liquid crystals, and including micro-encapsulated field affected materials
US6304660B1 (en) 1998-05-29 2001-10-16 Welch Allyn Data Collection, Inc. Apparatuses for processing security documents
CA2338635C (en) * 1998-07-25 2007-03-20 Vantico Limited Colour changing composition and colouring polymeric articles made therefrom
US6309690B1 (en) * 1999-04-01 2001-10-30 Microtrace, Inc. System for retrospective identification and method of marking articles for retrospective identification
US7038766B2 (en) * 1999-04-01 2006-05-02 Microtrace, Llc Identification particles and system and method for retrospective identification using spectral codes
US6630242B1 (en) 1999-07-30 2003-10-07 Dsm N.V. Radiation-curable composition with simultaneous color formation during cure
KR100443766B1 (en) 2000-07-04 2004-08-09 미쓰이 가가쿠 가부시키가이샤 Process for producing polar olefin copolymer and polar olefin copolymer obtained thereby
DE10048812B4 (en) * 2000-09-29 2005-07-28 Orga Systems Gmbh Data carrier with customizable by means of high-energy beam authenticity features
US7097796B2 (en) * 2003-05-13 2006-08-29 Bayer Materialscience Llc Method of preparing a decorated molded article
US8033450B2 (en) * 2006-03-13 2011-10-11 Smi Holdings, Inc. Expression codes for microparticle marks based on signature strings
US20080101666A1 (en) * 2006-10-30 2008-05-01 Cytyc Corporation Automated imaging system with slide marking
US8158224B2 (en) 2008-04-29 2012-04-17 Motorola Mobility, Inc. Method and apparatus for altering device appearance
CN106471092A (en) * 2014-05-30 2017-03-01 凯博勒有限公司 The system and method applying color-changing composition
GB201522491D0 (en) 2015-12-21 2016-02-03 3M Innovative Properties Co Tamper-evident label containing an irreversible photochromic substance
EP4034610A1 (en) * 2019-09-27 2022-08-03 Transitions Optical, Ltd. Dihydroquinoline photochromic compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5522763A (en) * 1978-08-08 1980-02-18 Dainippon Printing Co Ltd Image recording material

Also Published As

Publication number Publication date
US4812171A (en) 1989-03-14
GB2192006A (en) 1987-12-31
GB2192006B (en) 1990-01-24
EP0272298B1 (en) 1990-10-03
GB8615706D0 (en) 1986-08-06
GB8714888D0 (en) 1987-07-29
WO1988000223A1 (en) 1988-01-14
EP0272298A1 (en) 1988-06-29

Similar Documents

Publication Publication Date Title
JPH01500276A (en) Irreversible photochromism display
JPH01500740A (en) Labeling of articles with photochromic compounds
JP2931114B2 (en) Preparation and use of dyes
US4481276A (en) Photopolymerizable composition containing a combination of photoinitiators
JPS62184455A (en) Photopolymerizing composition
DE2653669B2 (en) Copy material
EP0135348B1 (en) Improvements in or relating to radiation sensitive compounds
CN1938370B (en) Method of coloring a coating composition
WO2007063339A2 (en) Laser-imageable marking compositions
JPS60193691A (en) Reversible picture forming material
US3579342A (en) Leuco triarylmethane/hexaarylbiimidazole color forming system containing a deactivator
US5240780A (en) Colored salts of polymeric sulfonate polyanions and dye cations, and light-absorbing coatings made therewith
US3887808A (en) Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole
JPS6250382A (en) Photochromic material
EP0175238A2 (en) Photosensitive composition
JPH082922B2 (en) Coloring and curable composition by energy rays
JPH02110174A (en) Water-base ink composition
WO1991010571A1 (en) Imaging process
JPH04234048A (en) Manufacture of line drawing and/or half-tone pattern
JPS61163987A (en) Photochromic material
JPH0749546B2 (en) UV coloring ink
JP2825166B2 (en) Forgery prevention printed matter and forgery prevention information detection method
JPS6167034A (en) Photosensitive luminescent composition
GB2242993A (en) Imaging process
JPS6169037A (en) Photochromic material