JP2011519420A - Optimized time / temperature indicator - Google Patents

Abstract

  The present invention relates to a time / temperature indicator comprising a colored spiropyran and a regulator capable of controlling the coloring and discoloration reaction rate. Modifier that must be able to form a spiropyran mixed solid having an amorphous, crystalline or mixed amorphous-crystalline structure.

Description

  The present invention relates to a time / temperature indicator containing a photochromic compound in a colored state and a regulator capable of controlling the coloring and decoloring reaction rates. The invention further relates to the use of a modifier to influence the coloration and decolorization reaction rates of spiropyran pigments.

  Discoloration or color temperature sensitive indicators for monitoring the handling of fresh products are well known in the art. Such perishables are, for example, foods, pharmaceuticals, biological materials, chemicals, coating compositions, adhesives, cosmetics, food additives, photographic supplies and vaccines. There is increasing interest in indicator systems and devices to monitor temperature and time as cumulative values of articles stored at a constant temperature for a period of time. Such indicator systems are used to provide a signal when an article reaches a point of degradation or danger due to excessive temperature exposure.

  Various types of dyes are used for time and temperature indicators. When irradiated with light of a specific wavelength, the dye changes color reversibly. By supplying energy in the form of light, these dye molecules change to a higher energy state, preferably a colored state, and leave this state again when the energy supply is interrupted, resulting in a colorless or difficult to color state. Return.

  The shelf life of fresh products varies from short periods (eg, hours or days) to fairly long periods (eg, months). As a result, a single dye is not widely acceptable as a time / temperature indicator.

  International application WO 99/39197 (Ciba) suggests time and temperature indicators comprising photochromic compounds which can be produced as solids, for example both in glass or crystalline form and in solution. Crystalline indicators typically exhibit a color change time of 1 day or longer, and amorphous indicators typically exhibit a color change time of less than 1 day. The color change time can be specifically set by selecting synthesis conditions or by changing the crystal growth process.

  US20060068315 discloses spiro dyes, aluminum quinoline complexes, porphyrins, porphins, indocyanine dyes, phenoxazine derivatives, phthalocyanine dyes, polymethylindolium dyes, polymethyl dyes, guaiazulenyl dyes, croconium dyes, polymethine indolium dyes, metal complexes Including a radiating antenna selected from IR dyes, cyanine dyes, squarylium dyes, chalcogenopyryl arylidene dyes, indolizine dyes, pyrylium dyes, quinoid dyes, quinone dyes, azo dyes, and mixtures or derivatives thereof, optionally A group consisting of aromatic hydrocarbon, phenolic ether, aromatic acid ester, long chain fatty acid ester having 6 or more carbon chains, polyethylene wax, and derivatives thereof It describes a color forming composition further comprising a melt additive of choice. The coloring composition is useful for forming an image on an optical disk. This document does not address the problems affecting the bleaching rate of time / temperature indicators.

  It is an object of the present invention to find a time / temperature system that can adjust the discoloration time for the shelf life of fresh products without changing the dye replacement pattern.

  It has been found that the problem is solved by adding a modifier to the spiropyran.

  Accordingly, the present invention relates to a time and temperature indicator comprising a spiropyran and a modifier capable of forming a spiropyran mixed solid having an amorphous, crystalline or mixed amorphous-crystalline structure.

Definition:
Spiropyran consists of a pyran ring linked to another heterocycle via a common spirocarbon center. Irradiation of colorless spiropyran with UV light causes non-uniform cleavage of C—O bonds and forms ring-opening colored species.

  Suitable spiropyrans are disclosed in WO05 / 075978 (Freshpoint), WO08 / 083925 (Freshpoint), WO08 / 090045 (Freshpoint) and European patent application EP08156605 (Ciba) filed on May 21, 2008. It is a thing.

［式中、
Ｒ３は、Ｈ、ハロゲン、Ｃ１〜Ｃ１２アルキル、Ｃ２〜Ｃ１２アルケニル、Ｃ２〜Ｃ１２アルキニル、Ｃ１〜Ｃ６アルカノイル、Ｃ１〜Ｃ６アルコキシ、Ｃ１〜Ｃ６アルキルチオ、Ｃ６〜Ｃ１４アリール、Ｃ４〜Ｃ１４ヘテロアリール、Ｃ３〜Ｃ８員非芳香族炭素環、Ｃ３〜Ｃ８員環非芳香族複素環、またはアジドからなる群から選択され、ここで、前記アルキル、アルケニル、アルキニル、アリール、ヘテロアリール、および非芳香族炭素環は、ハロゲン、ヒドロキシル、チオール、アミノ、アルコキシ、ニトロ、アジド、またはスルホから選択される１以上の基によって置換されていてもよく、
Ｒ４は、Ｃ１〜Ｃ１２アルキル、Ｃ２〜Ｃ１２アルケニル、Ｃ２〜Ｃ１２アルキニル、Ｃ１〜Ｃ６アルカノイル、Ｃ１〜Ｃ６アルコキシ、Ｃ１〜Ｃ６アルキルチオ、Ｃ６〜Ｃ１４アリール、Ｃ４〜Ｃ１４ヘテロアリール、Ｃ３〜Ｃ８員非芳香族炭素環、Ｃ３〜Ｃ８員環非芳香族複素環、ヒドロキシルまたは−ＣＨ＝ＣＨ−ＣＮからなる群から選択され、そして
ＹはＣ７〜Ｃ１５アルアルキルから選択され、ここで前記アルアルキルは、ハロゲン、好ましくはフッ素から選択される１以上の基によって置換されていてもよい］の１’，３’，３’−トリメチル−６−ニトロ−スピロ（２Ｈ−１−ベンゾピラン−２，２’−２Ｈ−インドール）のスピロピラン誘導体を含むＴＴＩを開示している。 International application No. WO05075978 has the formula (III):

