CN102007404A - Optimized time temperature indicator - Google Patents
Optimized time temperature indicator Download PDFInfo
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- CN102007404A CN102007404A CN2009801134829A CN200980113482A CN102007404A CN 102007404 A CN102007404 A CN 102007404A CN 2009801134829 A CN2009801134829 A CN 2009801134829A CN 200980113482 A CN200980113482 A CN 200980113482A CN 102007404 A CN102007404 A CN 102007404A
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- Prior art keywords
- time
- temperature indicator
- modifier
- pyrans
- spiro
- Prior art date
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- 150000002646 long chain fatty acid esters Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000000843 phenylene group Chemical class C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229960005486 vaccine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
- G01N31/229—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating time/temperature history
-
- 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
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K3/00—Thermometers giving results other than momentary value of temperature
- G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
- G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Biophysics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a time temperature indicator comprising a spiropyran in a colored state and a modifier which is able to control the coloration and decoloration kinetics. The modifier which must be able to form with the spiropyran mixed solids with an amorphous, crystalline or mixed amorphous-crystalline structure.
Description
Time-the temperature indicator that the present invention relates to comprise the photochromic compound of colored state and can control the modifier of colour developing and decolorization kinetic.The invention further relates to modifier and be used to influence the colour developing of spiro-pyrans pigment and the purposes of decolorization kinetic.
The variable color or the temperature sensitive indicator that adds lustre to that are used to monitor the perishable goods management are well known in the art.This type of perishable goods for example is, food, medicine, biomaterial, chemical substance, coating composition, bonding agent, cosmetics, food additives, photographic articles and vaccine.Under steady temperature, store the growing with each passing day of goods of regular period as the directive system of the temperature and time of accumulated value and the interest of equipment for monitoring.This type of directive system is used for sending signal when goods reach quality loss or unsafe condition point owing to excess temperature exposes.
In time-temperature indicator, use different types of dyestuff.When by the rayed of specific wavelength, their color of their modulations.Because the energy of supply light form, these dye molecules change into more high-energy attitude, preferred colored state, and they break away from this state again when interrupting the energy supply, return to their colourless or almost colourless ground state thus.
The storage life of perishable goods does not wait from short-term (for example a few hours or a couple of days) to quite long-term (for example several months).Therefore one type dyestuff can't generally be applicable to time-temperature indicator.
International Application No. WO 99/39197 (Ciba) both proposes can be with solid form, and for example glass or crystal form again can be with the time-temperature indicators that comprises photochromic compound of solution form manufacturing.The crystallization indicator showed common one day and the longer variable color time, and the amorphous indicator shows the variable color time less than one day usually.By selecting synthesis condition or change growing method, can the special setting variable color time.
US 20060068315 has described and has comprised volution dyestuff (spiro dye); Be selected from the aluminium quinoline complexes, porphyrin, porphines, indole cyanine dyes phenoxazine derivant, phthalocyanine dye, poly-methyl indol dyestuff, the polymethile dyestuff, the guaiazulenyl dyestuff, croconic acid dyes, poly-methine indoline dye, metal complex IR dyestuff, cyanine dye, side's acid (squarylium) dyestuff, the chalcogenopyryloarylidene dyestuff, the indolizine dyestuff, pyrylium dye, oxyketone dye, the quinone dyestuff, azo dyes, and composition thereof or the radiating antenna (radiation antenna) of derivant and be selected from aromatic hydrocarbons optional further comprising, phenolic ether, the aromatics acid esters, have 6 or the long-chain fatty acid ester of bigger carbochain, the color former of the fusion auxiliary agent of Tissuemat E and derivant thereof.This color former can be used for forming the image on the CD.The document does not solve the dynamic (dynamical) problem of fading of influence time-temperature indicator.
Target of the present invention is to find out the time-temperature hierarchy that can be adjusted to the storage life of perishable goods under the situation of the substitution pattern that does not change dyestuff the variable color time.
Have been found that adding modifier in spiro-pyrans has solved the problems referred to above.
Therefore, the present invention relates to comprise spiro-pyrans and can form the time-temperature indicator of modifier that have amorphous, crystallization or mix the hybrid solid of amorphous-crystalline texture with spiro-pyrans.
Definition:
Spiro-pyrans contains through shared spiral shell carbon center and is connected to pyranoid ring on another heterocycle.Shine the heterolytic fission that colourless spiro-pyrans causes the C-O key with ultraviolet ray, thereby form the open loop coloring matter.
Suitable spiro-pyrans is disclosed at WO05/075978 (Freshpoint), WO08/083925 (Freshpoint), WO08/090045 (Freshpoint) with in the European patent application EP of submitting on May 21st, 2,008 08156605 (Ciba).
