CN114561204B - Preparation method of composite photochromic sol solution - Google Patents
Preparation method of composite photochromic sol solution Download PDFInfo
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- CN114561204B CN114561204B CN202210450573.9A CN202210450573A CN114561204B CN 114561204 B CN114561204 B CN 114561204B CN 202210450573 A CN202210450573 A CN 202210450573A CN 114561204 B CN114561204 B CN 114561204B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Abstract
A process for preparing the composite photochromic sol solution from WO 3 Sol, TiO 2 Mixing the sol and the ZnO sol, and adding ultrapure water for dilution to obtain photochromic composite sol with the concentration of 0.2M; and adding a glycerol solution into the composite sol liquid, mixing and stirring the solution to finally form the photochromic liquid for use. And coating the photochromic liquid on the polyester film to form the photochromic polyester film. The formed film has fast color changing speed and excellent fading performance.
Description
Technical Field
The invention belongs to material science, and particularly relates to a photochromic polyester film.
Background
With the continuous development of science and technology and the progress of human society, the demand of people for material materials is also continuously increased. Among various new materials, photochromic materials are favored by researchers because they can undergo reversible color changes under irradiation with excitation light. The method has huge application prospect in the fields of optical information storage, large-area data display, intelligent glass, military anti-counterfeiting and the like.
The photochromic phenomenon is that when the compound is irradiated by light with a certain wavelength, the compound is converted into a product with another color through a series of chemical reactions; the absorption spectrum of the material is obviously changed due to the change of the molecular structure or the electronic configuration of the material before and after the reaction, and the change is reflected as color change. The product after color change can generate reversible reaction to restore to the original state under the action of irradiation or heating of light with another wavelength. The photochromic polyester film is an important product of photochromic materials, and compared with a block material, the photochromic polyester film has the advantages of easy extensibility, low thickness and the like, and has some unique physical properties of force, sound, heat, electricity, light and the like, so the photochromic polyester film has great application advantages in the subdivision industry.
The prior art generally improves the photochromic performance by adding additional substances to the photochromic material. The metal compound is a common additive, but the matching of the metal compound and the base film material is still a problem which is not easy to solve, and the technical problems of low color changing speed, low color fading speed and poor color changing effect of the photochromic film still exist at present. In particular, due to the additives, the film uniformity during the coating process is to be improved and the optical properties are to some extent affected.
In addition, the detection and verification of the photochromic performance of the film are indispensable important links in the film production, and the traditional method is to verify the photochromic performance of the film by a special instrument and measure whether the performance meets the performance requirement of the photochromic. The traditional measuring instruments comprise a spectrophotometer, a spectrometer, a scanning electron microscope, a transmission electron microscope, a diffractometer and the like, and the instruments have high measuring accuracy, but are usually expensive, high in specificity and relatively complex in operation, are usually used for sampling and detecting product samples, and are not suitable for large-scale production of factory production lines.
Disclosure of Invention
To solve one or more of the above problems, and the problems mentioned in the examples, the following solutions are proposed.
A preparation method of a composite photochromic sol solution comprises the following steps:
step 1: WO 3 Preparing sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =4 to obtain WO 3 A solution; adding oxalic acid into ultrapure water for dissolving, and heating and stirring in the dissolving process to obtain an oxalic acid solution, wherein the heating temperature is 45-63 ℃, and the stirring time is 5-10 min. Mixing WO 3 Solution and grassMixing the acid solutions, adding ultrapure water for dilution and stirring, standing for 6-10h to form colorless transparent WO 3 Sol with the concentration of 0.3M;
step 2: TiO 2 2 Preparing sol: c is to be 16 H 36 O 4 Adding Ti (butyl titanate) into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and preparing the TiO with sol concentration of 0.3M 2 Sol;
and 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in an absolute ethyl alcohol solution to form a suspension, adding a surfactant, and stirring at constant temperature to form ZnO sol with the concentration of 0.3M;
and 4, step 4: mixing the three sols, and adding ultrapure water for dilution to obtain photochromic composite sol with the concentration of 0.2M; WO in composite sol 3 、TiO 2 The molecular ratio of the ZnO to the ZnO is 22:1:1-15:1: 1;
and 5, step 5: adding a glycerol solution into the composite sol liquid, ensuring that the mass of the glycerol added into each 10ml of the composite sol liquid is 0.3g, mixing and stirring the solution to finally form the photochromic liquid for use, wherein the concentration of the glycerol is 5.6-8.5%.
