JP2016024089A - Liquid state change measurement device, and method for measuring change in liquid state - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid state change measurement device with which it is possible to measure a temporal change in a liquid including a fluid substance coated to a medium, without destroying the medium.SOLUTION: The present invention comprises: a shape measurement unit 2 having an image-capturing unit 2B for image-capturing the shade of a liquid 8 including a medium 9 generated by irradiation of light and a fluid substance, the unit 2 measuring the outer shape of the liquid; a permeation state measurement unit 3, having an optical system for dividing light from a light source unit 1 into reference light and measurement light and converting the interference light generated by interference between the reference light returning from a reference light path and the measurement light returning from the medium 9 into an interference signal, the unit 3 measuring a permeation state to the medium 9 on the basis of an optical interference tomographic measurement method; and a solidification state measurement unit 4 having an optical system for dividing light from the light source unit 1 into reference light heading toward the reference light path and measurement light heading toward a measurement light path and converting the interference light generated by interference between the reference light returning from the reference light path and the measurement light returning from the liquid into an interference signal, the unit 4 measuring the solidification state of the liquid 8 on the basis of a low-coherence dynamic light scattering method.SELECTED DRAWING: Figure 1

Description

  The present invention can measure the state change (behavior) of a liquid containing a fluid substance as a measurement target such as a droplet attached to the surface of the measurement target such as a sheet-like medium such as a film or coated paper in a non-contact manner. The present invention relates to a liquid state change measuring device and a liquid state change measuring method.

  Recently, using a printing machine, not only forms a document and an image by attaching a liquid such as an ink containing a fluid substance as a droplet to a printing medium such as a sheet medium such as a film or coated paper. Forming functional parts such as electronic circuits has been performed.

  In this type of printing machine, the state of the droplets attached to the sheet-like medium and the change (behavior) of the droplets with time are evaluated. This liquid state change or behavior evaluation result is used, for example, to improve the image quality, optimize the droplet application amount, optimize the printing speed, and improve the reliability of the functional component.

  Here, the state change and behavior of the droplet attached to the sheet-like medium are, for example, a temporal change in the shape of the droplet such as the height of the droplet and the width of the droplet, and the state of penetration of the droplet into the medium. Change, temporal change such as droplet coagulation.

As a technique for dynamically measuring the state of the droplet, a technique using a low-coherence interferometer device has been developed (see Patent Documents 1 to 4).
According to the techniques disclosed in Patent Documents 1 to 4, the particle diameter and particle distribution of the fluid substance in the liquid can be measured.

  However, when the techniques disclosed in Patent Documents 1 to 4 are applied to measurement of droplets attached to a print medium, the state of the droplets changes over time due to penetration or evaporation of the droplets into the medium. Therefore, there is an inconvenience that the state change of the liquid cannot be measured comprehensively.

This is because when the state of the droplet changes with time, Einstein-Stokes equation D = kT / 3πηd (D: diffusion coefficient, k: Boltzmann constant, T: absolute temperature, η: viscosity of liquid (solvent), d This is because the viscosity η of the liquid and the particle diameter d of the fluid substance simultaneously change in the particle diameter of the fluid substance.
In addition, when a droplet having a very small size is used as a measurement target, it is not easy to ensure the positional accuracy of the measurement target, and thus there is a disadvantage that the degree of solidification of the droplet cannot be evaluated with good reproducibility.

  The present invention has been made in view of the above circumstances, and provides a liquid state change measuring apparatus capable of measuring a temporal change in a state of a liquid containing a fluid substance applied to a medium without destroying the medium. For the purpose.

The liquid state change measuring device according to the present invention is:
A coating apparatus that applies a liquid containing a fluid substance to the medium; and at least an imaging unit that captures the shadow of each measurement target generated by light irradiated toward the liquid applied to the surface of the medium. A shape measuring unit that measures the outer shape of the liquid, and a reference light that splits coherent light from the light source unit into reference light that goes to the reference optical path and measurement light that goes to the measuring optical path, and returns from the reference optical path And an optical system that converts interference light generated by interference with the measurement light returning from the medium existing in the measurement optical path into an interference signal, to the liquid medium based on optical coherence tomography A penetrating state measuring unit for measuring a penetrating state of the light source, a reference light returning from the reference optical path, and the measurement, by dividing the low coherence light from the light source unit into reference light toward the reference optical path and measurement light toward the measuring optical path Present in the optical path A coagulation state for measuring the coagulation state of the liquid based on a low-coherence dynamic light scattering method having at least an optical system for converting the interference light generated by the interference with the measurement light returning from the liquid to be an interference signal And a measuring unit.

  According to the present invention, a temporal change in the state of a liquid containing a fluid substance applied to a medium can be measured without destroying the medium.

It is a block diagram which shows the principal part structure of the liquid state change measuring apparatus which concerns on the Example of this invention. It is a block diagram which shows schematic structure of the shape measurement part shown in FIG. It is the schematic of the image acquired by the shape measurement part shown in FIG. It is a block diagram which shows the principal part structure of the osmosis | permeation state measurement part shown in FIG. It is a block diagram which shows the principal part structure of the coagulation | solidification state measurement part shown in FIG. It is explanatory drawing when the hollow has arisen in the droplet shown in FIG. It is the schematic which shows an example of the autocorrelation function of the scattered light intensity acquired by the coagulation state measurement part shown in FIG. It is the schematic which shows an example of the time change of the diffusion coefficient inside the droplet measured by the solidification state measurement part shown in FIG. It is a figure which shows the position adjustment flow of a osmosis | permeation state measurement part. It is a figure which shows the position adjustment flow of a shape measurement part. It is a figure which shows the position adjustment flow of a coagulation | solidification state measurement part.

Hereinafter, a liquid state change measuring apparatus according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a block diagram showing a main configuration of a liquid state change measuring apparatus according to an embodiment of the present invention.

In FIG. 1, 1 is a light source unit, 2 is a shape measurement unit, 3 is a penetration state measurement unit, and 4 is a coagulation state measurement unit.
The light source unit 1 includes a light source 1a, a light extraction unit 1b, and condenser lenses 1c and 1c ′. The light source 1a is, for example, in the near-infrared wavelength region in which the center wavelength of the light is 0.7 to 2.0 micrometers. The light source 1a generates broadband light (coherent low coherence light, partial coherence low coherence light) that continuously spreads in this wavelength range.

