KR101605670B1 - Method for estimating state of ultraviolet rays curing resin and process for preparing the same - Google Patents

Abstract

1. A method of estimating the state of an ultraviolet curing resin comprising at least one main agent selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,
Wherein the ultraviolet curable resin is an ultraviolet curable resin present together with a base material containing a material that emits fluorescence by ultraviolet irradiation,
An irradiating step of irradiating the ultraviolet curable resin with ultraviolet rays having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator;
The fluorescence intensity at the wavelength of the fluorescence in which the latter is preferentially or selectively measured among the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator upon receiving the ultraviolet light irradiated in the irradiation step is measured A measuring step,
And an estimation step of estimating a state of the ultraviolet curing resin based on the fluorescence intensity measured in the measuring step.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of estimating the state of an ultraviolet-

The present invention is a method for estimating the state of an ultraviolet curing resin which is cured by ultraviolet irradiation.

Recently, in many industrial fields, ultraviolet curing method has been used as a curing method of an adhesive or a coating agent. The ultraviolet curing method has many advantages such as not dissipating harmful substances into the atmosphere, shortening the curing time, and being able to adapt to heat-sensitive materials as compared with a thermal curing method using thermal energy.

The ultraviolet curing method is generally used for an ultraviolet curing resin which is liquid before ultraviolet irradiation but changes to solid after ultraviolet irradiation. The ultraviolet curable resin includes at least one main agent selected from the group consisting of monomers and oligomers, and also includes a photopolymerization initiator. The photopolymerization initiator generates radicals and cations by receiving the ultraviolet light to be irradiated, and the resulting radicals and cations cause a curing reaction with monomers and oligomers. As the curing reaction proceeds, the monomer or oligomer changes to a polymer, resulting in a very large molecular weight and a low melting point. As a result, the ultraviolet curing resin can not maintain the liquid state and changes into a solid. Therefore, in the ultraviolet curing method, the degree of curing of the ultraviolet curing resin is determined according to the degree of polymerization.

On the other hand, it is difficult to judge whether the ultraviolet ray hardening resin is visually abnormal or not, and a method for easily judging the state of the ultraviolet ray hardening resin accompanying the hardening reaction is desired.

For example, Japanese Patent No. 2651036 (Patent Document 1) discloses a method for monitoring the degree of curing of a curable coating material, which method comprises a step of curing the ultraviolet curable material and a step of curing the ultraviolet curable material And a step of measuring light emission of the probe in order to measure the degree of curing of the ultraviolet curable material with respect to a material system comprising a probe including a fluorescent component that performs a light emission changing as a function.

Further, Japanese Patent No. 4185939 (Patent Document 2) discloses a method in which the photopolymerization initiator itself contained in the ultraviolet-curable resin itself is irradiated with the ultraviolet-curable resin under conditions of the ultraviolet-curable resin (for example, Discloses a method of estimating the state of an ultraviolet-curing resin based on knowledge that the observed fluorescence is correlated with the fluorescence of the ultraviolet curable resin. The method includes a step of causing the CPU (Central Processing Unit) The fluorescence measurement head section includes a step of irradiating the ultraviolet ray for measurement with the ultraviolet ray hardening resin to be subjected to the measurement, and a step of controlling the fluorescence intensity of the fluorescence emitted from the photopolymerization initiator contained in the ultraviolet ray hardening resin, From the measurement head, and the CPU reads the predetermined number of past fluorescence intensity data accumulated in the storage unit, Calculating a fluorescence intensity at the time point by performing an averaging process (moving average) on the basis of the calculated fluorescence intensity; and executing a state estimation process of the ultraviolet cured resin based on the calculated fluorescence intensity.

Japanese Patent No. 2651036 Japanese Patent No. 4185939

However, the method disclosed in Japanese Patent No. 2651036 is cost disadvantageous in that it uses a probe which emits light so as to change as a function of the degree of curing of the curable material, and furthermore, from the viewpoint of quality, It is often not allowed to add to the cured resin and it is often difficult to apply it to a general-purpose ultraviolet curing method.

Further, the method disclosed in Japanese Patent No. 4185939 discloses that when the ultraviolet-curing resin is present together with a substrate containing a material that emits fluorescence by irradiation with ultraviolet rays, it is contained in the substrate by ultraviolet irradiation There is a problem that fluorescence emitted from a material that emits fluorescence by ultraviolet irradiation interferes with measurement of fluorescence emitted from the photopolymerization initiator.

As a result of intensive investigation under such circumstances, the present inventors have found out a combination of both the wavelength of ultraviolet light irradiated in the irradiation step and the wavelength for measuring fluorescence emitted by receiving ultraviolet light irradiated in the irradiation step, In addition to these facts, the state of the ultraviolet-curing resin which exists together with the base material containing a material which emits fluorescence by ultraviolet irradiation and which is cured by irradiation with ultraviolet light based on the characteristics of the photopolymerization initiator is estimated And the present invention has been completed.

That is,

[1] A method for estimating the state of an ultraviolet curing resin comprising at least one subject selected from the group consisting of monomers and oligomers, and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,

Wherein the ultraviolet curable resin is an ultraviolet curable resin present together with a base material containing a material that emits fluorescence by ultraviolet irradiation,

An irradiating step of irradiating the ultraviolet curable resin with ultraviolet rays having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator;

A measurement for measuring the fluorescence intensity at a wavelength of fluorescence in which the latter is preferentially or selectively measured among fluorescence emitted from the material upon receiving the ultraviolet light irradiated in the irradiation step and fluorescence emitted from the photopolymerization initiator Step,

An estimation step of estimating a state of the ultraviolet curing resin based on the fluorescence intensity measured in the measuring step;

[2] The method according to any one of [1] to [5], wherein in the step of estimating, based on a temporal change in fluorescence intensity caused by a curing reaction of the ultraviolet curable resin during curing ultraviolet irradiation for causing a curing reaction of the ultraviolet- A method of estimating a state of an ultraviolet curable resin according to [1], which is a step of estimating a state of a resin;

[3] The method for estimating the state of ultraviolet-curing resin according to [2], wherein the estimating step is a step of estimating the state of the ultraviolet-curing resin by comparing a temporal change in the measured fluorescence intensity with a temporal change as a preset reference ;

[4] The method according to any one of [1] to [4], wherein the estimating step includes the steps of: obtaining a time required for the fluorescent intensity to generate a specific temporal change from a specific reference time point and comparing the obtained required time with a preset reference value A method of estimating the state of the ultraviolet curing resin according to [2];

[5] The method according to [1], wherein the estimating step is a step of estimating the state of the ultraviolet-curable resin based on the fluorescence intensity measured before the curing ultraviolet ray irradiation for generating the curing reaction of the ultraviolet- A method for estimating the state of a cured resin;

[6] The method according to [1], wherein the estimating step is a step of estimating the state of the ultraviolet-curable resin based on fluorescence intensity measured after curing ultraviolet irradiation for generating a curing reaction of the ultraviolet- A method for estimating the state of a cured resin;

[7] A process for producing a cured resin by curing an ultraviolet curable resin comprising at least one subject selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,
(A) a step of preparing an ultraviolet curable resin present together with a substrate containing a material containing a material that emits fluorescence by ultraviolet irradiation and a substrate containing a material that emits fluorescence by ultraviolet irradiation from an ultraviolet curable resin,

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(B) a step of irradiating curing ultraviolet ray to the prepared ultraviolet ray hardening resin to cure the ultraviolet ray hardening resin,

(C) a step of irradiating the cured ultraviolet-curable resin with ultraviolet light having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator,

(D) a wavelength of fluorescence in which the latter is preferentially or selectively measured among fluorescence emitted from the material and fluorescence emitted from the photopolymerization initiator upon receiving the ultraviolet light irradiated in the step (C) A step of measuring fluorescence intensity,

(E) a step of estimating the state of the cured ultraviolet-cured resin based on the fluorescence intensity measured in the step (D) and judging whether the quality of the ultraviolet-cured resin is good or bad. A method of producing an ultraviolet curable resin present together with a substrate containing a material that emits fluorescence by ultraviolet irradiation;

And the like.

According to the present invention, it is possible to easily estimate the state of the ultraviolet-curable resin present together with the base material containing the material that emits fluorescence by ultraviolet irradiation.

