WO2023189315A1

WO2023189315A1 - Liquid matter assessment method and liquid matter assessment device

Info

Publication number: WO2023189315A1
Application number: PCT/JP2023/008735
Authority: WO
Inventors: 卓哉小出; 康敏伊藤; 葉月中江; 翔太橋本; 崇南條
Original assignee: コニカミノルタ株式会社
Priority date: 2022-03-29
Filing date: 2023-03-08
Publication date: 2023-10-05

Abstract

A liquid matter assessment method according to the present invention is for assessing a liquid matter containing at least a solvent, a resin, and a non-reactive additive. The non-reactive additive is a fluorescent marker compound. The method comprises: a fluorescent spectrum observation step for acquiring a fluorescent spectrum in an arbitrarily defined excitation wavelength of the liquid matter; and a spectrum analysis step for acquiring data pertaining to a peak intensity shift degree from the acquired fluorescent spectrum on the basis of an interaction between the fluorescent marker compound and an object to be tested in the liquid matter.

Description

Liquid material evaluation method and liquid material evaluation device

The present invention relates to a liquid material evaluation method and a liquid material evaluation device, and in particular, to a liquid material evaluation method that can constantly detect minute fluctuations in water content, impurities, etc. in a liquid material without using a reactive fluorescent marker. Concerning methods of evaluating things.

In recent years, optical films such as polarizing plate protective films and retardation films for display devices such as liquid crystal displays and organic electroluminescent displays, as well as base films such as touch panel base films and gas barrier base films, have become available. First, with the expansion of applications such as substrate films for nanoimprints and substrate films for flexible electronic circuits, there was a need for a stable supply of high-quality optical films with high transparency and high functionality.
Here, in manufacturing a resin molded product, a process is known in which a desired product is obtained by dissolving the resin in a solvent and adding functional additives to the resin due to its high processability.
In-process products are composed of resins, additives, and solvents, and the quality of these products is affected by lot variations caused by different manufacturers. Furthermore, in factories, microscopic impurities were mixed in during storage or when piped, etc., which affected product quality.

Patent Documents 1 and 2 describe an evaluation system for monitoring fluctuations such as quality variations as described above, in which a fluorescent substance is added as a medium and the fluorescent substance reacts to remove trace impurities in the sample. A method of quantifying is disclosed.
Further, Patent Document 3 discloses a moisture detection method using a fluorescent substance that indirectly emits fluorescence by directly reacting with water to generate hydrogen peroxide.

However, in the techniques disclosed in Patent Documents 1 to 3, in order to detect fluorescence information of impurities, a reactive fluorescent marker agent is used to detect changes in the test object. That is, the added fluorescent marker compound itself becomes an impurity after reaction, degrading the performance of resin molded products such as films, and is unsuitable for the quality of modern optical films.

Japanese Patent Application Publication No. 2001-56327 JP2011-95111A International Publication No. 2029/039963

The present invention was made in view of the above-mentioned problems and circumstances, and its problem to be solved is to constantly detect minute fluctuations in water content, impurities, etc. in liquid materials without using reactive fluorescent marker agents. An object of the present invention is to provide a method for evaluating a liquid substance and an apparatus for evaluating a liquid substance.

In order to solve the above problem, the present inventor added a fluorescent marker compound as a non-reactive additive to a liquid material in the process of investigating the causes of the above problem, and thereby changed the peak intensity of the fluorescence spectrum of the liquid material. It was discovered that by measuring the amount, minute fluctuations in the amount of water or impurities in a liquid can be constantly detected without using a reactive fluorescent marker agent, leading to the present invention.
That is, the above-mentioned problems related to the present invention are solved by the following means.

1. A method for evaluating a liquid material containing at least a solvent, a resin, and a non-reactive additive, the method comprising:
the non-reactive additive is a fluorescent marker compound,
a fluorescence spectrum observation step of acquiring a fluorescence spectrum at an arbitrary excitation wavelength of the liquid;
A method for evaluating a liquid material, comprising: a spectral analysis step of acquiring data regarding a peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid material and the test object from the acquired fluorescence spectrum.

2. 2. The method for evaluating a liquid material according to claim 1, wherein a difference ΔSP in solubility parameters between the fluorescent marker compound and the test object in the liquid material is within a range of 6 to 22.

3. The method for evaluating a liquid material according to item 1 or 2, wherein the non-reactive additive is contained in a range of 1 to 5000 ppm by mass based on the liquid material.

4. The method for evaluating a liquid material according to any one of paragraphs 1 to 3, in which the spectrum analysis step is performed inline.

5. Any one of paragraphs 1 to 4, comprising a data processing step of calculating the content of the test object using a calibration curve based on the peak intensity included in the data regarding the degree of peak intensity shift. Evaluation method of the liquid material described.

6. An apparatus for evaluating a liquid material containing at least a solvent, a resin, and a non-reactive additive,
the non-reactive additive is a fluorescent marker compound,
a fluorescence spectrum observation unit that acquires a fluorescence spectrum of the liquid at an arbitrary excitation wavelength;
An evaluation device for a liquid substance, comprising: a spectrum analysis unit that acquires data regarding a peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid substance and the test object from the acquired fluorescence spectrum.

7. 7. The liquid material evaluation device according to claim 6, further comprising a data processing unit that calculates the content of the test object based on the peak intensity included in the data regarding the peak intensity shift degree using a calibration curve.

8. The liquid substance evaluation device according to item 6 or 7, further comprising an information display unit that displays data regarding the peak intensity shift degree.

By the above means of the present invention, there is provided a liquid substance evaluation method and a liquid substance evaluation apparatus that can constantly detect minute fluctuations in water content, impurities, etc. in a liquid substance without using a reactive fluorescent marker agent. can do.

Although the mechanism of expression or action of the effects of the present invention is not clear, it is speculated as follows.
For example, the following fluctuations were thought to be the cause of the variation in film quality (haze).
(i) Differences in impurities and stabilizers during production of delivered raw materials (ii) Differences in moisture content of resins and additives or pH of solvents during film production due to seasonal fluctuations during storage (iii) Outflow of metal ions due to differences in the degree of deterioration of piping due to differences in piping equipment at each factory or changes over time since the factory was built.Therefore, a reactive fluorescent marker agent that causes performance deterioration is added. In order to detect the above-mentioned fluctuations without any reaction, a non-reactive additive (non-reactive fluorescent marker compound) was added to a liquid containing raw materials and solutes, and the fluorescence spectrum was measured.
Furthermore, we prepared the liquid substances (i) to (iii) above, measured the fluorescence spectra of each liquid substance, and compared them with the fluorescence spectrum of the reference sample. As a result, the peak intensity of the non-reactive fluorescent marker compound shifted. I found out that it does.
Here, the reason why a highly accurate evaluation method was achieved without involving a chemical reaction between the fluorescent marker compound that does not react with the resin and the test object is as follows.
In contrast to the case where only the non-reactive fluorescent marker compound and the test object are present in the liquid, when the resin enters the liquid, the density becomes higher than when the two components are present, and intermolecular interactions are more likely to occur. becomes significantly more likely to occur. Furthermore, it is estimated that due to the interaction between the resin and the test object, it is possible to indirectly detect even if the signal of a non-reactive fluorescent marker compound is minute.
Furthermore, the amount of information obtained from multiple wavelength signals from the non-reactive fluorescent marker compound, the test object, and the resin has increased compared to the case of a single wavelength, making it easier to detect changes in fluorescence intensity.

As described above, by adding a fluorescent marker compound as a non-reactive additive to a liquid and measuring the amount of change in the peak intensity of the fluorescence spectrum of the liquid, it is possible to It is possible to constantly detect minute changes in moisture content, impurities, etc. in substances. As a result, since the minute fluctuations can be detected in real time, the time required for feedback in the manufacturing process can be significantly reduced, and manufacturing efficiency can be improved.

A diagram schematically showing a configuration example of a liquid material evaluation device of the present invention Flowchart showing a computer control procedure executed by the liquid material evaluation device of the present invention A diagram schematically showing an example of the dope preparation process, casting process, drying process, and winding process of the solution casting film forming method. Schematic diagram showing an example of a hard coat layer forming apparatus

The method for evaluating a liquid product of the present invention is a method for evaluating a liquid product containing at least a solvent, a resin, and a non-reactive additive, wherein the non-reactive additive is a fluorescent marker compound, and the non-reactive additive is a fluorescent marker compound. A fluorescence spectrum observation step of acquiring a fluorescence spectrum at an excitation wavelength of and a spectrum analysis step.
This feature is a technical feature common to or corresponding to each of the embodiments described below.

In an embodiment of the present invention, the difference ΔSP in solubility parameters between the fluorescent marker compound and the test object in the liquid is within a range of 6 to 22. This is preferable because interaction with the compound is likely to occur and the degree of shift in peak intensity can be easily obtained. Moreover, it is preferable in that it is easy to obtain transparency in products using liquid substances.

Furthermore, the content of the non-reactive additive in the range of 1 to 5,000 ppm by mass based on the liquid material makes it possible to achieve both the haze of the optical film using the liquid material and the measurement sensitivity of the fluorescence spectrum. This is preferable because it allows you to

In addition, by performing the spectrum analysis step in-line, it is possible to detect in real time the amount of water or impurities in the liquid, and the time required for feedback in the manufacturing process can be significantly reduced. This is preferable because manufacturing efficiency can be improved.

Further, it is preferable to include a data processing step of calculating the content of the test object using a calibration curve based on the peak intensity included in the data regarding the peak intensity shift degree. This is preferable in terms of improving manufacturing efficiency.