International Application No. WO 05075978 discloses and has comprised 1 ', 3 ' of formula (III), the TTI of the spiropyran derivatives of 3 '-trimethyl-6-nitro-spiral shell (2H-1-chromene-2,2 '-2H-indoles):
Wherein
R3 is selected from H, halogen, C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C1-C6 alkanoyl, C1-C6 alkoxy, C1-C6 alkylthio group, C6-C14 aryl, C4-C14 heteroaryl, the non-aromatic carbocyclic of C3-C8 unit, C3-C8 unit ring non-aromatic heterocyclic or azido; Wherein said alkyl, thiazolinyl, alkynyl, aryl, heteroaryl and non-aromatic carbocyclic can be replaced by one or more groups that are selected from halogen, hydroxyl, thiol, amino, alkoxy, nitro, azido or sulfo group;
R4 be selected from C1-C12 alkyl, C2-C12 thiazolinyl, C2-C12 alkynyl, C1-C6 alkanoyl, C1-C6 alkoxy, C1-C6 alkylthio group, C6-C14 aryl, C4-C14 heteroaryl, the non-aromatic carbocyclic of C3-C8 unit, C3-C8 unit ring non-aromatic heterocyclic, hydroxyl or-CH=CH-CN; And
Y is selected from the C7-C15 aralkyl, and wherein said aralkyl can be by one or more halogens that are selected from, and the group of preferred fluorine replaces.
Show particular instance below as disclosed spiro-pyrans among the WO05075978:
With ultraviolet ray or the initial colourless indicator of near ultraviolet ray irradiation, the pyranoid ring of the compound of this up-to-date style I is opened, and adjacent double bond convert transconfiguration to from cis, thereby produce isomeride II, and it has the strong absorption band in visible region and revert to Compound I after cutting off ultraviolet ray.
International publication WO08/083925 discloses the time-temperature indicator of the spiro-pyrans indicator that comprises at least a formula (I)
Wherein
R
1Be hydrogen ,-C
1-C
6Alkoxy, halogen ,-C
1-C
6Alkyl or-NO
2
R
2Be hydrogen or-C
1-C
6Alkoxy;
R
3Be NO
2Or halogen;
R
4Be hydrogen ,-C
1-C
6Alkoxy or halogen;
R
5Be hydrogen, halogen ,-C
1-C
6Alkoxy ,-COOH ,-COO-C
1-C
6Alkyl ,-CF
3Or phenyl;
R
11Be hydrogen or R
11And R
5Form benzyl ring together;
Y is phenyl, naphthyl, anthracene-9-base, 9H-fluorenes-9-base or residue
Wherein
R
6Be hydrogen, halogen ,-C
1-C
6Alkoxy ,-NO
2,-CF
3,-O-CF
3,-CN ,-COO-C
1-C
6Alkyl, phenyl or xenyl, 9H-fluorenes-9-base;
R
7Be hydrogen, halogen ,-CN ,-C
1-C
6Alkoxy or R
7And R
6Form benzyl ring together;
R
8Be hydrogen, halogen ,-CN or-C
1-C
6Alkoxy;
R
9Be hydrogen or halogen or CN;
R
10Be hydrogen or halogen or CN;
R
aBe-(CH
2) n-, wherein n=1-6 or-CH
2-CH=CH-
Show particular instance below as disclosed spiro-pyrans among the WO08/083925:
International publication WO08/090045 discloses the dimerization that comprises at least a formula I or II or the time-temperature indicator of trimerization spiro-pyrans indicator
Wherein
R
1-R
4Be independently of one another hydrogen ,-C
1-C
6Alkoxy, halogen, CF
3,-C
1-C
6Alkyl or-NO
2
R
5Be hydrogen, halogen ,-C
1-C
6Alkoxy ,-COOH ,-COO-C
1-C
6Alkyl ,-CF
3Or phenyl;
R
11Be hydrogen or R
11And R
5Form benzyl ring together;
R
aBe-C
1-C
6Alkyl
R
bBe-C
1-C
6Alkyl, or and R
aForm 5-6 unit ring together
L is a divalent linker;
L ' is that trivalent connects base.