Fig. 1 is a graph showing the relationship between the intensity of ultraviolet rays for measurement (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) (Vertical axis) measured by a fluorescence spectrum analyzer (horizontal axis) and the intensity of fluorescence emitted from a model sample (vertical axis), that is, a fluorescence spectrum.
Fig. 2 is a graph showing the relationship between the intensity of ultraviolet rays for measurement (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) (Vertical axis) measured by a fluorescence spectrum analyzer (horizontal axis) and the intensity of fluorescence emitted from a model sample (vertical axis), that is, a fluorescence spectrum.
Fig. 3 is a graph showing the relationship between the intensity of ultraviolet light for measurement and the ultraviolet ray for measurement (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) (Vertical axis) measured by a fluorescence spectrum analyzer (horizontal axis) and the intensity of fluorescence emitted from a model sample (vertical axis), that is, a fluorescence spectrum.
4 is a graph showing the correlation between the cumulative light amount (horizontal axis) of the curing ultraviolet ray irradiated on the demonstration sample and the intensity (vertical axis) of the fluorescence emitted from the demonstration sample, which is measured by the fluorescence intensity measuring apparatus.

(Mode for carrying out the invention)

The state estimation method of the present invention is a method for estimating the state of an ultraviolet curing resin comprising at least one subject selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,

Wherein the ultraviolet curable resin is an ultraviolet curable resin present together with a base material containing a material that emits fluorescence by ultraviolet irradiation,

An irradiating step of irradiating the ultraviolet curable resin with ultraviolet rays having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator;

The fluorescence intensity at the wavelength of the fluorescence in which the latter is preferentially or selectively measured among the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator upon receiving the ultraviolet light irradiated in the irradiation step is measured A measuring step,

And an estimation step of estimating the state of the ultraviolet curing resin based on the fluorescence intensity measured in the measuring step.

(Ultraviolet ray hardening resin)

The "ultraviolet curable resin" to be subjected to the state estimation method of the present invention is usually a liquid before ultraviolet irradiation, but changes (cures) to solid after ultraviolet irradiation. In the present specification, the term " ultraviolet curing resin " is used generically to include both the liquid state before ultraviolet irradiation and the solid state after ultraviolet irradiation.

The ultraviolet curable resin before (before curing) ultraviolet irradiation contains at least one subject and a photopolymerization initiator selected from the group consisting of monomers and oligomers, and may also contain various additives. Upon exposure to ultraviolet light, radicals or cations generated by the photopolymerization initiator cause a curing reaction (main chain reaction and crosslinking reaction) of the monomer and oligomer. With this curing reaction, the monomer and the oligomer change into a polymer, resulting in a very large molecular weight and a low melting point. As a result, the ultraviolet curing resin changes from a liquid to a solid.

Specific examples of the monomer and oligomer include polyester acrylate, urethane acrylate, polybutadiene acrylate, silicone acrylate and epoxy acrylate. The monomer is also referred to as a monomer, and is a raw material in the case of synthesizing a polymer by a curing reaction. The oligomer is also referred to as a low polymer and has a relatively low degree of polymerization with a polymerization degree of about 2 to 20.

It is considered that the monomer and oligomer rarely emit fluorescence in that the carrier (electron) takes a structure that is difficult to move smoothly in the molecule.

The ultraviolet curing resin is present together with a substrate containing a material that emits fluorescence by ultraviolet irradiation. A substrate containing a material capable of emitting fluorescence by ultraviolet irradiation is a substrate containing a material that emits fluorescence by ultraviolet irradiation, such as polyethylene terephthalate, polycarbonate, polyethersulfone or the like. Here, "present together with the substrate" means that the substrate and the ultraviolet curing resin coexist, and at least a part of the substrate and at least a part of the ultraviolet curing resin are in contact with each other. In addition, the substrate may contain a material that does not emit fluorescence by ultraviolet irradiation. The shape of the base material is not limited, but a film-like base material is preferable. Specifically, a film made of a material that emits fluorescence by ultraviolet irradiation, a film made of a material that does not emit fluorescence by ultraviolet irradiation, and an ultraviolet curable resin layer, and an ultraviolet curable resin layer is formed between each film And laminated films.

(Photopolymerization initiator)

The "photopolymerization initiator" in the state estimation method of the present invention is a photopolymerization initiator that emits fluorescence by ultraviolet irradiation. Such a photopolymerization initiator is roughly classified into (1) a radical polymerization initiator that generates a radical upon receiving ultraviolet rays, and (2) a cation polymerization initiator that generates a cation upon receiving ultraviolet light. The radical polymerization initiator is used when the subject is an acrylic monomer or oligomer thereof, and the cationic polymerization initiator is used when the subject epoxy monomer, vinyl ether monomer or oligomer thereof. A photopolymerization initiator comprising a mixture of a radical polymerization initiator and a cation polymerization initiator may be used.

The radical polymerization initiator is largely classified into a hydrogen extraction type and an intramolecular cleavage type depending on the generation process of a radical. Examples of the hydrogen-drawing type radical polymerization initiator include benzophenone and methyl orthobenzoylbenzoate. Examples of the intramolecular cleavage type radical polymerization initiator include benzoin ether, benzyldimethyl ketal,? -Hydroxyalkylphenone,? -Aminoalkylphenone, methyl oxovbenzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, Hydroxy-2-methyl-1-phenyl-propanone, benzyl dimethyl ketal and 1,2-hydroxyalkyl phenol .

As the cationic polymerization initiator, a diphenyliodonium salt can be mentioned.

In the present specification, the "photopolymerization initiator" is not limited to the one in which the photopolymerization initiator has the ability to initiate the photopolymerization reaction, and the photopolymerization initiator may be changed by contributing to the photopolymerization reaction, or the monomer or oligomer Or a substance which does not contribute to the initiation of the photopolymerization reaction by being not present around it. In most cases, the photopolymerization initiator after the contribution to the photopolymerization initiating reaction is bonded to the end of the polymer in a state where the initial molecular size is maintained or divided into two or more molecules.

When the original photopolymerization initiator molecules are cleaved, it is considered that at least some of the molecules after cleavage contribute to fluorescence emission.

The ultraviolet curing resin is configured to cure by receiving a ultraviolet ray to cause a curing reaction. Therefore, the photopolymerization initiator which generates such a curing reaction is required to have (1) high ability to generate active species (radical or acid) for initiating the curing reaction (quantum yield, molar extinction coefficient), (2) (3) the spectrum region of the excitation energy for exerting the ability of generating the active species is in the ultraviolet region, and the like. That is, the photopolymerization initiator has a molecular structure that is easily absorbed by ultraviolet rays, and is capable of imparting (electron) energy generated by ultraviolet absorption to other molecules.

It is considered that the fluorescence intensity emitted from the photopolymerization initiator changes depending on the chemical state of such photopolymerization initiator. Thus, based on the rate of change of fluorescence intensity among the temporal change of the fluorescence intensity to be measured, the time when the photopolymerization initiator is actually consumed is estimated. In many cases, the ultraviolet curing resin contains an amount of a photopolymerization initiator multiplied by a predetermined allowance ratio to the theoretical required amount in consideration of the yield and the temperature fluctuation. Therefore, "the photopolymerization initiator is" substantially consumed "means that the active species (radical or acid, etc.) sufficient to cause the curing reaction is generated from the photopolymerization initiator. If the photopolymerization initiator is " substantially consumed ", it is considered that the increase in the measured fluorescence intensity is suppressed. Thus, when the increase rate of the fluorescence intensity starts to decrease after the increase of the fluorescence intensity is started, when the increase is stopped (the change rate becomes zero) and when the fluorescence intensity is decreased (the change rate becomes negative value) It can be considered that the photopolymerization initiator is substantially consumed.

(Survey step)

"Irradiation step" in the state estimation method of the present invention means that the intensity of fluorescence emitted from a material that emits fluorescence by ultraviolet irradiation is lower than the intensity of ultraviolet radiation having a wavelength not exceeding the intensity of fluorescence emitted from the photopolymerization initiator , And irradiating the ultraviolet curing resin.

In the case of an ultraviolet curable resin present together with a base material containing a material that emits fluorescence by ultraviolet irradiation, the fluorescence emitted from the base material is disturbed by irradiation with ultraviolet light, in addition to the weak fluorescence intensity emitted from the photopolymerization initiator , It is often difficult to measure the fluorescence emitted by the photopolymerization initiator. Therefore, it is necessary to irradiate ultraviolet rays having the wavelengths described above. The method of selecting and determining the wavelength will be described later in the section of "(Selection and determination of the wavelength of ultraviolet light to be irradiated in the irradiation step and the wavelength of fluorescence to be measured in the measuring step)".

