TW201031907A - UV-curing resin status estimation method - Google Patents

Abstract

The present invention relates to a kind of UV-curing resin status estimation method, wherein the UV-curing resin includes a main agent composed of at least one group selected from free monomers and oligomers, and photopolymerization initiator that radiates fluorescent light by UV radiation, in which the UV curing resin is to coexist with a substrate containing material that radiates fluorescent light when radiated with UV. The aforementioned estimation method includes the following steps: a radiation step that radiates the UV-curing resin with UV having wavelength capable of radiating from the above material fluorescence intensity not exceeding the fluorescence intensity radiated from the photopolymerization initiator; a detection step, among the fluorescence light radiated from the above material radiated by the UV-radiation from the radiation step and the fluorescence light radiated from photopolymerization initiator, the later will be preferably or selectively chosen for detecting the fluorescence light intensity in the fluorescence wavelength; and an estimating step in which the fluorescence light intensity based on the above detection step is used to estimate the status of the UV curing resin.

Description

201031907 VI. Description of the Invention: [Technical Field of the Invention] The present invention is a method for estimating the state of an ultraviolet curable resin which is hardened by irradiation of ultraviolet rays. [Prior Art] In recent years, the ultraviolet curing method (ultraviolet Cudng method) has been used as a curing method for an adhesive or a coating agent in most industrial fields. The ultraviolet curing method is compared with the thermal curing method using thermal energy. It has many advantages such as not diffusing harmful substances into the atmosphere, and the curing time is short, and it is also suitable for materials having poor heat resistance. The ultraviolet curing method is an ultraviolet curing resin which is usually a liquid before ultraviolet irradiation and becomes a solid after ultraviolet irradiation. The ultraviolet curing resin comprises at least one selected from the group consisting of a monomer and a polymer. The main agent' further contains a photopolymerization initiator. The photopolymerization initiator receives a radical reaction or radical generated by ultraviolet irradiation to generate a radical or a cation to generate a hardening reaction with a monomer or a polymer. Along with this hardening reaction, after the monomer or the polymerizer becomes a polymer, not only the molecular weight becomes extremely large but the melting point is lowered. As a result, the ultraviolet curable resin became unable to maintain a liquid state and became solid. Therefore, in the ultraviolet curing method, the degree of hardening of the ultraviolet curable resin depends on the degree of polymerization. On the other hand, since it is difficult to judge the degree of hardening of the ultraviolet curable resin or the quality abnormality by visual inspection, a method of easily determining the state of the ultraviolet curable resin accompanying the curing reaction is required. For example, Japanese Patent No. 2,651,036 discloses a method of monitoring the degree of hardening of a coating material which can be hardened by 145989.doc 201031907. The method comprises the steps of including an ultraviolet curable material and containing as the ultraviolet curable material. The material of the fluorescent component that emits light in a manner that changes the degree of hardening of the genus is the luminescence of the measuring probe to determine the degree of hardening of the ultraviolet curable material. Further, Japanese Patent No. 4185939 discloses a state pure method of ultraviolet curable resin, which is based on the following: corresponding to the irradiation of ultraviolet curable resin by ultraviolet rays, the photopolymerization initiator contained in the ultraviolet curable resin itself will emit radiation The line hardening resin is as fine as the hardening degree. The method includes the following steps: coffee (1) mail... Pr〇cessing Umt, the towel processing unit) emits an irradiation command to the fluorescent measuring probe unit; The light-measuring probe portion is irradiated with ultraviolet light for measurement to the ultraviolet curable resin to be used, and the CPU receives the ultraviolet light for measurement, and the CPU obtains the fluorescent light emitted from the photopolymerization initiator contained in the ultraviolet curable resin from the probe portion for fluorescence measurement. Fluorescence intensity; the CPU reads a specific number of conventional fluorescence intensity data stored in the memory unit, and performs averaging processing (moving average) to calculate the fluorescence intensity at the time