Further comprising forming the photochromic liquid on a polyester film.
A coating film is formed on the photochromic liquid.
After the photochromic liquid was formed on the polyester film, the optical properties thereof were verified.
The verification method comprises a machine vision method.
The verification method comprises the step of using a neural network model to judge the picture.
WO in composite sol 3 、TiO 2 The molecular ratio to ZnO was 20:1: 1.
The concentration of glycerol was 8%.
The surfactant is diethanolamine.
The surfactant is triethanolamine.
A preparation process of a polyester film, and a composite photochromic sol solution prepared by the preparation method.
The invention has the advantages that:
based on the existing photochromic sol, a new sol preparation method and a new sol proportion are provided. Particularly, the combination of various metal compounds is provided to realize better optical performance, and the color changing speed and the fading speed which are far superior to those of the prior art are ensured by further adding glycerol and optimizing the proportion. On the basis, a simple and feasible method is provided for verifying the photochromic film on the existing production line, namely a pixel-based polyester film color-changing state discrimination model and a discrimination method thereof are provided, the discrimination model is trained according to a pre-collected sample image, and after the model training is finished, whether the input image contains the polyester film and the color-changing state of the film can be automatically discriminated according to the trained model. Compared with the traditional method, the method is more effective and can give consideration to accuracy, convenience and speed.
Detailed Description
Preparation method of photochromic sol
Step 1: WO 3 Preparing sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =4 to obtain WO 3 And (3) solution. Adding oxalic acid into ultrapure water for dissolving, and heating and stirring in the dissolving process to obtain an oxalic acid solution. Heating at 45-63 deg.C, and stirring for 5-10 min. Mixing WO 3 Mixing the solution with oxalic acid solution, adding ultrapure water for dilution and stirring, standing for 6-10h to form colorless transparent WO 3 Sol, concentration 0.3M.
Step 2: TiO 2 2 Preparation of sol: c is to be 16 H 36 O 4 Adding Ti (butyl titanate) into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and preparing the TiO with sol concentration of 0.3M 2 And (3) sol.
And 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in absolute ethanol solution to form suspension, adding surfactant, stirring at constant temperature to form ZnO sol, concentratingThe degree was 0.3M.
And 4, step 4: mixing the three sols, and adding ultrapure water for dilution to obtain the photochromic composite sol with the concentration of 0.2M. Preferably, WO in the composite sol 3 、TiO 2 The molecular ratio of ZnO to ZnO is 22:1:1-15:1: 1. The above-mentioned ratio is an optimum value after a large number of experiments if TiO 2 When the ratio of ZnO to ZnO is too low, the response performance of photochromism is reduced, and when the ratio is too high, agglomeration occurs among sol particles, and the physical properties of the film are reduced when the film is subsequently coated on a high polymer film. And may hinder the next step of glycerol and WO 3 The contact of molecules reduces the optical performance after film formation.
And 5, step 5: and adding a glycerol solution into the composite sol liquid, ensuring that the mass of the glycerol added into each 10ml of the composite sol liquid is 0.3g, and mixing and stirring the solution to finally form the photochromic liquid for use. Preferably, the glycerol concentration is 5.6-8.5%. Because glycerol has strong electron-pushing capacity and proper carbon chain length, OH of glycerol can be matched with WO 3 、TiO 2 Fully contacts with ZnO molecules, and improves the optical performance. Meanwhile, the addition of the glycerol can improve the wettability of the sol, so that the sol is more uniform when in contact with the film, and the uniformity is improved. Furthermore, the proportion of the three sols and the proportion of the three sols to the glycerol are selected through a large number of experiments, so that the optimal light response performance and light fading performance can be achieved.