Show particular instance below as disclosed spiro-pyrans among the WO08/090045:
The European patent application EP of submitting on March 21st, 2,008 08156605 discloses the time-temperature indicator that is used to indicate the temperature variation that takes place in time, and it comprises the spiro-pyrans indicator of at least a formula (I)
Wherein
R
1Be hydrogen ,-C
1-C
18Alkoxy, halogen ,-C
1-C
18Alkyl or-NO
2
R
2Be hydrogen or-C
1-C
18Alkoxy;
R
3Be NO
2Or halogen;
R
4Be hydrogen ,-C
1-C
18Alkoxy or halogen;
R
5Be hydrogen, halogen ,-C
1-C
18Alkoxy ,-COOH ,-COO-C
1-C
18Alkyl ,-CF
3Or phenyl;
R
6Be hydrogen or R
6And R
7Form benzyl ring together;
R
7Be hydrogen;
R
aBe hydrogen or-C
1-C
6Alkyl;
R
bBe hydrogen or-C
1-C
6Alkyl, or and R
aForm 5-6 unit ring together;
Y is-CH
2-COO-R
8Or-CH
2-CO-N (R
10)-R
9Or-CH
2-CO-N (R
10)-L-N (R
10) CO-CH
2-;
Wherein
R
8Be hydrogen, C
1-C
18Alkyl;
R
9Be hydrogen, C
1-C
18Alkyl, phenyl, 2,4, the 6-trimethylphenyl, by halogen ,-CF
3, C
1-C
6Alkyl ,-C
1-C
6Alkoxy, carboxyl ,-COO-C
1-C
6Alkyl replaces once or more than once phenyl;
R
10Be hydrogen, C
1-C
18Alkyl;
L is 1,3 phenylene or 1,4 phenylene, wherein this phenylene connect base optional by halogen ,-CF
3, C
1-C
18Alkyl ,-C
1-C
18Alkoxy, carboxyl ,-COO-C
1-C
18Alkyl ,-CONH
2,-CON (C
1-C
18Alkyl)
2, nitro replaces once or more than once; Or L is naphthalene, biphenylene or phenylene-O-phenylene, wherein this naphthalene, biphenylene or phenylene-O-phenylene connect base optional by halogen ,-CF
3, C
1-C
18Alkyl ,-C
1-C
18Alkoxy, carboxyl ,-COO-C
1-C
18Alkyl ,-CONH
2,-CON (C
1-C
18Alkyl)
2, nitro replaces once or more than once.
Show particular instance below as disclosed spiro-pyrans among the EP 08156605:
Target of the present invention is that influence transforms the conversion backward reaction that stabilizes and decide ground state from unstable high-energy state, in other words influences this dynamics to regulate this backward reaction according to the storage life of perishable goods.
The reaction rate that has been found that this conversion backward reaction not only depends on the molecular structure of temperature and dyestuff, and also the polarity with the local microenvironment of dyestuff becomes.
Modifier be can form have amorphous, crystallization or mix any compound of the hybrid solid of amorphous-crystalline texture.
This hybrid solid can form by fusion, melt formation, comes out to form, forms in the solvent or form by grinding machinery ground by being dispersed in by co-precipitation from solvent by congruent melting.
This modifier must can surround light-absorbing compound, causes the change in polarity of microenvironment thus by interaction.These interactions can comprise electrostatic interaction, Van der Waals force etc.
Therefore, the present invention relates to comprise spiro-pyrans and can form the time-temperature indicator of modifier that have amorphous, crystallization or mix the hybrid solid of amorphous-crystalline texture, this modifier thus with this spiro-pyrans
Be selected from: the CH that is selected from n=10-18
3-(CH
2)
n-COOC
1-C
18The ester of alkyl; Cholesteryl oleate; Citrate; P-hydroxybenzoate; Borneolacetate, or be selected from the dicarboxylic acids C of m=2-20
1-C
18Alkyl-O-OC-(CH
2)
m-COOC
1-C
18The ester of alkyl; Or be selected from the ester of sugar alcohol; Or this modifier
Be selected from C
6-C
20Alkylol; Or
Be selected from cyclic alcohol; Or
Be selected from polyvalent alcohol; Or
Be selected from polyethers; Or
Be selected from fatty acid; Or
Be selected from carboxylate; Or
Be selected from diterpenoid acid (diterpene acid); Or
Be selected from urea or imidazoles; Or
Be selected from cyclic ketones; Or
Be selected from 2,6-two-tert-butyl group-4-metoxyphenol or 4-hydroxy 3-methoxybenzene formaldehyde; Or
Be selected from chroman-6-ole; Or
Be selected from 4-isopropenyl-1-methylcyclohexene (R-limonene); Or
Be selected from naphthalene, phenanthrene; Or
Be selected from lauryl sodium sulfate; Or
Be selected from the Zn complex compound of hydroxynaphthoic acid; Or
Be selected from the adduct of the 2nd indolenin unit and this spiro-pyrans; Or
Be selected from the hybrid solid of two kinds of different spiro-pyrans.
Under any circumstance, colour developing and decolorization kinetic are controlled in the reversible photoinduction open loop of the pyranoid ring that this modifier can both be by influencing spiro-pyrans.According to the kind of modifier, influence L specially
*, a
*Or b
*Value.Therefore, can regulate the performance of fading according to the storage life of perishable goods.
Therefore, in one embodiment, this time-temperature indicator comprises the hybrid solid of spiro-pyrans and naphthalene.
In another embodiment, this time-temperature indicator comprises the hybrid solid of spiro-pyrans and cetanol.
In another embodiment, this time-temperature indicator comprises the hybrid solid of spiro-pyrans and lauryl sodium sulfate.
In another embodiment, this time-temperature indicator comprises the hybrid solid of the Zn complex compound of spiro-pyrans and hydroxynaphthoic acid.