(Measurement step)

The "measurement step" in the state estimation method of the present invention is a method in which ultraviolet light irradiated in the irradiation step is received and the latter of the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator is preferentially or selectively And the fluorescence intensity at the wavelength of the fluorescence is measured.

As described above, the photopolymerization initiator contained in the ultraviolet ray hardening resin emits fluorescence upon receiving ultraviolet rays, and at the same time, the material contained in the base material present together with the ultraviolet ray hardening resin also emits fluorescence by receiving the ultraviolet ray. That is, the photopolymerization initiator and the substrate emit fluorescence by receiving ultraviolet light, respectively. Therefore, when the fluorescence emitted from the photopolymerization initiator contained in the ultraviolet-curable resin contains the same wavelength range as the fluorescence emitted from the material contained in the base material present together with the ultraviolet-curable resin, the fluorescence emitted from the photopolymerization initiator Both the intensity of fluorescence and the intensity of fluorescence emitted from the material are measured at the same time and the change in the intensity of fluorescence emitted from the photopolymerization initiator contained in the ultraviolet curing resin can not be accurately grasped. Therefore, in order to grasp the intensity of fluorescence emitted from the photopolymerization initiator without being affected by the intensity of fluorescence emitted from the material, it is preferable that the wavelength of the ultraviolet light irradiated in the irradiation step (A) The wavelength of the fluorescence emitted from the material to be irradiated does not exceed the intensity of the fluorescence emitted from the photopolymerization initiator ", and (ii) the wavelength of the fluorescence for measuring the intensity in the measuring step is & A wavelength that allows ultraviolet rays to be irradiated in the irradiation step and allows the latter to be preferentially or selectively measured between fluorescence emitted from the material and fluorescence emitted from the photopolymerization initiator " . Here, it is very important that the above-mentioned (a) and (b) are not related to the non-linking requirement such that they exist independently of each other with technical requirements related thereto. With respect to the selected and determined measurement wavelength, a measurement filter (cut filter and / or color correction filter) capable of separating only the measurement wavelength at a wavelength, for example, is provided in the fluorescence intensity measuring section, May be preferentially or selectively measured.

(A method of selecting and determining the wavelength of ultraviolet light to be irradiated in the irradiation step and the wavelength of fluorescence to be measured in the measuring step)

The wavelength of the ultraviolet ray to be irradiated in the irradiation step and the wavelength of fluorescence to be measured in the measuring step can be selected and determined in accordance with, for example, the following method.

(I) An ultraviolet curing resin comprising at least one subject selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation is irradiated onto a substrate containing a material that emits fluorescence by ultraviolet irradiation , And a predetermined thickness to prepare a model sample.

(II) A curing ultraviolet ray having a predetermined wavelength is irradiated to a model sample produced in the above-mentioned process (I) at an arbitrary integrated amount of light, and the ultraviolet ray hardening resin is cured Make the model sample in step. Subsequently, the cumulative light quantity of the curing ultraviolet ray is changed, and a model sample having different curing steps is produced by the same method. In this way, a plurality of model samples in different curing stages are produced.

(III) For each of the plurality of model samples produced in the process (II), the intensity of fluorescence emitted by receiving the ultraviolet ray for fluorescence measurement to be irradiated is measured as a fluorescence spectrum using a fluorescence spectrum analyzer, (Fluorescence spectrum measured by a fluorescence spectrum analyzer (measured by a fluorescence spectrum analyzer)) for each wavelength of ultraviolet rays And the intensity of fluorescence emitted from the model sample).

(IV) From the waveform of the obtained fluorescence spectrum, it is possible to obtain a waveform having a waveform in which the intensity of fluorescence emitted from the model specimen varies depending on the curing step of the ultraviolet curing resin (that is, every accumulated amount of ultraviolet rays for curing) &Quot; wavelength of ultraviolet ray for fluorescence measurement to be irradiated ", which has a difference in the waveform of the fluorescence spectrum for each cumulative light quantity of the irradiated curing ultraviolet ray) is selected. Preferably, it is preferable to have a significant difference.

(V) Further, in a region of the spectrum of the light intensity spectrum for each cumulative light quantity of irradiated curing ultraviolet rays, a region exhibiting a significant difference (i.e., a "wavelength of fluorescence measured by a fluorescence spectrum analyzer") Select.

(Estimation step)

The "estimation step" in the state estimation method of the present invention is a step of estimating the state of the ultraviolet cured resin based on the fluorescence intensity measured in the measurement step. Here, as a method of "estimating the state of the ultraviolet ray hardening resin", for example, there is a method for estimating the state as described below.

(A feature seen in temporal changes in fluorescence intensity)

Wherein the estimating step includes a step of estimating a state of the ultraviolet curing resin based on a temporal change in fluorescence intensity caused by a curing reaction of the ultraviolet curing resin during curing ultraviolet irradiation for causing a curing reaction of the ultraviolet curing resin .

(1) state estimation for the degree of cure based on the rate of change of fluorescence intensity

It is considered that the fluorescence intensity to be radiated varies depending on the progress of the curing reaction of the ultraviolet ray hardening resin.

Thus, from the temporal change of the fluorescence intensity measured, the time when the degree of curing of the ultraviolet curing resin reaches the maximum curing degree is estimated based on the rate of change of the fluorescent intensity. The ultraviolet ray hardening resin often defines the standard value (catalog hardness) of the hardening degree by the manufacturers. The "maximum hardening degree" herein means a degree of hardening that the ultraviolet ray hardening resin can reach in each irradiation condition And the same applies to the following. In addition, this maximum curing degree does not always coincide with the standard value (catalog hardness).

It is considered that when the degree of curing of the ultraviolet curing resin reaches the maximum degree of curing, the increase in the measured fluorescence intensity is suppressed. Therefore, when the increase rate of the fluorescence intensity is decreased, the increase of the fluorescence intensity (the rate of change becomes zero) and the decrease of the fluorescence intensity (the change rate becomes a negative value) It can be considered that the degree of curing of the ultraviolet curing resin has reached the maximum degree of curing.

According to the state estimation on the degree of curing based on the rate of change of the fluorescent intensity, it is possible to easily estimate the point of time when the degree of curing of the ultraviolet cured resin reaches the maximum degree of curing. As a result, it is possible to avoid a situation where the irradiation time of the curing ultraviolet ray is insufficient and the curing reaction in the ultraviolet curing resin becomes insufficient. In particular, the properties of the ultraviolet ray-curable resin vary due to deterioration with the passage of time and temperature, but according to this method, the curing reaction can be generated at the optimum irradiation time at each treatment time.

(2) state estimation for the degree of cure based on the change in fluorescence intensity

It is considered that the fluorescence intensity to be radiated varies depending on the progress of the curing reaction of the ultraviolet ray hardening resin. Therefore, from the temporal change of the fluorescence intensity to be measured, the time point at which the ultraviolet-curable resin reaches the specific curing degree is estimated based on the amount of change before and after the change of the fluorescent intensity. As an example, a point of time when the difference or ratio of the fluorescent intensity to the fluorescence intensity before the start of increase exceeds a predetermined threshold value (threshold value) is found after the increase of the fluorescence intensity is started, and the curing degree of the ultraviolet- Can be regarded as having reached a specific degree of hardening. For example, it can be judged that the curing degree of the ultraviolet ray hardening resin has reached the maximum hardening degree, that is, the curing reaction of the ultraviolet ray hardening resin has progressed sufficiently, by appropriately selecting the change amount of the fluorescent intensity as the judgment reference. It is also possible to regard that the degree of curing of the ultraviolet curable resin reaches a specific degree of curing which is smaller than the maximum curing degree by using a change amount of a smaller fluorescence intensity as a criterion. In this case, the occurrence of a predetermined change in the fluorescence intensity is detected, and the curing is progressed to a desired degree of curing at that point, for example, to a degree that the member temporarily fixed with the ultraviolet curing resin does not largely move . Most of the ultraviolet ray hardening resin has a property that when the ultraviolet ray irradiation causes the hardening reaction to some extent, the hardening progresses gradually by the chain reaction without irradiation of ultraviolet ray. This chain reaction is promoted by heating the semi-cured ultraviolet curable resin. Such a curing method for stopping ultraviolet irradiation at a stage where the ultraviolet curing resin is not sufficiently cured is also possible. And is used when temporarily bonding by ultraviolet irradiation when bonding an ultraviolet curable resin to a substrate or another member. After temporary fixing, fine adjustment of the position of the base material or other member to be bonded may be performed because the ultraviolet curing resin is still thin. Such a curing method is also used in the case of collecting a plurality of products which have been semi-cured by a short-time ultraviolet ray irradiation and heating them to accelerate curing. In this case, the time for the entire curing treatment may be shortened as compared with the case where ultraviolet rays are irradiated to the maximum curing degree for each curing portion.