[Where:
R3 is H, halogen, C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C1-C6 alkanoyl, C1-C6 alkoxy, C1-C6 alkylthio, C6-C14 aryl, C4-C14 heteroaryl, C3- Selected from the group consisting of a C8 membered non-aromatic carbocycle, a C3 to C8 membered nonaromatic heterocycle, or an azide, wherein said alkyl, alkenyl, alkynyl, aryl, heteroaryl, and nonaromatic carbocycle are Optionally substituted by one or more groups selected from halogen, hydroxyl, thiol, amino, alkoxy, nitro, azide, or sulfo,
R4 is C1-C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C1-C6 alkanoyl, C1-C6 alkoxy, C1-C6 alkylthio, C6-C14 aryl, C4-C14 heteroaryl, C3-C8 member non-aromatic Selected from the group consisting of group carbocycles, C3-C8 membered non-aromatic heterocycles, hydroxyl or -CH = CH-CN, and Y is selected from C7-C15 aralkyl, wherein said aralkyl is halogen 1 ', 3', 3'-trimethyl-6-nitro-spiro (2H-1-benzopyran-2,2'-2H, preferably substituted by one or more groups selected from fluorine] A TTI comprising a spiropyran derivative of -indole) is disclosed.

Specific examples of spiropyran disclosed in WO05075978 are shown below:

  When an essentially colorless indicator is irradiated with UV light or near UV light, the pyran ring of the compound of formula I opens, and the adjacent double bond switches from the cis form to the trans form, resulting in a strong absorption band in the visible region. Which produces isomer II which returns to compound I after turning off UV light.

［式中、
Ｒ₁は、水素、−Ｃ₁〜Ｃ₆アルコキシ、ハロゲン、−Ｃ₁〜Ｃ₆アルキルまたは−ＮＯ₂であり、
Ｒ₂は、水素または−Ｃ₁〜Ｃ₆アルコキシであり、
Ｒ₃は、ＮＯ₂またはハロゲンであり、
Ｒ₄は、水素、−Ｃ₁〜Ｃ₆アルコキシまたはハロゲンであり、
Ｒ₅は、水素、ハロゲン、−Ｃ₁−Ｃ₆アルコキシ、−ＣＯＯＨ、−ＣＯＯ−Ｃ₁〜Ｃ₆アルキル、−ＣＦ₃またはフェニルであり、
Ｒ₁₁は、水素であるか、またはＲ₁₁とＲ₅とは一緒になってフェニル環を形成し、
Ｙは、フェニル、ナフチル、アントラセン−９−イル、９Ｈ−フルオレン−９−イルまたは残基

［式中、
Ｒ₆は、水素、ハロゲン、−Ｃ₁〜Ｃ₆アルコキシ、−ＮＯ₂、−ＣＦ₃、_-Ｏ−ＣＦ₃、−ＣＮ、−ＣＯＯ−Ｃ₁〜Ｃ₆アルキル、フェニルまたはビフェニル、９Ｈ−フルオレン−９−イルであり、
Ｒ₇は、水素、ハロゲン、−ＣＮ、−Ｃ₁〜Ｃ₆アルコキシであるか、またはＲ₇とＲ₆とは一緒になってフェニル環を形成し、
Ｒ₈は、水素、ハロゲン、−ＣＮ、または−Ｃ₁〜Ｃ₆アルコキシであり、
Ｒ₉は、水素またはハロゲンまたはＣＮであり、
Ｒ₁₀は、水素またはハロゲンまたはＣＮであり、
Ｒ_aは、−（ＣＨ₂）ｎ−（ｎ＝１〜６）または−ＣＨ₂−ＣＨ＝ＣＨ−である］
である］の少なくとも１つのスピロピラン指示薬を含む時間・温度指示薬を開示する。 International Publication No. WO08 / 083925 has the formula (I)

[Where:
R ₁ is hydrogen, —C ₁ -C ₆ alkoxy, halogen, —C ₁ -C ₆ alkyl or —NO ₂ ;
R ₂ is hydrogen or —C ₁ -C ₆ alkoxy;
R ₃ is NO ₂ or halogen;
R ₄ is hydrogen, —C ₁ -C ₆ alkoxy or halogen,
R ₅ is hydrogen, halogen, —C ₁ -C ₆ alkoxy, —COOH, —COO—C ₁ -C ₆ alkyl, —CF ₃ or phenyl;
R ₁₁ is hydrogen, or R ₁₁ and R ₅ together form a phenyl ring;
Y is phenyl, naphthyl, anthracen-9-yl, 9H-fluoren-9-yl or a residue

[Where:
R ₆ is hydrogen, halogen, -C ₁ -C _{6 alkoxy, -NO 2, -CF 3, -} O-CF 3, -CN, -COO-C 1 ~C 6 alkyl, phenyl or biphenyl, 9H-fluorene -9-yl,
R ₇ is hydrogen, halogen, —CN, —C ₁ -C ₆ alkoxy, or R ₇ and R ₆ together form a phenyl ring;
R ₈ is hydrogen, halogen, —CN, or —C ₁ -C ₆ alkoxy;
R ₉ is hydrogen, halogen or CN;
R ₁₀ is hydrogen or halogen or CN;
R _a is — (CH ₂ ) n— (n = 1 to 6) or —CH ₂ —CH═CH—]
A time / temperature indicator comprising at least one spiropyran indicator.