Preparation of sample 1:
step 1: WO 3 Preparing sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =4 to obtain WO 3 And (3) solution. 4mol/L concentrated hydrochloric acid solution can be added in the process. Adding oxalic acid into ultrapure water for dissolving, and heating and stirring in the dissolving process to obtain an oxalic acid solution. The heating temperature is 50 deg.C, and the stirring time is 10 min. Mixing WO 3 Mixing the solution with oxalic acid solution, adding ultrapure water for dilution and stirring, standing for 10h to form colorless transparent WO 3 Sol, concentration 0.3M.
Step 2: TiO 2 2 Preparing sol: c is to be 16 H 36 O 4 Adding Ti (butyl titanate) into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and preparing the TiO with sol concentration of 0.3M 2 And (3) sol. Acetic acid was added during the above process to adjust the reaction rate.
And 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in absolute ethyl alcohol solution to form suspension, adding diethanolamine, and stirring at constant temperature to form ZnO sol with a concentration of 0.3M.
And 4, step 4: mixing the three sols, and adding ultrapure water for dilution to obtain the photochromic composite sol with the concentration of 0.2M. WO in composite sol 3 、TiO 2 The molecular ratio to ZnO was 20:1: 1.
And 5, step 5: and adding a glycerol solution with the concentration of 8% into the composite sol liquid, ensuring that the mass of the glycerol added into each 10ml of the composite sol liquid is 0.3g, and mixing and stirring the solution to finally form the photochromic liquid for use.
Through inspection, the color change time is 35s under the illumination condition of 800nm, and the color fading time is 6 h. But of the general WO 3 The color-changing time of the color-changing sol is 90-120s, and the color-fading time is 10-20 h.
Preparation of sample 2:
step 1: WO 3 Preparing sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =3.5 to obtain WO 3 And (3) solution. 4.5mol/L concentrated hydrochloric acid solution can be added in the process. Adding oxalic acid into ultrapure water for dissolving, and heating and stirring in the dissolving process to obtain an oxalic acid solution. The heating temperature is 45 ℃ and the stirring time is 10 min. Mixing WO 3 Mixing the solution with oxalic acid solution, adding ultrapure water for dilution and stirring, standing for 8h to form colorless transparent WO 3 Sol, concentration 0.3M.
Step 2: TiO 2 2 Preparing sol: c is to be 16 H 36 O 4 Adding Ti (butyl titanate) into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and preparing the solutionGlue concentration of 0.3M TiO 2 And (3) sol. Acetic acid was added during the above process to adjust the reaction rate.
And 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in absolute ethanol solution to form suspension, adding triethanolamine, and stirring at constant temperature to form ZnO sol with concentration of 0.3M.
And 4, step 4: mixing the three sols, and adding ultrapure water for dilution to obtain the photochromic composite sol with the concentration of 0.2M. WO in composite sol 3 、TiO 2 The molecular ratio to ZnO was 18:1: 1.
And 5, step 5: and adding a glycerol solution with the concentration of 6% into the composite sol liquid, ensuring that the mass of the glycerol added into each 10ml of the composite sol liquid is 0.22g, and mixing and stirring the solution to finally form the photochromic liquid for use.
The test shows that the color change time is 46s under the illumination condition of 800nm, and the color fading time is 5.4 h. But of the general WO 3 The color-changing time of the color-changing sol is 90-120s, and the color-fading time is 10-20 h.
Preparation of sample 3:
step 1: WO 3 Preparation of sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =4 to obtain WO 3 And (3) solution. 4mol/L concentrated hydrochloric acid solution can be added in the process. Adding oxalic acid into ultrapure water for dissolving, and heating and stirring in the dissolving process to obtain an oxalic acid solution. The heating temperature is 50 deg.C, and the stirring time is 20 min. WO (International patent application) 3 Mixing the solution with oxalic acid solution, adding ultrapure water for dilution and stirring, standing for 15h to obtain colorless transparent WO 3 Sol, concentration 0.5M.
Step 2: TiO 2 2 Preparing sol: c is to be 16 H 36 O 4 Adding Ti (butyl titanate) into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and preparing the TiO with sol concentration of 0.3M 2 And (3) sol. Acetic acid was added during the above process to adjust the reaction rate.
And 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in absolute ethyl alcohol solution to form suspension, adding diethanolamine, and stirring at constant temperature to form ZnO sol with a concentration of 0.3M.