point; the CPU implements based on the calculated glory intensity The state estimation treatment of the ultraviolet curable resin. SUMMARY OF THE INVENTION However, the method disclosed in Japanese Patent No. 265 1036 discloses that the aspect of the probe that emits light in a manner that changes as a function of the hardening degree of the hardenable material is 'favorable to cost', and in terms of quality. In other words, it is not allowed to add the probe to the ultraviolet curable resin, and therefore it is often difficult to apply to the general ultraviolet curing method. Further, the method disclosed in Japanese Patent No. 4185939 has a problem in that when the ultraviolet curable resin coexists with a substrate containing a material that emits fluorescence by ultraviolet irradiation, 'by ultraviolet irradiation, The fluorescence emitted from the material contained in the substrate that is irradiated with fluorescence by ultraviolet irradiation will hinder the measurement of the fluorescence emitted by the photopolymerization initiator. The inventors of the present invention conducted an intensive study under the above-described circumstances, and as a result, found that both the wavelength of the ultraviolet ray to be irradiated in the irradiation step and the wavelength for measuring the fluorescence emitted by the party to the ultraviolet ray during the irradiation step. The combination of the present invention and the method of the present invention is successfully combined with the following method. The above method is a method for estimating the state of the ultraviolet curable resin, which is a material containing a material which emits fluorescence by irradiation with ultraviolet rays. The ultraviolet curable resin which is cured by ultraviolet irradiation based on the characteristics of the photopolymerization initiator. That is, the present invention provides the following method: [1] A method for estimating the state of an ultraviolet curable resin, which comprises a main agent comprising at least one of a group consisting of a free monomer and an oligomer, and ultraviolet rays. The method for estimating the state of the ultraviolet hard (tetra) fat of the photopolymerization initiator which emits and emits fluorescence, wherein the ultraviolet curable resin is coexisted with a substrate containing a material which emits glory by ultraviolet irradiation, and the ultraviolet curable resin of the present invention The state estimation method includes the steps of: irradiating the ultraviolet curable resin with an ultraviolet ray having a wavelength from which the intensity of the fluorescent light emitted from the material does not exceed the intensity of the light emitted from the photopolymerization initiator; 145989.doc 201031907 In both of the fluorescence emitted from the material and the glory emitted from the photopolymerization initiator, by ultraviolet irradiation in the above irradiation step, the latter is preferentially or selectively determined. a method for measuring the intensity of the fluorescence intensity in the wavelength of the emitted light; and estimating the above based on the firefly (four) degrees of the above-mentioned step [2] The method of estimating the state of the ultraviolet curable resin; [2] The method for estimating the state of the ultraviolet curable resin according to (1) above, wherein the estimating step is based on curing ultraviolet rays for causing a hardening reaction of the ultraviolet curable resin, a step of estimating the state of the ultraviolet curable resin caused by a temporal change in the intensity of the ultraviolet light generated by the curing reaction of the ultraviolet curable resin; [3] a method for estimating the state of the ultraviolet curable resin according to [2] above, Wherein the estimating step is a step of estimating the state of the ultraviolet curing resin by comparing the temporal change of the measured fluorescence intensity with a predetermined time change as a reference; [4] [2] A method for estimating a state of an ultraviolet curable resin, wherein the estimating step is a time required to obtain a specific temporal change in fluorescence intensity from a specific reference time point, and a time required for the obtaining a step of estimating the state of the ultraviolet curable resin by comparing with a preset reference value; [5] In the method for estimating the state of the ultraviolet curable resin according to the above [1], the estimating step is based on the fluorescence intensity measured before the irradiation with ultraviolet rays for curing the ultraviolet curable resin, and the ultraviolet curing is estimated. [Steps of the state of the resin; 145989.doc 201031907 [6J] The method for estimating the state of the ultraviolet curable resin as described above, wherein the estimating step is based on the ultraviolet light for curing the curing of the