WO2008124178A1 - Procédé et appareil de détermination des propriétés colorimétriques de pigment in situ - Google Patents

Procédé et appareil de détermination des propriétés colorimétriques de pigment in situ Download PDF

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Publication number
WO2008124178A1
WO2008124178A1 PCT/US2008/004625 US2008004625W WO2008124178A1 WO 2008124178 A1 WO2008124178 A1 WO 2008124178A1 US 2008004625 W US2008004625 W US 2008004625W WO 2008124178 A1 WO2008124178 A1 WO 2008124178A1
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Prior art keywords
acid
pigment
red
yellow
dye
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PCT/US2008/004625
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English (en)
Inventor
Da-Sheng Lin
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Sun Chemical Corporation
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Publication date
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Publication of WO2008124178A1 publication Critical patent/WO2008124178A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46—Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0218—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using optical fibers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/46—Measurement of colour; Colour measuring devices, e.g. colorimeters
    • G01J3/463—Colour matching
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids
    • G01N21/8507—Probe photometers, i.e. with optical measuring part dipped into fluid sample
    • G01N2021/8528—Immerged light conductor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/129—Using chemometrical methods

Definitions

  • the invention relates to the noninvasive measurement of pigment or ink composition by electronic absorption spectroscopy.
  • the invention describes methods and devices for analysis of pigment containing slurry or ink composition by a combination of UV/visible absorbance / reflectance and transmission spectroscopy and multivariate data analysis.
  • the present invention provides an apparatus for the in situ monitoring of a pigment or dye solution comprising:
  • spectrophotometer monitors radiation comprising UV/visible light transmitted through, absorbed or reflected by the irradiated sample,- and
  • the present invention also provides a pigment or dye solution prepared by a process that comprises monitoring using the apparatus of the present invention.
  • the present invention further provides an apparatus for monitoring in a cell a pigment or dye solution comprising:
  • spectrophotometer monitors radiation comprising UV/visible light transmitted through, absorbed or reflected by the irradiated sample,- and
  • the present invention also provides a method for in situ monitoring of a pigment or dye solution comprising the steps of:
  • the present invention further provides a pigment or dye solution prepared by the process of the present invention.
  • Figure 1 shows Yellow Slurry 14 from Example 1 (5 samples) % transmission data.
  • Figure 2 shows the reflectance using Colorcell of the Yellow Slurry 14 samples from Example 1.
  • Colorcell is a way for measurements using the reflectance spectrum in the visible range of products in the liquid state. It is recommended for color, whiteness or another property measurement based on reflectance phenomenon.
  • FIG. 3 shows the K and S values for the samples 74 A, B and C of Example 1.
  • the solid lines are K values whereas dotted lines are S values .
  • the normalized concentrations of the samples can be calculated.
  • Figure 4 shows the normalized concentrations of the 74 A, B and C samples.
  • Sample 74B red line
  • Sample 74A blue line, used as baseline
  • Sample 74A has higher concentration than Sample 74C (black line) .
  • Figure 5 shows the transmission measurement of the 74 A, B and C samples in Example 1.
  • the calculated %transmission of 74 A B and C based on the K/S coefficients. They match the actual measurements of % transmission. This proves the differences between these three samples are due to the differences in pigment concentration
  • Figure 6 shows the Reflectance over an infinite background of the 70, 71 and 74 A samples in Example 1.
  • the reflectance curve of 71 is closer to 74 A, but with a different curve shape. This indicates the effect of shading agent (PMP), not of concentration.
  • PMP shading agent
  • the parallel curves of 71 and 70 show the difference of 71 with 70 is due to the concentration difference. Concentration difference is due to the fact that the excess tetrazo in 71 decompose the pigment.
  • Figure 8 shows the K' s and S' values of the 70, 71 and 74 A samples in Example 1 calculated by equation 4. Profile K is shown in solid line) and Profile S in dotted line .
  • Figure 9 shows the normalized composition (concentration ratio) of the 70 and 71 samples of Example 1. In effect, Figure 9 shows the effect of pigment & PMP (shading agent) decomposition because of excess tetrazo in 71.