  The light extraction unit 1b is roughly composed of a beam splitter 1d and wavelength selection filters 1e and 1e '. The light extraction unit 1b includes, for example, a broadband light P1 having a center wavelength of 1.0 micrometer and a full width at half maximum of 50 nm, and a full width at half maximum of 200 nm at a center wavelength of 1.3 micrometers. The broadband light P1 ′ is extracted from the broadband light emitted from the light source 1a.

  The penetration state measuring unit 3 is composed of an optical interferometer device 3A having at least the optical system shown in FIG. 4, and the coagulation state measuring unit 4 is composed of an optical interferometer device 4A having at least the optical system shown in FIG.

  The light source 1 a is used as a common light source unit for the penetration state measurement unit 3 and the coagulation state measurement unit 4. The broadband light from the light source 1a is guided to the penetration state measuring unit 3 through the optical fiber 3a after adjusting the wavelength of the light, and to the coagulation state measuring unit 4 through the optical fiber 4a.

  Here, the light source 1a is used as the common light source unit as the light source of the permeation state measurement unit 3 and the light source of the coagulation state measurement unit 4, but a configuration using separate light sources that generate broadband light with low coherence, respectively. It can also be.

The liquid state change measuring device has a control processing unit 7. The control processing unit 7 includes a control unit 7A, a storage unit 7B, a processing unit 7C, and a display unit 7D. The control processing unit 7 is used in common for the shape measuring unit 2, the permeation state measuring unit 3, and the coagulation state measuring unit 4.
The control unit 7A controls the light emission of the light source unit 1, controls the coating device 10 that applies a liquid containing a fluid substance as a measurement target to the medium 9 as the measurement target, controls the shape measurement unit 2, and the penetration state. Control of the measurement unit 3 and control of the coagulation state measurement unit 4 are performed. Other details will be described sequentially.

As shown in FIG. 1, the medium 9 is placed on the sample table 11. The coating device 10 has, for example, a small hole (a spray nozzle). The small hole (jet nozzle) quantitatively discharges the liquid droplet 8 as a liquid toward the surface 9 a of the medium 9. Thereby, the droplet 8 is applied to the surface 9 a of the medium 9.
An observation window 11 a is formed on the sample table 11. The sample stage 11 can be moved and adjusted in the XY direction (the plane direction of the medium 9) by a position adjusting mechanism (not shown).

  The shape measuring unit 2 is roughly configured from an optical system including at least the light projecting unit 2A and the imaging unit 2B and the control processing unit 7, and has a function of measuring the outer shape of the measurement target. The control unit 7A performs light projection control of the light projecting unit 2A. In FIG. 2, the symbol Sf indicates the light projection control signal.

The light projecting unit 2A emits light toward the droplet 8 from a direction parallel to the surface 9a of the medium 9. The imaging unit 2B is schematically configured by a photographing optical system 2C and a light receiving unit 2D.
When the collimated light beam is irradiated from the light projecting unit 2A toward the droplet 8, a shadow of the droplet 8 and the medium 9 is generated, and the imaging unit 2B is irradiated toward the droplet 8 applied to the surface 9a of the medium 9. The shadow of each measurement object caused by light is imaged simultaneously. In FIG. 2, symbol Sf ′ indicates a reading control signal of the imaging unit 2B, and symbol G1 ′ indicates an image signal output from the imaging unit 2B.

The imaging unit 2B desirably employs a high-speed, high-magnification configuration in order to capture changes over time of the droplets 8 applied to the medium 9 by the coating apparatus 10.
Further, in order to obtain an accurate shape of the droplet 8, it is desirable that the photographing optical system 2C is a telecentric optical system.

For example, the control processing unit 7 includes a computer, and the image of the droplet 8 and the image of the medium 9 are stored and stored in the storage unit 7B in time series by the computer.
The processing unit 7C performs image analysis processing on the image G1 (see FIG. 3) stored in time series. Thereby, for example, information such as the height h, the contact angle θ, the contact width W, the contact area S, and the volume V of the droplet 8 is obtained using the image G1. These pieces of information are stored in the storage unit 7B in a one-to-one correspondence with the image G1.

  The information on the contact area S and the volume V is rotated on the basis of the center line O1 that bisects the width W of the image G1 assuming that the shape of the droplet 8 is isotropic. It can be obtained by calculation as being equal to the rotating body.

Next, a detailed optical system configuration of the optical interferometer device 3A of the penetration state measuring unit 3 will be described with reference to FIG. The optical interferometer device 3A functions to acquire an image using an optical coherence tomography method.
The optical interferometer device 3A is schematically configured by a light combining / dividing unit 22, a measurement optical system 23, a reference optical system 24, and an interference signal detecting unit 25.

  The broadband light P <b> 1 ′ from the light source unit 1 is collected by the condenser lens 1 c ′ and focused on the incident end face 3 a ′ of the light guide fiber 3 a. The broadband light P <b> 1 ′ propagates through the light guide fiber 3 a and is guided to the light combining / dividing unit 22.

  The light combining / dividing unit 22 is configured by, for example, a photocoupler (fiber coupler). The broadband light P <b> 1 ′ guided to the light guide fiber 3 a is split into measurement light P <b> 2 ′ and reference light P <b> 3 ′ by the light combining / dividing unit 22.

  For example, the light amount of the broadband light P1 'is divided by 1: 1 by the photocoupler. The measurement light P2 'is guided to a light guide fiber 21e' as a measurement optical path. The reference light P3 'is guided to the light guide fiber 21f' serving as a reference light path.

  Here, the light combining / dividing unit 22 functions as a light dividing unit that divides the optical path of the light from the light source unit 1 into the optical path of the measurement light P2 ′ and the optical path of the reference light P3 ′, and the measurement target. It has a function as a light combining unit that combines the measurement light P2 ′, which is reflected / scattered light from the medium 9, and the reference light P3 ′ to generate combined light.

  The measuring optical system 23 includes a collimating lens 23a, galvanometer mirrors (galvano scanners) 23b and 23c as scanning optical systems 23BC, a collimating lens 23d, and the sample stage 11 (see FIG. 1) described above. The medium 9 is provided facing the observation window 11a.

  The collimating lens 23a faces the incident / exit end face 21e "of the light guide fiber 21e '. The collimating lens 23a condenses the measurement light P2' emitted from the light guide fiber 21e 'and converts it into a parallel light beam P4'. The parallel light beam P4 ′ is guided to the galvanometer mirrors 23b and 23c.

  Here, both galvanometer mirrors 23b and 23c are driven to reciprocate. Thereby, three-dimensional tomographic image data described later is acquired. If one of the galvanometer mirrors 23b and 23c is driven, a one-dimensional tomographic image is obtained.