The evaluation device of the present invention is an evaluation device for a liquid material containing at least a solvent, a resin, and a non-reactive additive, wherein the non-reactive additive is a fluorescent marker compound, and an arbitrary excitation wavelength of the liquid material is provided. a fluorescence spectrum observation unit that acquires a fluorescence spectrum; and a spectrum analysis that acquires data regarding the degree of peak intensity shift based on the interaction between the fluorescent marker compound in the liquid and the test object from the acquired fluorescence spectrum. It is equipped with a section and a section. Thereby, minute fluctuations in the amount of water, impurities, etc. in the liquid can be constantly detected without using a reactive fluorescent marker.

The evaluation device of the present invention also includes a data processing unit that calculates the content of the test object using a calibration curve based on the peak intensity included in the data regarding the peak intensity shift degree; It is preferable to include an information display unit that displays data related to the information.

Hereinafter, the present invention, its constituent elements, and forms and aspects for carrying out the present invention will be explained. In this application, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.

[Summary of the method for evaluating liquid materials of the present invention]
The method for evaluating a liquid product of the present invention is a method for evaluating a liquid product containing at least a solvent, a resin, and a non-reactive additive, wherein the non-reactive additive is a fluorescent marker compound, and the non-reactive additive is a fluorescent marker compound. A fluorescence spectrum observation step of acquiring a fluorescence spectrum at an excitation wavelength of and a spectrum analysis step.
Further, the method for evaluating a liquid material of the present invention may include a data processing step of calculating the content of the test object using a calibration curve based on the peak intensity included in the data regarding the degree of peak intensity shift. , it is possible to detect variations in the content of the substance to be inspected, which is preferable in terms of improving manufacturing efficiency.

In the present invention, the "liquid material" may contain at least a solvent, a resin, and a non-reactive additive, and the amount of residual solvent may be 1000 mass ppm or more.
Specific examples of such liquids include, for example, dope for forming an optical film, an adhesive liquid for bonding an optical film and a polarizer, a coating liquid for forming a hard coat layer to protect the film, A coating liquid for forming an antistatic layer, a water-based coating liquid used for forming a near-infrared reflective film (e.g., a coating liquid for forming a high refractive index layer, a coating liquid for forming a low refractive index layer), or a coating liquid using these coating liquids. Residual solvent after coating, coating material for coating products used in ink applications, electrolyte in batteries, coating solution for protecting positive electrode active materials, coating solution for coating automobile parts, Examples include engine oil, photosensitive materials before UV curing in the semiconductor field, and solutions containing polymers such as gelatin in the food field.
Note that details of the dope, the coating liquid for forming a hard coat layer, the coating liquid for forming an antistatic layer, and the coating liquid for forming a high refractive index layer and a low refractive index layer will be described later.

In the present invention, the "non-reactive additive" according to the present invention refers to a compound that does not form a covalent bond or an ionic bond (does not change its structure) with at least an object to be tested. However, the non-reactive additive according to the present invention is a compound that can change the degree of peak intensity shift through interaction with the test object due to hydrogen bonding, van der Waals forces, or the like.
Specifically, it is preferable for the non-reactive additive to be a compound that does not have a single absorption wavelength in the visible light region for application in the optical region, since the liquid material will not be colored.
Non-reactive additives include, for example, non-reactive fluorescent marker compounds. In addition, non-reactive fluorescent marker compounds may be used as long as they emit fluorescence, and those that have functions derived from antioxidants, dyes, phase difference regulators, wavelength regulators, size regulators, and additives may be used. Also good.

As the antioxidant (AO agent), commonly known ones can be used, and lactone-based, sulfur-based, phenol-based, double bond-based, hindered amine-based, and phosphorus-based compounds are particularly preferred. Can be used. The above-mentioned phenolic compound preferably has a 2,6-dialkylphenol structure, such as "Irganox 1076" and "Irganox 1010" commercially available from BASF Japan Co., Ltd., and "Irganox 1010" commercially available from ADEKA Co., Ltd. Examples include "ADEKA STAB AO-50".

Examples of the dye include compounds having absorption wavelengths in the near-infrared region and compounds having absorption wavelengths in the near-ultraviolet region.
The compound having an absorption wavelength in the near-infrared region (also referred to as a "near-infrared absorbing composition") may be used as an additive for adjusting absorption waveforms. It is preferable to add at least one kind of absorption modifier from the viewpoint of spectral characteristics. As the near-infrared absorption modifier used in the present invention, it is preferable to use a near-infrared absorption dye having a maximum absorption wavelength in the wavelength range of 650 to 800 nm.
Near-infrared absorbing dyes (NIR dyes) suitable for the present invention include, for example, cyanine dyes, squarylium dyes, croconium dyes, azo dyes, anthraquinone dyes, naphthoquinone dyes, phthalocyanine dyes, naphthalocyanine dyes, quaterylene dyes, and dithiol metal complex dyes. Examples include dyes and the like. Among these, cyanine dyes and squarylium dyes are preferred, and squarylium dyes are particularly preferred, from the viewpoint of detecting changes in fluorescence intensity depending on the amount of variation in the object to be inspected.

The compound having an absorption wavelength in the near-ultraviolet region (also referred to as a "near-ultraviolet absorbing composition") may be used as an additive for adjusting the absorption waveform. It is preferable to add at least one kind of agent from the viewpoint of spectral characteristics. As the near-ultraviolet absorption modifier used in the present invention, it is preferable to use a near-ultraviolet absorbing dye having a maximum absorption wavelength in the wavelength range of 300 to 400 nm.
Suitable near-ultraviolet absorbing dyes for the present invention (NUV dyes include, for example, merocyanine dyes, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers) Examples include absorbers, oxanilide-based UV absorbers, nickel complex salt-based UV absorbers, and inorganic UV absorbers. Among these, merocyanine-based Dyes are particularly preferred.

The "resin" in the present invention can be changed as appropriate depending on the use of the liquid material, and may be a thermoplastic resin or a thermosetting resin. Specific examples include cycloolefin resin (COP resin), triacetyl cellulose resin (TAC resin), acrylic resin, urethane resin, polyvinyl alcohol resin, polyimide resin, and the like.

The "solvent" in the present invention can be changed as appropriate depending on the use of the liquid material, and includes organic solvents, water, and the like.
Examples of organic solvents include, as will be described later, chlorinated solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; methanol, ethanol, isopropanol, n-butanol, and 2-butanol. Alcohol solvents such as butanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl formamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; and the like. These solvents may be used alone or in combination of two or more.

In the present invention, the "test object" refers to elemental ions and charged compounds (ionic compounds and polar compounds), and when the charged elemental ions and compounds mix into the liquid material, they do not react. It causes an interaction between the additive and the test object, and has the role of changing the degree of shift in peak intensity of non-reactive additives. That is, the test object is the fluorescence obtained by exciting the non-reactive additive at an arbitrary excitation wavelength using a spectrofluorometer and measuring part or all of the fluorescence wavelength of 250 to 950 nm. A compound that fluctuates fluorescence intensity at the excitation wavelength and fluorescence wavelength at the maximum fluorescence intensity in the spectrum.

Test objects suitable for the present invention include water, lithium, sodium, potassium, magnesium, calcium, strontium, metal ions such as chromium, iron, and copper, halogen element ions such as fluorine, chlorine, and bromine, benzene, and acetone. , ethanol, methanol, formamide, etc.

In the present invention, "peak intensity shift degree" refers to the change in the fluorescence wavelength and fluorescence intensity of a characteristic peak of a non-reactive additive (fluorescent marker compound) depending on the amount of change in the test object in the liquid. , refers to the amount of change in the fluorescence intensity of the fluctuated peak.
From the peak intensity shift degree, not only can the amount of variation in the content of the test object be estimated, but also the test object can be identified.

Further, in the liquid material of the present invention, the difference ΔSP in solubility parameters between the non-reactive additive (fluorescent marker compound) and the test object is preferably within the range of 6 to 22, and preferably within the range of 14 to 22. It is more preferable that there be. When the solubility parameter difference ΔSP is within the above range, interaction between the non-reactive additive and the test object is likely to occur, and the peak intensity shift degree can be easily obtained. Furthermore, it is easy to obtain transparency in products using liquid materials. The reason why ΔSP is set to 6 or more is because when the SP values of the fluorescent marker compound and the test object become close, the fluorescent marker compound and the test object have excellent compatibility, and therefore, the fluorescent marker compound and the test object have excellent compatibility. This is to prevent such a situation that the peak intensity shift degree corresponding to the amount of the mixed substance to be tested cannot be obtained correctly because the particles aggregate without any structural change.

The solubility parameter is an index for evaluating the physical properties of a substance, particularly the solubility behavior of a solvent, and Hildebrand's SP value (solubility parameter; δ) is conventionally used. The "SP value" is a physical property value specific to a substance expressed as the square root of the cohesive energy density of the substance.
In addition, this SP value is the Hansen solubility parameter proposed by Hansen as a parameter that takes into account the polarity of the substance by dividing it into three components: dispersion force term (δD), polarity term (δP), and hydrogen bond term (δH). (HSP value) is expressed as the following formula.
SP value = (δD ² + δP ² + δH ² ) ^0.5

The Hansen solubility parameter (HSP value) is based on the idea that "two substances with similar intermolecular interactions are likely to dissolve in each other," and is composed of the following three parameters. can be regarded as coordinates in a three-dimensional space (also called "Hansen space"). It is considered that the closer the distance between the coordinates of two substances, the higher their affinity for each other and the easier they are to dissolve.
δD: Energy due to intermolecular dispersion force δP: Energy due to intermolecular dipole interaction δH: Energy due to intermolecular hydrogen bonding

Note that the method of calculating δD, δP, and δH in the Hansen solubility parameters is not particularly limited, and may be calculated by inputting the chemical structure into software, or may be calculated experimentally. It is preferable to input and calculate.