Specific examples of spiropyran as disclosed in WO08 / 083925 are shown below:

［式中、
Ｒ₁〜Ｒ₄は互いに独立して、水素、−Ｃ₁〜Ｃ₆アルコキシ、ハロゲン、ＣＦ₃、−Ｃ₁〜Ｃ₆アルキルまたは−ＮＯ₂であり、
Ｒ₅は、水素、ハロゲン、−Ｃ₁〜Ｃ₆アルコキシ、−ＣＯＯＨ、−ＣＯＯ−Ｃ₁〜Ｃ₆アルキル、−ＣＦ₃またはフェニルであり、
Ｒ₁₁は水素であるか、またはＲ₁₁とＲ₅とは一緒になってフェニル環を形成し、
Ｒ_aは−Ｃ₁〜Ｃ₆アルキルであり、
Ｒ_bは−Ｃ₁〜Ｃ₆アルキルであるか、またはＲ_aと一緒になって５〜６員環を形成し、
Ｌは二価リンカーであり、
Ｌ’は三価リンカーである］
の少なくとも１つの二量体または三量体スピロピラン指示薬を含む時間・温度指示薬を開示している。 International publication WO 08/090045 is based on formula I or II.

[Where:
R _{1 to} R ₄ are each independently hydrogen, —C _{1 to} C ₆ alkoxy, halogen, CF ₃ , —C _{1 to} C ₆ alkyl or —NO ₂ ;
R ₅ is hydrogen, halogen, —C ₁ -C ₆ alkoxy, —COOH, —COO—C ₁ -C ₆ alkyl, —CF ₃ or phenyl;
R ₁₁ is hydrogen, or R ₁₁ and R ₅ together form a phenyl ring;
R _a is —C ₁ -C ₆ alkyl;
R _b is —C ₁ -C ₆ alkyl, or together with R _a forms a 5-6 membered ring;
L is a bivalent linker,
L ′ is a trivalent linker]
A time and temperature indicator comprising at least one dimer or trimer spiropyran indicator.

Specific examples of spiropyran disclosed in WO08 / 090045 are shown below:

［式中、
Ｒ₁は、水素、−Ｃ₁〜Ｃ₁₈アルコキシ、ハロゲン、−Ｃ₁〜Ｃ₁₈アルキルまたは−ＮＯ₂であり、
Ｒ₂は水素またはＣ₁〜Ｃ₁₈アルコキシであり、
Ｒ₃はＮＯ₂またはハロゲンであり、
Ｒ₄は水素、Ｃ₁〜Ｃ₁₈アルコキシまたはハロゲンであり、
Ｒ₅は水素、ハロゲン、−Ｃ₁〜Ｃ₁₈アルコキシ、−ＣＯＯＨ、−ＣＯＯ−Ｃ₁〜Ｃ₁₈アルキル、−ＣＦ₃またはフェニルであり、
Ｒ₆は水素であるか、またはＲ₆とＲ₇とは一緒になってフェニル環を形成し、
Ｒ₇は水素であり、
Ｒ_aは水素または−Ｃ₁〜Ｃ₆アルキルであり、
Ｒ_bは水素もしくは−Ｃ₁〜Ｃ₆アルキルであるか、またはＲ_aと一緒になって５〜６員環を形成し、
Ｙは−ＣＨ₂−ＣＯＯ−Ｒ₈または−ＣＨ₂−ＣＯ−Ｎ（Ｒ₁₀）−Ｒ₉であるか、または−ＣＨ₂−ＣＯ−Ｎ（Ｒ₁₀）−Ｌ−Ｎ（Ｒ₁₀）ＣＯ−ＣＨ₂−
［ここで、
Ｒ₈は水素、Ｃ₁〜Ｃ₁₈アルキルであり、
Ｒ₉は水素、Ｃ₁〜Ｃ₁₈アルキル、フェニル、メシチル、ハロゲンで１回以上置換されたフェニル、−ＣＦ₃、Ｃ₁〜Ｃ₆アルキル、−Ｃ₁〜Ｃ₆アルコキシ、カルボキシ、−ＣＯＯ−Ｃ₁〜Ｃ₆アルキルであり、
Ｒ₁₀は水素、Ｃ₁〜Ｃ₁₈アルキルであり、
Ｌは１，３フェニレンまたは１，４フェニレン（ここで、フェニレンリンカーは場合によってハロゲン、−ＣＦ₃、Ｃ₁〜Ｃ₁₈アルキル、Ｃ₁〜Ｃ₁₈アルコキシ、カルボキシ、−ＣＯＯ−Ｃ₁〜Ｃ₁₈アルキル、−ＣＯＮＨ₂、−ＣＯＮ（Ｃ₁〜Ｃ₁₈アルキル）₂、ニトロによって１回以上置換されている）、であるか、またはＬはナフタレン、ビフェニレンもしくはフェニレン−Ｏ−フェニレンである（ここで、ナフタレン、ビフェニレンもしくはフェニレン−Ｏ−フェニレンリンカーは場合によってハロゲン、−ＣＦ₃、Ｃ₁〜Ｃ₁₈アルキル、−Ｃ₁〜Ｃ₁₈アルコキシ、カルボキシ、−ＣＯＯ−Ｃ₁〜Ｃ₁₈アルキル、−ＣＯＮＨ₂、−ＣＯＮ（Ｃ₁〜Ｃ₁₈アルキル）₂、ニトロによって１回以上置換されている）である］
である］の少なくとも１つのスピロピラン指示薬を含む時間・温度指示薬を開示する。 European Patent Application EP08156605, filed on March 21, 2008, is a time / temperature indicator showing the change in temperature over time, which has the formula (I)