The hybrid solid that in another embodiment should time-temperature indicator comprises the adduct of spiro-pyrans and the 2nd indolenin unit and this spiro-pyrans.
In another embodiment, this time-temperature indicator comprises the hybrid solid of two kinds of different spiro-pyrans.
Suitable modifier further comprises the C8-C30 alkylol, as cetanol; Salt, as lauryl sodium sulfate, metal complex is as the Zn complex compound of hydroxynaphthoic acid.
This modifier also can be the synthetic accessory substance of spiro-pyrans.An example of accessory substance is the adduct of the 2nd indolenin unit and this spiro-pyrans.
This modifier also can be second spiro-pyrans, for example
With
Mixed crystal.
This modifier can be ester also, as is selected from the CH of n=10-18
3-(CH
2)
n-COOC
1-C
18The ester of alkyl is as butyl laurate, isopropyl myristate; Stearinic acid methyl esters (methyl stearate), or be selected from cholesteryl oleate, triethyl citrate, p-hydroxybenzoate (alkyl paraben, for example methyl p-hydroxybenzoate, butyl p-hydroxybenzoate), o-hydroxybenzoate, alkyl salicylate for example, gaultherolin for example, or the ester of borneolacetate, or be selected from the dicarboxylic acids C of m=2-20
1-C
18Alkyl-O-OC-(CH
2)
m-COOC
1-C
18The ester of alkyl, as sebacinic acid dialkyl (DAS di alkyl sebacate), sebacinic acid dibutyl ester (dibutyl sebacate) for example.
This modifier also can be the ester of sugar alcohol, as dehydrating sorbitol monooleate or sorbitan monolaurate.
This modifier also can be long-chain C
6-C
20Alcohol is as hexadecane-1-alcohol, octadecane-1-alcohol, polyethylene mono-alcohol.
This modifier can be cyclic alcohol also, as 1,7, and 7-trimethyl dicyclo [2.2.1] 2-2-in heptan alcohol (borneol) or 1,3,3-trimethyl dicyclo [2.2.1] heptan-2-alcohol (fenchol).
This modifier also can be polyvalent alcohol, as glycerine (the third-1,2, the 3-triol), D-sorbite, polycaprolactone glycol.
This modifier also can be polyethers, as polyglycol or polypropylene glycol, for example Macrogol 4000.
This modifier also can be fatty acid, as stearinic acid (stearic acid).
This modifier also can be carboxylate, as calcium stearate or dolomol.
This modifier can be diterpenoid acid also, as colophonic acid.
This modifier also can be urea.
This modifier also can be imidazoles.
This modifier can be phenol also, as 2, and 6-two-tert-butyl group-4-metoxyphenol or 4-hydroxy 3-methoxybenzene formaldehyde (vanillic aldehyde).
This modifier also can be chroman-6-ole (3,4-dihydro-2H-1-chromene-6-alcohol), as tocopherol (vitamin E).
This modifier also can be 4-isopropenyl-1-methylcyclohexene (R-limonene).
The mol ratio of modifier and spiro-pyrans is＞10%, preferred＞25.
All above-mentioned modifier can both influence the dynamics of fading.
Therefore, the time-temperature indicator that the invention further relates to as definition in the claim 1 influences the dynamic (dynamical) purposes of fading of spiro-pyrans.
Can form under the situation of melt with this spiro-pyrans at this modifier, the present invention further comprises the method for preparation time-temperature indicator, comprises the following steps
A) mix spiro-pyrans and modifier,
B) admixture that obtains in a) of heating is with the formation melt,
C) cooling is at b) in the melt that obtains with acquisition crystallization or amorphous solid, or
D) be dissolved in the admixture that obtains in a) in the solvent and make this crystalline mixture to obtain mixed crystal or hybrid solid.
Temperature in the step b) is 50-200 ℃.
Temperature in the step c) is preferably 0 ℃ to room temperature.
Solvent in the steps d can be an alcohol.
The invention further relates to and measure aging-and the method for the quality of temperature-sensitive product, comprise the following steps:
A) time-temperature indicator according to claim 1 that will comprise spiro-pyrans and modifier is printed onto in the substrate,
B) by with the ultraviolet ray irradiation, activate this indicator, especially photoinduced colour developing,
C) the optional protective that applies the colour developing of photoinduction again that prevents this indicator,
D) determine time-bleaching level of or temperature-induce, and, determine the quality of this product according to this bleaching level.
Suitable base material is inorganic and organic material, preferably those that know from traditional layer and packing technique.For example, can mention polymkeric substance, glass, metal, paper, cardboard etc.
" printing " is meant the printing of any kind, as letterpress, for example, aniline printing, impression; Lithography, for example offset printing or lithographic printing; Intaglio printing, for example photogravure; Serigraphy and nonimpact printing method such as ink jet printing, stylus printing, electrotype method, thermography etc.