According to the state estimation on the degree of curing based on the amount of change in fluorescence intensity, it is possible to easily estimate the time point at which the curing degree of the ultraviolet curing resin reaches the maximum curing degree. As a result, it is possible to avoid a situation in which the curing reaction time of the curing ultraviolet ray is insufficient and the curing reaction of the ultraviolet curing resin becomes insufficient. In particular, the properties of the ultraviolet ray-curable resin vary due to deterioration with the passage of time and temperature, but according to this method, the curing reaction can be generated at the optimum irradiation time at each treatment time.

(3) state estimation for the degree of cure based on the absolute value of fluorescence intensity

It is considered that the fluorescence intensity to be radiated varies depending on the progress of the curing reaction of the ultraviolet ray hardening resin. Therefore, from the temporal change of the fluorescence intensity to be measured, the time when the curing degree of the ultraviolet curable resin reaches the specific curing degree is estimated based on the absolute value of the fluorescence intensity. As an example, it can be considered that the point at which the fluorescence intensity measured exceeds the predetermined threshold value, and the degree of curing of the ultraviolet curable resin reaches a specific degree of curing. The specific curing degree is the same as the above case in that it may be an arbitrary degree of curing having a value smaller than the maximum curing degree or the maximum curing degree.

According to the state estimation on the degree of curing based on the absolute value of the fluorescence intensity, it is possible to easily estimate the time point at which the curing degree of the ultraviolet curing resin reaches the maximum curing degree. As a result, it is possible to avoid a situation in which the curing reaction time of the curing ultraviolet ray is insufficient and the curing reaction of the ultraviolet curing resin becomes insufficient. According to this method, in the case where the curing operation is repeatedly performed under relatively stable conditions, the curing reaction can be caused to occur at the optimum irradiation time at each processing time.

(4) Estimation of the state of ultraviolet-curing resin by comparison with reference temporal change

In a production line or the like, the same type of ultraviolet curing resin is repeatedly cured under substantially the same irradiation conditions. Therefore, by taking a representative temporal change in fluorescence intensity for each type of ultraviolet-curing resin in advance, and taking a temporal change as a reference as a representative temporal change in the fluorescence intensity, by comparing with the temporal change as the reference, It is practical and effective to estimate the state of the cured resin. The comparison between the temporal change in the obtained fluorescence intensity and the temporal change as a reference includes not only the fluorescence intensity at an instant (absolute value) but also the characteristic change of the fluorescence intensity at a predetermined time from a certain point of time And extracted.

According to the estimation of the state of the ultraviolet curable resin by comparison with the temporal change as a reference, it is possible to easily estimate the state of the ultraviolet curable resin relative to the temporal change as a reference. Further, by monitoring the deviation from the reference temporal change, it is possible to detect an abnormality such as an ultraviolet curing resin early.

According to the estimation of the state of the ultraviolet-curable resin based on the time required until the above-mentioned fluorescence intensity develops a specific temporal change, by comparing the time required for the fluorescence intensity to generate a specific temporal change to a reference value, Or more. As a result, it is possible to suppress the occurrence of large quantities of defective products and the like, and to improve the production yield.

(5) Estimation of the state of the ultraviolet-curing resin based on the time required for the fluorescence intensity to cause a specific temporal change

When the same type of ultraviolet cured resin is repeatedly processed under the same irradiation conditions as in the above state estimation method, a temporal change in fluorescence intensity with respect to a representative sample is obtained in advance, and a temporal change It is practical and effective to perform the estimation of the state of the ultraviolet curing resin. As an example, the state of the ultraviolet curing resin is estimated by obtaining the time required until a specific temporal change occurs in the temporal change of the fluorescent intensity, and comparing the required time with the predetermined reference value.

(6) Estimation of state of ultraviolet cured resin before and after irradiation of curing ultraviolet ray

In a production line or the like, it is possible to estimate the state of the ultraviolet-curable resin before and after the irradiation of the ultraviolet rays for curing and to manufacture more efficiently if the presence or absence of the ultraviolet ray is judged. That is, before the curing ultraviolet ray is irradiated, the type of the ultraviolet curing resin is mistaken, the amount of the ultraviolet curing resin is miscorrected, the quality of the ultraviolet curing resin is changed, and the unintended curing reaction And so on. Further, at the time of irradiation of the curing ultraviolet ray (at the end of the irradiation), the type of the ultraviolet curing resin is mistaken, the amount of the ultraviolet curing resin is miscorrected, the quality of the ultraviolet curing resin is changed, And so on. As one example, the state of the ultraviolet curable resin is estimated based on the fluorescence intensity measured before irradiation of the curing ultraviolet ray for generating the curing reaction of the ultraviolet curable resin.

According to the estimation of the state of the ultraviolet-curable resin prior to the irradiation of the ultraviolet ray for curing, it is possible to check the abnormality of the ultraviolet-cured resin before generating the curing reaction. Thus, ultraviolet ray for curing need not be irradiated to the ultraviolet ray hardening resin which is abnormal from the beginning. Therefore, the production efficiency of the production line and the like can be improved.

Likewise, by estimating the state of the ultraviolet-curable resin after irradiation of the ultraviolet ray for curing (at the end of the irradiation), it is possible to check whether or not the ultraviolet-cured resin having undergone the curing reaction has an abnormality. As a result, it is possible to find an ultraviolet curable resin which is unsuitable for specifications such as insufficient irradiation of curing ultraviolet ray or excessive irradiation. As one example, the state of the ultraviolet curing resin is estimated based on the fluorescence intensity measured after irradiation of the curing ultraviolet ray for generating the curing reaction of the ultraviolet ray curing resin.

(State estimating device)

A state estimating apparatus which is one embodiment for realizing the state estimating method of the present invention will be described below.

The state estimating apparatus includes a state estimating unit. The state estimating unit includes a central processing unit (CPU), a display unit, an operating unit, a storage unit, and an irradiation warning unit.

The CPU outputs an irradiation instruction of ultraviolet rays for fluorescence measurement to the head for fluorescence measurement in accordance with an operation instruction from the operation unit and an irradiation state signal from the curing ultraviolet irradiation apparatus. The CPU illuminates or flashes the irradiation warning part in order to promote protection against ultraviolet rays for fluorescence measurement emitted from the fluorescent measurement head part in response to an irradiation instruction of ultraviolet ray for fluorescence measurement for the fluorescent measurement head part do. Then, the CPU receives the fluorescence intensity measured by the fluorescent measurement head, estimates the state of the ultraviolet-curable resin to be the object, and outputs the estimation result or the like to the display unit. At the same time, the CPU outputs a signal (analog or digital) indicating the fluorescence intensity measured by the head for fluorescence measurement to an external device or the like. Further, the CPU reads various data previously stored from the storage unit, and stores the measured data and the like in the storage unit.

The display unit includes, for example, a display such as a liquid crystal display (LCD) or a cathode ray tube (CRT), and displays a graph of fluorescence intensity change received from the CPU.

The operation unit is made up of various switches and receives an operation from the user and outputs an operation instruction to the CPU in accordance with the operation.

The irradiation warning unit is composed of, for example, an LED or a lamp, and indicates to the user or the like at a position close to the state estimation apparatus that ultraviolet rays for fluorescence measurement are being irradiated.

The storage unit is composed of, for example, an EEPROM (Electrically Erasable Programmable Read Only Memory) or the like, and stores measurement data and various kinds of data correlated with the type of ultraviolet curing resin.

The fluorescence measurement head section includes a light projecting driving circuit, a light projecting element, a half mirror, an optical filter, a light receiving element, a HPF (High Pass Filter), an amplifying circuit, a Sample and Hold (S / H) Digital converter (ADC).

The projection driving circuit applies a pulse-shaped voltage to the light-projecting element at a predetermined cycle in accordance with an instruction to irradiate ultraviolet rays for fluorescence measurement received from the CPU. The light emitting element is made of, for example, an ultraviolet LED, and emits ultraviolet rays for fluorescence measurement according to the pulse voltage applied by the light projecting drive circuit and emits the ultraviolet rays. In the embodiment of the present invention, the light emitting element emits ultraviolet rays for fluorescence measurement having a main emission peak at 365 nm.