As the HSP value, a registered value or an estimated value in HSPiP 5th Edition 5.0.10.1, which is commercially available software, can be used. This software is available at https://www. hansen-solubility. It can be obtained from sites such as com/. Furthermore, methods for estimating HSP based on such software include, for example, C. M. The document “Hansen Solubility Parameters: A User's Handbook, Second Edition” by Hansen et al.
Press, 2007).

The SP value of the fluorescent marker compound contained in the liquid of the present invention is preferably within the range of 5 to 10, the SP value of the resin is preferably within the range of 10 to 20, and the The SP value of the test object is preferably within the range of 10 to 20, and the SP value of the test object is preferably within the range of 9 to 30.
Furthermore, the difference ΔSP in solubility parameters between the solvent and the resin is preferably within the range of 6 to 22.

<Fluorescence spectrum observation process>
The fluorescence spectrum observation step is a step of acquiring a fluorescence spectrum of a liquid material at an arbitrary excitation wavelength.
"Arbitrary excitation wavelength" refers to the fluorescent fingerprint of the liquid or the fluorescence spectrum obtained by changing the excitation wavelength by several nanometers in advance, and among the obtained fluorescence spectra, it indicates the fluorescence spectrum that is effective for measurement. Select the excitation wavelength as an arbitrary excitation wavelength. In particular, it is preferable to select an excitation wavelength with a high intensity among the acquired fluorescence spectra as an arbitrary excitation wavelength, but the excitation wavelength is not limited to an excitation wavelength that exhibits a high-intensity fluorescence spectrum. Good too.
Such an excitation wavelength is, for example, preferably within the range of 200 to 900 nm, and more preferably within the ranges of 200 to 400 nm and 680 to 900 nm.

The means to obtain a fluorescence spectrum by irradiating a liquid material with light of an arbitrary excitation wavelength includes an irradiation unit that irradiates the liquid material with light of an excitation wavelength, and a method that captures the fluorescence from the liquid material excited by the light of the excitation wavelength. It is preferable to have a configuration including a light receiving unit that receives light.
The details of the irradiation unit and the light receiving unit will be explained later in connection with the liquid substance evaluation device.

In the fluorescence spectrum observation step, specifically, the irradiation unit irradiates the liquid material with light of an arbitrary excitation wavelength, and the light receiving unit receives the fluorescence from the liquid material excited by the irradiation. In addition, in the fluorescence spectrum observation step, each fluorescence spectrum may be acquired using a plurality of excitation wavelengths.

<Spectral analysis process>
The spectrum analysis step is a step of acquiring data regarding the peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid and the test object from the fluorescence spectrum acquired in the fluorescence spectrum observation step.
The "data regarding the peak intensity shift degree" includes data on the fluctuated peak fluorescence intensity and the amount of change in the fluorescence intensity, the fluctuated peak fluorescence wavelength, and the amount of change in the fluorescence wavelength. Moreover, the spectrum analysis step may include simply acquiring the data, or may include analyzing the acquired data.
Examples of means for acquiring data regarding the degree of shift in peak intensity include a general personal computer.

<Data processing process>
The data processing step includes at least a step of calculating the content of the test object using a calibration curve created in advance based on the peak intensity included in the data regarding the degree of peak intensity shift obtained in the spectrum analysis step. It is.
A calibration curve is created by using a liquid material whose contents of the test object and fluorescent marker compound are known, irradiating the liquid material with light of an arbitrary excitation wavelength, and calculating the fluorescence spectrum from the liquid material excited by the irradiation. Data on fluorescence intensity and fluorescence wavelength is acquired in advance, and the information is created based on this acquired data. In the calibration curve, for example, the vertical axis represents the fluorescence peak intensity, and the horizontal axis represents the content of the test object.
Examples of the means for calculating the content of the inspection object include a general personal computer.

After the data processing step, it is preferable to display data such as the calculated content of the test object, the excitation wavelength of the irradiated light, the fluorescence wavelength and fluorescence intensity of the liquid material, on the information display section.

[Configuration of liquid material evaluation device]
The liquid product evaluation device (hereinafter also simply referred to as “evaluation device”) of the present invention can be applied to manufacturing processes using various forms of liquid materials depending on the purpose, and can be used to evaluate the fluorescence of liquid materials in-line. The spectrum is constantly measured, and the liquid material is evaluated by identifying the amount of variation in the content of the test object in the liquid material and identifying the test object.
The evaluation device of the present invention is an evaluation device for a liquid material containing at least a solvent, a resin, and a non-reactive additive, wherein the non-reactive additive is a fluorescent marker compound, and an arbitrary excitation wavelength of the liquid material is provided. a fluorescence spectrum observation unit that acquires a fluorescence spectrum; and a spectrum analysis that acquires data regarding the degree of peak intensity shift based on the interaction between the fluorescent marker compound in the liquid and the test object from the acquired fluorescence spectrum. It is equipped with a section and a section.
The evaluation device also includes a data processing unit that calculates the content of the test object using a calibration curve based on the peak intensity included in the data regarding the peak intensity shift degree, and a data processing unit that displays the data regarding the peak intensity shift degree. It is preferable to include an information display section.

FIG. 1 is a diagram schematically showing a configuration example of a liquid material evaluation apparatus according to the present invention.
As shown in FIG. 1, the evaluation device 100 is installed in-line in a manufacturing process using liquid materials, and includes a fluorescence spectrum observation section 110, and a computer 120 having a spectrum analysis section, a data processing section, and an information display section. ing.

<Fluorescence spectrum observation section>
The fluorescence spectrum observation unit 110 includes an irradiation unit 111 that irradiates a liquid with light of an arbitrary excitation wavelength, and a light reception unit 112 that receives fluorescence from the liquid excited by the light of the excitation wavelength and measures the fluorescence spectrum. It is preferable that the configuration has the following.

The irradiation unit 111 irradiates the liquid material with light of an arbitrary excitation light wavelength to generate fluorescence from the fluorescent marker compound.
The irradiation unit 111 preferably includes, for example, an LED driver 111a, an LED light source 111b, an irradiation fiber collimator 111c, and the like. Then, the LED driver 111a supplies a current to turn on the LED light source 111b, and thereby the liquid material is irradiated with light of an arbitrary excitation wavelength from the LED light source 111b via the irradiation fiber collimator 111c.
Furthermore, as the irradiation unit, commercial products can be used, such as a high-power LED light source (manufactured by Ocean Photonics, LSM series) and a high-power UV-Vis fiber light source unit (manufactured by Hamamatsu Photonics, L10290). It will be done.

Furthermore, the wavelength range of the excitation light is preferably within the range of visible light. Here, the wavelength of the excitation light irradiated from the irradiation unit can be arbitrarily changed by the user inputting multiple excitation wavelengths that indicate a fluorescence spectrum effective for measurement using a keyboard, mouse, etc. It has become. A plurality of excitation wavelengths exhibiting fluorescence spectra effective for the measurement can be selected from the fluorescence spectra obtained by acquiring the fluorescence fingerprint of the liquid or the fluorescence spectra obtained by changing the excitation wavelength by several nanometers in advance. It is preferable that

The light receiving unit 112 receives the fluorescence emitted from the fluorescent marker compound when it is irradiated with excitation light, measures the excitation light wavelength, fluorescence wavelength, and fluorescence intensity from the received fluorescence, and sends the measured data to the spectrum analysis section (computer 120 ).
The light receiving unit 112 is preferably composed of, for example, a spectroscope 112a, a light receiving fiber collimator 112b, and the like. Then, the fluorescence wavelength and fluorescence intensity of the fluorescence received by the spectrometer 112a via the light-receiving fiber collimator 112b are measured, and the data is transmitted to the spectrum analysis section (computer 120).
As the spectrometer, commercially available products can be used, such as a small fiber optical spectrometer (manufactured by Ocean Photonics, USB2000) and a multichannel spectrometer (manufactured by Hamamatsu Photonics, PMA-12).

Note that the irradiation fiber collimator 111c connected to the LED light source 111b is placed near the piping through which the liquid flows (for example, reference numeral P1 in FIG. 1) or the liquid pump P2 so that the liquid can be irradiated with light. It is located in Further, a light-receiving fiber collimator 112b connected to the spectrometer 112a is also arranged near the pipe P1 through which the liquid flows and the liquid pump P2 so as to be able to receive fluorescence from the liquid. Further, it is preferable that the irradiation fiber collimator 111c and the light receiving fiber collimator 112b are covered with a light shielding cover 113.

<Spectrum analysis section>
The spectrum analysis unit acquires data regarding the peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid and the test object from the fluorescence spectrum acquired by the spectrum observation unit. Then, the obtained data regarding the peak intensity shift degree is transmitted to the data processing section.

<Data processing section>
The data processing section calculates the content of the test object from the data regarding the peak intensity shift degree acquired by the spectrum analysis section, using a calibration curve created in advance. Data regarding the calculated content and peak intensity shift degree is transmitted to the information display section.

<Information display section>
The information display section performs display according to the instructions of the display signal input from the data processing section, and specifically displays data regarding the peak intensity shift degree and the content of the test object. Specifically, the data regarding the peak intensity shift degree includes the excitation wavelength of the light irradiated to the liquid material, the fluorescence spectrum at the excitation wavelength, and the peak intensity shift degree (characteristic peak fluorescence wavelength and amount of change in fluorescence intensity). ) etc.
Further, the information display section includes, for example, an LCD (Liquid Crystal Display), and performs display using, for example, a dot matrix method.

For example, a general computer (personal computer) 120 is used as the spectrum analysis section, data processing section, and information display section. Note that a dedicated integrated circuit (ASIC) may be provided when handling a very large amount of data or in applications requiring ultra-high-speed processing.
Further, the computer 120 centrally controls the entire operation of the evaluation device 100, and includes a memory, a control section, a calculation processing section, and the like. Further, the user can input measurement processing conditions and the like into the computer 120 using the keyboard and mouse.