[Where:
R ₁ is hydrogen, —C ₁ -C ₁₈ alkoxy, halogen, —C ₁ -C ₁₈ alkyl or —NO ₂ ;
R ₂ is hydrogen or C ₁ -C ₁₈ alkoxy;
R ₃ is NO ₂ or halogen,
R ₄ is hydrogen, C ₁ -C ₁₈ alkoxy or halogen;
R ₅ is hydrogen, halogen, —C ₁ -C ₁₈ alkoxy, —COOH, —COO—C ₁ -C ₁₈ alkyl, —CF ₃ or phenyl;
R ₆ is hydrogen, or R ₆ and R ₇ together form a phenyl ring;
R ₇ is hydrogen;
R _a is hydrogen or —C ₁ -C ₆ alkyl;
R _b is hydrogen or —C ₁ -C ₆ alkyl, or together with R _a forms a 5-6 membered ring;
Y is —CH ₂ —COO—R ₈ or —CH ₂ —CO—N (R ₁₀ ) —R ₉ , or —CH ₂ —CO—N (R ₁₀ ) —LN (R ₁₀ ) CO —CH ₂ —
[here,
R ₈ is hydrogen, C ₁ -C ₁₈ alkyl,
R ₉ is hydrogen, C ₁ -C ₁₈ alkyl, phenyl, mesityl, phenyl substituted one or more times by halogen, —CF ₃ , C ₁ -C ₆ alkyl, —C ₁ -C ₆ alkoxy, carboxy, —COO— C ₁ -C ₆ alkyl;
R ₁₀ is hydrogen, C ₁ -C ₁₈ alkyl,
L is 1,3 phenylene or 1,4 phenylene (wherein the phenylene linker is optionally halogen, —CF ₃ , C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, carboxy, —COO—C ₁ -C ₁₈ Alkyl, —CONH ₂ , —CON (C ₁ -C ₁₈ alkyl) ₂ , substituted one or more times by nitro), or L is naphthalene, biphenylene or phenylene-O-phenylene (wherein , naphthalene, halogenated optionally biphenylene or phenylene -O- phenylene linker, -CF _3, C _{1 ~C 18} alkyl, -C ₁ -C ₁₈ alkoxy, carboxy, -COO-C _{1 ~C 18} alkyl, -CONH ₂ a -CON (C ₁ -C ₁₈ alkyl) _2, is substituted one or more times by nitro)]
A time / temperature indicator comprising at least one spiropyran indicator.

Specific examples of spiropyran disclosed in EP08156605 are shown below:

  The object of the present invention is to affect the reaction rate in order to influence the reverse transition reaction from an unstable high energy state to a stable ground state, in other words, to adjust the reverse reaction to the shelf life of fresh products. It is to affect.

  It has been found that the reaction rate of the reverse transfer reaction is not only dependent on the temperature and the molecular structure of the dye, but is also a function of the polarity of the local microenvironment of the dye.

  A modifier is any compound capable of forming a mixed solid having an amorphous, crystalline or mixed amorphous-crystalline structure. Mixed solids can be melted, co-melted, co-precipitated from a solvent, dispersed in a solvent, or mechanically formed by grinding.

  The modifier should be able to surround the light absorbing compound, thus causing a change in the polarity of the microenvironment by interaction. Examples of these interactions include electrostatic interaction and van der Waals force.

Accordingly, the present invention relates to a time and temperature indicator comprising a spiropyran and a modifier that can be formed with a spiropyran mixed solid having an amorphous, crystalline structure or mixed amorphous-crystalline structure, wherein the modifier is:
_{CH 3 - (CH 2) n} -COOC 1 ~C 18 alkyl (n = 10 to 18), cholesterol oleate, citric acid esters, p- hydroxybenzoate, bornyl acetate or dicarboxylic acid C ₁ -C ₁₈ alkyl -O, _{-OC- (CH 2) m -COOC 1} ~C 18 alkyl (m = 2 to 20) ester selected from or selected from esters selected from sugar alcohols, or modifier,
Selected from C ₆ -C ₂₀ alkyl alcohols, selected from cyclic alcohols, selected from polyalcohols, selected from polyethers, selected from fatty acids, or carvone Selected from salts of acids, selected from diterpenic acids, selected from urea or imidazole, or selected from cyclic ketones, or 2,6-di-t-butyl-4- Selected from methoxyphenol or 4-hydroxy-3-methoxybenzaldehyde, or selected from chroman-6-ol, or selected from 4-isopropenyl-1-methylcyclohexene (R-limonene); Or selected from naphthalene, phenanthrene, or sodium dodecyl sulfate It is selected from um, or are selected from Zn complex of hydroxy naphthoic acid, or is selected from the adducts for spiropyran second indolenine units, or are selected from two different spiropyran mixed solids.

In any case, the modifier can control the coloration and discoloration kinetics by affecting the light-induced reversible ring opening of the spiropyran pyran ring. Depending on the type of modifier, the L ^* , a ^* or b ^* value is specifically affected. Thus, the bleaching behavior can be adapted according to the shelf life of the fresh product.

  Thus, in one embodiment, the time and temperature indicator comprises a mixed solid of spiropyran and naphthalene.

  In another embodiment, the time and temperature indicator comprises a mixed solid of spiropyran and cetyl alcohol.

  In another embodiment, the time and temperature indicator comprises a mixed solid of spiropyran and sodium dodecyl sulfate.

  In another embodiment, the time and temperature indicator comprises a mixed solid of spiropyran and a Zn complex of hydroxynaphthoic acid.

  In another embodiment, the time and temperature indicator comprises a mixed solid of spiropyran and an adduct of a second indolenine unit to spiropyran.