Preferably in the after-applied protective that prevents the colour developing of photoinduction again of this reversible indicator of step c), especially colour filter agent.Under the situation of the indicator of UV-sensitivity, consider only can see through the yellow filtering agent of typical wavelengths greater than the light of 430 nanometers.
This protective can be the protective described in PCT application PCT/EP/2007060987 (Ciba).Therefore, this protective can be attached to the below time-clear, colorless or transparent coloured extinction protective seam of temperature indicator layer, it is characterized in that this extinction protective seam comprises the ultraviolet light absorber of the 1-50 weight % of polymeric binder and this layer general assembly (TW).
Further explain the present invention by embodiment.
Embodiment 1
Spiro-pyrans/as the naphthalene of retarding agent
The fine grinding powder of the leuco compound of 5 gram (11.9 mM) following formulas
In mortar, mix and fine-powdered with naphthalene (5.0 grams, 39 mMs).Under 60-70 ℃, this dyestuff and naphthalene fusion form green solution, and it is cooled to room temperature.Make ink formulations with this curing mixture efflorescence and with the gained potpourri subsequently.
With uviol lamp this spiro-pyrans/naphthalene powder was excited (charge) 10 seconds.
Following table is presented at the dynamics of fading under 2 ℃.
This table shows that naphthalene changes decolorization kinetic.
The L of spiro-pyrans/naphthalene system
*-value less (31.0, compare) with 38.8.L
*The increase of value is suitable.
The a of independent spiro-pyrans
*Value is approaching constant, a of spiro-pyrans/naphthalene system
*Value reduces slightly.
The b of spiro-pyrans/naphthalene system
*It is faster that value increases ground.
Embodiment 2
Spiro-pyrans/as the lauryl sodium sulfate of retarding agent
The fine grinding powder of the leuco compound of 5 gram following formulas
With the fully efflorescence in mortar of 5.0 gram (17.33 mM) lauryl sodium sulfate (SDS), subsequently under constant agitation with this mixture heated to 60-70 ℃, dyestuff began fusion and formed potpourri with SDS this moment.Whole process cost 10-15 minute.Subsequently this potpourri is cooled to RT and, is used to make water-base preparation subsequently subsequently with this solid efflorescence.
With uviol lamp this spiro-pyrans/lauryl sodium sulfate powder is excited 5 seconds.
Following table is presented at the dynamics of fading under 2 ℃.The contrast spiro-pyrans excites 10 seconds.
This table shows that lauryl sodium sulfate changes decolorization kinetic.
The L of spiro-pyrans/lauryl sodium sulfate system
*-value obviously less (21.5, compare) with 38.8, and it is faster to increase ground.
The a of independent spiro-pyrans
*Value is approaching constant, a of spiro-pyrans/lauryl sodium sulfate system
*Value reduces.
The b of spiro-pyrans/lauryl sodium sulfate system
*It is faster that value increases ground.
Embodiment 3
Spiro-pyrans/as the Zn complex compound of the 2-hydroxyl-3-naphthoic acid of retarding agent
In exemplary program, 5.0 gram (11.97 mM) spiro-pyrans
Zn complex compound fully efflorescence in mortar with 5.0 gram (11.3 mM) 2-hydroxyl 3-naphthoic acids.When physical mixed, form light red.This potpourri is not fused together.This potpourri is used to make water-base preparation subsequently.
With uviol lamp the Zn complex compound powder of this spiro-pyrans/2-hydroxyl-3-naphthoic acid is excited 10 seconds.
Following table is presented at the dynamics of fading under 2 ℃.
This table shows that this Zn complex compound changes decolorization kinetic.
The L of spiro-pyrans/Zn complex compound system
*-value obviously less (20.0, compare) with 38.8.Increase quite.
Since the redness of this potpourri, a
*Value is high.
The b of spiro-pyrans/Zn complex compound system
*Be worth smaller.The increase of the b value of these two kinds of systems is suitable.
Embodiment 4
Spiro-pyrans/cetanol TTI
The fine grinding powder of the leuco compound of 5 gram (11.97 mM) following formulas
In mortar, mix and fine-powdered with cetanol (5.0,20.62).Under 60-70 ℃, this dyestuff and cetanol are fused together under constant agitation.Make this potpourri be cooled to room temperature.Make ink formulations with this curing mixture efflorescence and with the gained potpourri subsequently.
With uviol lamp this spiro-pyrans/cetanol powder is excited 10 seconds.
Embodiment 5
The following example shows that fade properties also greatly depends on the purity of sample.According to synthetic, in the gained spiro-pyrans, comprise common accessory substance more or less, its verified right and wrong are photochromic.It more or less is the adduct of the 2nd indolenin unit and this spiro-pyrans and has formula:
Accessory substance A
Used spiro-pyrans has following formula
Spiro-pyrans A
With uviol lamp spiro-pyrans A/ accessory substance A (25.5%) powder and spiro-pyrans A/ accessory substance A (5.4%) are excited 10 seconds.