Next, an example of a process for acquiring data regarding the degree of shift in the peak intensity of a liquid in the liquid substance evaluation apparatus 100 configured as described above will be described with reference to FIG. 2.
FIG. 2 is a flowchart showing a control procedure performed by the computer 120 in the liquid material evaluation apparatus.
As shown in Figure 2, a group of fluorescence spectra were measured using a spectrophotometer in advance by changing the fluorescence fingerprint or excitation wavelength by several nanometers (for example, by 5 nm) for a fluorescent marker compound in a liquid substance to be measured. , the LED light source is switched to an LED light source that emits an excitation wavelength effective for measurement selected by the user (step S1).

Next, the liquid material is irradiated with excitation light from the switched LED light source (irradiation unit) (step S2). The irradiation time, irradiation intensity, etc. of the excitation light are appropriately set depending on the fluorescent marker compound in the liquid. In addition, at this time, the liquid material may be transported by a transport mechanism so as to be irradiated at a desired position, or if the liquid material is a dope or a coating liquid, it may be transported in-line in the film forming apparatus. It is preferable to do so.

Next, the liquid substance is irradiated with excitation light, and the fluorescence from the fluorescent marker compound in the liquid substance excited by the light of the excitation wavelength is received as a spectroscopic spectrum by a spectrometer (light receiving unit), that is, the fluorescence spectrum is observed. (Step S3), the peak wavelength and intensity are measured based on the fluorescence spectrum, that is, data regarding the peak intensity shift degree is acquired (spectrum analysis) (Step S4), and the acquired data is transmitted to a computer.
Based on the data regarding the peak intensity shift degree transmitted to the computer, the content of the test object is calculated based on a calibration curve prepared in advance, that is, data processing is performed (step S5).
It is determined whether the calculated content of the inspection object is within the specified value range (step S6), and if it is within the range (step S6; YES), it is determined that there is no abnormality and the process ends. If it is outside the range (step S6; NO), it is determined that there is an abnormality, and a warning is issued by display or sound (step S7), and the abnormality is displayed, such as the location, time, and type of abnormality where the abnormality occurred. An occurrence record is taken (step S8), and the process ends.

<Application example of liquid substance evaluation device>
(Application example 1)
A case will be described in which the liquid substance evaluation device of the present invention is applied during the film forming process of an optical film.
The optical film can be formed by a solution casting method or a melt casting method, but in the following description, an example in which the solution casting method is used will be described.
FIG. 3 is a diagram schematically showing an example of a dope preparation process, a casting process, a drying process, and a winding process of the solution casting film forming method.
A fine particle dispersion liquid in which a solvent and a matting agent are dispersed by a dispersing machine passes from a charging tank 41 through a filter 44 and is stocked in a stock tank 42. On the other hand, the cycloolefin resin, which is the main dope, is dissolved in the melting pot 1 together with the solvent and the fluorescent marker compound according to the present invention, and the matting agent stored in the stock pot 42 is appropriately added and mixed. Form a dope. The obtained main dope is filtered from the filter 3 and stock pot 4 to the filter 6, additives are added through the confluence pipe 20, mixed in the mixer 21, and the liquid is sent to the pressure die 30.

On the other hand, additives (for example, ultraviolet absorbers, etc.) are dissolved in a solvent, passed from the additive charging tank 10 through the filter 12, and stored in the stock tank 13. Thereafter, it passes through a filter 15, passes through a conduit 16, and is mixed with the main dope by a confluence pipe 20 and a mixer 21.

The main dope fed to the pressure die 30 is cast onto a metal belt-shaped support 31 to form a web 32, which is peeled off at a predetermined peeling position 33 after drying to obtain an original film. The peeled web 32 is passed through a number of transport rollers and dried until a predetermined amount of residual solvent is reached, and then stretched by a stretching device 34 to a predetermined stretching ratio in the longitudinal direction or the width direction. At the same time, the solvent is heated to a predetermined amount of residual solvent. After stretching, the film is dried by a drying device 35 while being passed through conveying rollers 36 until a predetermined amount of residual solvent is reached, and then wound into a roll by a winding device 37.

In the solution casting film forming method as described above, the liquid material evaluation device of the present invention is preferably arranged as follows, depending on the purpose of detecting the identity of the liquid material.
(1) When the purpose is to detect the state of the dope before filtration, it is preferable to arrange it between the liquid feeding pump 2 and the filter 3.
(2) When the purpose is to detect the state of the dope before the confluence pipe 20, it is preferable to arrange it between the filter 6 and the conduit 8 or between the filter 15 and the conduit 16.
(3) When the purpose is to detect the state of the dope after merging, it is preferable to arrange it between the mixer 21 and the pressure die 30.
By arranging the liquid substance evaluation device of the present invention during the process of solution casting film forming method, for example, the fluorescence spectrum of the dope (liquid substance) can be measured at any time, and the water content in the dope can be measured at any time. If there is a minute change in the amount or impurities, it can be detected easily and quickly.

The dope used in the solution casting film forming method may contain at least a solvent, a resin, and a non-reactive additive (fluorescent marker compound).
The resin used in the dope according to the present invention is preferably a cycloolefin resin, an acrylic resin, a triacetylcellulose resin, or the like. The cycloolefin resin will be explained below.

《Cycloolefin resin》
The cycloolefin resin contained in the dope according to the present invention is preferably formed from a resin composition containing at least one hydrogen bond accepting group. In general, cycloolefin resins are hydrophobic resins, so they tend to separate if there is moisture when formed into a film, which is not preferable from the perspective of transparency, but resin compositions containing at least one hydrogen bond-accepting group By forming hydrogen bonds with the hydroxyl groups of alcohols and hydroxyl groups of hindered phenol compounds, it is possible to maintain transparency even when it contains some moisture; Strength is improved.
"Hydrogen bond-accepting group" refers to a functional group that accepts a hydrogen atom when forming a hydrogen bond.

Examples of the hydrogen bond-accepting group include an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an allyloxycarbonyl group, a cyano group, and an amide group. group, an imide ring-containing group, a triorganosiloxy group, a triorganosilyl group, an acyl group, an alkoxysilyl group having 1 to 10 carbon atoms, a sulfonyl-containing group, and a carboxy group. To explain these polar groups in more detail, examples of the alkoxy groups include methoxy and ethoxy groups; examples of the acyloxy groups include alkylcarbonyloxy groups such as acetoxy and propionyloxy groups; and arylcarbonyloxy groups such as benzoyloxy groups; examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups; examples of allyloxycarbonyl groups include phenoxycarbonyl groups and naphthyloxycarbonyl groups. Examples of triorganosiloxy groups include trimethylsiloxy groups, triethylsiloxy groups, etc.; examples of triorganosilyl groups include trimethylsilyl groups, triethyl groups, etc. Examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.

The amount of the cycloolefin resin containing the hydrogen bond-accepting group contained in the resin component is not particularly limited, but the content is preferably 10 to 100% by mass. If the content is 10% by mass or more, the resulting ring-opened copolymer will easily exhibit solubility in solvents such as toluene or dichloromethane, so it is preferable. It is more preferable that the amount is within the range of % by mass.

Examples of the cycloolefin resin according to the present invention include the following (co)polymers.

[In the formula, p is 0 or 1, and m is 0 or an integer of 1 or more. R ¹ to R ⁴ each independently represent a hydrogen atom, a hydrocarbon group, a halogen atom, or a hydrogen bond-accepting group. Furthermore, two or more of R ¹ to R ⁴ may be bonded to each other to form an unsaturated bond, a monocyclic ring, or a polycyclic ring, and this monocyclic ring or polycyclic ring may have a double bond. or may form an aromatic ring. ]
In the present invention, the preferred proportion of hydrogen bond-accepting groups in the cycloolefin resin is that in general formula (I), 1 to 2 of R ¹ to R ⁴ have hydrogen bond-accepting groups.

Furthermore, the proportion of hydrogen bond-accepting groups in the cycloolefin resin can be identified using, for example, carbon-13 nuclear magnetic resonance ( ¹³ CNMR) spectroscopy.

Further, in the general formula (I), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms, and at least one of R ² and R ⁴ is One is a polar hydrogen bond-accepting group other than a hydrogen atom or a hydrocarbon group, and p and m are m=1 and p=0 from the viewpoint of having a high glass transition temperature and excellent mechanical strength. Something is preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl and propyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl such as vinyl, allyl and propenyl groups; Groups include aromatic groups such as phenyl, biphenyl, naphthyl, and anthracenyl groups. These hydrocarbon groups may be substituted, and examples of the substituents include halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and phenylsulfonyl groups.

The preferred molecular weight of the cycloolefin resin according to the present invention is 0.2 to 5 cm ³ /g, more preferably 0.3 to 3 cm ³ /g, particularly preferably 0.4 to 1. 5 cm ³ /g, and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average The molecular weight (Mw) is preferably in the range of 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

By having the intrinsic viscosity [η] inh, number average molecular weight, and weight average molecular weight within the above ranges, the heat resistance, water resistance, chemical resistance, and mechanical properties of the cycloolefin resin and the cycloolefin resin film according to the present invention can be improved. As a result, the molding processability is improved.

The glass transition temperature (Tg) of the cycloolefin resin according to the present invention is usually 110°C or higher, preferably 110 to 350°C, more preferably 120 to 250°C, particularly preferably 120 to 220°C. When Tg is 110° C. or higher, deformation due to use under high temperature conditions or secondary processing such as coating and printing is suppressed, which is preferable. Further, it is preferable that the Tg is 350° C. or less because deterioration of the resin due to molding or heat during molding is suppressed.

As the cycloolefin resin described above, commercially available products can be preferably used. Examples of commercially available products are those sold by JSR Corporation under the trade names Arton G, Arton F, Arton R, and Arton RX. and can be used.