  In another embodiment, the time and temperature indicator comprises a mixed solid of two different spiropyrans.

  Suitable regulators further include C8-C30 alkyl alcohols such as cetyl alcohol, salts such as sodium dodecyl sulfate, metal complexes such as Zn complex of hydroxynaphthoic acid.

  The modifier may also be a byproduct of spiropyran synthesis. An example of a by-product is the addition of a second indolenine unit to spiropyran.

の混合結晶でもあり得る。 The modifier is a second spiropyran, such as

It can also be a mixed crystal.

The modifier is selected from esters such as CH ₃ — (CH ₂ ) _n —COOC ₁ -C ₁₈ alkyl (n = 10-18), such as lauric acid butyl ester, myristic acid isopropyl, stearic acid methyl ester, Or oleic acid cholesterol, citric acid triethyl ester, p-hydroxybenzoate (alkyl parabens such as methyl paraben, butyl paraben), o-hydroxybenzoates such as salicylic acid alkyl esters such as salicylic acid methyl ester, or esters selected from bornyl acetate, or dicarboxylic acid C ₁ -C ₁₈ alkyl _{-O-OC- (CH 2) m} -COOC 1 ~C 18 alkyl (m = 2 to 20), for example sebacic acid dialkyl esters, for example, d is selected from sebacic acid dibutyl ester It may also be in the ether.

  The modifier may also be an ester of a sugar alcohol such as sorbitan monooleate or sorbitan monolaurate.

The modifier may also be a long chain C ₆ -C ₂₀ alcohol such as hexadecan-1-ol, octadecan-1-ol, polyethylene monoalcohol.

  The regulator is 1,7,7-trimethylbicyclo [2.2.1] heptane-2-ol (borneol) or 1,3,3-trimethylbicyclo [2.2.1] heptane-2- It can also be a cyclic alcohol such as oar (fenkyl alcohol).

  The modifier may also be a polyalcohol such as glycerol (propane-1,2,3-triol), sorbitol, polycaprolactone diol.

  The modifier can also be a polyether, such as polyethylene glycol or polypropylene glycol, such as polyglycol 4000.

  The modifier can also be a fatty acid such as stearic acid.

  The modifier can also be a salt of a carboxylic acid, such as calcium stearate or magnesium stearate.

  The modifier can also be a diterpenic acid, such as abietic acid.

  The modifier can also be urea.

  The modifier can also be imidazole.

  The modifier can also be a phenol, such as 2,6-di-tert-butyl-4-methoxyphenol or 4-hydroxy-3-methoxybenzaldehyde (vanillin).

  The modifier can also be chroman-6-ol (3,4-dihydro-2H-1-benzopyran-6-ol), for example tocopherol (vitamin E).

  The modifier can also be 4-isopropenyl-1-methylcyclohexene (R-limonene).

  The molar ratio of modifier to spiropyran is> 10%, preferably> 25.

  All of the modifiers can affect the bleaching reaction rate.

  Accordingly, the present invention further relates to the use of a time and temperature indicator as defined in claim 1 for influencing the bleaching rate of spiropyran.

If the modifier is capable of forming a melt with spiropyran, the present invention is a method for producing a time and temperature indicator comprising:
a) mixing the spiropyran and the regulator;
b) heating the mixture obtained in a) to form a melt;
c) cooling the melt obtained in b) to obtain a crystalline or amorphous solid, or d) dissolving the mixture obtained in a) in a solvent and crystallizing the resulting mixture, The method further includes a step of obtaining a mixed crystal or mixed solid.

  The temperature in step b) is 50-20 ° C. The temperature in step c) is preferably 0 ° C. to room temperature.

  The solvent in step d may be an alcohol.

The present invention further provides a method for determining the quality of aging and temperature sensitive products:
a) printing a time / temperature indicator according to claim 1 on a substrate comprising spiropyran and a regulator;
b) activation of the indicator by irradiation with UV light, in particular the step of light-induced coloring;
c) optionally applying a protector that prevents new light-induced coloration of the indicator; and d) determining the quality of the product taking into account the degree of time or temperature-induced discoloration and the degree of discoloration. Relates to the method of including.

  Suitable substrate materials are both inorganic and organic materials, preferably those known from conventional lamination and packaging techniques. Examples include polymer, glass, metal, paper, cardboard and the like.

  “Printing” means any type of printing, such as letterpress printing, eg flexographic printing, pad printing, lithographic printing, eg offset printing or lithographic printing, intaglio printing, eg gravure printing, screen printing and non-impact printing methods, For example, it means ink jet printing, pin printing, electrography, thermography and the like.

  After step c), preferably a protector, in particular a color filter, is applied which prevents new photo-induced coloring of the reversible indicator. For a UV sensitive indicator, consider a yellow filter that is transparent only to light having a typical wavelength longer than 430 nm.

  The protector may be as described in PCT application PCT / EP / 2007060987 (Ciba). Therefore, the protector has a colorless light-absorbing protective layer that is bonded to the lower layer of the time / temperature indicator, characterized in that the protective layer contains a polymer binder and is 1 to 50% by mass relative to the total mass of the UV light absorber layer. It may be a transparent or colored transparent light-absorbing protective layer.

  The invention is further illustrated by examples.