Following table is presented at the dynamics of fading under 2 ℃.
This table shows that the L initial value does not rely on the amount of existing accessory substance.But, when amount of by-products is higher, the reduction of fading.Therefore, this accessory substance serves as retarding agent.
Spiro-pyrans A/ accessory substance A (25.5%) is redder (referring to high a
*Value)
More blue and the color of spiro-pyrans A/ accessory substance A (5.4%) becomes yellow and (sees b
*Value).
Embodiment 6
The following example shows that also accessory substance also can serve as promoter.
When having more accessory substance, decolorization rate is higher.
Used spiro-pyrans has following formula
With uviol lamp spiro-pyrans B/ accessory substance B (32%) powder and spiro-pyrans B/ accessory substance B (13.6%) powder and spiro-pyrans B/ accessory substance B (0.3%) powder are excited 10 seconds.
Following table is presented at the dynamics of fading under 2 ℃.
Embodiment 7
Following table is enumerated the melt blend as basic spiro-pyrans based on LF2807 (GSID2074)
In first row, mention the LF2807 conduct of 5% carrying capacity and the comparison of the compound of hereinafter mentioning.These apply with 10% carrying capacity, this means in the final printed matter 5% spiro-pyrans content:
From above as can be seen, the melt blend of whole series is all implemented with LF2807, and all these is 1: 1 ratio and implements down at 150 ℃.
Usually, the color of the melt blend under the excited state is in the scope identical with fusion LF2807, in red blue area.But, intensity of colour, fading rate and behavior and the marked change of relevant pot life scope.
Special circumstances are to use vanillic aldehyde as the bath component among the LF4064, and it shows low intensity of colour and the colour developing of the intense violet color under unexcited state.In this case, most probably, vanillic aldehyde forms known purple Indolenin-Methin dyestuff as the reaction of aldehyde and spiro-pyrans and when the balance.
Urea as bath component forms two-phase system in melting process, therefore do not expect the eutectic (LF4054) that forms these two kinds of compounds.Therefore, the character of gained potpourri is very similar to the character of independent fusion LF2807.
Other melt blend of great majority shows dynamic (dynamical) difference, because their high intensity of colour and long pot life scope, the most significant potpourri of Que Dinging is LF3903 and LF3929 at first.
Embodiment 8
Following table is enumerated the melt blend as basic spiro-pyrans based on LF3155 (GSID3655)
In first row, mention the LF3155 conduct of 5% carrying capacity and the comparison of the compound of hereinafter mentioning.These apply with 10% carrying capacity, this means in the final printed matter 5% spiro-pyrans content:
From above as can be seen, the melt blend of whole series is all implemented with LF3155, and all these is 1: 1 ratio and fusion under assigned temperature.From above as can be seen, compare with reality acquisition mixed crystal or solid solution, only the intensity of colour of compound just improves slightly under a few cases.
LF3155。But in most of the cases dynamics changes, and this reaches a conclusion: tocopherol also is used for the melt mixed with LF3155.Unfortunately, gained LF3993 can't test in our standard water-based inks system owing to very high viscosity.Therefore, it is tested in NC and vinyl ink:
From above as can be seen, intensity of colour is at downside, and the vinyl printed matter is because its better fade properties and show longer pot life scope surprisingly.As if in NC, photostability is higher, but must confirm this result.
Embodiment 10
Based on LF4005,1: 1
Claims (29)
1. comprise spiro-pyrans and can form the time-temperature indicator of modifier that have amorphous, crystallization or mix the hybrid solid of amorphous-crystalline texture, wherein this modifier with this spiro-pyrans
Be selected from: the CH that is selected from n=10-18
3-(CH
2)
n-COOC
1-C
18The ester of alkyl; Cholesteryl oleate; Citrate; P-hydroxybenzoate; Borneolacetate, or be selected from the dicarboxylic acids C of m=2-20
1-C
18Alkyl-O-OC-(CH
2)
m-COOC
1-C
18The ester of alkyl; Or be selected from the ester of sugar alcohol; Or this modifier
Be selected from C
6-C
20Alkylol; Or
Be selected from cyclic alcohol; Or
Be selected from polyvalent alcohol; Or
Be selected from polyethers; Or
Be selected from fatty acid; Or
Be selected from carboxylate; Or
Be selected from diterpenoid acid; Or
Be selected from urea or imidazoles; Or
Be selected from cyclic ketones; Or
Be selected from 2,6-two-tert-butyl group-4-metoxyphenol or 4-hydroxy 3-methoxybenzene formaldehyde; Or
Be selected from chroman-6-ole; Or
Be selected from 4-isopropenyl-1-methylcyclohexene (R-limonene); Or
Be selected from naphthalene, phenanthrene; Or
Be selected from lauryl sodium sulfate; Or
Be selected from the Zn complex compound of hydroxynaphthoic acid; Or
Be selected from the adduct of the 2nd indolenin unit and this spiro-pyrans; Or
Be selected from the hybrid solid of two kinds of different spiro-pyrans.