And 4, step 4: mixing the three sols, and adding ultrapure water for dilution to obtain the photochromic composite sol with the concentration of 0.4M. WO in composite sol 3 、TiO 2 The molecular ratio to ZnO was 22:1: 1.
And 5, step 5: and adding 8.5% glycerol solution into the composite sol liquid, ensuring that the mass of glycerol added into each 10ml of composite sol liquid is 0.1g, mixing and stirring the solution, and finally forming the photochromic liquid for use.
The test shows that the color change time is 30s and the fading time is 7h under the illumination condition of 800 nm. WO commonly known in the art 3 The color-changing time of the color-changing sol is 90-120s, and the color-fading time is 10-20 h.
Furthermore, if the film prepared subsequently has electrochromic properties simultaneously and/or independently, the composite sol can be diluted by adding ultrapure water, EDOT and PSS-Na are added, the mixture is mixed and stirred, then acid is added to adjust the pH value to be about 2, then the temperature is controlled to be 35 ℃, initiator is uniformly added and stirred for 4 hours, the ultrapure water is added for dilution again, the obtained liquid is filtered, large-particle precipitates are removed, and finally the aqueous dispersion of the photochromic material with the solid content of 0.7% is obtained. Wherein the mass ratio of the solid substance of the composite sol to the mass of EDOT and PSS-Na is preferably as follows: 1.1: 1: 2.3. according to a large number of experimental observations, WO can be realized in the aqueous dispersion of the color-changing material prepared by the method 3 、TiO 2 The material core formed with ZnO part is covered with polymer material to realize electrochromic performance. This is an additional option and is not a necessary step to implement the invention.
Process for preparing photochromic polyester film
The photochromic sol liquid is formed on a polyester film by various methods such as spraying, dipping, brushing and the like, thereby forming a polyester film with photochromic performance.
Generally, the photochromic sol liquid is sprayed, dipped and brushed on one surface of a polyester film, then the polyester film is dried, and a layer of polyester film is covered on the polyester film as a covering film after the drying, so that the photochromic film is protected and is prevented from being damaged in the using process.
Of course, in order to detect the performance of the photochromic sol solution, a polyester material can also be added to directly form a film.
On-line verification process for color changing and fading performance of (III) photochromic polyester film
In general, in a production line, the conventional film optical performance detection means is not suitable for reasons of complex operation, poor environmental adaptability and the like. This makes it impossible to perform online verification on the production line, which affects production efficiency. To this end, the present invention proposes a simple, efficient way of using machine vision. The method comprises the following specific steps:
step 1, obtaining the images of the photochromic polyester film after color change and the images after color change on line
Irradiating the polyester film by using a light source arranged on the production line, and shooting an image of the photochromic polyester film after color change by using a color change detection camera arranged on the production line after irradiation is finished; then turning off the light source or transmitting the polyester film to a light area without light source to realize fading; and shooting the discolored image of the photochromic polyester film by using a discoloring detection camera arranged on the production line. It is noted here that since the method is used on a production line, two cameras are continuously photographed. The performance of each part of the polyester film on the production line can be detected without stopping the production line. Of course, to save on computational cost, both cameras are taking pictures at a certain sampling frequency.
Step 2 image-based photochromic polyester film detection and positioning
And (3) detecting the coverage range and the position of the photochromic polyester film in the image from the image obtained in the step (1), and outputting corresponding coordinates.
It is known that the spectral distributions of the photochromic polyester film after discoloration and after discoloration are similar to each other, and the color tone distribution of the film in the image is expressed. Assuming that a digital Image is acquired, which has three channels of RGB (red, green and blue), it is first transformed into HIS (hue, saturation, brightness) space, making its color hue components independent. Defining:
Pre-selecting a plurality of sample images of polyester film, all sample images forming a set
Including two types of images of photochromic polyester film after color change and after color fading
And
，
and separately calculate each image
Color tone channel of
Calculating the average value of the faded color tones according to the image classification
And average value of color tone after color change
。
Let x and y denote the spatial coordinates of a single pixel of a channel in the image, then
Representing images
Is x, y coordinates in the hue channel H. Let the pixel value range be [0, 1 ]]And divided into 256 gray levels.