ultraviolet curable resin Fluorescence intensity, a step of estimating the state of the ultraviolet curable resin; [7] A method for producing an ultraviolet curable resin, comprising at least one selected from the group consisting of a monomer and an oligomer A method for producing a cured resin obtained by curing a main component and an ultraviolet curable resin φ which is a photopolymerization initiator which emits fluorescence by ultraviolet irradiation, and comprises the following steps: (Α) is contained by irradiation with ultraviolet rays Substrate and extraneous line hardening resin for fluorescing materials, prepared and contained by ultraviolet light (B) irradiating the prepared ultraviolet curable resin with ultraviolet rays for curing to cure the ultraviolet curable resin; (C) irradiating the hardened ultraviolet curable resin with the ultraviolet curable resin that coexists with the substrate that irradiates the fluorescent material; An ultraviolet ray having a wavelength from the above-mentioned material that does not exceed the intensity of the fluorescent light emitted from the photopolymerization initiator; (D) is subjected to the above steps (the ultraviolet ray in the sputum is made from the above material) The latter is determined by the fluorescence intensity in the fluorescence wavelength of the preferential or selective measurement of both the emitted fluorescent light and the fluorescent light emitted from the photopolymerization initiator; and (E) based on the above steps ( The fluorescence intensity measured in D) is estimated by the state of the cured ultraviolet curable resin, and the quality of the ultraviolet curable resin is judged to be good or bad. I45989.doc 201031907 [Effects of the Invention] The state of the ultraviolet curable resin coexisting with the substrate containing the material which emits the fluorescent material by ultraviolet irradiation can be easily estimated from the present month. [Embodiment] The state estimation method of the present invention comprises at least a selected one selected from the group consisting of a monomer and an oligomer, and the main component of the species, and irradiated by ultraviolet irradiation. The state of the ultraviolet curable resin of the # A t β && agent is estimated to be an external line curing resin, and the substrate coexisting with a material containing a material that emits fluorescence by ultraviolet irradiation. The ultraviolet ray hardening resin is irradiated with ultraviolet rays having a wavelength of which the intensity of the fluorescent light emitted from the material does not exceed the intensity of the fluorescent light emitted from the photopolymerization initiator; The line irradiation is performed by measuring the fluorescence intensity of the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator, and the latter is determined by the fluorescence intensity of the fluorescene length of the Eucalyptus or the selective measurement; In the above-mentioned measurement (4), the fluorescence intensity is measured, and the state of the ultraviolet curable resin is pushed. (Ultraviolet curing resin) The ultraviolet ray hardening is applied to the state estimation method of the present invention. Lipid "before ultraviolet irradiation is typically a liquid, to change after ultraviolet irradiation (hardening) in a solid helmet. In the present specification, the term "ultraviolet-curing resin" is used in the generic meaning including the liquid state before ultraviolet irradiation and the solid state of 145989.doc 201031907 after ultraviolet irradiation. The ultraviolet curable resin before ultraviolet irradiation (before curing) contains a main component and a photopolymerization initiator selected from at least one of a group consisting of a monomer and an oligomer, and may further contain various additives. The radical or cation generated by the photopolymerization initiator by irradiation with ultraviolet rays generates a hardening reaction (main chain reaction, crosslinking reaction, etc.) of the monomer and the polymer. Then, with the hardening reaction, the monomer and the oligomer become a polymer, so that the molecular weight becomes extremely large and the melting point is lowered. As a result, the ultraviolet curable resin changes from a liquid to a solid. Specific examples of the monomer and the oligomer include polyester acrylate, amine sulfonate acrylate, polybutadiene acrylate, fluorenone acrylate, and epoxy acrylate. The monomer is also referred to as a monolith, and is a state in which a polymer is synthesized by a hardening reaction. The oligomer is also referred to as a low polymer, and has a relatively low degree of polymerization of a polymerization degree of about 2 to 20. Since the monomer and the oligomer form a carrier (electron) which is difficult to move smoothly in the molecule, it is considered that almost no fluorescence is emitted. The