の無色化合物の微粉末を乳鉢中、ナフタレン（５．０ｇ、３９ｍｍｏｌ）と混合し、微粉砕した。６０〜７０℃で、色素およびナフタレンを融解させて、緑色溶液を形成し、これを室温まで冷却した。凝固した混合物を次いで粉砕し、得られた混合物を用いてインク配合物を作製した。 Example 1
Formula of 5 g (11.9 mmol) of spiropyran / naphthalene as inhibitor

The colorless compound fine powder was mixed with naphthalene (5.0 g, 39 mmol) in a mortar and pulverized. At 60-70 ° C., the dye and naphthalene were melted to form a green solution that was cooled to room temperature. The solidified mixture was then crushed and the resulting mixture was used to make an ink formulation.

  Spiropyran / naphthalene powder was charged with a UV lamp for 10 seconds. The table below shows the fading rate at 2 ° C.

この表は、ナフタレンが変色速度を修飾することを示す。
Ｌ^＊値はスピロピラン／ナフタレン系よりも小さい（３８．８と比較して３１．０）。Ｌ^＊値の増加は同程度である。
ａ^＊値はスピロピラン単独についてほぼ一定であり、スピロピラン／ナフタレン系については若干減少する。
ｂ^＊値は、スピロピラン／ナフタレン系よりも迅速に増加する。

This table shows that naphthalene modifies the rate of color change.
The L ^* value is smaller than the spiropyran / naphthalene system (31.0 compared to 38.8). The increase in L ^* value is comparable.
The a ^* value is almost constant for spiropyran alone and slightly decreases for the spiropyran / naphthalene system.
The b ^* value increases more rapidly than the spiropyran / naphthalene system.

の無色化合物の微粉末を、５．０ｇ（１７．３３ｍｍｏｌ）のドデシル硫酸ナトリウム（ＳＤＳ）とともに乳鉢中で十分に粉砕し、次いで混合物を一定して撹拌しながら６０〜７０℃まで加熱すると、色素が融解し始め、ＳＤＳとの混合物を形成し始めた。全処理過程は、１０〜１５分かかった。混合物を室温まで冷却し、固体を粉末化し、次いで水性配合物を形成させた。 Example 2
Spiropyran / sodium dodecyl sulfate 5g formula as inhibitor

A fine powder of the colorless compound was thoroughly ground in a mortar with 5.0 g (17.33 mmol) of sodium dodecyl sulfate (SDS), and the mixture was then heated to 60-70 ° C. with constant stirring to yield a dye. Began to melt and began to form a mixture with SDS. The entire process took 10-15 minutes. The mixture was cooled to room temperature, the solids were pulverized and then an aqueous formulation was formed.

  Spiropyran / sodium dodecyl sulfate powder was charged with a UV lamp for 5 minutes. The table below shows the fading rate at 2 ° C. A comparative spiropyran was charged for 10 seconds.

この表は、ドデシル硫酸ナトリウムが変色速度を修飾することを示す。
Ｌ^＊値はスピロピラン／ドデシル硫酸ナトリウム系（３８．８と比較して２１．５）よりも著しく小さく、より迅速に増加する。
ａ^＊値は、スピロピラン単独についてはほぼ一定であり、スピロピラン／ドデシル硫酸ナトリウム系については減少する。
ｂ^＊値は、スピロピラン／ドデシル硫酸ナトリウム系についてはより迅速に増加する。

This table shows that sodium dodecyl sulfate modifies the rate of color change.
The L ^* value is significantly smaller than the spiropyran / sodium dodecyl sulfate system (21.5 compared to 38.8) and increases more rapidly.
The a ^* value is almost constant for spiropyran alone and decreases for the spiropyran / sodium dodecyl sulfate system.
The b ^* value increases more rapidly for the spiropyran / sodium dodecyl sulfate system.

を、５．０ｇ（１１．３ｍｍｏｌ）の２−ヒドロキシ３−ナフトエ酸のＺｎ複合体と乳鉢中で十分に粉砕した。物理的混合によって若干赤色に着色した。混合物をあわせて融解しなかった。混合物を用いて次いで水性配合物を形成させた。 Example 3
2-Hydroxy-3-naphthoic acid spiropyran / Zn complex as inhibitor In a typical procedure, 5.0 g (11.97 mmol) spiropyran

Was thoroughly ground in a mortar with 5.0 g (11.3 mmol) of 2-hydroxy-3-naphthoic acid Zn complex. Colored slightly red by physical mixing. The mixture did not melt together. The mixture was then used to form an aqueous formulation.

  A spiropyran / Zn complex of 2-hydroxy-3-naphthoic acid powder was charged with a UV lamp for 10 seconds.

  The table below shows the fading rate at 2 ° C.

この表は、Ｚｎ複合体が変色速度を修飾することを示す。
Ｌ^＊値はスピロピラン／Ｚｎ複合体系について著しく小さい（３８．８と比較して２０．０）。増加は同程度である。
混合物の赤色のために、ａ^＊値は高い。
ｂ^＊値はスピロピラン／Ｚｎ複合体系については若干小さい。ｂ値の増加は、両系において同程度である。

This table shows that the Zn complex modifies the discoloration rate.
The L ^* value is significantly smaller for the spiropyran / Zn composite system (20.0 compared to 38.8). The increase is about the same.
Due to the red color of the mixture, the a ^* value is high.
The b ^* value is slightly smaller for the spiropyran / Zn composite system. The increase in b value is similar in both systems.

の無色化合物の微粉末を乳鉢中でセチルアルコール（５．０，２０．６２）と混合し、微粉末化した。６０〜７０℃で、色素およびセチルアルコールを一定撹拌下、あわせて融解させた。混合物を室温まで冷却させた。凝固した混合物を次いで粉砕し、得られた混合物を用いてインク配合物を作製した。 Example 4
Spiropyran / cetyl alcohol TTI
5 g (11.97 mmol) formula

The colorless compound fine powder was mixed with cetyl alcohol (5.0, 20.62) in a mortar to make a fine powder. At 60 to 70 ° C., the dye and cetyl alcohol were melted together under constant stirring. The mixture was allowed to cool to room temperature. The solidified mixture was then crushed and the resulting mixture was used to make an ink formulation.