"solvent"
Examples of the solvent contained in the dope according to the present invention include organic solvents.
Examples of the organic solvent include chlorinated solvents such as chloroform and dichloromethane; aromatic solvents such as toluene, xylene, benzene, and mixed solvents thereof; and methanol, ethanol, isopropanol, n-butanol, and 2-butanol. Alcohol solvents; methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethyl formamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; and the like. These solvents may be used alone or in combination of two or more.

Further, the organic solvent is preferably a mixed solvent of a good solvent and a poor solvent, and the good solvent is, for example, dichloromethane as a chlorinated organic solvent, methyl acetate, ethyl acetate as a non-chlorinated organic solvent, etc. , amyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1- Propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, etc. Among them, dichloromethane is preferred. The good solvent is preferably used in an amount of 55% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, based on the total amount of the solvent.

The poor solvent is preferably an alcoholic solvent, and the alcoholic solvent is preferably selected from methanol, ethanol, and butanol from the viewpoint of improving strippability and enabling high-speed casting. Among these, it is preferable to use methanol or ethanol. When the proportion of alcohol in the dope is high, the web gels, making it easier to peel off from the metal support, and when the proportion of alcohol is low, it is difficult to use cycloolefin resins and other compounds in non-chlorinated organic solvent systems. It also plays a role in promoting the dissolution of.
In the present invention, from the viewpoint of improving the flatness of the resulting optical film, it is preferable to form the film using a dope having an alcohol concentration within the range of 0.5 to 15.0% by mass.

《Non-reactive additives》
Examples of non-reactive additives (fluorescent marker compounds) contained in the dope according to the present invention include the aforementioned antioxidants (for example, Irganox 1076 (manufactured by BASF Japan), dyes (NIR dyes, NUV dyes), etc. .

《Other additives》
In addition, matting agents such as plasticizers, retardation increasing agents, and silica particles described in JP-A-2017-90872 can be added to the dope according to the present invention.

(Application example 2)
Next, a case will be described in which the liquid substance evaluation apparatus of the present invention is applied during the process of applying a coating liquid for a hard coat layer to be applied to a functional film.
FIG. 4 is a schematic diagram showing an example of a hard coat layer forming apparatus used when manufacturing a functional film.
The hard coat layer forming apparatus is a so-called roll-to-roll type apparatus. The hard coat layer forming device 130 includes a feed roller 132a,

conveyance rollers

133a, 133b, 133c, 133d, and 133e, a hard coat layer forming coating liquid application device 134, a heating drying section 135, a conveyance roller 136, and an ultraviolet ray It includes an irradiation device 137 and a winding roller 132b.

In such a hard coat layer forming device 130, a film 131 having a base material and a functional layer is fed out from a feeding roller 132a. Then, the coating liquid for forming a hard coat layer is applied by the coating liquid coating device 134 onto the functional layer of the film 131 or the base material after being fed out by the roller. Note that it is preferable to eliminate static electricity from the film before applying the coating liquid for forming a hard coat layer.
Examples of the coating liquid application device include a die coater, a gravure coater, and a comma coater.

The base material coated with the coating liquid for forming a hard coat layer is conveyed to the heating drying section 135 via

conveyance rollers

133b and 133c. In the drying section, the solvent in the coating liquid is dried. The drying means is not particularly limited, and hot air drying, infrared drying, and microwave drying are used. Although four drying devices are shown in the heating drying section 135 in FIG. 4, the drying is not limited to using a plurality of drying devices in this way, and drying can be performed using only one drying device. Good too. The drying temperature at this time is appropriately set at a temperature that allows removal of the solvent used, but is usually 70 to 120°C.

The base material coated with the coating liquid for forming a hard coat layer is conveyed via a conveyance roller 133d for ultraviolet irradiation by an ultraviolet irradiation device 137.
In the ultraviolet irradiation device 137, the ultraviolet curing resin is cured by the irradiated ultraviolet light. As the ultraviolet irradiation device, for example, an ultraviolet lamp such as a high pressure UV lamp (high pressure mercury lamp) or a metal halide lamp can be used. Although an ultraviolet irradiation device is shown in FIG. 4, other curing devices such as a heating device may be used depending on the curing resin used. In the case of polysiloxane hard coat materials, after coating, after drying the solvent, heat treatment is performed within a temperature range of 50 to 150°C for 30 minutes to several days in order to promote curing and crosslinking of the hard coat material. It is preferable.

When using an active energy ray-curable resin, its reactivity varies depending on the irradiation wavelength, illumination intensity, and light amount of the active energy ray, so it is necessary to select optimal conditions depending on the resin used. For example, when an ultraviolet lamp is used as the active energy ray, the illumination intensity is preferably 50 to 1500 mW/cm ² and the irradiation energy amount is preferably 50 to 1500 mJ/cm ² .

A hard coat layer is formed on the base material or functional layer by the ultraviolet irradiation treatment.
The thickness of the formed hard coat layer is preferably 0.1 to 20 μm, more preferably 1 to 15 μm, and even more preferably 3 to 10 μm. If it is 0.1 μm or more, hard coat properties tend to improve, and if it is 20 μm or less, curling of the hard coat layer is small and flexibility tends to be maintained.

In addition, although the form in which the hard coat layer is formed on the base material or the functional layer has been described above, the hard coat layer is not limited to this form, and the hard coat layer may be formed on other intermediate layers, etc. .

In the above-described hard coat layer forming apparatus, the liquid material evaluation apparatus of the present invention is applied to, for example, the coating liquid applying apparatus 134, the vicinity of the conveying roller 133b immediately after applying the hard coat layer forming coating liquid, or the drying part. It is preferable to arrange it between the conveyance roller 133c and the conveyance roller 133d during drying, or near the conveyance roller 133d immediately after drying.
By arranging the liquid substance evaluation device of the present invention during the hard coat layer forming process, it is possible to monitor, for example, the fluorescence spectrum of the coating liquid for forming the hard coat layer or the coated film of the hard coat layer at any time. It is possible to easily and quickly detect minute fluctuations in the water content, impurities, etc. of the coating solution for forming a hard coat layer or the coating film.

Furthermore, the hard coat layer forming coating liquid used in the hard coat layer forming step may contain at least a solvent, a resin, and a non-reactive additive (fluorescent marker compound).

"resin"
Examples of the resin used in the coating liquid for forming a hard coat layer according to the present invention include thermosetting resins and active energy ray-curing resins. Active energy ray-curable resins are preferred because they are easy to mold. Such cured resins can be used alone or in combination of two or more. Moreover, a commercially available product or a synthetic product may be used as the cured resin.

Active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams.
As the active energy ray-curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and is cured by irradiation with active energy rays such as ultraviolet rays or electron beams to form an active energy ray hard coat layer. is formed. Typical active energy ray-curable resins include ultraviolet curable resins and electron beam curable resins, but ultraviolet curable resins that are cured by ultraviolet irradiation are preferred. One type of active energy ray-curable resin may be used alone, or two or more types may be used in combination.

As the UV-curable resin, for example, UV-curable urethane acrylate resin, UV-curable polyester acrylate resin, UV-curable epoxy acrylate resin, UV-curable polyol acrylate resin, UV-curable epoxy resin, etc. are preferably used. Among these, UV-curable urethane acrylate resins and UV-curable polyol acrylate resins are preferred.

Ultraviolet curable urethane acrylate resin is generally made by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and then adding 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate (hereinafter acrylate includes methacrylate). 2-hydroxypropyl acrylate) can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by Dainippon Ink Co., Ltd.) and 1 part of Coronate L (manufactured by Nippon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. It will be done. As the ultraviolet curable urethane acrylate resin, commercially available products may be used, and examples of commercially available products include Beam Set (registered trademark) 575, 577 (manufactured by Arakawa Chemical Industry Co., Ltd.), Shiko (registered trademark) UV series, etc. be able to.

Examples of ultraviolet curable polyester acrylate resins include those formed by reacting polyester polyol with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as described in JP-A-59-151112. Those described can be used.

Examples of ultraviolet curable epoxy acrylate resins include those produced by making epoxy acrylate into oligomers, adding a reactive diluent and a photopolymerization initiator to the oligomers, and reacting them. Those described can be used.

Examples of UV-curable polyol acrylate resins include ethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol. Examples include pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate. As the ultraviolet curable polyol acrylate resin, commercially available products may be used, and examples of the commercially available products include Sartomer SR295 and SR399 (manufactured by Sartomer Co., Ltd.).

Additionally, a polymerizable silicone compound may be used in combination with an ultraviolet curable resin (or alone). The polymerizable silicone compound is preferably used in combination with the ultraviolet curable resin.

A polymerizable silicone compound is a compound that has a main skeleton (silicone skeleton) formed by siloxane bonds and a polymerizable group in the molecule.

The polymerizable group is a group that can be polymerized with the ultraviolet curable resin, and includes groups having a polymerizable double bond such as a (meth)acryloyl group and a (meth)acryloyloxy group. Preferably it is a (meth)acryloyl group. Therefore, the preferred polymerizable silicone compound is preferably silicone (meth)acrylate or silicone (meth)acrylate oligomer (hereinafter collectively referred to as silicone (meth)acrylate).

In addition, the polymerizable silicone compound is an organically modified polymerizable silicone compound that contains a moiety in the molecule that improves compatibility with the ultraviolet curable resin. It is preferable that there be. Such organically modified polymerizable silicone compounds include, for example, urethane-modified, amino-modified, alkyl-modified, epoxy-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkyl polyether-modified, epoxy/polyether-modified or polyether-modified. Examples include polymerizable silicone compounds.