ultraviolet curable resin is coexistent with a substrate containing a material that emits fluorescence by ultraviolet irradiation. The material containing the material which emits fluorescence by ultraviolet irradiation is a material containing, for example, polyethylene terephthalate, polycarbonate, or a hard bond which is irradiated with ultraviolet light. Here, the term "coexistence with a substrate" means that the substrate and the ultraviolet curable resin coexist, and at least a portion of the substrate is in contact with at least a portion of the ultraviolet curable resin. Further, the substrate may contain a material that does not emit fluorescence by ultraviolet light. The shape of the substrate is not limited, and a substrate of the form of film 145989.doc 201031907 is preferred. Specifically, a laminate film including a film containing a material that emits fluorescence by ultraviolet irradiation, a film including a material that does not emit fluorescence by ultraviolet irradiation, and a layer of an ultraviolet curing resin are provided, and each film is used. A layer of an ultraviolet curing resin is provided between them. (Photopolymerization initiator) The "photopolymerization initiator" in the state estimation method of the present invention means a photopolymerization initiator which emits fluorescence by ultraviolet irradiation. It is classified into (1) a radical polymerization initiator which generates a radical by ultraviolet irradiation, and (2) a cationic polymerization initiator which generates a cation by irradiation with ultraviolet rays. The radical polymerization initiator is used in the case where the main component is an acrylic monomer or an acrylic valence polymer, and the cationic polymerization initiator is used as an epoxy resin monomer, a vinyl ether monomer, or the like. The case of the oligomer. A photopolymerization initiator containing a mixture of a radical polymerization initiator and a cationic polymerization initiator may also be used. The radical polymerization initiator is roughly classified into a mouse type and an intramolecular cleavage type according to the generation process of a radical. As the hydrogen radical-type radical polymerization initiator, benzophenone and methyl phthalate are exemplified. Examples of the radical polymerization initiator which is an intramolecular cleavage type include benzamidine ether, benzyl dimercapto ketal, α-hydroxyalkylphenone, α-aminoalkylphenone, and ketobenzoquinone. Methyl formate, 4-benzylidene- 4,-methyldiphenyl sulfide, #propyl thioxanthone, diethyl thioxanthene, diethylamino) benzoic acid ethyl ester, 2-carboxyl -2-mercapto-purine _ stupyl propyl ketone benzyl dimethyl ketal and 1,2α-pyrogenic benzene broth | As the cationic polymerization initiator, a diphenyl iodine salt can be cited. Further, in the present specification, the "photopolymerization initiator" is not limited to the ability to retain the luminescent polymerization reaction of 145989.doc 201031907, and includes the following, that is, since the initial photopolymerization initiator promotes photopolymerization The reaction is changed so that the monomer or the polymer which is a target of the photopolymerization reaction does not exist around the photopolymerization initiator, and is a substance which does not promote photopolymerization. The photopolymerization initiator which promotes the light-initiation reaction is, in most cases, still substantially maintains the original molecular size, or is bonded to the polymer in the state of being split into two or more molecules. End. When the initial photopolymerization initiates the cleavage of the φ agent, at least a portion of the cleavage molecule A is believed to promote fluorescence emission. The ultraviolet curable resin is configured to be hardened by exposure to ultraviolet rays to cause a hardening reaction. Therefore, the photopolymerization initiator which produces the hardening reaction has the following J. biomass. (1) The ability to generate an active species (free radical or acid, etc.) for initiating a hardening reaction; · ΤΓ 1篁 thousand leather, Mohr absorbance coefficient), (2) generate reactive species with high reactivity, (3) use WV to stimulate the ability to produce active species

The spectral domain of energy is the ultraviolet green V ’ j C domain. That is, the photopolymerization initiator employs a molecular weight 纟 _ _ _ _ , σ structure which is easy to absorb ultraviolet rays, and is easy to supply (electron) energy generated by absorbing ultraviolet rays to other molecules. It is considered that the intensity of the fluorescence emitted from the photopolymerization initiator varies depending on the chemical state of the photopolymerization start J. Therefore, the photopolymerization is estimated based on the change rate of the stop fluorescence intensity caused by the temporal change of the measured camp light intensity.