  The parallel light beam P4 'is guided to the collimating lens 23d as scanning light from the side of the back surface 9b (see FIG. 1) opposite to the front surface 9a. The collimating lens 23d plays a role of converting scanning light into spot light P5 'as shown in an enlarged manner in FIG.

  In this embodiment, the principal ray of the parallel light beam P4 ′ is parallel to the optical axis O of the collimating lens 23d, that is, perpendicularly enters the back surface 9b from the back surface 9b opposite to the front surface 9a of the medium 9. Because of the configuration, accurate acquisition of tomographic images can be facilitated.

  The medium 9 is two-dimensionally scanned with the spot light P5 'through the observation window 11a as shown in an enlarged view in FIG. In FIG. 1, an arrow Z indicates the direction of the optical axis O of the collimating lens 23d, and arrows X and Y indicate a scanning direction orthogonal to the optical axis direction Z.

  When the droplet 8 adheres to the surface 9 a of the medium 9, the droplet 8 penetrates into the medium 9 as time passes. In FIG. 1, reference numeral 9 d indicates the interface of the permeation region 9 c at time t <b> 2 when time t has elapsed, where t <b> 1 is the time when the droplet 8 adhered to the surface 9 a of the medium 9.

  The permeation region 9c spreads with the passage of time after the droplet 8 adheres to the surface 9a of the medium 9, and permeates in the thickness direction of the medium 9, thereby increasing the depth of the permeation region 9c. The measurement of the penetration state of the droplet 8 into the medium 9 will be described in detail later.

  Here, the permeation region 9c is a region in which the void inside the medium 9 is filled with the droplet 8, and the interface 9d is a state in which the void inside the medium 9 is filled with the droplet 8. A boundary surface between the region (penetration region 9 c) and a region where the voids inside the medium 9 are not filled with the droplets 8.

  A part of the spot light P <b> 5 ′ is scattered and reflected on the back surface 9 b of the medium 9, and the remaining part reaches the inside of the medium 9. Further, a part of the spot light P <b> 5 ′ is absorbed inside the medium 9.

  Part of the spot light P5 'that has reached the inside of the medium 9 is reflected at the interface 9d of the permeation region 9c, and the remaining part is refracted at the interface 9d to reach the inside of the permeation region 9c.

  The reflected light reflected by the interface 9d of the permeation region 9c and the reflected / scattered light reflected by the back surface 9b of the medium 9 are collected by the collimator lens 23d as shown in FIG. P4 ′ or measurement light P2 ′ is guided to the galvanometer mirrors 23b and 23c.

  The measurement light P2 ′ guided to the galvanometer mirrors 23b and 23c is converged by the collimator lens 23a and guided to the incident / outgoing end face 21e ″ of the light guide fiber 21e ′, and propagates through the light guide fiber 21e ′ for light synthesis / Guided to the dividing unit 22.

  The reference optical system 24 includes collimating lenses 24a and 24b and a reference mirror 24c. The collimating lens 24a faces the incident / exit end face 21f ″ of the light guide fiber 21f ′.

  The collimating lens 24a plays a role of converting the reference light P3 ′ emitted from the incident / exit end face 21f ″ into a parallel light beam. The reference light P3 ′ is condensed by the collimating lens 24b and totally reflects the reference light P3 ′. It is guided to the reference mirror 24c.

  The reference light P3 ′ reflected by the reference mirror 24c is collected by the collimator lens 24b, guided through the original optical path to the collimator lens 24a, and incident / exit end face 21f of the light guide fiber 21f ′ by the collimator lens 24a. ”And propagates through the light guide fiber 21 f ′ and is guided to the light combining / dividing unit 22.

  The measurement light P2 ′ guided to the light combining / dividing unit 22 by the light guide fiber 21e ′ and the reference light P3 ′ guided to the light combining / dividing unit 22 by the light guide fiber 21f ′ are combined and guided as interference light P6 ′. The light is guided to the interference signal detector 25 via the optical fiber 21g ′.

  Here, the optical path length from the light combining / dividing unit 22 to the back surface 9b of the medium 9 and the optical path length from the light combining / dividing unit 22 to the reference mirror 24c are equal to each other, but a tomographic image of the medium 9 is acquired. The optical path length may be varied within a possible range.

  The interference signal detection unit 25 includes condenser lenses 25a and 25b and a photoelectric conversion member 25c. The interference light P6 ′ is emitted from the exit end face 21g ″ of the light guide fiber 21g ′, condensed by the condensing lens 25a to be a parallel light beam, and then converged by the condensing lens 25b and irradiated to the photoelectric conversion member 25c. Is done.

  The photoelectric conversion member 25c photoelectrically converts the interference light P6 '. The photoelectric conversion signal S1 photoelectrically converted by the photoelectric conversion member 25c is input to the control processing unit 7.

  In addition to the light emission control of the light source 1, the control unit 7A controls the vibration of the galvanometer mirrors 23b and 23c, the discharge control of the droplet 8 by the coating device 10, the acquisition timing control of the photoelectric conversion signal S1, and the processing of the processing unit 7C. Control, storage control of the storage unit 7B, and display control of the display unit 7D are performed.

  The control unit 7A includes hardware such as a CPU, a ROM, and a RAM, and a predetermined control program. The processing unit 7C processes the photoelectric conversion signal S1 with a software program according to the optical coherence tomography method, and constructs a tomographic image of the medium 9 using image intensity data (luminance data) based on the photoelectric conversion signal S1. It has a function.

(Basic principle of tomographic image acquisition)
In the optical coherence tomography method, a photodetecting element (not shown) including a spectroscopic element (not shown) and a line sensor is used as the photoelectric conversion member 25c.
This photodetection element can detect a spectrum over the entire wavelength band of the broadband light P1 ′.

  The interference light P6 'includes measurement light P2' that is return light from the back surface 9b of the medium 9 and the inside of the medium 9, and reference light P3 'from the reference mirror 24c. Here, in the medium 9 of the measurement optical system 23, it is assumed that return light is generated only from the position of the optical path length equal to the optical path length from the light combining / dividing unit 22 to the reference mirror 24c. Light is observed.