2. according to the time-temperature indicator of claim 1, wherein said modifier is the nonpolar modifier that is selected from naphthalene, phenanthrene.
3. according to the time-temperature indicator of claim 1, comprise the hybrid solid of spiro-pyrans and naphthalene.
4. according to the time-temperature indicator of claim 1, comprise the hybrid solid of spiro-pyrans and cetanol.
5. according to the time-temperature indicator of claim 1, comprise the hybrid solid of spiro-pyrans and lauryl sodium sulfate.
6. according to the time-temperature indicator of claim 1, comprise the hybrid solid of the Zn complex compound of spiro-pyrans and hydroxynaphthoic acid.
7. according to the time-temperature indicator of claim 1, comprise the hybrid solid of the adduct of spiro-pyrans and the 2nd indolenin unit and this spiro-pyrans.
8. according to the time-temperature indicator of claim 1, comprise the hybrid solid of two kinds of different spiro-pyrans.
9. according to the time-temperature indicator of claim 1, wherein said modifier is selected from: the CH that is selected from n=10-18
3-(CH
2)
n-COOC
1-C
18The ester of alkyl; Cholesteryl oleate; Citrate; P-hydroxybenzoate; Borneolacetate, or be selected from the dicarboxylic acids C of m=2-20
1-C
18Alkyl-O-OC-(CH
2)
m-COOC
1-C
18The ester of alkyl; Or be selected from the ester of sugar alcohol.
10. according to the time-temperature indicator of claim 9, wherein said modifier is selected from butyl laurate, isopropyl myristate, stearinic acid methyl esters, or be selected from cholesteryl oleate, triethyl citrate, methyl p-hydroxybenzoate, butyl p-hydroxybenzoate, gaultherolin, or borneolacetate, or sebacinic acid dibutyl ester.
11. according to the time-temperature indicator of claim 1, wherein said modifier is selected from sugar alcohol.
12. according to the time-temperature indicator of claim 11, wherein said sugar alcohol is dehydrating sorbitol monooleate or sorbitan monolaurate.
13. according to the time-temperature indicator of claim 1, wherein said modifier is selected from C
6-C
20Alcohol.
14. according to the time-temperature indicator of claim 13, wherein said alcohol is selected from hexadecane-1-alcohol, octadecane-1-alcohol, polyethylene mono-alcohol.
15. according to the time-temperature indicator of claim 1, wherein said modifier is selected from cyclic alcohol.
16. according to the time-temperature indicator of claim 15, wherein said cyclic alcohol is selected from 1,7,7-trimethyl dicyclo [2.2.1] 2-2-in heptan alcohol (borneol) or 1,3,3-trimethyl dicyclo [2.2.1] heptan-2-alcohol (fenchol).
17. according to the time-temperature indicator of claim 1, wherein said modifier is selected from polyvalent alcohol.
18. according to the time-temperature indicator of claim 17, wherein said polyvalent alcohol is selected from glycerine (the third-1,2, the 3-triol), D-sorbite, polycaprolactone glycol.
19. according to the time-temperature indicator of claim 1, wherein said modifier is selected from polyethers.
20. according to the time-temperature indicator of claim 19, wherein said polyethers is selected from polyglycol or polypropylene glycol or Macrogol 4000.
21. according to the time-temperature indicator of claim 1, wherein said modifier is selected from fatty acid, preferred stearinic acid.
22. according to the time-temperature indicator of claim 1, wherein said modifier is selected from carboxylate, preferred calcium stearate or dolomol.
23. according to the time-temperature indicator of claim 1, wherein said modifier is selected from diterpenoid acid, preferred colophonic acid.
24. according to the time-temperature indicator of claim 1, wherein said modifier is selected from urea or imidazoles.
25. according to the time-temperature indicator of claim 1, wherein said modifier is selected from 2,6-two-tert-butyl group-4-metoxyphenol or 4-hydroxy 3-methoxybenzene formaldehyde (vanillic aldehyde).
26. according to the time-temperature indicator of claim 1, wherein said modifier is tocopherol (vitamin E) or R-limonene.
27. according to each time-temperature indicator of claim 1-26, the mol ratio of wherein said modifier and spiro-pyrans is＞10%, preferred＞25.
28. according to claim 1-26 each time-temperature indicator influence dynamic (dynamical) purposes of fading.
