Colorimetric sensors

• US 7,767,143 B2
• Filed: 06/27/2006
• Issued: 08/03/2010
• Est. Priority Date: 06/27/2006
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Rakow, Neal A., Wendland, Michael S., Weiss, Douglas E., Palazzotto, Michael C.
• Primary Examiner(s): Griffin; Walter D
• Assistant Examiner(s): Mui; Christine T
• Application Number:
  US11/426,729
• Publication Number:
  US 20070297944A1
• Time in Patent Office: 1,498 Days
• Field of Search: 422/82.05, 422/82.09, 422/56, 422/1, 422/55, 422/50, 422/60, 422/58, 422/68.1, 359/588, 428/306.6, 428/349, 250/474, 250/472.1, 250/208.1, 264/425
• US Class Current: 422/400
• CPC Class Codes: G01J 1/04 Optical or mechanical part supplementary adjustable parts
• CPC Class Codes: G01J 1/0437 using masks, aperture plates, spatial light modulators, spatial filters, e.g. reflective filters
• CPC Class Codes: G01J 1/429 applied to measurement of ultraviolet light using counting tubes G01T
• CPC Class Codes: G01J 1/50 using change in colour of an indicator, e.g. actinometer
• CPC Class Codes: H01L 27/144 Devices controlled by radiation
• CPC Class Codes: H01L 27/1446 in a repetitive configuration

Abstract

Colorimetric sensors comprising a reflective surface and a curable layer are disclosed. Devices comprising the colorimetric sensors and methods of making the sensors and devices are also disclosed. Methods of using the sensors and devices in numerous applications are also disclosed.

Claims

1. A colorimetric sensor for measuring exposure to radiation or thermal energy, said colorimetric sensor comprising:

a support substrate;

a reflective surface on said support substrate; and

a curable layer over said reflective surface, said curable layer comprising a functionalized polymer having pendant free-radically polymerizable groups, the functionalized polymer comprising the reaction product of (i) a polymer reactant having functional groups thereon, the functional group selected from a nucleophilic group or an electrophilic group and (ii) a bifunctional reactant comprising a reactive group capable of undergoing a nucleophilic/electrophilic reaction with the functional groups of the polymer reactant and at least one pendant free-radically polymerizable group;

wherein said sensor undergoes polymerization of said pendant free-radically polymerizable groups resulting in a change in one or more optical properties upon exposure to (i) a threshold amount of radiation or (ii) a threshold amount of thermal energy.

2. The colorimetric sensor of claim 1, wherein said support substrate comprises a polymer film or sheet, an all-polymeric mirror film, a glass substrate, an inorganic substrate, a ceramic substrate, a silicon wafer, a fabric sheet, or a combination thereof

3. The colorimetric sensor of claim 1, wherein said curable layer further comprises one or more polymerizable monomers alone or in combination with at least one non-functionalized polymer.

4. The colorimetric sensor of claim 1, wherein said curable layer further comprises at least one non-functionalized polymer.

5. The colorimetric sensor of claim 1, wherein said curable layer comprises (a) one or more polymerizable monomers and (b) said functionalized polymer.

6. The colorimetric sensor of claim 1, further comprising at least one additional layer over said curable layer, said at least one additional layer comprising an optically clear protective layer, a masking layer, or a combination thereof.

7. The colorimetric sensor of claim 1, wherein said one or more optical properties comprise a color, an optical thickness, a reflectance spectrum value, or a combination thereof.

8. The colorimetric sensor of claim 1, wherein said sensor either displays a first color or is colorless when viewed through said curable layer, and when exposed to a threshold amount of radiation or thermal energy either (i) undergoes a color change from said first color to a second color, (ii) undergoes a color change from said first color to a colorless condition, or (iii) undergoes a color change from a colorless state to a color-containing state.

9. An array comprising two or more colorimetric sensors, at least one of which comprises the colorimetric sensor of claim 1.

10. A device comprising:

the colorimetric sensor of claim 1, and

a housing at least partially enclosing the colorimetric sensor, wherein the housing comprises at least one opening positioned above said curable layer, said at least one opening providing a restricted view of an upper surface of said curable layer.

11. A method of detecting exposure of an article to a threshold amount of radiation or thermal energy, said method comprising the steps of:

providing an article;

providing the colorimetric sensor of claim 1;

exposing (i) the article and (ii) the sensor to a radiation or thermal energy source, and

monitoring the sensor for a change in one or more optical properties resulting from exposure to the threshold amount of radiation or thermal energy.