The half mirror is disposed on the same optical axis as the light transmitting element and transmits the ultraviolet ray for fluorescence measurement emitted from the light transmitting element while changing the propagation path of the fluorescence emitted by the ultraviolet ray hardening resin to be measured and is guided to the optical filter . For example, the reflecting surface of the half mirror is formed by metal deposition.

The optical filter is arranged to remove extraneous light such as ultraviolet rays for fluorescence measurement emitted from the light emitting element, and is configured to attenuate light in the ultraviolet region and transmit light in the visible region. In the embodiment of the present invention, the optical filter is a filter of a dielectric multilayer film that transmits light having a wavelength of 410 nm or more.

The light receiving element is composed of, for example, a photodiode, generates a current according to the intensity of the fluorescence transmitted through the optical filter, and outputs the current to the HPF.

The HPF removes the direct current component and the low frequency component from the fluorescence intensity signal received from the light receiving element, and allows only the signal exceeding the predetermined frequency to pass through to extract the component generated by the ultraviolet ray for fluorescence measurement.

The amplifier circuit amplifies the signal that has passed through the HPF at a predetermined amplification rate (current-voltage conversion rate), and outputs the amplified signal to the S / H circuit.

The S / H circuit samples the received light intensity signal in synchronism with the light emission timing of the light emitting element, holds the sampled signal value until the next sampling, The maximum amplitude value of the signal is measured, and the measured maximum amplitude value is maintained in each cycle.

The analog-to-digital converter converts the voltage signal (analog signal) output from the S / H circuit into a digital value and outputs it to the CPU.

Next, the outline of the optical system of the head for fluorescence measurement will be described.

The optical measuring head further comprises a focusing lens. The ultraviolet rays for fluorescence measurement emitted from the light projecting element are focused on a specific diameter range of the ultraviolet curable resin through the focusing lens so that the ultraviolet curing resin, the half mirror, the focusing lens, . Fluorescence emitted from the ultraviolet curing resin propagates in the same direction as the ultraviolet ray for fluorescence measurement in the opposite direction, and is reflected by the half mirror to change the propagation path. Further, the fluorescence enters the light receiving element through the optical filter. The distance from the irradiation surface of the light emitting element to the focusing lens and the distance from the focusing lens to the ultraviolet hardening resin are made to be substantially the same.

The intensity of fluorescence emitted from a material contained in the substrate is measured by a fluorescence intensity measuring device (for example, OL301, manufactured by K.K.) using ultraviolet light for fluorescence measurement not exceeding the intensity of fluorescence emitted from the photopolymerization initiator (For example, an LED having an irradiation wavelength characteristic of the ultraviolet ray) having a wavelength of irradiation of ultraviolet rays. The same fluorescent intensity measuring apparatus as described above is irradiated with ultraviolet light for fluorescence measurement which is irradiated in the irradiating step and the fluorescence emitted from the material contained in the substrate and the fluorescence emitted from the photopolymerization initiator (For example, a cut filter) for eliminating the wavelength that allows the latter to be preferentially or selectively measured.

(State estimation of ultraviolet curing resin)

For example, the state of the ultraviolet-curable resin is estimated according to the following process. Hereinafter, four kinds of patterns A to D will be described in order. This state estimation is described in Japanese Patent No. 4185939 except that polyester resin is used as the base material.

(Pattern A)

First, the CPU judges whether it is immediately after the irradiation of the curing ultraviolet ray is started (hereinafter referred to as step 11). In the case immediately after the initiation of the curing ultraviolet ray irradiation, the fluorescence intensity acquired with the previous fluorescence intensity is set, and the process returns to step 11.

If it is determined in step 11 that it is not immediately after the start of irradiation of the curing ultraviolet ray, the CPU determines whether or not it is after the start of increase of the fluorescent intensity. Further, the start of increase in fluorescence intensity means after the CPU judges in step 12 that the start of increase in fluorescence speed is detected.

If not after the start of increase in fluorescence intensity, the CPU calculates the change rate from the difference between the fluorescence intensity obtained this time and the previous fluorescence intensity. Then, the CPU determines whether or not the calculated change speed is greater than zero. If the calculated change rate is greater than zero, the CPU determines that the fluorescence intensity starts to increase (hereinafter referred to as step 12), stores the fluorescence intensity at that time as the reference fluorescence intensity, and returns to the original process . On the other hand, if the calculated change speed is not greater than zero, the CPU returns to the original process. Further, the value for judging the onset of increase in fluorescence intensity may be a predetermined positive value other than zero.

When the fluorescence intensity starts to increase, the CPU determines whether or not the amount of change in the fluorescence intensity with respect to the reference fluorescence intensity exceeds a preset threshold value. Specifically, the CPU judges whether or not the difference of the fluorescence intensity obtained this time with respect to the reference fluorescence intensity exceeds a threshold value, or whether or not the ratio of the fluorescence intensity obtained this time to the reference fluorescence intensity exceeds the threshold value. Which judgment criterion is to be adopted may be specified by the user in advance. When the amount of change in the fluorescent intensity with respect to the reference fluorescence intensity exceeds a predetermined threshold value, the CPU regards that the degree of curing of the ultraviolet curable resin has reached the maximum degree of curing and returns to the original processing (step 11).

On the other hand, when the amount of change in the fluorescent intensity with respect to the reference fluorescence intensity does not exceed the predetermined threshold value, the CPU returns to the original processing (step 11).

(Pattern B)

The CPU determines whether or not irradiation of the curing ultraviolet ray is started based on the irradiation state signal from the curing ultraviolet irradiation device. If irradiation of the curing ultraviolet ray is not started, the CPU returns to the start point (hereinafter referred to as step 21).

When irradiation of curing ultraviolet light is started, the CPU issues an instruction to irradiate the fluorescent measuring head with ultraviolet light for fluorescence measurement (hereinafter referred to as step 22). Then, the head for fluorescence measurement irradiates an ultraviolet curable resin for ultraviolet rays for fluorescence measurement. The CPU receives the ultraviolet light for fluorescence measurement and acquires the fluorescence intensity of the fluorescence emitted from the photopolymerization initiator contained in the ultraviolet curable resin from the fluorescence measurement head.

Subsequently, the CPU stores the acquired fluorescence intensity in the storage section and determines whether or not a predetermined number of fluorescence intensity data is accumulated in the storage section. If the predetermined number or more of fluorescent intensity data is not accumulated, the CPU returns to step 22.

When a predetermined number or more of fluorescence intensity data is accumulated, the CPU reads a predetermined number of fluorescence intensity data from the storage section and executes an averaging process (moving average) to calculate the fluorescence intensity at that time point.

Further, the CPU executes the state estimation processing of the ultraviolet-cured resin based on the calculated fluorescence intensity (hereinafter referred to as step 23). Specifically, the CPU calls and executes a subroutine including a processing flow as described below.

Subsequently, the CPU outputs a result of the state estimation processing to the display unit or the like to determine whether or not the measurement end condition is satisfied. As the measurement termination conditions, it was determined that a predetermined time had passed since the initiation of curing ultraviolet light irradiation, and in step 23, for example, a specific result such as that the curing degree of the ultraviolet curing resin reached the maximum curing degree was obtained And the like are appropriately adopted. If the measurement end condition is not satisfied, the CPU returns to step 22. On the other hand, when the measurement end condition is satisfied, the CPU returns to the start time (step 21).

(Pattern C)

The CPU acquires specific information such as an ultraviolet ray hardening resin and an irradiation condition inputted from a user or the like and reads a specific temporal change and a required time from the storage unit or the like based on the acquired specific information. Then, the CPU determines whether or not a specific temporal change occurs in the obtained fluorescence intensity.

When a certain temporal change occurs in the obtained fluorescence intensity, the CPU calculates the time required from the start of irradiation of the curing ultraviolet ray. Further, the CPU determines whether or not the deviation of the calculated required time with respect to the reference required time is equal to or larger than a preset threshold value. When the deviation of the calculated required time with respect to the standard required time is not equal to or more than a predetermined threshold value, the CPU estimates that the target ultraviolet curing resin is normal. On the other hand, when the deviation of the calculated required time with respect to the standard required time is equal to or larger than a preset threshold value, the CPU estimates that the target ultraviolet hardening resin is abnormal. Then, the CPU returns to the original processing.