  Spiropyran / cetyl alcohol powder was charged with a UV lamp for 10 seconds.

Example 5
The following example shows that bleaching properties are also strongly dependent on sample purity. Depending on the synthesis, the spiropyran obtained contains some common by-products, and the resulting spiropyran has proven to be non-photochromic. This is effectively an adduct of the second indolenine unit to spiropyran and has the following general structure:

を有する。 The spiropyran used was

Have

  Spiropyran A / Byproduct A (25.5%) powder and Spiropyran A / Byproduct A (5.4%) were charged by a UV lamp for 10 seconds.

  The table below shows the fading rate at 2 ° C.

表は、Ｌ初期値が存在する副生成物の量に依存しないことを示す。しかし、副生成物の量が多いと、漂白は減少する。したがって、副生成物は遅延剤として作用する。
スピロピランＡ／副生成物Ａ（２５．５％）は赤みが強い（高いａ^＊値を参照）。
スピロピランＡ／副生成物Ａ（５．４％）は青みが強く、色が黄色に変化する（ｂ^＊値を参照）。

The table shows that the L initial value is independent of the amount of by-products present. However, bleaching is reduced when the amount of by-products is high. Thus, the by-product acts as a retarder.
Spiropyran A / by-product A (25.5%) is highly reddish (see high a ^* value).
Spiropyran A / by-product A (5.4%) is highly bluish and changes color to yellow (see b ^* value).

Example 6
The following examples also show that by-products can also act as accelerators. The bleaching rate increases as more by-products are present.

を有する。 The spiropyran used was

Have

  Spiropyran B / Byproduct B (32%) powder and Spiropyran B / Byproduct B (13.6%) powder and Spiropyran B / Byproduct B (0.3%) powder were charged by UV lamp for 10 seconds It was.

  The table below shows the fading rate at 2 ° C.

に基づく融解混合物を記載する。 Example 7
The table below shows LF2807 (GSID2074) as basic spiropyran.

A melt mixture based on is described.

  In the first column, melted LF2807 is listed at a 5% loading as compared to the following compound. These are applied at a loading of 10%, resulting in a 5% spiropyran content in the final print.

ａ）ＵＶ活性化後の色の濃さ
ｂ）２℃にて
ｃ）インク製造前に融解させた化合物

a) Color intensity after UV activation b) At 2 ° C. c) Compound melted before ink production

  As can be seen from the table above, the various dissolution mixtures were performed with LF2807, all at a ratio of 1: 1 at 150 ° C.

  In general, the color of the charged dissolved mixture is in the same range as the molten LF2807, and is a reddish blue region. However, color strength, bleaching speed and behavior and associated usefulness period vary greatly.

  Special is the use of vanillin as a melt component in LF4064, which exhibits a low concentration of color and a strong purple color in an uncharged state. In this case, the vanillin almost certainly reacts with spiropyran as an aldehyde to form the known purple indolenine-methine dye in equilibrium.

  Urea as a melting component forms a two-phase system during melting and therefore the formation of a co-crystal (LF4054) of both compounds is not expected. The properties of the resulting mixture are therefore very similar to those of molten LF2807 alone.

  Most other melt mixtures differed in speed, and the most interesting mixtures initially identified were LF3903 and LF3929 due to their high concentration of color and long usefulness period.

に基づく融解混合物を記載する。第一列で、ＬＦ３１５５は、下記化合物との比較として５％装填量で記載する。これらは１０％装填量で適用され、これは最終プリント中５％スピロピラン含量であることを意味する： Example 8
The table below shows LF3155 (GSID3655) as a basic spiropyran.

A melt mixture based on is described. In the first row, LF3155 is listed at 5% loading as compared to the following compound. These are applied at 10% loading, which means a 5% spiropyran content in the final print:

ａ）ＵＶ活性化後の色の濃さ
ｂ）２℃で測定
ｃ）比較のために化合物を５％の装填量で測定
ｄ）化合物を粉砕し、その後Ｆｌｅｘｉｐｒｏｏｆ印刷機で印刷した

a) Color strength after UV activation b) Measured at 2 ° C. c) Compound measured for comparison at 5% loading d) Compound crushed and then printed on a Flexiprof press

  As can be seen from the above, various dissolution mixtures were performed with LF3155, all in a 1: 1 ratio and melted at the stated temperature. As can be seen from the above, the color depth of the compound could only be slightly improved in very few cases compared to the case where a mixed crystal or solid solution was actually obtained.

  LF3155. However, the reaction rate varied in most cases, which led to the conclusion that tocopherol was also used in the molten mixture with LF3155. Unfortunately, the resulting LF3993 could not be tested due to the very high viscosity of our standard aqueous ink system. This was therefore tested with NC and vinyl ink:

  As can be seen from the above description, the color intensity is lower, and the vinyl-based prints have an unexpectedly long useful time due to their excellent bleaching properties. In NC, light fastness seems to be high, but the results must be confirmed.