12. The method of claim 11, wherein the article comprises a curable article, an article moving through a processing line, an article subjected to a sterilization process, an article forming a part of or used in combination with a germicidal lamp, an article forming a part of or used in combination with clothing or other wearable items, or a portion of a human body.

13. The method of claim 11, wherein the method comprises a continuous process in which the article travels along a path through one or more process stations.

14. The method of claim 11, wherein said exposing step comprises two or more separate process steps in which (i) the article and (ii) the sensor are exposed to a radiation or thermal energy source in the two or more separate process steps.

20. The colorimetric sensor of claim 1, wherein said at least one pendant free-radically polymerizable functional group of the bifunctional reactant comprises a vinyl group, a vinyloxy group, a (meth)acrylic group, a (meth)acryloyl group, a (meth)acryloxy group, a propargyl group, a (meth)acrylamido group, or an acetylenic functional group.

21. The colorimetric sensor of claim 1, wherein said reactive group of the bifunctional reactant comprises a hydroxyl group, a secondary amino group, an oxazolinyl group, an oxazolonyl group, an acetyl group, an acetonyl group, a carboxyl group, an isocyanato group, an epoxy group, an aziridinyl group, an acyl halide group, a vinyloxy group, or a cyclic anhydride group.

23. The colorimetric sensor of claim 1, further comprising at least one additional layer over said curable layer, said at least one additional layer being temporarily bonded to said curable layer.

24. The colorimetric sensor of claim 1, further comprising a masking layer over a portion of said curable layer, said masking layer forming a pattern over said curable layer.

15. A method of measuring an amount of exposure of an article to radiation or thermal energy, said method comprising the steps of:

providing an article;

providing a colorimetric sensor having a first set of optical properties and comprising;

a support substrate;

a reflective surface on the support substrate; and

a curable layer over the reflective surface, the curable layer comprising a functionalized polymer having pendant free-radically polymerizable groups, the functionalized polymer comprising the reaction product of (i) a polymer reactant having functional groups thereon, the functional group selected from a nucleophilic group or an electrophilic group and (ii) a bifunctional reactant comprising a reactive group capable of undergoing a nucleophilic/electrophilic reaction with the functional groups of the polymer reactant and at least one pendant free-radically polymerizable group;

exposing the article and the sensor to a radiation or thermal energy source so as to (1) polymerize the pendant free-radically polymerizable groups and (2) produce a colorimetric sensor having a second set of optical properties, and

comparing the second set of optical properties to the first set of optical properties.

16. The method of claim 15, wherein said exposing step comprises two or more separate process steps in which the article and sensor are exposed to a radiation or thermal energy source, and the sensor provides an indication of a cumulative amount of radiation or thermal energy from said two or more separate process steps.

17. The method of claim 15, wherein said comparing step comprises measuring a change in a spectral blueshift of the sensor.

18. A method of tailoring a colorimetric sensor to exhibit a change in one or more optical properties upon exposure to a predetermined amount of radiation or thermal energy, said method comprising the steps of:

choosing a specific amount of radiation or thermal energy;

formulating a curable composition that (1) polymerizes a functionalized polymer having pendant free-radically polymerizable groups and (2) exhibits a change in one or more optical properties when (i) applied over a reflective surface at a curable layer thickness, and (ii) subsequently exposed to the specific amount of radiation or thermal energy;

providing a support substrate having the reflective surface thereon; and

applying the curable composition over the reflective surface so as to form a curable layer having the curable layer thickness, wherein the curable composition comprises the functionalized polymer having pendant free-radically polymerizable groups and the functionalized polymer comprises the reaction product of (i) a polymer reactant having functional groups thereon, the functional group selected from a nucleophilic group or an electrophilic group and (ii) a bifunctional reactant comprising a reactive group capable of undergoing a nucleophilic/electrophilic reaction with the functional groups of the polymer reactant and the at least one pendant free-radically polymerizable functional group.

19. The method of claim 18, further comprising:

positioning the sensor in proximity to or on an article that is to be exposed to radiation or thermal energy; and

exposing the sensor and article to an amount of radiation or thermal energy.

22. The method of claim 18, further comprising:

covering the curable layer with at least one additional layer so as to sandwich the curable layer between the reflective surface and the at least one additional layer.