The initiator is essentially eliminated. Further, in the ultraviolet curable resin, a specific margin ratio is multiplied by considering the change in yield or temperature, etc.

On the amount of 所得$虫# A t nine polymerization initiator. Therefore, the photopolymerization initiator is "substantially consumed", which means that only a sufficient amount of active species (free radicals or acids, etc.) which generate a hardening reaction is produced from photopolymerization. It is considered that if the photopolymerization initiator is "substantially consumed", the increase in the fluorescence intensity measured will be suppressed. Therefore, when the increase in the fluorescence intensity is started, the increase in the fluorescence intensity is reduced, the increase in the fluorescence intensity is stopped (the change speed is zero), and the fluorescence intensity is decreased (the change rate is a negative value). And the characteristics are considered to be substantially consumed as a photopolymerization initiator. (Irradiation step) The "irradiation step" in the state estimation method of the present invention means that the intensity of the fluorescent light emitted from the material which is irradiated with ultraviolet light by the ultraviolet curing resin is not more than the above The step of irradiating ultraviolet rays at a wavelength of the intensity of the fluorescence emitted by the photopolymerization initiator. It is often used because it is not only weak in the intensity of the fluorescent light emitted from the photopolymerization initiator but also in the case of an ultraviolet curing resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation. It is difficult to measure the fluorescence emitted by the photopolymerization initiator due to the ultraviolet light irradiation and the fluorescence emitted from the substrate. Therefore, it is necessary to irradiate the ultraviolet light having the wavelength described above. For the selection of the wavelength, the determination method will be described in the column "(Selection of the wavelength of the ultraviolet light to be irradiated in the irradiation step and the wavelength of the fluorescence measured in the measurement step, determination method)" (measurement step) The "measurement step" in the state estimation method of the present invention means that the ultraviolet light irradiated by the above-mentioned irradiation step causes the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator to be emitted. The latter 145989.doc •12· 201031907 The measurement procedure for measuring the fluorescence intensity in the fluorescent wavelengths that are preferentially or selectively measured. As described above, the photopolymerization initiator contained in the ultraviolet curable resin is irradiated with ultraviolet light, but at the same time, the material contained in the substrate coexisting with the ultraviolet curable resin is also irradiated with the ultraviolet rays. Radiated fluorescence. That is, the photopolymerization initiator and the substrate are respectively irradiated with ultraviolet rays to emit fluorescence. Therefore, when the fluorescent light emitted from the photopolymerization of the ultraviolet curable resin is contained in the same wavelength range as the fluorescent light emitted from the material contained in the substrate coexisting with the ultraviolet curable resin, The intensity of the fluorescent light emitted from the photopolymerization initiator and the intensity of the fluorescent light emitted from the material are simultaneously measured, so that it is difficult to accurately grasp the photopolymerization initiator contained in the ultraviolet curing resin. The intensity of the fluorescence of the radiation changes. Therefore, in order to prevent the intensity of the fluorescence emitted from the photopolymerization initiator from being disturbed by the intensity of the fluorescence emitted from the above material, the following two become important yA) as the irradiation in the irradiation step The wavelength of the ultraviolet light of the climber is selected and determined as "the wavelength of the intensity of the fluorescent light emitted from the material contained in the substrate does not exceed the intensity of the light emitted from the photopolymerization initiator A" (B) In the step of measuring the intensity of the fluorescent wave, selecting and determining "the ultraviolet light in the above-mentioned irradiation step, so that the light emitted from the material and the fluorescent light emitted from the photopolymerization initiator" The latter is wavelength determined by preference or selectivity." It is extremely important that the above (A) and (8) are related technical requirements' rather than the independent non-relational elements. Then, the measurement wavelength determined by the selection and determination can be set by the measurement unit of the fluorescence intensity. 