  • Figure 10 shows the normalized composition (concentration ratio) of 70, 71 and 74 A samples in Example 1. In effect, Figure 10 shows the profile similarity of 70 & 71. Both have PMP shading agent. 74 A has no shading agent but has same concentration as 70.
  • Figure 11 shows the % transmission profile of dilutes sample 71 and sample 74 A. In effect, Figure 11 shows that after the correction of dilution effect, sample 74A is very close to sample 71.
  • Figure 12 shows the relative transmission of the yellow sample of Example 2. Different Exposure Times (ET) were employed for different wavelengths.
  • Figure 13 shows the normalized transmission data of yellow sample of Example 2.
  • Figure 14 shows the relative transmission of the blue sample of Example 2. Different Exposure Times (ET) were employed for different wavelengths.
  • Figure 15 shows the normalized transmission data of blue sample of Example 2.
  • Figure 16 shows the wet reflectance data of the blue samples (80_73C and 80_73D) of Example 3.
  • Figure 17 shows the relative transmission of the blue samples (80_73C and 80_73D with different film thickness) of Example 3.
  • Figure 18 shows the relative transmission of the blue samples (80_73C and 80_73D; one film thickness) of Example 3.
  • Figure 19 shows the absorption coefficients related to the scattering of 80_73C and 80_73D of Example 3.
  • Figure 20 shows the absorption coefficients of 80_73C and 80_73D of Example 3 in a normalized way.
  • Figure 21 shows the scattering coefficients of the 80_73C and 80_73D blue samples of Example 3.
  • Figure 22 shows the reflectance data from conventional (dry) method of the blue samples (80_73C and 80_73D) of Example 3.
  • Figure 23 shows a comparison results between the wet and dry results for the blue samples (80_73C and 80_73D) of Example 3.
  • the present invention is directed to an apparatus and methods for real-time/on-line monitoring of color properties in situ, without the removal of aliquots for sampling.
  • the present invention also relates to the monitoring of color properties of pigment and dye solutions in a cell.
  • aliquots can be removed from a sample and added in the cell or can be pumped on line using a tube in and out of the cell.
  • the present invention relates to methods and devices for in-situ measurement (in line or real time) or measurement in a tank, vessel or process line of various properties of pigment or dye solutions such as pigment slurry, pigment dispersion and ink compositions .
  • the invention describes the use of UV/visible absorbance, reflective or transmission spectroscopy to monitor the composition of samples containing pigments or dyes.
  • radiation passes through a transparent layer of solid, liquid or gas, certain frequencies of radiation may be selectively removed by absorption.
  • absorption of radiation occurs when electromagnetic energy is transferred to the atoms or molecules of the sample and these particles are promoted from a low energy (ground) state to higher energy, or excited states. Because atoms and molecules have a limited number of discrete, quantified energy levels, for absorption of radiation to occur, the energy of the exciting photon must match the energy difference between the ground state and one of the excited states of the absorbing species.
  • the invention describes using absorbance, reflection or transmission spectroscopy for on-line monitoring of pigment concentration and color properties in samples containing at least one pigment .
  • the present invention comprises an apparatus for in situ monitoring of pigment or dye composition formation.
  • the apparatus of the invention comprises a UV/visible light source, a transmission probe comprising two arms, a spectrophotometer, a data analysis system, and a compartment in which liquid or meltdown samples flow through .
  • the apparatus of the present invention comprises a data acquisition system and a data analysis system for the in situ monitoring of samples containing pigments or dyes.
  • the data acquisition system comprises hardware and software components to collect and process optical spectra.
  • the hardware components include the light source, optical filters, optical fibers, optical probe (s), spectrophotometer, detector and any other components needed to generate light emission, transmit the light to the measurement location, and transmit emitted radiation from the measurement location to the detector system for storage of the optical signals.
  • the light source may comprise a steady-state Xe arc lamp, or the like.
  • a substantially monochromatic radiation from the lamp is directed via a first arm of the probe to irradiate the pigment or dye solution sample (the "Sample") flowing through a vessel.