In this state, if the position where the return light is generated is changed in the optical axis direction in the measurement optical system 23 while the optical path length from the light combining / dividing unit 22 to the reference mirror 24c is fixed, the reference from the light combining / dividing unit 22 is performed. There is a difference between the optical path length to the mirror 24c and the optical path length from the light combining / dividing unit 22 to the position where the return light is generated (referred to as an optical path difference), and the distance between the interference fringes becomes narrower as the optical path difference increases.
In other words, the interval between the observed interference fringes is determined by the position where the return light is generated.

  Since the return light from the back surface 9b of the medium 9 and each part inside the medium 9 is synthesized with the interference light P6 ′, the fringe spacing of the interference fringes based on the observed spectral interference light also corresponds to this. It becomes.

  When the photoelectric conversion signal S1 based on the spectrum interference light is Fourier-transformed in the processing unit 7C, spectrum decomposition is performed according to the interval between the interference fringes, and thereby the generation position of the return light is specified.

  The amplitude of the spectrum interference light is determined corresponding to the intensity of the return light, and the spectrum intensity of the signal after the Fourier transform (Fourier transform signal) increases as the intensity of the return light from the generation position becomes large.

  That is, the fact that the spectral intensity of the Fourier transform signal corresponding to a certain return light generation position is relatively large means that the intensity of reflected or scattered light at the return light generation position is relatively large.

Accordingly, if the luminance distribution corresponding to the return light generation position is determined according to the spectral intensity of the Fourier transform signal, a one-dimensional tomographic image in the thickness direction of the medium 9 can be acquired.
If these processes are performed while the galvanometer mirrors 23b and 23c are scanned two-dimensionally, a two-dimensional tomographic image of the medium 9 can be obtained.

  The storage unit 7B stores a function of storing the tomographic images in chronological order, data necessary for estimating the interface 9d, data necessary for calculating the penetration speed, for example, a scale of the tomographic image, a tomographic image acquisition time, and the like. And a function of storing a software program necessary for the processing unit 7C to perform signal processing. The display unit 7D has a function of displaying at least a tomographic image.

(Details of measurement of the permeation region 9c)
A one-dimensional tomographic image or two-dimensional tomographic image before the droplet 8 is attached to the surface 9a of the medium 9 is acquired by the optical interferometer device 3A, and this is stored as an initial one-dimensional tomographic image or two-dimensional tomographic image in the storage unit 7B. Save to memory.

  Next, the droplet 8 is adhered to the surface of the medium 9 by the coating device 10, and a one-dimensional tomographic image or a two-dimensional tomographic image is created by the optical interferometer device 3A at a predetermined time interval, and is sequentially stored in the storage unit 7B. Thereby, the time change of the osmosis | permeation area | region 9c, ie, the time change of the osmosis | permeation state of the medium 9, can be measured.

  Further, when the porosity inside the medium 9 is measured by another measuring device (not shown) and the filling rate at the time of penetration of the droplet 8 is calculated from this porosity, the optical interferometer device 3A is used. From the measured size of the permeation region 9c, the permeation amount of the droplet 8 can also be estimated.

  The measurement position by the penetration state measuring unit 3 is adjusted by the scanning optical system 23BC and the reference optical system 24 of the optical interferometer device 3A so that the whole area of the penetration area 9c of the droplet 8 previously applied to the medium 9 can be measured. do it.

  However, it may be difficult to determine the measurement position, for example, when the application amount of the droplet 8 is very small or when the amount of penetration into the medium 9 is small. In such a case, a tomographic image of the coating apparatus 10 is acquired with the medium 9 removed from the sample stage 11.

  In this case, the coating device 10 may be moved in a direction along the optical axis O of the collimator lens 23d. When a three-dimensional shape of the coating apparatus 10 is acquired by acquiring a two-dimensional tomographic image of the coating apparatus 10, the shape of a small hole (a spray hole or a spray nozzle) that ejects the droplet 8 is observed. This is stored and stored in advance in the storage unit 7B as positional information of small holes (injection holes) that are three-dimensional observation data.

  The positional information of the three-dimensional observation data stored in the storage unit 7B and the angle of the galvano mirror 23b as the scanning optical system 23BC of the optical interferometer device 3A can be made to correspond one-to-one.

  Therefore, when the coordinates corresponding to the position of the small hole in the three-dimensional observation data are designated on the computer of the control processing unit 7, the control unit 7A drives the galvano mirror 23b to determine the actual position of the small hole (injection hole). As a center, the position can be adjusted so that the measuring light P2 ′ can be scanned in a direction orthogonal to the optical axis O of the collimator lens 23d. By this adjustment, the positional accuracy of the measurement of the permeation region 9c into the medium 9 can be ensured.

Next, a detailed optical system configuration of the optical interferometer device 4A of the coagulation state measurement unit 4 shown in FIG. 1 will be described with reference to FIG. The optical interferometer device 4A functions to measure the solidification state of the liquid based on the low coherence dynamic light scattering method.
The optical interferometer device 4 </ b> A is generally configured by a light combining / dividing unit 32, a measurement optical system 33, a reference optical system 34, and an interference signal detection unit 35.

  The broadband light P1 from the light source unit 1 is collected by the condenser lens 1c and focused on the incident end face 4a 'of the light guide fiber 4a. The broadband light P <b> 1 propagates through the light guide fiber 4 a and is guided to the light combining / dividing unit 32.

  The light combining / dividing unit 32 is configured by, for example, a photocoupler (fiber coupler). The broadband light P1 guided to the light guide fiber 4a is split into measurement light P2 and reference light P3 by the light combining / dividing unit 32.

  For example, the light amount of the broadband light P1 is divided by 1: 1 by the photocoupler. The measurement light P2 is guided to a light guide fiber 21e as a measurement optical path. The reference light P3 is guided to the light guide fiber 21f as a reference light path.

  The light combining / dividing unit 32 functions as a light dividing unit that divides the optical path of the light from the light source unit 1 into the optical path of the measurement light P2 and the optical path of the reference light P3, and the reflection from the medium 9 as the measurement target. It has a function as a light combining unit that combines the measurement light P2 that is the scattered light and the backscattered light and the reference light P3 to generate a combined light.

  The measuring optical system 33 includes a collimating lens 33a, galvanometer mirrors (galvano scanners) 33b and 33c as scanning optical systems 33BC, a collimating lens 33d, and the sample stage 11.

  The collimating lens 33a faces the incident / exit end face of the light guide fiber 21e. The collimating lens 33a condenses the measurement light P2 emitted from the light guide fiber 21e and converts it into a parallel light beam P4. The parallel light beam P4 is guided to the galvanometer mirrors 33b and 33c.