In addition, when a specific temporal change does not occur in the acquired fluorescence intensity, the CPU returns to the original processing.

(Pattern D)

A flow chart according to the estimation of the state of the ultraviolet curing resin before and after irradiation of the curing ultraviolet ray will be described below.

The CPU determines whether or not the curing ultraviolet ray is irradiated or irradiated based on the irradiation state signal of the curing ultraviolet ray from the curing ultraviolet ray irradiation apparatus. Which judgment criterion is to be adopted may be specified by the user in advance. In the case where the curing ultraviolet ray is not irradiated before or after the irradiation, the CPU waits before or after irradiation of the curing ultraviolet ray.

In the case of before or after the curing ultraviolet ray irradiation, the CPU acquires specific information such as the ultraviolet ray hardening resin and the irradiation condition before or after irradiation of the curing ultraviolet ray, and based on the acquired specific information, (Step 41). Then, the CPU issues an irradiation command to the fluorescent measurement head (step 42). Then, the head for fluorescence measurement irradiates ultraviolet ray for fluorescence measurement to the target ultraviolet ray hardening resin. Then, the CPU receives the mold and the ultraviolet ray for measurement, and obtains the fluorescence intensity of the fluorescence emitted by the photopolymerization initiator contained in the ultraviolet-cured resin from the fluorescence measurement head.

Subsequently, the CPU stores the obtained fluorescence intensity in the storage section and determines whether or not a predetermined number of fluorescence intensity data is stored in the storage section (step 42). When a predetermined number or more of fluorescence intensity data is not stored, the CPU repeatedly executes the steps 41 to 42. [

When a predetermined number or more of fluorescence intensity data is accumulated, the CPU reads a predetermined number of fluorescence intensity data from the storage section and executes an averaging process to calculate the fluorescence intensity at that time point.

The CPU also determines whether or not the deviation of the calculated fluorescence intensities of the calculated fluorescence intensities with respect to the reference fluorescence intensities read in step 41 is equal to or greater than a preset threshold value. When the deviation of the fluorescence intensity at that point of time calculated based on the reference fluorescence intensity is not equal to or more than a predetermined threshold value, the CPU estimates that the ultraviolet cured resin before or after irradiation of the curing ultraviolet ray is normal. On the other hand, when the deviation of the fluorescence intensity at the time point calculated based on the reference fluorescence intensity is equal to or greater than a predetermined threshold value, the CPU presumes that the ultraviolet cured resin before irradiation or after irradiation is abnormal. Then, the CPU ends the processing.

Further, based on the measurement result of the fluorescence intensity obtained above, the adhesiveness of the base material and the ultraviolet curing resin can be evaluated. The method for evaluating the adhesion of the base material and the ultraviolet-curable resin includes a reference selection step and an evaluation step.

(Reference selection step)

The " reference selection step " is a step for selecting a criterion for judging good adhesion and poor adhesion for a sample of the same kind (substrate and ultraviolet ray hardening resin).

For example, first, a plurality of samples for reference selection of the same kind are measured for fluorescence intensity as described above, and then the adhesiveness of the sample is evaluated by a known adhesion evaluation method. Samples for reference of the same kind refer to samples having the same type of base material and ultraviolet curable resin and having the same thickness of the base material and ultraviolet curable resin. Examples of known adhesiveness evaluation methods include a peeling test such as a cutter knife test or a peeling test.

From the fluorescence intensity measurement result and the known adhesiveness evaluation method, if the fluorescence intensity is higher than a predetermined intensity, the fluorescent intensity value (reference value), which can be assumed as good adhesion, is selected for a homogeneous sample.

(Evaluation step)

The " evaluation step " is an evaluation step for evaluating the adhesion of the base material and the ultraviolet curing resin, based on the reference value selected in the reference selection step.

For example, the fluorescence intensity is measured for a sample for evaluation similar to that used for the reference selection, and if the fluorescence intensity is higher than the reference value selected in the reference selection step, it can be estimated that the sample has good adhesiveness. The fluorescence intensity was measured for a sample of the same type as the sample used for the reference selection. If the fluorescence intensity is lower than the reference value selected in the reference selection step, it can be estimated that the adhesion to the sample is not good. In this way, it is possible to perform the adhesion evaluation without providing a sample of the same kind to a test involving destruction of a sample such as a peel test.

This adhesion evaluation can be performed in-line.

The state of the ultraviolet-curing resin is estimated by combining the method of evaluating the adhesion between the ultraviolet-curing resin and the substrate and the method of estimating the state of the ultraviolet-curing resin of the present invention, and the adhesiveness between the resin and the substrate is also evaluated .

Finally, a method for producing a cured resin by curing an ultraviolet curing resin containing at least one subject selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation will be described.

In this manufacturing method,

(A) a step of preparing an ultraviolet curable resin present together with a substrate containing a material containing a material that emits fluorescence by ultraviolet irradiation and a substrate containing a material that emits fluorescence by ultraviolet irradiation from an ultraviolet curable resin,

(B) a step of irradiating curing ultraviolet ray to the prepared ultraviolet ray hardening resin to cure the ultraviolet ray hardening resin,

(C) a step of irradiating the cured ultraviolet-curable resin with ultraviolet light having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator,

(D) fluorescence in the wavelength of the fluorescence at which the latter is preferentially or selectively measured among the fluorescence emitted from the material upon receiving the ultraviolet light irradiated in the step (C) and the fluorescence emitted from the photopolymerization initiator A step of measuring the strength,

(E) a step of estimating the state of the cured ultraviolet-cured resin based on the fluorescence intensity measured in the step (D), and judging whether the quality of the ultraviolet-cured resin is good or bad.

According to such a manufacturing method, it is possible to judge whether the quality of the ultraviolet ray hardening resin is good or bad, more easily and quickly, without having to select and inspect a product containing the ultraviolet ray hardening resin. Further, since the quality of the ultraviolet-curing resin can be judged to be good or bad, the result of the judgment can be judged to be poor, so that the product defect can be noticed early and as a result, And the production conditions of the product (for example, irradiation dose of curing ultraviolet rays, etc.) can be changed early. Especially, when the product is continuously produced, the present production method is suitable. Such a product includes a polarizing film.

In the step (A), an ultraviolet curing resin present together with a substrate containing a material that emits fluorescence by ultraviolet irradiation is prepared from a substrate containing a material that emits fluorescence by ultraviolet irradiation and an ultraviolet curing resin. Specifically, a process of applying the ultraviolet-curable resin to the substrate may be mentioned. This substrate may contain a material that does not emit fluorescence by ultraviolet irradiation. For example, a laminated film in which a film made of a material that emits fluorescence by ultraviolet irradiation and a film made of a material that does not emit fluorescence by irradiation of ultraviolet rays are laminated with an ultraviolet curing resin to form an ultraviolet cured resin layer between the films And the like.

The step (B) is a step of curing the ultraviolet curable resin by irradiating ultraviolet ray for curing to the ultraviolet curable resin prepared in the step (A). The wavelength and irradiation time of the curing ultraviolet ray are appropriately selected according to the type of the ultraviolet curing resin and the like.

Step (C) is a step of irradiating a cured ultraviolet-curing resin with ultraviolet rays (fluorescence measurement ultraviolet rays) having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator , The same operation as the irradiation step of the above-described state estimation method of the present invention is performed for the cured ultraviolet-curing resin obtained in the step (B). The ultraviolet ray for fluorescence measurement may be irradiated at a predetermined interval, for example, every predetermined period of time, or may be continuously irradiated. It is preferable to continuously irradiate the ultraviolet ray for fluorescence measurement. By continuously irradiating ultraviolet ray, the fluorescence intensity can be continuously measured in the step (D) described later. As a result, the quality of the ultraviolet ray- , Information on minor changes in quality can be obtained, quality abnormalities can be detected sooner, and ultraviolet ray hardening resin can be manufactured more stably.

The step (D) is a step of irradiating the ultraviolet light irradiated in the step (C) to the wavelength of fluorescence which allows the latter to be preferentially or selectively measured among fluorescence emitted from the material and fluorescence emitted from the photopolymerization initiator Is the same as the measurement step of the state estimation method of the present invention.