  • Sample the pigment or dye solution sample
  • Substantially monochromatic light generally comprises radiation having a very narrow band of wavelengths, comprising a variation of about 1 nm or less.
  • the transmitted light is then collected by a second arm of the probe and directed to a spectrophotometer to generate an absorbance, reflection or transmission profile which is then processed by a data analysis system.
  • the emission level from the light source may be attenuated such that the spectrometer is not saturated.
  • an in-line short-pass filter is positioned to block the spectrophotometer from excess radiation.
  • the probe is preferably a fiber optic probe connected to a spectrophotometer.
  • the probe may contain a light source as described above or alternatively may be connected to a light source.
  • the probe is inserted into a tank, vessel or directly into a process pipe line or a cell which the pigment or dye solution sample (the "Sample") flows through.
  • the probe is capable of transmitting at least one substantially monochromatic radiation from the light source to irradiate the Sample.
  • the probe also contains a sensor that collects light transmitted through or reflected from the irradiated sample.
  • the probe relays the information collected in connection with light transmission and reflection by the Sample back to the spectrophotometer.
  • the radiation absorbed by the Sample is calculated in the probe or spectrophotometer by subtracting the sum of the radiation reflected by and transmitted through the Sample from the radiation emitted by the light source.
  • a cell attached to or being a part of the spectrophotometer is employed instead of a probe.
  • a Sample is added or flown through this cell which is then irradiated for measurements of light transmission and reflection by the Sample.
  • the Path Length in a spectrophotometer is defined as the distance that the irradiated light travels through the Sample in the cell or probe as described above.
  • Radiation comprising UV/visible light transmitted through, absorbed or reflected by the irradiated sample is monitored in the spectrophotometer and analyzed using a data analysis system that correlates said absorbance, reflection and/or transmission to at least one predetermined color property.
  • the probe is maintained at a substantially constant temperature.
  • a change in the temperature of the probe can cause a change in the temperature of the Sample which in turn can influence the reflection and absorption of light in the Sample.
  • the probe operates at a temperature in the range from 2O 0 C. More preferably, the probe operates at a temperature in the range from 3O 0 C to 12O 0 C. Even more preferably, the probe operates at a temperature in the range from 6O 0 C to HO 0 C.
  • the invention may comprise a flow-cell for measuring pigment content and color properties.
  • a flow-cell preferably shows only a small variation in baseline absorbance at the high temperatures required to measure molten polycarbonate. More preferably, a majority of the variation for the flow- cell is corrected for using chemometric statistical techniques, such as baseline correction and the like.
  • a standard probe is possible by positioning the probe at some distance from the Sample or reactor surface. Generally, standard probes are positioned about 3 mm, but not more than 200 mm, from the flow-cell surface. As will be understood by those of ordinary skill in the art, in the plant environment, it may be necessary to secure the probe in some type of retaining device that is heated to the same temperature as a reaction mixture flow to make the pigment or dye composition, such as a flange or the like.
  • the probe may be a high temperature fiber-optic probe such as probes supplied by Equitech International Corporation (Aiken, S.C.), and Ocean Optics (Dunedin, FIa.) Guided Wave . RTM . type probes, and the like.
  • High temperature probes may be positioned closer to the reactor to deliver increased amounts of light to the Sample, thereby increasing the quality of spectra collected.
  • the probe may be a dip-stick which is actually immersed in the Sample, such as probes provided by HELLMA Gmbh & Co . KG., (Mullheim, Germany), Ocean Optics (Dunedin, FIa.) Guided Wave. RTM. type probes, and the like.
  • the Sample may comprise a pigment solution.
  • the pigment may be organic or inorganic.