  Here, both galvanometer mirrors 33b and 33c are driven to reciprocate. As a result, three-dimensional image data is acquired. If one of the galvanometer mirrors 33b and 33c is driven, one-dimensional image data can be obtained.

  The parallel light beam P4 is guided to the collimating lens 33d. As shown in an enlarged view in FIG. 1, the collimating lens 33d plays a role of converting the parallel light beam P4 into convergent light P5.

  When the droplet 8 adheres to the surface 9 a of the medium 9, the droplet 8 penetrates into the medium 9 as time passes. Further, the solvent of the droplets 8 evaporates with time, and the fluid substance increases in concentration and solidifies. The measurement of the solidification state of the droplet 8 attached to the medium 9 will be described later.

A part of the convergent light P <b> 5 is scattered and reflected on the surface of the droplet 8, and the remaining part reaches the inside of the droplet 8. Further, a part of the convergent light P5 is absorbed in the medium 9.
Part of the convergent light P5 that has reached the inside of the droplet 8 is reflected by the fluid substance.

  The reflected light reflected on the surface of the droplet 8 and the backscattered light reflected inside the droplet 8 are collected by the collimating lens 33d as shown in FIG. 5, and are collimated (also called return light) P4. Alternatively, it is guided to the galvanometer mirrors 33b and 33c as the measurement light P2.

  The measurement light P2 guided to the galvanometer mirrors 33b and 33c is converged by the collimator lens 33a, guided to the incident / exit end face of the light guide fiber 21e, propagates through the light guide fiber 21e, and is guided to the light combining / dividing unit 32. It is burned.

  The reference optical system 34 includes collimating lenses 34a and 34b and a reference mirror 34c. The collimating lens 34a faces the incident / exit end face of the light guide fiber 21f.

  The collimating lens 34a plays a role of converting the reference light P3 emitted from the incident / exit end face into a parallel light beam. The reference light P3 is collected by the collimating lens 34b and guided to the reference mirror 34c that totally reflects the reference light P3.

  The reference light P3 reflected by the reference mirror 34c is collected by the collimator lens 34b, guided to the collimator lens 34a through the original optical path, and focused by the collimator lens 34a on the incident / exit end face of the light guide fiber 21f. Then, it propagates through the light guide fiber 21f and is guided to the light combining / dividing unit 32.

  The measurement light beam P2 guided to the light combining / dividing unit 32 by the light guide fiber 21e and the reference light P3 guided to the light combining / dividing unit 32 by the light guide fiber 21f are combined and combined as interference light P6 to the light guiding fibers 21g1, 21g2. To the interference signal detector 35.

Here, the interference signal detector 35 includes an optical system including collimator lenses 35a1 and 35b1 and a detection member 35c1, and an optical system including collimator lenses 35a2 and 35b2 and a photoelectric conversion member 35c2.
The position of the reference mirror 34c can be adjusted by the position adjusting mechanism 40.

  The photoelectric conversion members 35c1 and 35c2 photoelectrically convert the interference light P6. The photoelectric conversion signals S2 and S3 photoelectrically converted by the photoelectric conversion members 35c1 and 35c2 are input to the control processing unit 7. The control processing unit 7 is configured by the same hardware as that of the penetration state measuring unit 3.

  Similarly to the control process of the penetration state measuring unit 3, the control unit 7A controls the vibration of the galvano mirrors 33b and 33c, the acquisition timing control of the photoelectric conversion signals S2 and S3, and the processing unit 7C in addition to the light emission control of the light source 1. Process control, storage control of the storage unit 7B, and display control of the display unit 7D.

  The control unit 7A includes hardware such as a CPU, a ROM, and a RAM, and a predetermined control program. The processing unit 7C processes the photoelectric conversion signals S2 and S3 by a software program according to the low coherence dynamic scattering method and the optical coherence tomography method.

  As a result, numerical data and image data including the shape of the droplet 8, the internal structure information, and the internal structure information of the medium 9 are acquired in time series and stored in the storage unit 7B. These pieces of information are displayed on the display unit 7D as necessary.

  Depending on the combination of the droplet 8 and the medium 9, as shown in FIG. 6, a circular recess 8 a is formed on the upper surface of the droplet 8 as time passes after the droplet 8 adheres to the medium 9. This may cause the depression 8a to gradually increase. In this case, the volume V calculated by the shape measuring unit 2 has an error corresponding to the presence of the depression 8a.

In such a case, the size of the depression 8a is calculated from the outer shape of the droplet 8 obtained by the coagulation state measurement unit 4, and the volume V calculated by the shape measurement unit 2 is corrected.
Note that the incident angle of the convergent light P5 on the droplet 8 or the medium 9 can be adjusted by adjusting the scanning optical system 33BC of the optical interferometer device 4A with a position adjusting mechanism (not shown). The shape can be easily measured.

  Since the optical interferometer device 4A operates as a low-coherence interferometer, if the scanning optical system 33BC and the position adjustment mechanism 40 are fixed at arbitrary positions, intensity information of reflected light and backscattered light generated at a specific position can be obtained. A change with time can be observed.

  The fixed positions of the scanning optical system 33BC and the position adjustment mechanism 40 are determined based on the shape measurement results of the droplet 8 and the medium 9 measured in advance. For example, when the shape measurement function of the coagulation state measurement unit 4 is used to obtain the temporal change in the shape of the three-dimensional droplet 8 as numerical data and image data, the three-dimensional position information of these data is acquired. Corresponds to driving information of the scanning optical system 33BC and the position adjusting mechanism 40 on a one-to-one basis.

  Therefore, if the coordinates of an arbitrary point in the three-dimensional position information of the acquired data are designated by the computer of the control processing unit 7, the scanning optical system 33BC and the position adjustment are performed so that the control unit 7A satisfies the corresponding driving conditions. The mechanism 40 can be adjusted.

  By such adjustment, for example, a specific point (see FIG. 1) in the center of the droplet 8 and in the vicinity of the surface of the medium 9 is set as the measurement point Q, and reflected light generated from the measurement point Q and backscattering are obtained. Light can be selectively detected.

The designation of the measurement point Q may be performed once or a plurality of times. After determining the measurement point Q, the medium 9 or the sample stage 11 is moved in the horizontal direction. Thereby, the application location of the droplet 8 to be applied next is set so as not to overlap the application location of the droplet 8 applied to the medium 9 before the parallel movement.
That is, the medium 9 is set so that the application position of the droplet 8 on the medium 9 and the permeation region 9c of the medium 9 do not interfere with each other in the previous measurement and the current measurement.