The step (E) is a step of estimating the state of the cured ultraviolet-cured resin based on the fluorescence intensity measured in the step (D) to judge whether the quality of the ultraviolet-cured resin is good or bad. The same operation as in the estimation step of the state estimation method is performed. The state of the cured ultraviolet-curable resin is estimated, and a criterion for judging the quality of the ultraviolet-curable resin to be good and bad is determined. That is, whether or not the curing reaction of the ultraviolet ray hardening resin is substantially finished. For example, if the fluorescence intensity measured in the step (D) is a predetermined value or more, it is judged that the curing reaction of the ultraviolet ray hardening resin is substantially finished and a good product is produced. On the other hand, when the fluorescence intensity measured in the step (D) is lower than the predetermined value, it is judged that the product is defective in a state in which the curing reaction of the ultraviolet curing resin is not finished. When it is judged that the product is defective, for example, the production is stopped and it is confirmed whether or not the production conditions (for example, the irradiation amount of the ultraviolet ray for curing) and the type of the substrate are normal, And the manufacture is restarted.

      (Example)

An outline of an embodiment for realizing the state estimation method of ultraviolet ray hardening resin according to the embodiment of the present invention will be described below.

The method for estimating the state of the ultraviolet curable resin according to the embodiment of the present invention estimates the state of the ultraviolet curable resin disposed on the sample stand using the state estimating apparatus and the curing ultraviolet irradiating apparatus. Then, the state estimating device estimates the state of the ultraviolet curing resin causing the curing reaction by the ultraviolet rays for curing from the curing ultraviolet ray irradiating device.

The state estimating apparatus comprises a head for fluorescence measurement and a state estimating unit. The fluorescence measuring head unit irradiates the ultraviolet ray for fluorescence measurement for measuring fluorescence toward the ultraviolet ray hardening resin and receives the fluorescence emitted from the ultraviolet ray hardening resin in accordance with the irradiation instruction of the ultraviolet ray for fluorescence measurement received from the state estimating unit, And outputs the measured fluorescence intensity to the state estimating unit.

The state estimating section instructs the head for fluorescence measurement to emit ultraviolet rays for fluorescence measurement based on the irradiation state signal of the curing ultraviolet ray from the curing ultraviolet irradiation apparatus. The state estimating unit estimates the state of the ultraviolet curing resin based on the fluorescence intensity measured in the fluorescent measuring head.

The curing ultraviolet irradiation device comprises an ultraviolet irradiation head part and an irradiation control part. The ultraviolet ray irradiation head unit irradiates the ultraviolet ray hardening resin with ultraviolet ray for curing in accordance with an irradiation instruction of the ultraviolet ray for curing from the irradiation control unit. The irradiation control section gives an irradiation instruction of the ultraviolet ray for hardening to the ultraviolet irradiation head section in accordance with an instruction from the outside of the user or the like and outputs an irradiation state signal of the ultraviolet ray for hardening to the state estimation section in synchronization with the irradiation instruction .

Next, an example of a method of selecting and determining a wavelength of ultraviolet light to be irradiated in the irradiation step and a wavelength of fluorescence to be measured in the measuring step will be described.

10 g of an epoxy resin (Epikote YX8000; manufactured by Japan Epoxy Resin Co., Ltd.) and 4 g of a photo cationic polymerization initiator (SP-500; manufactured by Kabushiki Kaisha ADEKA), which is a photopolymerization initiator that emits fluorescence by irradiation with ultraviolet rays, And mixed to prepare an ultraviolet curable resin (X).

As a material for emitting fluorescence by ultraviolet irradiation, a film made of polyethylene terephthalate (hereinafter abbreviated as PET) was used. As a material that does not emit fluorescence by ultraviolet irradiation, a film made of polyvinyl alcohol (hereinafter abbreviated as PVA) and a film made of cycloolefin polymer (hereinafter abbreviated as COP) were used. These films were used as substrates.

An ultraviolet curing resin (X) was placed on a film made of PVA and a film made of COP. A film made of PET, a film made of PVA on which the ultraviolet ray hardening resin X is placed and a film made of COP on which the ultraviolet ray hardening resin X is placed are closely contacted with each other using a film applicator (LPA 3301, manufactured by Fuji Plasma Chemical Co., Ltd.) A film made of PET, a film made of PVA, and a film made of COP were laminated in this order to prepare a film having a layer of the ultraviolet curable resin (X) between each film. Thus, a film was obtained in which the ultraviolet curing resin was an ultraviolet curing resin present together with a substrate containing a material that emits fluorescence by ultraviolet irradiation.

Subsequently, the produced film was placed in an exposure apparatus (CV-1100-G manufactured by Fusion Uvu Systems Japan K.K.) set to irradiate a curing ultraviolet ray having a predetermined wavelength, and the inside of the exposure apparatus was irradiated at a predetermined constant speed A model sample irradiated with ultraviolet rays at an arbitrary integrated light quantity (specifically, 0 mJ / cm 2, 750 mJ / cm 2, 1050 mJ / cm 2) was produced. Thus, three kinds of model samples were prepared in the other curing step in the curing step from the uncured state to the completely cured state of the ultraviolet ray hardening resin (X).

Subsequently, the three kinds of model samples thus prepared were irradiated with ultraviolet light for fluorescence measurement, which was irradiated by the apparatus, using Fluorescence Spectrum Analyzer (Fluoro Max-3, manufactured by Horiba Seisakusho Co., Ltd.) 1: 250 nm, Fig. 2: 300 nm, Fig. 3: 350 nm) by irradiating the ultraviolet ray for fluorescence measurement (Fig. 1 to Fig. (Parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2), fluorescence spectrum (horizontal axis: The wavelength of fluorescence measured by a fluorescence spectrum analyzer, and the vertical axis: the intensity of fluorescence emitted from the model sample).

It was confirmed that in each of the irradiated ultraviolet ray for curing (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) There was no difference in the waveform of the spectrum. That is, it has been found that there is no " wavelength of the ultraviolet ray for fluorescence measurement to be irradiated " having a waveform in which the intensity of fluorescence emitted from the model sample changes with the curing step of the ultraviolet-

On the other hand, in FIG. 2 (300 nm), the difference in the waveform of the fluorescence spectrum in each integrated light quantity (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) , And it has been found that there is a " wavelength of ultraviolet ray for fluorescence measurement to be irradiated " having a waveform in which the intensity of fluorescence emitted from the model specimen changes in accordance with the curing step of the ultraviolet curable resin.

From the above results, 300 nm was selected as the wavelength of the ultraviolet ray for fluorescence measurement to be irradiated.

In the waveform of the fluorescence spectrum at each cumulative light quantity (parameter A: 0 mJ / cm 2, parameter B: 750 mJ / cm 2, parameter C: 1050 mJ / cm 2) of the irradiated curing ultraviolet ray from FIG. 2 (300 nm) , It was found that the fluorescence intensity was significantly different in the wavelength region of 450 nm or more.

From the above results, 450 nm or more was selected as the wavelength of fluorescence measured by the fluorescence spectrum analyzer.

By following the above method, it is possible to control the wavelength of the ultraviolet ray for fluorescence measurement (that is, the intensity of fluorescence emitted from the material contained in the base material) emitted from the photopolymerization initiator Of the fluorescence emitted from the material contained in the base material and the fluorescence emitted from the photopolymerization initiator are preferentially or selectively selected from the wavelengths of the fluorescence measured in the measuring step ) Can be selected and determined.

Next, an example of a test example for demonstrating the state estimation method of the ultraviolet ray hardening resin of the present invention will be described.

10 g of an epoxy resin (Epikote YX8000; manufactured by Japan Epoxy Resins Co., Ltd.) and 4 g of a photo cationic polymerization initiator (SP-500; manufactured by ADEKA Corporation) which is a photopolymerization initiator that emits fluorescence by ultraviolet irradiation were placed in a brown screw tube And the mixture was weighed and mixed to prepare an ultraviolet ray hardening resin (Y). The ultraviolet curable resin (Y) contains the same monomer and photopolymerization initiator as the ultraviolet curable resin (X).

As a material for emitting fluorescence by ultraviolet irradiation, a film made of PET was used, and a film made of PVA and a film made of COP were used as a material which does not emit fluorescence by ultraviolet irradiation. These films were used as substrates.

An ultraviolet curing resin (Y) was placed on a film made of PVA and a film made of COP. A film made of PET, a film made of PVA on which the ultraviolet ray hardening resin (Y) is placed, and a film made of COP on which the ultraviolet ray hardening resin (Y) is placed are closely contacted with each other using a film applicator (LPA 3301; manufactured by Fuji Plasma Co., A film made of PET, a film made of PVA, and a film made of COP were laminated in this order, and a film having a layer of the ultraviolet curable resin (Y) was formed between each film. Thus, a film was obtained in which the ultraviolet curing resin was an ultraviolet curing resin present together with a substrate containing a material that emits fluorescence upon irradiation with ultraviolet rays.