For example, when the ultraviolet curable resin includes an ultraviolet curable urethane acrylate resin, the polymerizable silicone compound is preferably a urethane-modified silicone (meth)acrylate. Urethane-modified silicone (meth)acrylate is produced by, for example, reacting a silicone compound having OH at both ends with a polyvalent isocyanate to obtain a terminal isocyanate silicone compound, and then combining the terminal isocyanate silicone compound with the hydroxyl group-containing (meth)acrylate. Obtained by reacting.

Commercially available products can be used as the polymerizable silicone compound, and examples of the commercially available products include EBECRYL1360, EBECRYL350, KRM8495 (manufactured by Daicel Allnex), CN9800, and CN990 (manufactured by Arkema).

Note that the polymerizable silicone compound also forms a polymer, so it becomes a polymerizable component of the resin.

It is preferable to use a photopolymerization initiator (radical polymerization initiator) for the ultraviolet curable resin. As photopolymerization initiators, benzoin and its alkyl ethers such as penzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy- Acetophenones such as 2-phenylacetophenone and 1-hydroxycyclohexylphenyl ketone; Anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; Thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds can be used. These can be used alone or in combination of two or more. In addition, it can be used in combination with photoinitiation aids such as tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate. can. Commercially available photopolymerization initiators may be used, such as Irgacure (registered trademark) -184, 819, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (manufactured by BASF Japan Co., Ltd.), Darocure (registered trademark)-1173 (manufactured by Merck Co., Ltd.), Ezacure-KIP150, TZT (manufactured by DKSH Japan Co., Ltd.), Kayacure (registered trademark) BMS, DMBI (manufactured by Nippon Kayaku Co., Ltd.), and the like. The amount of these photopolymerization initiators used is preferably 0.5 to 30 parts by weight, more preferably 1 to 25 parts by weight, based on 100 parts by weight of the polymerizable component of the resin.

Examples of thermosetting resins include polysiloxane hard coats.

The starting material for the polysiloxane hard coat is represented by the general formula RmSi(OR')n. R and R' represent an alkyl group having 1 to 10 carbon atoms, and m and n are integers satisfying the relationship m+n=4. A starting material in which a hydrolyzable group such as a methoxy group or an ethoxy group is substituted with a hydroxyl group is generally referred to as a polyorganosiloxane hard coat. By applying this and heating and curing it, a dehydration condensation reaction is promoted, and by curing and crosslinking, a hard coat is formed.

As the polyorganosiloxane hard coat, commercially available products can be used, such as Surcoat series (manufactured by Doken), SR2441 (Dow Corning Toray Co., Ltd.), KF-86 (Shin-Etsu Silicone Co., Ltd.), Perma-New (registered trademark) 6000. (California Hardcoating Company), etc. can be used.

In addition, in the case of a polysiloxane hard coat, after coating and drying the solvent, heat treatment is performed at a temperature of 50°C or higher and 150°C or lower for 30 minutes to several days in order to accelerate curing and crosslinking of the hard coat. I need. In consideration of the heat resistance of the coated substrate and the stability of the substrate when rolled, it is preferable to perform the treatment at 40° C. or higher and 80° C. or lower for 2 days or more.

The blending amount of the curable resin (including the above-mentioned polymerizable silicone compound) in the coating solution for forming the hard coat layer is 40 to 90% by mass with respect to the total 100% by mass (in terms of solid content) of the hard coat layer. It is preferably 50 to 85% by mass, and more preferably 50 to 85% by mass.

"solvent"
Examples of the solvents contained in the coating solution for forming a hard coat layer according to the present invention include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, The solvent can be appropriately selected from organic solvents such as methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture of these can be used.
The amount of solvent in the hard coat layer forming coating liquid is appropriately set in an amount that can dissolve and disperse the cured resin, and is approximately 20 to 80% by weight based on 100% by weight of the coating liquid.

《Non-reactive additives》
Non-reactive additives (fluorescent marker compounds) contained in the coating solution for forming a hard coat layer according to the present invention include the above-mentioned antioxidants (for example, Irganox 1076 (manufactured by BASF Japan) and dyes (NIR dyes, NUV dyes), etc.

《Other additives》
The coating liquid for forming a hard coat layer may contain metal oxide particles described in JP 2018-196322A for the purpose of giving the hard coat layer an infrared shielding function and improving mechanical strength. preferable.
Furthermore, a surfactant can be added to the coating liquid for forming a hard coat layer to impart leveling properties, water repellency, slipperiness, and the like. The type of surfactant is not particularly limited, and acrylic surfactants, silicone surfactants, fluorine surfactants, etc. can be used. In particular, from the viewpoint of leveling properties, water repellency, and slipperiness, it is preferable to use a fluorine-based surfactant. Examples of fluorine-based surfactants include Megafac (registered trademark) F series (F-430, F-477, F-552 to F-559, F-561, F-562, etc.) manufactured by DIC Corporation. ), Megafac (registered trademark) RS series (RS-76-E, etc.) manufactured by DIC Corporation, Surflon (registered trademark) series manufactured by AGC Seimi Chemical Co., Ltd., POLYFOX series manufactured by OMNOVA SOLUTIONS, T&K TOKA Corporation Commercially available products such as the ZX series manufactured by Daikin Industries, Ltd., the Optool series manufactured by Daikin Industries, Ltd., and the Ftergent (registered trademark) series manufactured by Neos Corporation (602A, 650A, etc.) can be used.

The method for producing the coating liquid for forming a hard coat layer is not particularly limited, and can be obtained by adding each component to a solvent and mixing appropriately. The addition order and addition method are not particularly limited, and each component may be added and mixed one after another while stirring, or may be added and mixed all at once while stirring.

In the hard coat layer forming step according to the present invention, the base material used is not particularly limited, but from the viewpoint of flexibility etc., it is preferably a resin base material, and it may be transparent or opaque. It's okay. In applications where transparency in visible light is required from the point of view of design, such as automotive applications, it is preferable to be transparent in the visible light region.

As the resin base material, for example, polyolefin film (polyethylene, polypropylene, etc.), polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, etc. can be used, and polyester film is preferable. Although the polyester film (hereinafter referred to as polyester) is not particularly limited, it is preferably a polyester having film-forming properties whose main components are a dicarboxylic acid component and a diol component. Among polyesters, terephthalic acid and 2,6-naphthalene dicarboxylic acid are the main dicarboxylic acid components, and ethylene glycol and 1,4-cyclohexanedimethanol are the diol components, in terms of transparency, mechanical strength, and dimensional stability. Polyester as a constituent component is preferred. Among them, polyesters whose main constituents are polyethylene terephthalate and polyethylene naphthalate, copolyesters consisting of terephthalic acid, 2,6-naphthalene dicarboxylic acid, and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferred.

The thickness of the base material is preferably 10 to 300 μm, more preferably 20 to 150 μm. Further, the base material may be a stack of two or more sheets, and in this case, the types thereof may be the same or different.

The resin base material can be manufactured by a conventionally known general method. The resin base material may be an unstretched film, a unidirectionally stretched film, or a biaxially stretched film. Stretched films are preferred from the viewpoint of improving strength and suppressing thermal expansion.

The functional layer formed on the base material may be any functional layer as long as it is a thin film that provides some function on the base material. Examples of functional layers include optical films that transmit or reflect/absorb specific light rays (e.g., antireflection films, infrared shielding films, ultraviolet shielding films, etc.), and barrier films that suppress the transmission of oxygen and/or water vapor. , polarizing film, retardation film, photosensitive film, etc.

Here, the film having a base material and a functional layer is sufficient as long as it has a base material and a functional layer. There are also forms in which a functional layer is provided on the intermediate layer, forms in which another intermediate layer is provided on the opposite side of the base material to the functional layer, forms in which another intermediate layer is provided on the functional layer, etc. include.

The material constituting the functional layer is appropriately selected depending on the desired functional layer. For example, metal oxides such as aluminum, silica, zirconia, tantalum oxide, titanium oxide, tin oxide, and tin-doped indium oxide, metal oxynitrides such as silicon oxynitride, metals such as silver, gold, and copper, and fluoride. Examples include metal fluorides such as magnesium, polymers, and conductive polymers such as polythiophene. It is preferable that the functional layer contains a polymer because the conductivity is low and the effects of the present invention can be more easily obtained.

The functional layer can contain various additives as necessary. Specifically, various anionic, cationic or nonionic surfactants; dispersants such as polycarboxylic acid ammonium salts, allyl ether copolymers, benzenesulfonic acid sodium salts, graft compound dispersants, polyethylene glycol type nonionic dispersants; It may contain various known additives such as a pH adjuster and an antifoaming agent.

The thickness of the functional layer is appropriately set so as to satisfy the required function, and is, for example, about 10 nm to 100 μm.

(Application example 3)
Furthermore, the liquid substance evaluation device of the present invention can be applied during the process of applying a coating liquid for forming an antistatic layer to be provided on a near-infrared reflective film.
In this case, the coating liquid for the antistatic layer can be applied using a coating liquid coating device (such as a gravure coater) in the same manner as in Application Example 2 described above. Specifically, in an apparatus for forming an antistatic layer, the liquid substance evaluation apparatus of the present invention can be used, for example, in a coating liquid applicator, near a conveyance roller immediately after applying a coating liquid for forming an antistatic layer, During drying in the subsequent drying section, it is preferable to arrange it near the conveyance roller immediately after drying.

By disposing the liquid material evaluation device of the present invention during the antistatic layer forming process as described above, it is possible to monitor, for example, the fluorescence spectrum of the antistatic layer forming coating solution or the applied antistatic layer coating film at any time. It is possible to easily and quickly detect minute fluctuations in the water content, impurities, etc. of the coating solution for forming an antistatic layer or the coating film.

As the coating solution for forming an antistatic layer, a coating solution for forming an antistatic layer containing a known conductive composition can be used, and the coating solution contains at least a solvent, a resin, and a non-reactive additive (fluorescent marker compound). All you have to do is stay there.