145989.doc 201031907 For example, the wavelength measurement filter can be separated only for the measurement wavelength (cut filter and/or color) The filter is corrected, and the measurement wavelength can be determined preferentially or selectively. (Selection of the wavelength of the ultraviolet ray to be irradiated in the irradiation step and the wavelength of the luminescence measured in the measurement step. Determination method) The wavelength of the ultraviolet ray to be irradiated in the irradiation step and the wavelength of the luminescence measured in the measurement step are, for example, the following The method of choice is to make a decision. (I) a base sample is prepared by applying a UV curable resin to a substrate containing a material that emits fluorescence by ultraviolet irradiation at a fixed thickness, wherein the ultraviolet curable resin is selected from the group consisting of monomers and A main component of at least one of a group consisting of a polymer and a photopolymerization initiator which emits fluorescence by irradiation with ultraviolet rays. (II) The model sample prepared in the above step (1) is irradiated with ultraviolet rays for curing having a specific wavelength in an arbitrary cumulative amount of light to prepare a model sample in which the ultraviolet curable resin is in an unhardened state to a completely hardened state. Next, the amount of accumulated light of the ultraviolet rays for hardening was changed, and the model samples having different hardening stages were prepared by the same method. A plurality of model samples at different hardening stages were prepared in the above manner. (III) For the plurality of model samples prepared in the above step (II), the intensity of the camping light emitted by the ultraviolet light irradiated by the fluorescent measurement is measured using a Rauma spectrum analyzer, and the fluorescent spectrum is 'by this' The wavelength type of the ultraviolet light to be used for the measurement of the fluorescence (for example, the display in each figure), and the cumulative amount of light for the ultraviolet light to be irradiated (that is, the display in each parameter in the same figure), the fluorescence spectrum is obtained. (horizontal axis: wavelength determined by a fluorescent spectrum analyzer 145989.doc 201031907, longitudinal pumping: intensity of fluorescence emitted from the model sample). 〇v) according to the waveform of the acquired fluorescence spectrum, select the intensity of the fluorescence emitted from the model sample corresponding to the hardening stage of the ultraviolet hardening tree (ie, the amount of each of the irradiated ultraviolet rays) The wavelength of the ultraviolet light for the fluorescence measurement to be irradiated is changed by the waveform of the change (that is, the difference between the waveform of the camping light and the krypton in each of the ten light amounts of the hardened light to be irradiated). It is better to have significant differences. (V) Further, in the waveform of the fluorescence spectrum in each of the integrated light amounts of the ultraviolet light for curing, a region showing a significant difference is selected (that is, "single light measured by a fluorescence spectrum analyzer" The wavelength"). (Pushing step) The "estimation step" in the state estimation method of the present invention is a step of estimating the state of the ultraviolet curable resin based on the fluorescence intensity measured in the above measuring step. Here, as a method of "estimating the state of the ultraviolet curable resin", for example, a method for estimating the state as described below can be cited. (It can be regarded as a characteristic of the temporal change of the fluorescence intensity.) The above-mentioned estimation step is based on the curing of the ultraviolet curing resin in the irradiation of the ultraviolet light for curing in which the ultraviolet curing resin is hardened. The temporal change in light intensity is used to estimate the state of the above ultraviolet curable resin. (1) Estimation of the state of the degree of hardening based on the change rate of the fluorescence intensity It is considered that the intensity of the emitted fluorescence is changed in accordance with the degree of progress of the ultraviolet curing resin 145989.doc •15·201031907. Therefore, based on the rate of change of the fluorescence intensity in the temporal change of the measured fluorescence intensity, the time point at which the degree of hardening of the ultraviolet curable resin reaches the maximum degree of hardening is estimated. In addition, in the ultraviolet curable resin, the specification value (catalog hardness) of the degree of hardening is often specified by the manufacturer, and the term "maximum degree