Subsequently, the produced film was placed in an exposure apparatus (CV-1100-G manufactured by Fusion Uvu Systems, Japan) set in advance to irradiate a curing ultraviolet ray having a predetermined wavelength, and the inside of the exposure apparatus was irradiated at a predetermined constant speed The specimen was irradiated with ultraviolet rays at an arbitrary accumulated light amount (specifically, 0 mJ / cm 2, 50 mJ / cm 2, 100 mJ / cm 2, 300 mJ / cm 2, 600 mJ / cm 2 and 1000 mJ / cm 2). Thus, six kinds of demonstration samples were prepared in the other curing step in the curing step from the uncured state to the fully cured state of the ultraviolet ray hardening resin (Y).

Subsequently, in a fluorescent intensity measuring apparatus (OL301, manufactured by Canon Inc.), a light source thereof is changed to an LED lamp (output wavelength characteristic: 310 nm), and then a filter for cutting a wavelength of 450 nm or less for fluorescence measurement is provided . Then, the intensity of fluorescence emitted by receiving the ultraviolet ray for fluorescence measurement irradiated by the apparatus was measured for the six kinds of demonstration samples prepared above.

The results obtained are shown in Fig. 4 (abscissa: cumulative light amount of curing ultraviolet ray irradiated on the demonstration test sample, longitudinal axis: fluorescence intensity emitted from the demonstration sample, as measured by a fluorescence intensity measuring apparatus).

As is apparent from Fig. 4, the intensity of curing ultraviolet light irradiated to the demonstration sample is increased, and the intensity of fluorescence emitted from the demonstration sample, which is measured by the fluorescence intensity measuring apparatus, increases, The relationship was positively correlated. Further, from the results of the curing behavior analysis of the " used ultraviolet ray hardening resin " by infrared spectroscopy, if the accumulated light intensity of the irradiated ultraviolet ray for curing becomes 200 mJ / cm2 or more, the curing reaction of the ultraviolet ray hardening resin is almost I already know that it is finished. As a result of analyzing the results of the above test examples, it was found that when the intensity of fluorescence emitted from the test sample measured by the fluorescence intensity measuring apparatus reached 0.4 V or higher, the curing reaction of the ultraviolet curable resin was almost completed (I.e., the state of the ultraviolet curing resin).

(SP-500; manufactured by ADEKA KABUSHIKI KOGYO CO., LTD.), Which is a photopolymerization initiator that emits fluorescence by ultraviolet irradiation, was mixed with an epoxy resin (Epikote YX8000; manufactured by Japan Epoxy Resin Co., Ltd.) It was prepared.

The prepared ultraviolet curable resin is applied to the side of the film made of PET made in contact with the PVA and the side in contact with the PVA of the film made of the COP, and a film made of PET coated with an ultraviolet hardening resin, a film made of PVA and a UV curable resin A film made of PET, a film made of PVA, and a film made of COP were laminated in this order, and then a film made of COP was continuously adhered to each other by using a film applicator (LPA 3301; manufactured by Fuji Plasma Co., Ltd.) , And a film having an ultraviolet curable resin layer between each film was continuously produced. The produced film was placed in an exposure machine (CV-1100-G manufactured by Fusion Uvei Systems Japan K.K.) set to be irradiated with ultraviolet ray for curing having a predetermined wavelength and passed through the exposure machine at a constant speed, And the resulting film was continuously irradiated with ultraviolet rays for fluorescence measurement by means of a fluorescence intensity measuring apparatus OL301 (manufactured by Kabushiki Kaisha Sentec), and the ultraviolet ray for fluorescence measurement And continuously measures the intensity of the emitted fluorescence to check whether or not the value of the fluorescence intensity to be measured is equal to or larger than a predetermined value which can be judged as a state in which the curing reaction of the ultraviolet ray hardening resin previously set is substantially finished. This makes it easier to judge whether or not a film of good quality is continuously produced.

A film made of polycarbonate, a film made of PVA, and a film made of COP were laminated in this order in the same manner as above except that a film made of polycarbonate was used instead of the film made of PET, The state of the ultraviolet-curable resin can be estimated by carrying out the same process as described above for a film having an ultraviolet-curable resin layer. A film made of polyethersulfone, a film made of PVA, and a film made of COP were laminated in this order in the same manner as above except that a film made of polyethersulfone was used instead of the film made of PET, The state of the ultraviolet-curable resin can be estimated by preparing a film having an ultraviolet-curable resin layer between the films and performing the same process as described above for the produced film.

A film made of PET, a film made of PVA, and a film made of PET are laminated in this order, except that a film made of PET is used instead of the film made of COP. The state of the ultraviolet cured resin can be estimated by preparing a film having a resin layer and conducting the same process as described above for the produced film.

According to the present invention, it is possible to realize a method which can be applied to an ultraviolet curable resin existing together with a base material containing a material that emits fluorescence by ultraviolet irradiation, and estimates the state of the ultraviolet curable resin based on the characteristics of the photopolymerization initiator .

Claims (7)

1. A method of estimating the state of an ultraviolet curing resin comprising at least one main agent selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,
Wherein the ultraviolet curable resin is an ultraviolet curable resin present together with a base material containing a material that emits fluorescence by ultraviolet irradiation,
An irradiating step of irradiating the ultraviolet curable resin with ultraviolet rays having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator;
The fluorescence intensity at the wavelength of the fluorescence in which the latter is preferentially or selectively measured among the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator upon receiving the ultraviolet light irradiated in the irradiation step is measured A measuring step,
An estimation step of estimating a state of the ultraviolet curing resin based on the fluorescence intensity measured in the measuring step
Wherein the ultraviolet curable resin is a thermoplastic resin. The method according to claim 1,
The method according to any one of claims 1 to 3, wherein in the step of estimating, based on a temporal change in fluorescence intensity caused by a curing reaction of the ultraviolet-curing resin during irradiation of ultraviolet rays for curing to cause a curing reaction of the ultraviolet- And estimating the state of the ultraviolet-curable resin. 3. The method of claim 2,
Wherein said estimating step is a step of estimating a state of said ultraviolet-curable resin by comparing a temporal change in fluorescence intensity measured and a temporal change that is a preset reference. 3. The method of claim 2,
Wherein the step of estimating is a step of obtaining a time required for the fluorescence intensity to generate a specific temporal change from a specific reference time point and comparing the obtained required time with a preset reference value to estimate the state of the ultraviolet- A method for estimating the state of a resin. The method according to claim 1,
Wherein said estimating step is a step of estimating the state of said ultraviolet-curable resin based on fluorescence intensity measured before irradiation of said ultraviolet ray for curing to cause said curing reaction of said ultraviolet-curable resin. The method according to claim 1,
Wherein said estimating step is a step of estimating a state of said ultraviolet-curable resin based on a fluorescence intensity measured after irradiation of ultraviolet rays for curing to cause a curing reaction of said ultraviolet-curable resin. A method for producing a cured resin by curing an ultraviolet curing resin comprising at least one subject selected from the group consisting of monomers and oligomers and a photopolymerization initiator that emits fluorescence by ultraviolet irradiation,
(A) a step of preparing an ultraviolet curable resin present together with a substrate containing a material containing a material that emits fluorescence by ultraviolet irradiation and a substrate containing a material that emits fluorescence by ultraviolet irradiation from an ultraviolet curable resin,
(B) a step of irradiating curing ultraviolet ray to the prepared ultraviolet ray hardening resin to cure the ultraviolet ray hardening resin,
(C) a step of irradiating the cured ultraviolet-curable resin with ultraviolet light having a wavelength at which the intensity of fluorescence emitted from the material does not exceed the intensity of fluorescence emitted from the photopolymerization initiator,
(D) fluorescence in the wavelength of the fluorescence at which the latter is preferentially or selectively measured among the fluorescence emitted from the material upon receiving the ultraviolet light irradiated in the step (C) and the fluorescence emitted from the photopolymerization initiator A step of measuring the strength,
(E) a step of estimating the state of the cured ultraviolet-cured resin based on the fluorescence intensity measured in the step (D) and judging whether the quality of the ultraviolet-cured resin is good or bad
Wherein the ultraviolet curable resin is present together with a substrate containing a material that emits fluorescence by ultraviolet irradiation.

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