"resin"
The resins used in the coating solution for forming an antistatic layer according to the present invention include polyester resin, acrylic modified polyester resin, polyurethane, acrylic resin, vinyl resin, vinylidene chloride resin, polyethyleneimine vinylidene resin, polyethyleneimine, polyvinyl alcohol, modified Polyvinyl alcohol, cellulose ester resin, gelatin and the like are preferred. The details of these resins are as described in Japanese Patent No. 5811536.

"solvent"
Examples of the solvent contained in the coating solution for forming an antistatic layer according to the present invention include water or an organic solvent, and examples of the organic solvent include methyl ethyl ketone, acetone, acetylacetone, and the like.

《Non-reactive additives》
Non-reactive additives (fluorescent marker compounds) contained in the coating solution for forming an antistatic layer according to the present invention include the above-mentioned antioxidants (for example, Irganox 1076 (manufactured by BASF Japan) and dyes (NIR dyes, NUV dyes), etc.

《Conductive composition》
The conductive composition contained in the coating solution for forming an antistatic layer according to the present invention includes, for example, polyaniline and its derivatives, preferably water-soluble sulfonated polyaniline, organic solvent-soluble polypyrrole, that is, long-chain alkyl group substituent bond. Examples include polypyrrole, polythiophene and derivatives thereof.

Moreover, it is preferable to also use metal oxides as the conductive composition. Examples of metal oxides include ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅ , etc., or composite oxides thereof. In particular, SnO ₂ (tin oxide) is preferred from the viewpoint of miscibility with the binder, conductivity, transparency, and the like. As an example of containing a different element, Sb, Nb, a halogen element, etc. can be added to _SnO2 . The amount of these different elements added is preferably in the range of 0.01 to 25 mol%, particularly preferably in the range of 0.1 to 15 mol%.
Specific examples of the above conductive composition are as described in Japanese Patent No. 5811536.

(Application example 4)
Furthermore, the liquid substance evaluation device of the present invention can also be applied during the process of forming a near-infrared reflective film. That is, it can be applied during the process of coating a coating solution for a high refractive index layer and a low refractive index layer formed on a transparent support, and in this case as well, the coating can be carried out in the same manner as in Application Example 2 described above. A coating liquid for a high refractive index layer or a low refractive index layer can be applied using a liquid coating device (such as a gravure coater).
Specifically, in an apparatus for forming a high refractive index layer and a low refractive index layer, the liquid substance evaluation apparatus of the present invention is, for example, a coating liquid coating apparatus, a coating liquid coating apparatus for forming a high refractive index layer or a low refractive index layer, etc. It is preferable to arrange it near the transport roller immediately after applying the liquid, during drying in the drying section after application, or near the transport roller immediately after drying.

By disposing the liquid substance evaluation device of the present invention during the process of forming a high refractive index layer or a low refractive index layer, for example, the coating liquid for forming a high refractive index layer or a low refractive index layer, the coating The fluorescence spectrum of the coating film of the high refractive index layer or low refractive index layer can be measured at any time. If there is a change, it can be detected easily and quickly.

As the coating liquid for forming a high refractive index layer and the coating liquid for forming a low refractive index layer, known coating liquids for forming a high refractive index layer and coating liquid for forming a low refractive index layer (see, for example, Japanese Patent No. 5593916) are used. It is sufficient that it contains at least a solvent, a resin, and a non-reactive additive (fluorescent marker compound).

"resin"
Examples of the resin used in the coating liquid for forming a high refractive index layer according to the present invention include hydrophilic resins.
Examples of the hydrophilic resin include water-soluble resins, water-dispersible resins, colloid-dispersed resins, and mixtures thereof. Specific examples of hydrophilic resins include acrylic, polyester, polyamide, polyurethane, and fluorine resins, such as polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, casein, starch, agar, and carrageenan. , polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, cellulose, hydroxyl ethyl cellulose, carboxyl methyl cellulose, hydroxyl ethyl cellulose, dextran, dextrin, pullulan, water-soluble polyvinyl butyral, and other polymers. Among these, polyvinyl alcohol is preferred.
One type of polymer used as the binder resin may be used alone, or two or more types may be mixed and used as necessary.

There is no particular restriction on the molecular weight of the polymer used as the binder resin for the high refractive index layer, but polyvinyl alcohol obtained by hydrolyzing vinyl acetate preferably has an average degree of polymerization of 1,000 or more, particularly 1,500 to 1,500. 5000 is preferably used. Furthermore, the degree of saponification is preferably 70 to 100%, particularly preferably 80 to 99.5%.

"solvent"
When using a water-soluble resin, a mixture containing water as the main component and optionally a hydrophilic organic solvent can be used.

Examples of hydrophilic solvents include alcohols such as methanol, ethanol, 2-propanol, and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethyl ether. , ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, ketones such as acetone, methyl ethyl ketone, acetylacetone, and cyclohexanone, and aromatic carbonization such as benzene, toluene, and xylene. Examples include hydrogen, aliphatic hydrocarbons such as heptane, hexane, pentane, decane, and cyclohexane, and one or more of these can be used. From an environmental point of view, it is particularly preferable to use water and alcohols as the solvent for the coating solution.

《Non-reactive additives》
Non-reactive additives (fluorescent marker compounds) contained in the coating solution for forming a high refractive index layer according to the present invention include the above-mentioned antioxidants (for example, Irganox 1076 (manufactured by BASF Japan) and dyes (NIR dyes, NUV dye), etc.

《Metal oxide》
The coating liquid for forming a high refractive index layer according to the present invention preferably contains a metal oxide.
Examples of such metal oxides include TiO ₂ (titanium oxide), SiO ₂ , ZrO ₂ , Al ₂ O ₃ , ZnO, Sb ₂ O ₃ , ZrSiO ₄ , zeolite, and the like.

As the coating liquid for forming a low refractive index layer, a known coating liquid for forming a low refractive index layer can be used, as long as it contains at least a solvent, a resin, and a non-reactive additive (fluorescent marker compound).

"resin"
As the resin contained in the coating liquid for forming a low refractive index layer, a small amount of the hydrophilic binder resin contained in the coating liquid for forming a high refractive index layer mentioned above can be used.

"solvent"
As the solvent contained in the coating liquid for forming a low refractive index layer, the solvent contained in the coating liquid for forming a high refractive index layer mentioned above can also be used.

《Non-reactive additives》
Non-reactive additives (fluorescent marker compounds) contained in the coating solution for forming a low refractive index layer according to the present invention include the above-mentioned antioxidants (for example, Irganox 1076 (manufactured by BASF Japan) and dyes (NIR dyes, NUV dye), etc.

《Metal oxide》
The coating liquid for forming a low refractive index layer according to the present invention also preferably contains the metal oxide contained in the above-mentioned coating liquid for forming a high refractive index layer.

The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. In addition, in the following examples, unless otherwise specified, operations were performed at room temperature (25° C.). Further, unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively.

[Sample 1]
(Resin 1)
As the resin containing the cycloolefin polymer, hydrogenated norbornene resin ("Arton G7810" manufactured by JSR Corporation) was used. Hereinafter, this cycloolefin resin will be referred to as "COP".

(Preparation of liquid material 1)
Liquid material (dope for optical film) 1 having the following composition was prepared. First, dichloromethane was added to a pressurized dissolution tank. Next, the COP was charged into a pressurized dissolution tank while being stirred. Next, an antioxidant ("Irganox 1076" manufactured by BASF Japan Co., Ltd.) was added as a fluorescent marker compound, and completely dissolved while stirring.
COP: 100 parts by mass Dichloromethane: 280 parts by mass Irganox1076: 100 parts by mass

[Sample 2]
(Preparation of liquid material 2)
Liquid material (dope for optical film) 2 was prepared in the same manner as in the preparation of liquid material 1 except that the solvent (dichloromethane) was not added.

[Sample 3]
(Preparation of liquid material 3)
A liquid material (dope for optical film) 3 was prepared in the same manner as in the preparation of liquid material 1 except that COP was not added.

[Sample 4]
(Preparation of liquid material 4)
Liquid material (dope for optical film) 4 was prepared using the same procedure as in the preparation of liquid material 1, except that the fluorescent marker compound was changed to Elecut S-418 (manufactured by Takemoto Yushi Co., Ltd.) (reactive additive: chelating agent). did.

[Sample 5]
(Preparation of liquid material 5)
A liquid material (dope for optical film) 5 having the following composition was prepared. First, dichloromethane and ethanol (92% by mass of dichloromethane, 8% by mass of ethanol) were added to a pressurized dissolution tank. Next, the COP was charged into a pressurized dissolution tank while being stirred. Next, an antioxidant ("Irganox 1076" manufactured by BASF Japan Co., Ltd.) was added as a fluorescent marker compound, and completely dissolved while stirring.
COP: 100 parts by mass Dichloromethane: 260 parts by mass Ethanol: 22 parts by mass Irganox1076: 100 parts by mass

[Sample 6]
(Preparation of liquid material 6)
A liquid material (dope for optical film) 6 was prepared in the same manner as in the preparation of liquid material 5, except that the resin was changed to cellulose acylate (degree of acetyl group substitution: 2.80).

[Sample 7]
(Preparation of liquid material 7)
Liquid material (dope for optical film) 7 was prepared in the same manner as in the preparation of liquid material 5, except that the resin was changed to Delpet 80N (manufactured by Asahi Kasei Chemicals, polymethyl methacrylate).

[Sample 8]
(Preparation of liquid material 8)
A liquid material (dope for optical film) 8 was prepared in the same manner as in the preparation of liquid material 5, except that the fluorescent marker compound was changed to the following compound A (NIR dye) (100 mass ppm).