  When the medium 9 is moved horizontally or in parallel, the height of the surface 9a of the medium 9 may change due to, for example, the difference in thickness at each location of the medium 9. In such a case, the vertical position adjustment of the surface 9a of the medium 9 is performed again. Details of the position adjustment will be described later.

After adjustment of the measurement position is completed, the droplet 8 is applied to the surface 9a of the medium 9, and reflected light and backscattered light generated inside the droplet 8 are acquired as time-series data by the coagulation state measurement unit 4. .
For example, when the droplet 8 is a pigment ink, the pigment particles as the fluid substance in the droplet 8 are in Brownian motion in the solvent.

  In this case, since the information obtained as the interference signal is a change in light intensity caused by the Brownian motion of the pigment particles, the coagulation state measurement unit 4 operates as a low coherence dynamic light scattering measurement device.

  In general, in the low-coherence dynamic light scattering apparatus, the temporal fluctuation of the intensity of the interference signal caused by the Brownian motion of the particles in the droplet 8 is evaluated and analyzed using a time correlation function or a power spectrum.

  The particle size distribution can be quantified as a static characteristic by calculation, analysis, or the like using the diffusion coefficient D of the contained particles in the droplet 8 represented by the Einstein-Stokes equation or the diffusion coefficient D.

  Further, when the solidification state measuring unit 4 is applied to the measurement of the droplet 8, the particle diameter, the solvent viscosity, and the droplet temperature in the droplet 8 change with time for the droplet 8 applied to the medium 9. It is assumed that Therefore, it is necessary to measure these dynamic characteristics.

  As a method of evaluating the dynamic characteristics, for example, the intensity of the acquired interference signal is divided at equal time intervals, or a value corresponding to the diffusion coefficient D in the time interval is calculated by moving average processing, and this value This is done by examining changes over time.

  In order to obtain a value corresponding to the diffusion coefficient D, a time correlation function (R (τ)) of the intensity (scattered light intensity) of the interference signal in the time interval is obtained. The graph is, for example, as shown in FIG. The slope of this graph varies depending on the state of particle Brownian motion at the measurement point Q, and becomes steeper as the Brownian motion becomes more intense (see FIG. 7A), and becomes slower as the Brownian motion becomes milder (see FIG. 7B). ), And a value corresponding to the diffusion coefficient D of the particles.

  By examining the temporal change of this time correlation function (R (τ)), the state change of the Brownian motion of the particles in the droplet 8 can be known. That is, the change in the solidification state of the droplet 8 can be measured. After the application of the droplet 8 to the medium 9, the value corresponding to the measured diffusion coefficient D generally decreases gradually with time as the viscosity of the droplet 8 increases due to solvent penetration or evaporation. .

  Thereby, for example, a graph in which the diffusion coefficient D changes with time as shown in FIG. 8 is acquired, and it can be quantitatively grasped that coagulation is promoted. If the viscosity of the solvent in the droplet 8 does not change or if the change in the viscosity of the solvent is known, the state as a change in particle diameter can be determined from the relationship between the Einstein-Stokes equation and the graph shown in FIG. Changes can be quantified.

  In order to measure the same droplet 8 using the shape measuring unit 2, the infiltration state measuring unit 3 and the coagulation state measuring unit 4 simultaneously, the measurement position is adjusted with respect to the application position of the droplet 8. This position adjustment will be described with reference to FIGS. 9 to 11 showing a flow of position adjustment and measurement.

FIG. 9 shows a position adjustment flow of the penetration state measuring unit 3. FIG. 10 shows a position adjustment flow of the shape measuring unit 2. FIG. 11 shows a position adjustment flow of the coagulation state measurement unit 4.
First, the position adjustment of the penetration state measuring unit 3 will be described.

  First, the measurement position adjustment of the penetration state measuring unit 3 is started (S.1). Next, the medium 9 is set on the sample stage 11, the droplet 8 is applied to the medium 9, and the infiltration region 9c of the droplet 8 is measured by the infiltration state measuring unit 3 (S.2).

A tomographic image is acquired by the infiltration state measurement unit 3 and it is determined whether or not the infiltration region 9c has been observed (S.3).
In S.3, when the permeation region 9c is confirmed using a tomographic image, the coordinates of the position to be set as the measurement center of the measurement region are designated while viewing the tomographic image displayed on the display unit 7D (S.3). 4).

  The position of the scanning optical system 23BC is automatically adjusted by an adjustment mechanism (not shown) so that the position designated on the display unit 7D becomes the measurement center of the measurement region (S.5).

Next, the sample stage 11 is moved by a position adjusting mechanism (not shown) to adjust the position of the medium 9 in the plane direction, and the measurement region (application portion of the droplet 8) of the medium 9 is updated (S.6).
Thereby, the adjustment of the measurement position of the penetration state measuring unit 3 is completed (S.14).

  In S.3, when the infiltration region 9c is not confirmed using the tomographic image, it is determined whether or not to adjust by another method (S.7). Returning to S.2, the droplet 8 is again applied to the medium 9, and the determination of S.3 is made.

  In S.7, when adjusting by another method, the medium 9 is removed from the sample stage 11, and the coating apparatus 10 is moved along the direction of the optical axis O of the collimating lens 23d as necessary, to thereby apply the coating apparatus. The tip of 10 is brought close to the sample stage 11 (S.8).

  Next, the tomographic image of the coating apparatus 10 is measured by the penetration state measuring unit 3 (S.9). The tomographic image acquired by this measurement is displayed on the display unit 7D to determine whether or not a small hole (injection hole) is observed (S.10).

  When no small hole (injection hole) is confirmed in the tomographic image displayed on the display unit 7D, S.I. Returning to step 8, measurements S.8 to S.10 are performed again. When a small hole (injection hole) is confirmed in the tomographic image displayed on the display unit 7D, the coordinates of the measurement center are set so that the position corresponding to the small hole (injection hole) is the center of the measurement region on the tomographic image. Specify (S.11).

  Next, the position of the scanning optical system 23BC is automatically adjusted by an adjustment mechanism (not shown) so that the position designated on the display unit 7D becomes the measurement center of the measurement region (S12). Thus, the position adjustment of the infiltration state control unit 3 can be performed based on the spatial position of the small hole (injection hole).

Next, the coating apparatus 10 is driven along the direction of the optical axis O, the coating apparatus 10 is returned to the original position, and the medium 9 is set on the sample stage 11 (S.13).
Thereby, the adjustment of the measurement position of the penetration state measuring unit 3 is completed (S.14).
Note that the scanning range of the measurement region can be adjusted by adjusting the swing range of the scanning optical system.