For an image
Definition set
：
Indicating the color-changed image
Wherein all hue values satisfy the set of pixel coordinates of equation (4).
In the above-mentioned two formulas, the first and second formulas,
、
indicating a predefined empirical threshold, taken as preferred
5。
And (3) comparing the new unknown image with the known sample image, and acquiring the pixel coordinates of the image with the color tone similar to that of the sample image according to the formulas (3) and (4), so as to approximately obtain the position of the polyester film in one unknown image and infer the color change state of the film.
Step 3, distinguishing model and distinguishing method for polyester film color changing state based on pixels
Training a discrimination model according to the sample image and the pixel coordinates meeting the conditions in the sample image in the step 2, and identifying whether the image comprises a polyester film or not and the color change and fading states of the polyester film; after the model training is finished, the image to be detected is input into the model, and the model automatically outputs the judgment result of the input image, namely whether the image contains the polyester film or not and the color changing and fading states of the polyester film.
Before training, a plurality of sample images comprising faded and discolored polyester films are prepared, and the sample image set in the step 2 can be used
. And several sample images were prepared separately without the polyester film.
For an image
Defining a two-dimensional matrix corresponding thereto
、
：
In a clear view of the above, it is known that,
、
in a two-dimensional matrix corresponding to the size of the Image space of the original Image, if the color tone of a pixel at a certain position in the original Image is close to that of the faded sample (equation (3) is satisfied), the two-dimensional matrix is used as a color tone correction matrix
Otherwise
；
The same is true.
Further, defining:
in the formula (7), the reaction mixture is,
representing a convolution operation, the convolution windows are all 31, namely:
in the formula (9), the reaction mixture is,
expressing the convergence speed parameter of the excitation function, controlling the convergence speed of the excitation function, having a certain influence on the model performance, and taking the parameter as an optimal value
.
The convolution window defined by equation (7) is used to extract low-scale spatial distribution features in the image, describing the local pixel distribution of the image, which is correlated with the sample image and can be used to identify the color change state of the mylar.
Further, defining:
in the formula (I), the compound is shown in the specification,
the expression takes the window maximum, p, q represent the space coordinate in the maximum window, and take the integer.
Is a bias variable.
、
Represents the matrix in the above formula (7)
、
The value of the corresponding coordinate.
The above equation is used to downsample the input matrix.
Further, defining:
in the formula (I), the compound is shown in the specification,
representation and matrix
、
Middle coordinate
The corresponding linear weight is given to the corresponding linear weight,
、
the value of the matrix corresponding coordinate in expression (10),
is a bias variable.
The excitation function defined for equation (9).
The above formula is used for extracting the spatial distribution characteristic of the input matrix after down-sampling, i.e. the high-scale spatial distribution characteristic of the image, describing the overall pixel distribution of the image, and is also used for identifying the color change state of the polyester film.
Further, defining:
in the formula (I), the compound is shown in the specification,
、
respectively represent and matrix
Corresponding to the linear weight at the coordinate(s),
the value of the coordinate corresponding to the matrix E in expression (11) is expressed.
Equation (12) relates the aforementioned modeled image features to the state variables to be recognized, respectively.
Is a binary vector of elements
，
. When in use
When the Image of the input Image contains a polyester film, the Image is displayed on a display unit
When the Image is a faded polyester film, the Image is represented by
When the Image is included, the color-changed polyester film is included in the Image; otherwise, when
In the case where the Image does not include the discolored polyester film, the discolored polyester film is not included.
Equations (5) - (12) jointly define a discrimination model for the color change state of the pixel-based mylar film. Wherein, the formulas (5) and (6) are defined
、
Is the input of the model, defined by equation (12)
And outputting the model. The model training method is as follows.
As mentioned above, several image samples are prepared, and the matrix corresponding to each image sample is obtained according to the formulas (5) and (6) and defined in step 2
、
。
The parameters of the models (7) - (12) are assigned initial values, wherein the linear weight can be assigned to 1 and the bias variable can be assigned to 0.