  • the Sample comprises a pigment selected from the group consisting of Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow.37, Pigment Yellow 63, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 106, Pigment Yellow 114, Pigment Yellow 121, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 136, Pigment Yellow 174, Pigment Yellow 176, Pigment Yellow 188, Pigment Orange 5, Pigment Orange 13, Pigment Orange 16, Pigment Orange 34, Pigment Red 2, Pigment Red 9, Pigment Red 14, Pigment Red 17, Pigment Red 22, Pigment Red 23, Pigment Red 37, Pigment Red 38, Pigment Red 41, Pigment Red 42, Pigment Red 112, Pigment red 122, Pigment Red 146, Pigment Red 170, Pig
  • the Sample comprises a dye.
  • the classes of dyes suitable for use in present invention may be selected from acid dyes, natural dyes, direct dyes (either cationic or anionic), basic dyes, and reactive dyes.
  • the acid dyes also regarded as anionic dyes, are soluble in water and mainly insoluble in organic solvents and are selected, from yellow acid dyes, orange acid dyes, red acid dyes, violet acid dyes, blue acid dyes, green acid dyes, and black acid dyes.
  • European Patent 0 745 651 incorporated herein by reference, describes a number of acid dyes which are suitable for use in the present invention
  • the yellow acid dyes selected include Acid Yellow 1 International Color Index or C.I. 10316); Acid Yellow 7 (CI. 56295); Acid Yellow 17 (CI. 18965); Acid Yellow 23 (CI. 19140); Acid Yellow 29 (CI. 18900); Acid Yellow 36 (CI. 13065); Acid Yellow 42 (CI. 22910); Acid Yellow 73 (CI. 45350); Acid Yellow 99 (CI. 13908); Acid Yellow 194; and Food Yellow 3 (CI. 15985).
  • the orange acid dyes selected include Acid Orange 1 (CI. 13090/1); Acid Orange 10 (CI. 16230).; Acid Orange 20
  • the red acid dyes selected include Acid Red 1. (CI. 18050); Acid Red 4 (CI. 14710); Acid Red 18 (CI. 16255), Acid Red 26
  • the violet acid dyes selected include Acid Violet 7 (CI. 18055); and Acid Violet 49 (CI. 42640) .
  • the blue acid dyes selected include Acid Blue 1 (CI. 42045); Acid Blue 9 (CI. 42090); Acid Blue 22 (CI. 42755); Acid Blue 74 (CI. 73015); Acid Blue 93 (CI. 42780); and Acid Blue 158A
  • the green acid dyes selected include Acid Green 1 (CI. 10028); Acid Green 3 (CI. 42085); Acid Green 5 (CI. 42095); Acid Green 26 (CI. 44025); and Food Green 3 (CI. 42053) .
  • the black acid dyes selected include Acid Black 1 (CI. 20470); Acid Black 194 (BASANTOL . TM . X80, available from BASF Corporation, an azo/l:2 CR- complex.
  • the direct dyes selected for use in the present invention include Direct Blue 86 (CI. 74180); Direct Blue 199; Direct Black 168; Direct Red 253; and Direct Yellow 107/132 (CI. Not Assigned) .
  • the direct dyes are commonly- used in coloration of pulp paper.
  • the natural dyes selected for use in the present invention include Alkanet (CI. 75520,75530); Annafto (CI. 75120); Carotene (CI. 75130); Chestnut; Cochineal (CI. 75470); Cutch (CI. 75250, 75260); Divi-Divi; Fustic (CI. 75240); Hypernic (CI. 75280); Logwood (CI. 75200); Osage Orange (CI. 75660); Paprika,- Quercitron (CI. 75720); Sanrou (CI. 75100); Sandal Wood (CI. 75510, 75540, 75550, 75560); Sumac; and Tumeric (CI. 75300).
  • the reactive dyes selected for use in the present invention include Reactive Yellow 37 (monoazo dye) ; Reactive Black 31 (disazo dye) ; Reactive Blue 77 (phthalo cyanine dye) and Reactive Red 180 and Reactive Red 108 dyes.
  • a data analysis system comprises hardware and software components to perform spectral analysis to extract information of interest.
  • the hardware components include components to transfer the generated optical signals to a device with software for applying chemometrics and other mathematical analysis techniques to relate the measured absorbance to a reaction parameter or a color property of interest.