FIG. 10 shows a position adjustment flow of the shape measuring unit 2.
First, the measurement position adjustment of the shape measuring unit 2 is started (S.20). Next, the medium 9 is set on the sample stage 11, the droplet 8 is applied to the medium 9, and the outer shape of the droplet 8 is measured by the shape measuring unit 2 (S.21).
In step S.21, the setting of the medium 9 on the sample stage 11 may not be performed when the position adjustment of the penetration state measuring unit 3 has already been performed.

  Next, it is determined whether or not the shape of the droplet 8 has been acquired correctly (S.22). When the droplet 8 is applied to the medium 9, the droplet 8 has a substantially hemispherical shape due to its surface tension. When the image of the droplet 8 is displayed on the screen of the display unit 7D, for example, when the image of the droplet 8 is missing or distorted, the shape of the droplet 8 cannot be acquired correctly. Judge that

  If it is determined in S.22 that the outer shape of the droplet 8 has not been acquired correctly, the position of the optical system of the imaging unit 2B is adjusted and the position of the light projecting unit 2A in the irradiation direction is adjusted (S.23). ), Returning to S.22, it is determined again whether or not the outer shape of the droplet 8 has been correctly acquired.

  When the outer shape of the droplet 8 can be obtained correctly, the sample stage 11 is moved by a position adjusting mechanism (not shown) to adjust the position of the medium 9 in the plane direction, and the measurement region (application location) of the droplet 8 is adjusted. Is updated (S.24). Thereby, the adjustment of the measurement position of the shape measuring unit 2 is completed (S.25).

Simultaneously with the position adjustment of the shape measuring unit 2, adjustment of the measurement position of the solidified state measuring unit 4 is started (S.31).
The solidification state measuring unit 4 acquires a tomographic image of the droplet 8 and a tomographic image of the medium 9 (S.32).

Next, this tomographic image is displayed on the display unit 7D, and a measurement point Q (see FIG. 1) for measuring the solidification state of the droplet 8 is designated (S.33).
The position of the scanning optical system 33BC is automatically adjusted so that reflected light and scattered light from the position corresponding to the measurement point Q can be detected (S.34).

Next, the sample stage 11 is driven to translate the medium 9 (S.35). Thereby, the application | coating location (application position) of the droplet 8 to the medium 9 is updated.
When the sample base 11 is driven to move the medium 9 in parallel, the vertical position (position in the height direction) of the surface 9a of the medium 9 may be displaced in the optical axis direction. Therefore, before applying the droplet 8 to a new application position, a tomographic image of the medium 9 is acquired by the coagulation state measurement unit 4 (S.36).

  Next, it is determined whether or not there is a vertical shift between the medium surface of the tomographic image of the medium 9 acquired in step S.36 and the medium surface of the tomographic image acquired in step S.32. .37).

  If there is a vertical shift between the medium surface of the tomographic image of the medium 9 acquired in step S.32 and the medium surface of the tomographic image of the medium 9 acquired in step S.36, it is acquired in step S.32. The scanning optical system 33BC is automatically adjusted in a direction coinciding with the medium surface of the tomographic image of the medium 9 (S.38). Next, the processes of steps S.36 and S.37 are executed.

  In step S.37, if there is no vertical shift between the medium surface of the tomographic image of the medium 9 acquired in step S.32 and the medium surface of the tomographic image of the medium 9 acquired in step S.36, solidification is performed. The adjustment of the measurement position of the state measurement unit 4 is completed (S.39).

  Next, from the tomographic image of the droplet 8, a location where the solidification state inside the droplet 8 is to be measured is selected as a measurement point Q (see FIG. 1), and scanning is performed so that position coordinate data corresponding to this location can be acquired. The optical system 33BC and the position adjustment mechanism 40 are adjusted. In addition, you may change suitably the adjustment order of the measurement position of the shape measurement part 2, the osmosis | permeation state measurement part 3, and the coagulation | solidification state measurement part 4 as needed.

  When the adjustment of the measurement positions of the shape measurement unit 2, the permeation state measurement unit 3, and the coagulation state measurement unit 4 is completed, the medium 9 is translated in the horizontal direction, and the application location of the droplet 8 on the medium 9 is updated. Then, it is confirmed again using the solidification state measuring unit 4 that the vertical position of the surface 9a of the medium 9 has not changed before and after the movement.

  The tomographic image of the medium 9 acquired by the coagulation state measurement unit 4 after the parallel movement is compared with the tomographic image of the medium 9 acquired by the coagulation state measurement unit 4 before the parallel movement, and the position of the surface 9a of the medium 9 is in the vertical direction. If it has changed, the position of the scanning optical system 33BC of the coagulation state measurement unit 4 is adjusted by an amount corresponding to the amount of change, and the position of the reference mirror 34c is adjusted by the position adjustment mechanism 40. Thereby, the adjustment of the measurement position is finally completed.

  In the optical coherence tomography measurement, the resolution of the acquired tomographic image in the measurement optical axis direction (the optical axis direction of the collimator lens 33d) increases as the bandwidth of the light used increases. When the position adjustment of the coagulation state measurement unit 4 is performed using the optical coherence tomography measurement function, the wavelength band of light to be used may be switched in order to obtain a high-resolution tomographic image. This switching can be performed, for example, by changing the wavelength selection filter 1e in the light source unit 1 to one that can extract light with a desired bandwidth.

  Application of the droplet 8 to the medium 9, measurement of the outer shape of the droplet 8, measurement of the penetration state of the droplet 8 into the medium 9, and measurement of the solidification state of the droplet 8 are, for example, an electrical trigger. The timing is matched by the signals, and at the same time or with a slight time difference.

  After each measurement is started, the droplet 8 is attached to the medium 9. Measurement is performed until the temporal change in the outer shape of the droplet 8, the temporal change in the infiltration state of the droplet 8, and the change in the solidification state of the droplet 8 are saturated as behavior information acquired by each of these measurements. . These pieces of information or data are stored in the storage unit 7B in time series.

  Before performing a new measurement, the measurement area of the medium 9 is updated. At this time, the position adjustment with respect to the change in the vertical position of the surface 9a of the medium 9 is performed by the same operation as that performed in the measurement position adjustment. These operations are repeated for one of the combinations of the droplet 8 and the medium 9 to perform measurement.