29. determine aging-and the method for the quality of temperature-sensitive product, it comprises the following steps:
A) time-temperature indicator according to claim 1 that will comprise spiro-pyrans and modifier is printed onto in the substrate,
B) by with the ultraviolet ray irradiation, activate described indicator, especially photoinduced colour developing,
C) the optional protective that applies the colour developing of photoinduction again that prevents described indicator,
D) determine time-bleaching level of or temperature-induce, and, determine the quality of product according to this bleaching level.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08154635.0 | 2008-04-16 | ||
| EP08154635 | 2008-04-16 | ||
| PCT/EP2009/053948 WO2009127529A1 (en) | 2008-04-16 | 2009-04-02 | Optimized time temperature indicator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102007404A true CN102007404A (en) | 2011-04-06 |
Family
ID=39717538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801134829A Pending CN102007404A (en) | 2008-04-16 | 2009-04-02 | Optimized time temperature indicator |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2269056A1 (en) |
| JP (1) | JP5453393B2 (en) |
| CN (1) | CN102007404A (en) |
| IL (1) | IL208160A0 (en) |
| WO (1) | WO2009127529A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891410A (en) * | 2016-04-14 | 2016-08-24 | 梧州市产品质量检验所 | Detection method of abietic acid in rosin |
| CN106568528A (en) * | 2016-10-31 | 2017-04-19 | 深圳九星印刷包装集团有限公司 | Water-loss sensitive time indication device |
| CN110375878A (en) * | 2019-06-14 | 2019-10-25 | 中国科学院大学 | A kind of irreversible thermochromism indicator solution, the temperature monitor containing it and application |
| CN110519985A (en) * | 2017-03-31 | 2019-11-29 | 弗劳恩霍夫应用研究促进协会 | Low temperature indicator mixture, the device and method for monitoring the temperature transition under low temperature |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110139059A1 (en) * | 2008-05-21 | 2011-06-16 | Basf Se | Time temperature indicator comprising indolenin based spiropyrans containing a n-acetylamido or n-acetylester side chain |
| ES2376559B1 (en) | 2011-04-11 | 2013-01-24 | Universidad Pública de Navarra | DEVICE FOR MONITORING TIME AND TEMPERATURE CONDITIONS. |
| NO20110590A1 (en) | 2011-04-15 | 2012-04-02 | Keep It Tech As | Time-temperature indicator system, method of its manufacture and combination comprising said time-temperature indicator system. |
| NO331993B1 (en) | 2011-04-15 | 2012-05-21 | Keep It Technologies As | Time-temperature indicator system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0796678B2 (en) * | 1989-05-22 | 1995-10-18 | サカタインクス株式会社 | Shading material |
| JP2962035B2 (en) * | 1992-04-03 | 1999-10-12 | 松下電器産業株式会社 | Photochromic composition and optical recording medium using the same |
| JP3505401B2 (en) * | 1998-09-16 | 2004-03-08 | 株式会社東芝 | Method for preparing erasable image forming material |
| US8277749B2 (en) * | 2004-02-02 | 2012-10-02 | Freshpoint Holdings S.A. | Time-temperature indicator based on valence isomerizations |
| US8076058B2 (en) * | 2004-09-30 | 2011-12-13 | Hewlett-Packard Development Company, L.P. | Color forming compositions and associated methods |
| US7538070B2 (en) * | 2005-06-07 | 2009-05-26 | Xerox Corporation | Thermochromic recording medium |
-
2009
- 2009-04-02 CN CN2009801134829A patent/CN102007404A/en active Pending
- 2009-04-02 EP EP09732219A patent/EP2269056A1/en not_active Withdrawn
- 2009-04-02 WO PCT/EP2009/053948 patent/WO2009127529A1/en active Application Filing
- 2009-04-02 JP JP2011504410A patent/JP5453393B2/en not_active Expired - Fee Related
-
2010
- 2010-09-15 IL IL208160A patent/IL208160A0/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891410A (en) * | 2016-04-14 | 2016-08-24 | 梧州市产品质量检验所 | Detection method of abietic acid in rosin |
| CN106568528A (en) * | 2016-10-31 | 2017-04-19 | 深圳九星印刷包装集团有限公司 | Water-loss sensitive time indication device |
| CN106568528B (en) * | 2016-10-31 | 2019-12-27 | 深圳九星印刷包装集团有限公司 | Water loss sensitive time indicator |
| CN110519985A (en) * | 2017-03-31 | 2019-11-29 | 弗劳恩霍夫应用研究促进协会 | Low temperature indicator mixture, the device and method for monitoring the temperature transition under low temperature |
| CN110375878A (en) * | 2019-06-14 | 2019-10-25 | 中国科学院大学 | A kind of irreversible thermochromism indicator solution, the temperature monitor containing it and application |
Also Published As
| Publication number | Publication date |
|---|---|
| IL208160A0 (en) | 2010-12-30 |
| JP2011519420A (en) | 2011-07-07 |
| JP5453393B2 (en) | 2014-03-26 |
| WO2009127529A1 (en) | 2009-10-22 |
| EP2269056A1 (en) | 2011-01-05 |
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