  • chemometrics is the science of relating measurements made on a chemical system or process to the state of the system via application of mathematical or statistical methods.
  • the data analysis system monitors absorbance, reflection or transmission correlated to at least one predetermined component or color property of the monitored Sample and uses statistical and chemometrics techniques to correlate the absorbance, reflection or transmission values to that Sample component or color property.
  • the monitored radiation is correlated to predetermined color properties of any composition containing a pigment, a dye or a combination of several pigments and dyes.
  • the color properties measured or determined include and are not limited to shade, opacity and tinting.
  • the monitored radiation preferably comprises at least two substantially monochromatic wavelengths in the range of about 400 to 700 nm.
  • the apparatus of the present invention further comprises computer readable media comprising software code.
  • the pigment component or color property of interest is measured during production of the pigment or dye solution. Irradiation and monitoring of light absorbed, reflected or transmitted is performed on combinatorial libraries of samples.
  • the method may include the step of applying a predetermined selection test to determine whether any one of a set of pre- selected components or color properties needs to be adjusted.
  • computer readable media comprising software code for performing the methods of the invention.
  • Irradiation and collection of spectra of the Sample containing a pigment may be performed using a viewing port or a side tube on a reactor.
  • a Sample from a reactor may be siphoned into a side arm or flow-cell for UV absorbance measurements and then returned back to the reactor.
  • the apparatus may be used for monitoring samples which are combinatorial libraries of samples dispersed in a 96-well microtiter plate reactor or other type of array.
  • the probe can also be inserted into an existing recirculation loop of a tank, vessel or any section of the process line with multi equipments.
  • Measurement of pigment or dye composition contents may be performed on a flow of liquid or molten meltdown samples.
  • samples may be measured under static (stopped- flow) conditions wherein the flow of sample is stopped for a short period of time (e.g. 0.1 to 10 sec) sufficient for an absorbance reading.
  • the use of stopped flow enhances signal resolution.
  • gas bubbles or any other inhomogeneities present in the flowing stream of material will induce errors in spectral measurements. These errors can be reduced by performing the spectral measurements under stopped- flow conditions, whereby inhomogeneities in the material do not interfere with the optical beam.
  • Absorbance measurements may be taken at a unique wavelength, or at multiple wavelengths.
  • the absorbance spectrum may be monitored at one wavelength for univariate analysis, or at more than one wavelength for multivariate analysis.
  • the absorbance, reflection & transmission characteristics of the Sample are analyzed using statistical techniques.
  • the absorbance characteristics of the Sample may be analyzed using univariate linear regression calibration methods
  • the absorbance characteristics of the Sample may be determined using multivariate calibration algorithms such as Partial Least Squares Regression (PLS) , Principal Components Regression (PCR), and the like (see e.g. Beebe, K. R., et al . , Chemometrics : A Practical Guide, Wiley, New York, N. Y., pp. 183-339 (1998)).
  • multivariate calibration models are generally more robust than univariate models due to enhanced outlier detection capabilities and increased tolerance toward slight shifting in peak position or band shape.
  • multivariate calibration models allow for measurement of more than one variable or component of interest.
  • PLS models may be used to correlate the sources of variation in the spectral data with sources of variation in the Sample.
  • the PLS model is validated by statistical techniques.
  • Such statistical techniques include, but are not limited to, leave one out cross-validation, Venetian blinds, and random subsets (see e.g. Beebe, K. R., et al . , Chemometrics : A Practical Guide, Wiley, New York, N. Y. (1998)).
  • an absorbance spectrum comprising a distinct range of wavelengths is preferably monitored.
  • the presence and/or amount of multiple Sample components is determined for each Sample.
  • a sufficient number of known samples is used to generate the model such that the 95% confidence interval and the 95% prediction interval are suitable for routine screening of polymer production.
  • PCA principal component analysis
  • PCA is used to identify a lower-dimensional coordinate system that captures the variance in a data set.
  • the first principal component is the axis along the direction of the primary source of variation,- the second principal component is the axis along the second most major source of variation; the third principal component is the axis along the third most major source of variation, and so forth.