  The same droplet 8 is measured using the shape measuring unit 2, the infiltration state measuring unit 3 and the coagulation state measuring unit 4 simultaneously. Based on the information acquired by the shape measuring unit 2 and the penetration state measuring unit 3, the amount of liquid remaining on the surface 9 a of the medium 9 and the liquid that has penetrated into the medium 9 with respect to the droplet 8 applied to the medium 9. The amount can be measured.

  Further, by calculating these differences, the vaporized liquid amount can be obtained quantitatively over time. Thereby, the temporal change of the drying amount of the liquid is estimated.

  Further, the information obtained by the solidification state measuring unit 4 can know the temporal change in the solidification state of the droplet 8 attached to the surface 9a of the medium 9, and the measurement result of the behavior state of the droplet 8, that is, It is possible to specify the solidification characteristics of the droplet 8 related to the permeability, volatility, etc. of the droplet 8 with respect to the medium 9.

  Further, for example, assuming that the fluid substance in the droplet 8 does not penetrate into the medium 9, it is possible to specify the change in the concentration of the solvent and the viscosity of the solvent over time from the amount of decrease in the solvent on the surface 9 a of the medium 9. . From this result and the measurement result of the solidification state of the droplet 8, a change in the particle diameter of the fluid substance can be estimated. These can be specified by the processing unit 7C.

  According to this embodiment, since the position of each measuring unit is adjusted in advance with respect to the measurement target before the measurement of the measurement target, the reproducibility of the measurement of the outer shape of the droplet 8, the droplet 8 The reproducibility of the state of penetration of the liquid into the medium 9 and the reproducibility of the solidification state of the droplet 8 are improved.

DESCRIPTION OF SYMBOLS 1 ... Light source part 2 ... Shape measurement part 3 ... Penetration state measurement part 4 ... Coagulation state measurement part 7 ... Control processing part 8 ... Droplet (liquid)
9 ... Medium 9a ... Surface 11 ... Sample stage 2A ... Projection unit 2B ... Imaging unit

JP2013-205145A JP2012-032308 JP-A-2005-121600 JP 2003-106979 A

Claims (10)

An application device for applying a liquid containing a fluid substance to the medium;
A shape measuring unit that measures at least the outer shape of the liquid having at least an imaging unit that images the shadow of each measurement target generated by light irradiated toward the liquid applied to the surface of the medium;
Measurement of coherent light from the light source unit divided into reference light traveling toward the reference optical path and measurement light traveling toward the measurement optical path, and returning from the reference light returning from the reference optical path and the medium existing in the measurement optical path An infiltration state measuring unit for measuring an infiltration state of the liquid into the medium based on an optical coherence tomography method having at least an optical system that converts interference light generated by interference with light into an interference signal;
Splitting the low-coherence light from the light source unit into reference light toward the reference optical path and measurement light toward the measurement optical path, and reference light returning from the reference optical path and measurement light returning from the liquid existing in the measurement optical path; And a coagulation state measurement unit for measuring the coagulation state of the liquid based on a low-coherence dynamic light scattering method. A liquid state change measuring device.   The liquid state change measuring apparatus according to claim 1, wherein the coating apparatus applies the liquid as droplets. A storage unit for storing the outer shape of the liquid applied to the medium, the permeation state of the liquid into the medium, and the solidified state of the liquid in time series;
Based on the temporal change of the outer shape state stored in the storage unit, the temporal change of the permeation state, and the temporal change of the coagulation state, the temporal change of the drying amount of the liquid is obtained. The liquid state change measuring device according to claim 1 or 2, wherein A storage unit for storing the outer shape of the liquid applied to the medium, the permeation state of the liquid into the medium, and the solidified state of the liquid in time series;
Based on the temporal change of the outer shape state stored in the storage unit, the temporal change of the permeation state, and the temporal change of the coagulation state, the temporal change of the liquid concentration and the liquid The time change of the particle diameter of the fluid substance in the liquid is obtained from this result and the measurement result of the solidification state. The liquid state change measuring device according to 1. The coating apparatus has an injection hole for injecting the liquid as droplets,
The penetration state measurement unit includes a position adjustment mechanism that adjusts a measurement region of the medium, and the position adjustment mechanism calculates a spatial position of the injection hole based on a tomographic image acquired by the penetration state measurement unit. 5. The liquid state change measuring device according to claim 2, wherein the position adjustment of the measurement region is performed on the basis of a spatial position of the injection hole.   The solidification state measurement unit includes a position adjustment mechanism that adjusts the measurement position of the liquid, and a control unit that controls the position adjustment mechanism. The adjustment of the measurement position is performed by the solidification state measurement unit. The position adjustment mechanism is automatically controlled so that the measurement position corresponding to the coordinates can be measured by acquiring an image in advance and designating coordinates on the tomographic image. The liquid state change measuring device according to any one of claims 2 to 5.   The light source of the permeation state measurement unit and the light source of the coagulation state measurement unit are a common light source unit, and the wavelength of light output from the common light source unit is adjusted and used as light of each light source. The liquid state change measuring device according to any one of claims 1 to 6. An application step of applying a liquid having a fluid substance as a measurement target to a medium as a measurement target;
The outer shape of the liquid, the penetration state of the liquid into the medium, and the solidification state of the liquid are simultaneously measured, and the information on the outer shape, the information on the penetration state, and the information on the solidification state are sequentially sequentially. A storage step for storing;
A calculation step for obtaining a dry amount of the liquid based on information stored in the storage step;
The liquid state change measuring method characterized by including. An application step of applying a liquid having a fluid substance as a measurement target to a medium as a measurement target;
The outer shape of the liquid, the penetration state of the liquid into the medium, and the solidification state of the liquid are measured, and the information on the outer shape, the information on the penetration state, and the information on the solidification state are sequentially stored in time. A memory step to
Based on the information stored in the storage step, the concentration of the fluid substance and the viscosity of the liquid are obtained, and the particle diameter time of the fluid substance is obtained based on the estimation result and the information on the solidification state. Specific steps to identify global changes,
The liquid state change measuring method characterized by including.   The information related to the outer shape of the liquid is acquired by the shape measuring unit according to any one of claims 1 to 7, and the information related to the penetration state of the liquid into the medium is determined according to claims 1 to 7. The information on solidification of the liquid is acquired by the penetration state measuring unit according to any one of claims 1 to 7, and the information on the solidification of the liquid is acquired by the solidification state measuring unit according to any one of claims 1 to 7. Item 10. The liquid state change measuring method according to Item 8 or Item 9.