Inputting according to models (7) - (12)
、
Computing corresponding outputs
。
Assigning a set of truth values to each sample based on whether the sample image contains a polyester film and the corresponding color change status
Calculating the difference value between the model output value and the true value:
and calculating according to (13) iterative calculation by using back propagation algorithm
Minimum value of (c). In the formula
、
To control the parameters, satisfy
Appropriately adjusted according to the sample data
、
Is helpful to improve the performance of the model. Accordingly, preferred values can be taken
,
.
When in use
After the minimum value is reached, corresponding iteration parameters such as linear weight, bias variable and the like are used as the optimal solution of the model. And finishing the model training.
And (3) giving a test image to be distinguished, defining the image according to the formulas (5) and (6) and the step 2 to obtain corresponding model input, inputting the model and obtaining an output value.
If output
And is and
if so, determining that the test image comprises the color-changed polyester film; if output
And are each and every
If so, determining that the test image comprises the faded polyester film; otherwise if it is not
The polyester film is not included in the test image.
Through the specific algorithm design and the setting of the excitation function and the cost function, the method can be suitable for a polyester film production line, and the color-changing performance and the light-fading performance can be accurately judged.
Step 4 model-based performance verification of photochromic polyester film
And (3) after the detection process is carried out, the conveyor belt rotates at a constant speed, the camera shoots images at a certain frame rate, corresponding judgment output values of the images are calculated according to the methods in the steps (2) and (3), and the shot time stamps and the judgment output values are stored in a correlation mode so as to implement performance verification.
During the color changing period, if the images shot by the film color changing detection camera do not comprise the polyester film after color changing through model discrimination, the recording performance does not reach the standard, and the corresponding images and the time stamps are recorded at the same time; during fading, if the images taken by the film fading detection camera do not include faded (i.e., faded) polyester film through model discrimination, the recording performance does not meet the standards, and the corresponding images and time stamps are recorded at the same time.
The test specimens were manually inspected using a high-precision spectrophotometer and compared to the automated validation methods described herein, with the results of comparison being seen in the table below. The contrast test sample comprises 700 parts (corresponding to images comprising 700 pieces of polyester film), wherein the polyester film sample which reaches the standard after color change and the image thereof are 300 parts, the polyester film sample which reaches the standard after color change and the image thereof are 200 parts, and the polyester film sample which reaches the standard after color change and the polyester film sample which does not reach the standard after color change and the image thereof are 100 parts respectively. According to the comparative test results, the detection accuracy is (287+192+94+91)/700 × 100% = 94.9%. It can be seen that the method herein verifies that the accuracy is within the acceptable range as shown in the following table compared to the classical manual fit of various equipment methods, but the time duration used is greatly reduced (the time duration is reduced by more than 95%). More importantly, due to the extremely high efficiency, the method can be used for carrying out online quick inspection on all products and is applied to the continuous detection of large-scale polyester film products without adopting a manual spot inspection mode. Considering the error of spot check, the actual accuracy is higher than that of manual work.
It will be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described in detail herein, many other variations or modifications can be made, which are consistent with the principles of this invention, and which are directly determined or derived from the disclosure herein, without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (5)
1. A process for producing a polyester film, characterized by: comprises that
The preparation method of the composite photochromic sol solution comprises the following steps:
step 1: WO 3 Preparing sol: adding Na into ultrapure water 2 WO 4 ·2H 2 O, stirring to dissolve, adding a mineral acid solution to acidify until the pH is =4 to obtain WO 3 A solution; dissolving ultrapure water in oxalic acid, heating and stirring to obtain oxalic acid solution, wherein the heating temperature is 45-63 deg.C, and stirring for 5-10min, and adding WO 3 Mixing the solution with oxalic acid solution, adding ultrapure water for dilution and stirring, standing for 6-10h to obtain colorless transparent WO 3 Sol with the concentration of 0.3M;