  • Principal component scores for a spectrum may be computed by projecting the spectrum into a coordinate system which is defined by the major principal components calculated for a database of spectra.
  • plotting the spectral descriptors as a function of their principal component scores generates a two-dimensional spectral descriptor plot.
  • the spectral descriptor plot provides for the direct comparison of all the spectra in the database. Because the position of each spectral descriptor in the plot is defined by the major components of variation in the spectra, spectra of similar shape will preferably generate spectral descriptors which fall near each other in the spectral plot. Conversely, spectra of dissimilar shape will preferably generate spectral descriptors which fall far from each other in the spectral plot.
  • all or part of the steps in the method of the present invention may be coded or otherwise written in computer software, in a variety of computer languages including, but not limited to, C, C++, Pascal, Fortran, Visual Basic. RTM., Microsoft Excel, MATLAB . RTM ., Mathematica .RTM. , Java, and the like. Accordingly, additional aspects of the present invention include computer software for performing one or more of the method steps set forth herein.
  • the software code may be compiled and stored in executable form on computer readable media as, for example, computer ROM, floppy disk, optical disk, hard disks, cd ROM, or the like.
  • T C - a- sinh(b- S- C c • x) + b- cosh(b- S- C e ⁇ x)
  • Figure 3 shows the K and S values for the samples 74 A, B and C.
  • the solid lines are K values whereas dotted lines are S values.
  • the normalized concentrations of the samples were calculated.
  • the red line shows sample 74 B to be higher concentration than sample 74 C.
  • Figure 6 shows that the infinite reflectance curve of the SL14 71 is closer to SL14 74A than the SL14 70 sample, but with different shape, indicating that it is due to different shading, and to the concentration.
  • Figure 8 shows the K's and S' values, calculated by the equation 4. As shown in Figures 9 and 10, the samples are distinct (with something different on it - shading) and not only from the same material with different dilutions are (curves not parallel) . The curves in Figure 10 indicate that the sample 71 is closer to the 74 profile (almost parallel) than the sample 70.
  • Figure 11 shows that sample 71 will be very close to the 74 A if the dilution effect is corrected. Accordingly, sample 74 A has almost the same curve in transmission comparing to sample 70, but they are from different products because of different shading. The conclusion comes only using the reflectance and analyzing with the transmission measurements .
  • Sample 71 is more concentrated than the 70 explaining the curve with less transmission, but its color is more closer to the 74 A ( is more parallel after removing the effect of the concentration ) .
  • sample 70 is different from Sample 71 due to different "shading (mass tone)", and not to the concentration.
  • Figure 6 to Figure 11 show the differences. This means Multicell can measure the shade difference of the pigment slurry.
  • the transmission Path Length was lO ⁇ m.
  • the transmission Path Length was lOO ⁇ m. The cell automatically selects the best Path Length for optimum transmission
  • Table 4 shows relative difference values. These values were calculated using transmission curves "as if" they were reflectance curves. These show significant differences between samples .
  • Multicell using an apparatus of the present invention can physically handle all pigment dispersion samples tested without any problem.
  • Two Blue Dispersion Samples shows different transmission curves.
  • Figures 17 and 18 show the transmission data obtained from Multicell using an apparatus of the present invention. The data are shown both in a not-normalized way (many thickness) and a normalized way (one thickness) . All the transmission data are relative, not absolute.
  • Figures 19, 20 and 21 show the absorption and scattering coefficients calculated from the measurements above.
  • Figure 19 show the absorption coefficients related to the scattering of 80_73D.
  • Figures 20 shows the absorption coefficients in a normalized way, and Figure 21 does the same with the scattering coefficients.
  • Figure 21 shows that the absorption coefficient of 80_73D is greater than 80_73C in all the visible spectrum. This information can be used to evaluate the tinting strength of the samples.
  • meltdowns are applied on a surface in order to provide complete hiding.