Example 9

Example 10
Based on LF4005, 1: 1

Example 11
Based on LF4035, 1: 1

Claims (29)

A time / temperature indicator, wherein the indicator comprises a spiropyran and a modifier that can be formed of an amorphous, crystalline structure or spiropyran mixed solid having a mixed amorphous-crystalline structure, the modifier comprising:
CH ₃ — (CH ₂ ) _n —COOC ₁ -C ₁₈ alkyl (n = 10-18), cholesterol oleate, citrate ester, p-hydroxybenzoate, ester selected from bornyl acetate, or dicarboxylic acid C _1- C ₁₈ alkyl _{-O-OC- (CH 2) m} -COOC 1 ~C 18 alkyl ester selected from (m = 2 to 20) or is selected from esters selected from sugar alcohols; or the adjustment The agent
Selected from C ₆ -C ₂₀ alkyl alcohols, selected from cyclic alcohols, selected from polyalcohols, selected from polyethers, selected from fatty acids, or carvone Selected from salts of acids, selected from diterpenic acid, selected from urea or imidazole, or selected from cyclic ketones, or 2,6-di-t-butyl-4 Selected from -methoxyphenol or 4-hydroxy-3-methoxybenzaldehyde or selected from chroman-6-ol or selected from 4-isopropenyl-1-methylcyclohexene (R-limonene) Or selected from naphthalene, phenanthrene, or dodecyl sulfate Selected from thorium, selected from a Zn complex of hydroxynaphthoic acid, selected from an adduct of a second indolenine unit to spiropyran, or selected from a mixed solid of two different spiropyrans, Time / temperature indicator.   The time / temperature indicator according to claim 1, wherein the regulator is a nonpolar regulator selected from naphthalene and phenanthrene.   The time / temperature indicator according to claim 1, comprising a mixed solid of spiropyran and naphthalene.   The time / temperature indicator according to claim 1, comprising a mixed solid of spiropyran and cetyl alcohol.   The time / temperature indicator according to claim 1, comprising a mixed solid of spiropyran and sodium dodecyl sulfate.   The time / temperature indicator according to claim 1, comprising a mixed solid of spiropyran and a Zn complex of hydroxynaphthoic acid.   The time / temperature indicator according to claim 1, comprising a mixed solid of spiropyran and an adduct of the second indolenine unit to spiropyran.   The time / temperature indicator of claim 1 comprising a mixed solid of two different spiropyrans. An ester selected from CH ₃ — (CH ₂ ) _n —COOC ₁ -C ₁₈ alkyl (n = 10-18), cholesterol oleate, citrate ester, p-hydroxybenzoate, bornyl acetate, or is selected from esters selected from esters selected or sugar alcohol, from C ₁ -C ₁₈ alkyl -O-OC- dicarboxylic acid _{(CH 2) m -COOC 1 ~C} 18 alkyl (m = 2 to 20) The time / temperature indicator according to claim 1.   The modifier is selected from lauric acid butyl ester, myristic acid isopropyl, stearic acid methyl ester, or oleic acid cholesterol, citric acid triethyl ester, methyl paraben, butyl paraben, salicylic acid methyl ester, or bornyl acetate, or sebacic acid The time / temperature indicator according to claim 9, which is selected from dibutyl esters.   The time / temperature indicator according to claim 1, wherein the regulator is selected from sugar alcohols.   The time / temperature indicator according to claim 11, wherein the sugar alcohol is sorbitan monooleate or sorbitan monolaurate. The time / temperature indicator according to claim 1, wherein the regulator is selected from C ₆ -C ₂₀ alcohols.   The time / temperature indicator according to claim 13, wherein the alcohol is selected from hexadecan-1-ol, octadecan-1-ol, and polyethylene monoalcohol.   The time / temperature indicator according to claim 1, wherein the adjusting agent is selected from cyclic alcohols.   The cyclic alcohol is 1,7,7-trimethylbicyclo [2.2.1] heptane-2-ol (borneol) or 1,3,3-trimethylbicyclo [2.2.1] -heptane-2- The time / temperature indicator according to claim 15, which is selected from all (fenkyl alcohol).   The time / temperature indicator according to claim 1, wherein the adjusting agent is selected from polyalcohols.   The time / temperature indicator according to claim 17, wherein the polyalcohol is selected from glycerol (propane-1,2,3-triol), sorbitol, and polycaprolactone diol.   The time / temperature indicator according to claim 1, wherein the regulator is selected from polyethers.   The time / temperature indicator according to claim 19, wherein the polyether is selected from polyethylene glycol, polypropylene glycol or polyglycol 4000.   The time / temperature indicator according to claim 1, wherein the regulator is selected from fatty acids, preferably stearic acid.   The time / temperature indicator according to claim 1, wherein the regulator is selected from a salt of a carboxylic acid, preferably calcium stearate or magnesium stearate.   The time / temperature indicator according to claim 1, wherein the regulator is selected from diterpenic acid, preferably abietic acid.   The time / temperature indicator according to claim 1, wherein the adjusting agent is selected from urea or imidazole.   The time / temperature indicator according to claim 1, wherein the regulator is selected from 2,6-di-t-butyl-4-methoxyphenol or 4-hydroxy-3-methoxybenzaldehyde (vanillin).   The time / temperature indicator according to claim 1, wherein the adjusting agent is tocopherol (vitamin E) or R-limonene.   27. A time / temperature indicator according to any one of claims 1 to 26, wherein the molar ratio of modifier to spiropyran is> 10%, preferably> 25%.   27. Use of a time / temperature indicator according to any one of claims 1 to 26 for influencing the bleaching reaction rate. A method for determining the quality of an aging sensitive and temperature sensitive product comprising the following steps:
a) printing the time / temperature integrator of claim 1 on a substrate comprising spiropyran and a modifier;
b) activation of the indicator by irradiation with UV light, in particular photo-induced coloring,
c) optionally including a step of applying a protector that prevents new light-induced coloration of the indicator; and d) determining the quality of the product taking into account the degree of time or temperature-induced discoloration and the degree of discoloration. ,Method.