[Sample 9]
(Preparation of liquid material 9)
A liquid material (dope for optical film) 9 was prepared in the same manner as in the preparation of liquid material 5, except that the fluorescent marker compound was changed to the following compound B (NUV dye) (100 mass ppm).

[Sample 10]
(Preparation of liquid material 10)
A liquid material (dope for optical film) 10 was prepared with the same composition as liquid material 5.

[Sample 11]
(Preparation of liquid material 11)
A liquid material (dope for optical film) 11 was prepared in the same manner as in the preparation of liquid material 5, except that the amount of the fluorescent marker compound added was changed to 5000 mass ppm.

[Sample 12]
(Preparation of liquid material 12)
A liquid material (dope for optical film) 12 was prepared in the same manner as in the preparation of liquid material 5, except that the amount of the fluorescent marker compound added was changed to 10,000 mass ppm.

[Samples 13-15 and 17]
(Preparation of liquids 13 to 15 and 17)
Liquids (dopes for optical films) 13 to 15 and 17 were prepared with the same composition as Liquid 5.

[Sample 16]
(Preparation of liquid material 16)
A liquid material (dope for optical film) 16 was prepared with the same composition as liquid material 9.

[Samples 18 and 19]
(Preparation of liquids 18 and 19)
Liquids (optical film dope) 18 and 19 were prepared with the same composition as Liquid 8.

[Sample 20]
(Preparation of liquid material 20)
Beam Set 577 (manufactured by Arakawa Chemical Industries, Ltd.) (urethane resin) was used as the ultraviolet curable resin, and methyl ethyl ketone (MEK) was added as a solvent. Furthermore, 0.08% by mass of a fluorine-based surfactant (trade name: Ftergent (registered trademark) 650A, manufactured by Neos Co., Ltd.) was added, and then 100% by mass of Irganox 1076 was added as a fluorescent marker compound, and the total solid content was adjusted to 40 parts by mass to prepare a liquid material (coating liquid for forming a hard coat layer) 20.

[Sample 21]
(Preparation of liquid material 21)
While 10 parts by mass of a 3% by mass boric acid aqueous solution was heated and stirred at 45°C, 5% by mass of polyvinyl alcohol (PVA-117H, degree of polymerization 1700, degree of saponification 99.5 mol%, manufactured by Kuraray Co., Ltd.) was added as a resin. After adding 80 parts by mass of an aqueous solution, 1 part by mass of a 1% by mass aqueous solution of a surfactant (Rapisol A30, manufactured by NOF Corporation) was added, 9 parts by mass of pure water was added as a solvent, and then Irganox 1076 was added as a fluorescent marker agent. A liquid material (coating liquid for forming a low refractive index layer) 21 was prepared by adding 100 mass ppm of .

[evaluation]
<Sensitivity of peak intensity shift degree>
For each of the liquids prepared above, an excitation wavelength exhibiting the highest intensity fluorescence spectrum was selected as an effective excitation wavelength for measurement from a group of fluorescence spectra measured in advance using a spectrophotometer while changing the excitation wavelength in 5 nm increments.
The spectrophotometer used was a spectrofluorometer F-7100 (manufactured by Hitachi High-Tech Science).
For liquids 1 to 3, 5 to 7, 11 and 12 using Irganox 1076 as a fluorescent marker compound, 280 nm was selected as the effective excitation wavelength for measurement. In addition, Irganox 1076 was used as a fluorescent marker compound, but in liquid material 10 where the test object is magnesium ions, the effective excitation wavelength for measurement is 330 nm, and in liquid material 13 where the test object is benzene, it is effective for measurement. For liquid material 14 where the test object is acetone, the effective wavelength for measurement is 260 nm.For liquid material 15 where the test object is strontium chloride, the effective wavelength for measurement is 250 nm. For the liquid material 17, which is methanol, 290 nm was selected as the effective wavelength for measurement, and for the

liquid materials

20 and 21, where the test object was sodium ions, 300 nm was selected as the effective excitation wavelength for measurement. In addition, using Compound A, for liquid material 8 where the test target is water, the effective excitation wavelength for measurement is 680 nm, and for liquid material 18 where the test target is formamide, the effective wavelength for measurement is 690 nm. For liquid material 19 whose target substance is magnesium chloride, 700 nm was selected as an effective wavelength for measurement. In addition, using Compound B, 330 nm is selected as the effective excitation wavelength for measurement for liquid material 9 where the test object is water, and 340 nm is selected as the effective wavelength for measurement for liquid material 16 where the test object is ethanol. did.

Next, for each liquid substance, use the test target as shown in the table below, and if the test target is water, adjust the water content to 0.1% by mass and 1.0% by mass. Water was added. Moreover, when the test object was a magnesium ion or a sodium ion, the magnesium ion or sodium ion was added so that the content of the magnesium ion or sodium ion was 0.01% by mass and 0.1% by mass. Here, in the case of magnesium ions, _MgCl2 was added, and in the case of sodium ions, NaCl was added. Furthermore, when the test object was benzene, acetone, or formamide, benzene, acetone, or formamide was added so that the contents of the benzene, acetone, or formamide were 0.1% by mass and 1.0% by mass. When the object to be tested was strontium chloride, strontium chloride was added so that the content of the strontium chloride was 0.01% by mass and 0.1% by mass. Moreover, when the test object was ethanol or methanol, ethanol or methanol was added so that the content of the ethanol or methanol was 1% by mass and 10% by mass.
Next, each liquid material to which the test object had been added was irradiated with light having the effective excitation wavelength to measure its respective fluorescence spectrum, and the peak top fluorescence wavelength and peak intensity were measured. Then, the amount of change in fluorescence wavelength and the amount of change in peak intensity (peak intensity shift degree) due to changes in the content of the test object were calculated, and evaluation was performed based on the obtained peak intensity shift degree based on the following criteria. A, AA, and AAA of the following standards were determined to be at a level that poses no problem in practice.
(standard)
AAA: The amount of change in fluorescence wavelength exceeds 3.0%, and the amount of change in peak intensity exceeds 5.0%.
AA: The amount of change in fluorescence wavelength is more than 1.5% and not more than 3.0%, and the amount of change in peak intensity is more than 1.0% and not more than 5.0%.
A: The amount of change in fluorescence wavelength is more than 0.3% and not more than 1.5%, and the amount of change in peak intensity is more than 0.1% and not more than 1.0%.
B: The amount of change in fluorescence wavelength is 0.3% or less, and the amount of change in peak intensity is 0.1% or less.

<Haze value>
One hour after starting the production of films using Liquids 1 to 14, the haze of the films obtained was measured using a haze meter (NDH, manufactured by Nippon Denshoku Industries Co., Ltd.). Then, the measured haze was evaluated based on the following criteria. A, AA, and AAA of the following standards were determined to be at a level that poses no problem in practice.
AAA: Haze is 0.1% or less.
AA: Haze is more than 0.1% and less than 0.5%.
A: Haze is more than 0.5% and less than 1%.
B: Haze exceeds 1%.

Note that the SP values and ΔSP of the solvent, resin, marker compound, and test object used in the preparation of each sample were calculated by the method described above and shown in the table below.

As shown in the above results, it is recognized that by using the liquid material evaluation method of the present invention, the sensitivity of the peak intensity shift degree is superior to that of the comparative example, and it is possible to reduce film quality variations.

INDUSTRIAL APPLICABILITY The present invention can be applied to a liquid material evaluation method and a liquid material evaluation device that can constantly detect minute fluctuations in water content, impurities, etc. in a liquid material without using a reactive fluorescent marker. can.

1

Melting pot

3, 6, 12, 15

Filter

4, 13

Stock pot

2, 5, 11, 14

Liquid feeding pump

8, 16 Conduit 10 Additive charging pot 20 Merging tube 21 Mixer 30 Pressure die 31 Metal support 32 Web 33 Peeling position 34 Stretching device 35 Drying device 36 Conveyance roller 37 Winding device 41 Preparation pot 42 Stock pot 43 Pump

Claims

A method for evaluating a liquid material containing at least a solvent, a resin, and a non-reactive additive, the method comprising:
the non-reactive additive is a fluorescent marker compound,
a fluorescence spectrum observation step of acquiring a fluorescence spectrum at an arbitrary excitation wavelength of the liquid;
A method for evaluating a liquid material, comprising: a spectral analysis step of acquiring data regarding a peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid material and the test object from the acquired fluorescence spectrum.
The method for evaluating a liquid material according to claim 1, wherein a difference ΔSP in solubility parameters between the fluorescent marker compound and the test object in the liquid material is within a range of 6 to 22.
The method for evaluating a liquid material according to claim 1 or 2, wherein the non-reactive additive is contained in a range of 1 to 5000 ppm by mass based on the liquid material.
The method for evaluating a liquid material according to any one of claims 1 to 3, wherein the spectrum analysis step is performed inline.
Any one of claims 1 to 4, comprising a data processing step of calculating the content of the test object based on the peak intensity included in the data regarding the peak intensity shift degree using a calibration curve. Evaluation method of the described liquid material.
An apparatus for evaluating a liquid material containing at least a solvent, a resin, and a non-reactive additive,
the non-reactive additive is a fluorescent marker compound,
a fluorescence spectrum observation unit that acquires a fluorescence spectrum of the liquid at an arbitrary excitation wavelength;
An evaluation device for a liquid substance, comprising: a spectrum analysis unit that acquires data regarding a peak intensity shift degree based on the interaction between the fluorescent marker compound in the liquid substance and the test object from the acquired fluorescence spectrum.
The liquid material evaluation device according to claim 6, further comprising a data processing unit that calculates the content of the test object based on the peak intensity included in the data regarding the peak intensity shift degree and using a calibration curve.
The liquid material evaluation device according to claim 6 or 7, further comprising an information display unit that displays data regarding the peak intensity shift degree.