  • K/S the ratio between absorption and scattering coefficient
  • the tinting strength is usually measured in the most absorbing wavelength. In this wavelength, scattering of the colored sample is usually small compared to scattering of the white used in the meltdown and can be neglected. Besides this, absorption of the white can be neglected when compared to absorption of the colored sample. Under these conditions, the K/S ratio of two different meltdowns gives the relative tinting strength. This is shown in the mathematical relationship bellow: V ⁇ sample I x _schreib sample I 2
  • Figure 21 shows the reflectance data from conventional (dry) method.
  • Figure 24 compares the wet and dry results for the blue samples .
  • tinting strength is measured at 630 nm. In this region, the calculated data gives 102.7% (wet method) and 98.9% (conventional method) for 8073 -D tinting strength. According to accepted margins of error in the industry (up to ⁇ 5%) , the two methods give the same tinting strength.

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Abstract

La présente invention concerne des procédés et des dispositifs destinés à mesurer in situ les composants pigmentaires d'intérêt au cours de la fabrication de pigment ou de solutions colorantes. La présente invention décrit l'irradiation d'un échantillon avec de la lumière UV/visible, et la génération d'un profil d'absorbance corrélé avec des types et des concentrations de pigments ainsi qu'avec les propriétés colorantes des pigments dans l'échantillon.
PCT/US2008/004625 2007-04-10 2008-04-10 Procédé et appareil de détermination des propriétés colorimétriques de pigment in situ WO2008124178A1 (fr)

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US92282807P 2007-04-10 2007-04-10
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Cited By (5)

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WO2012092986A1 (fr) * 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment de la surface d'une boue minérale à base d'eau
EP3091349A1 (fr) 2015-05-08 2016-11-09 The Procter and Gamble Company Procédé de contrôle de la qualité d'une composition cosmétique présentant des propriétés de coloration
US9688609B2 (en) 2014-11-04 2017-06-27 Noxell Corporation Telescoping synthesis of 2-methoxymethyl-P-phenylenediamine
US9695109B2 (en) 2014-11-04 2017-07-04 Noxell Corporation Telescoping synthesis of 2-methoxymethyl-p-phenylenediamine
US9758469B2 (en) 2014-11-04 2017-09-12 Noxell Corporation Process for the preparation of 2-substituted-1,4-benzenediamines and salts thereof

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US6753956B2 (en) * 1998-05-27 2004-06-22 Georgia Tech Research Corp. Automated analysis system for a dyebath
US20050235740A1 (en) * 2004-04-27 2005-10-27 Guido Desie Method to improve the quality of dispersion formulations

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012092986A1 (fr) * 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment de la surface d'une boue minérale à base d'eau
WO2012093039A1 (fr) * 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment superficiel à base d'une suspension aqueuse de substances minérales
CN103429671A (zh) * 2011-01-07 2013-12-04 Omya发展股份公司 水基矿物质浆料表面增白方法
CN103429671B (zh) * 2011-01-07 2016-06-01 Omya国际股份公司 水基矿物质浆料表面增白方法
RU2592520C2 (ru) * 2011-01-07 2016-07-20 Омиа Интернэшнл Аг Способ отбеливания поверхности водной минеральной суспензии
US9556320B2 (en) 2011-01-07 2017-01-31 Omya International Ag Process for water based mineral material slurry surface whitening
US9688609B2 (en) 2014-11-04 2017-06-27 Noxell Corporation Telescoping synthesis of 2-methoxymethyl-P-phenylenediamine
US9695109B2 (en) 2014-11-04 2017-07-04 Noxell Corporation Telescoping synthesis of 2-methoxymethyl-p-phenylenediamine
US9758469B2 (en) 2014-11-04 2017-09-12 Noxell Corporation Process for the preparation of 2-substituted-1,4-benzenediamines and salts thereof
EP3091349A1 (fr) 2015-05-08 2016-11-09 The Procter and Gamble Company Procédé de contrôle de la qualité d'une composition cosmétique présentant des propriétés de coloration
WO2016182868A1 (fr) 2015-05-08 2016-11-17 The Procter & Gamble Company Procédé pour le contrôle de la qualité d'une composition cosmétique aux propriétés colorantes

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