step 2: TiO 2 2 Preparing sol: adding butyl titanate into absolute ethyl alcohol, adding ultrapure water into the solution to perform polycondensation reaction, and obtaining the productTo a sol concentration of 0.3M TiO 2 Sol;
and 3, step 3: preparation of ZnO Sol: will (CH) 3 COO) 2 Zn·2H 2 Dissolving O in an absolute ethyl alcohol solution to form a suspension, adding a surfactant, and stirring at constant temperature to form ZnO sol with the concentration of 0.3M;
and 4, step 4: mixing the three sols and adding ultrapure water for dilution to obtain photochromic composite sol with the concentration of 0.2M; WO in composite sol 3 、TiO 2 The molecular ratio to ZnO is 20:1: 1;
and 5, step 5: adding a glycerol solution into the composite sol liquid, ensuring that the mass of glycerol added into every 10ml of the composite sol liquid is 0.3g, mixing and stirring the solution to finally form photochromic liquid for use, wherein the concentration of the glycerol is 5.6-8.5%;
(II) forming the photochromic liquid on the polyester film;
after the photochromic liquid is formed on the polyester film, carrying out optical performance verification on the polyester film, wherein the verification method comprises the steps of carrying out input image judgment by using a neural network model;
definition of
For the input of the model, define
Outputting the model; wherein
For a two-dimensional matrix of a size corresponding to the spatial dimension of the input image, if a pixel at a position in the input image is close to the hue of the faded sample
Otherwise
The same process is carried out; when in use
When it is indicated that the input image contains a polyester film, when it is
When the polyester film is discolored, the indication image includes
When the color change is detected, the color change indicates that the input image includes the polyester film after color change; otherwise, when
When the color of the input image is changed, the input image does not contain the polyester film after the color change;
for images
Definition set
Representing an image after fading
A set of pixel coordinates in which all hue values satisfy equation (3):
definition set
Indicating the color-changed image
A set of pixel coordinates in which all hue values satisfy equation (4):
wherein the content of the first and second substances,
representing images
Has coordinates in the hue channel H of
A pixel of (a);
is the average of the hues of the faded color,
is the average value of the color tone after color change;
represents a predefined empirical threshold;
wherein the excitation function of the neural network model is of the form:
2. The process of claim 1, wherein: a coating film is formed on the photochromic liquid.
3. The process of claim 1, wherein: the verification method comprises a machine vision method.
4. The process of claim 1, wherein: the concentration of glycerol was 8%.
5. The process of claim 1, wherein: the surfactant is diethanolamine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090373A (en) * | 1996-02-21 | 2000-07-18 | Kao Corporation | Ultraviolet-screening composite particulate and process for the production thereof |
| CN101148585A (en) * | 2007-11-01 | 2008-03-26 | 中国地质大学（武汉） | Method for preparing weak excitation photochromism WO3 powder by utilizing n-propanol hybridization |
| JP2019137796A (en) * | 2018-02-13 | 2019-08-22 | 国立大学法人山口大学 | Photochromic complex |
| CN111391445A (en) * | 2020-04-07 | 2020-07-10 | 西北工业大学 | Photochromic film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3047434B2 (en) * | 1990-03-27 | 2000-05-29 | 株式会社トクヤマ | Photochromic molding |
| CN112812521B (en) * | 2021-02-05 | 2023-07-11 | 河南银金达新材料股份有限公司 | PETG antibacterial composite film and preparation method thereof |
-
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- 2022-04-27 CN CN202210450573.9A patent/CN114561204B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090373A (en) * | 1996-02-21 | 2000-07-18 | Kao Corporation | Ultraviolet-screening composite particulate and process for the production thereof |
| CN101148585A (en) * | 2007-11-01 | 2008-03-26 | 中国地质大学（武汉） | Method for preparing weak excitation photochromism WO3 powder by utilizing n-propanol hybridization |
| JP2019137796A (en) * | 2018-02-13 | 2019-08-22 | 国立大学法人山口大学 | Photochromic complex |
| CN111391445A (en) * | 2020-04-07 | 2020-07-10 | 西北工业大学 | Photochromic film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WO_3-TiO_2-ZnO溶胶的制备及其光致变色性能研究;陈伟龙等;《人工晶体学报》;20141231;第43卷(第12期);第3113-3117页 * |
| WO3-TiO2-ZnO 复合薄膜的制备与光致变色性能研究;陈伟龙;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》;20170315(第03期);第28-30页、第33-34页、第36-37页、第52页 * |
| 醇对钨青铜粉体光致变色影响的研究;霍丽华等;《黑龙江大学自然科学学报》;20081231;第25卷(第06期);第755-758页 * |
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