of hardening" refers to the hardening of the ultraviolet curable resin under each irradiation condition. The degree is the same in the following cases. Further, the maximum degree of hardening does not necessarily coincide with the specification value (catalog hardness). It is considered that if the degree of hardening of the ultraviolet curable resin reaches the maximum degree of hardening, ❹ can suppress an increase in the measured fluorescence intensity. Therefore, as the fluorescence intensity increases, when the rate of increase in the fluorescence intensity decreases, when the increase in fluorescence intensity stops (the rate of change becomes zero), and when the fluorescence intensity decreases (the rate of change becomes negative), etc. After the characteristics, it can be considered that the degree of hardening of the ultraviolet curing resin reaches the maximum degree of hardening. The time at which the degree of hardening of the ultraviolet curable resin reaches the maximum degree of hardening can be easily estimated based on the state of the degree of hardening based on the change speed of the fluorescence intensity. In this way, it is possible to avoid the situation in which the hardening reaction in the ultraviolet curable resin is insufficient due to insufficient irradiation time of the ultraviolet rays for curing. In particular, the ultraviolet curable resin deteriorates due to temperature or long-term use, and the properties thereof change, and according to this method, the hardening reaction can be produced at the optimum irradiation time at each treatment time. (2) Estimation of the state of the degree of hardening based on the amount of change in the fluorescence intensity It is considered that the intensity of the emitted fluorescence changes depending on the degree of progress of the hardening reaction of the ultraviolet curable resin. Therefore, the time point at which the ultraviolet curable resin reaches a specific degree of hardening is estimated based on the amount of change before and after the change in the fluorescence intensity in the temporal change of the measured camp light intensity 145989.doc 201031907. As an example, after the fluorescence intensity starts to increase, it is found that the difference or ratio of the fluorescence intensity before the start of the relative increase in the fluorescence intensity exceeds a predetermined threshold, and the degree of hardening of the ultraviolet curing resin is considered to be reached. Specific degree of hardening. For example, the degree of hardening of the ultraviolet curable resin can be judged to be the maximum degree of hardening by appropriately selecting the amount of change in the fluorescence intensity as the criterion for judging, that is, the Φ hardening reaction of the ultraviolet curable resin is sufficient. Further, the degree of hardening of the ultraviolet curable resin can be regarded as a specific degree of hardening which is less than the maximum degree of hardening by changing the amount of change in the smaller fluorescence intensity as a criterion. In this case, it is possible to capture a certain degree of change in the intensity of the fluorescence, and to determine that the degree of hardening has proceeded to a desired degree at the point in time, for example, the component which is temporarily attached to the ultraviolet curing resin cannot be largely used. The degree of hardening of movement. Most of the ultraviolet curable resins have such a property that if the hardening reaction is carried out to some extent by ultraviolet irradiation, the hardening can be gradually performed by the interlocking anti-Φ after the ultraviolet rays are not irradiated. This chain reaction can be promoted by heating the semi-hardened ultraviolet-curing tree. Thus, a method of curing the ultraviolet curable resin by stopping ultraviolet irradiation at a stage where the ultraviolet curable resin is not sufficiently cured in this manner can also be employed. When the ultraviolet curable resin is bonded to a substrate or other members, it can be used in a case where ultraviolet irradiation is required to carry out the application. After the temporary adhesion, the position of the bonded substrate or other components can be adjusted by the ultraviolet curing resin, and the hardening method can also be used in the following cases: After the door is smashed, the outer part of the door is irradiated to make the bonded part reach the semi-hardened state. 145989.doc 201031907 'The product is concentrated and heated to promote hardening. If the cured portion is irradiated with ultraviolet rays until the maximum degree of hardening is obtained, the overall time of the hardening treatment can be shortened. It is possible to estimate the state of the degree of hardening based on the amount of change in the intensity of the fluorescence, and it is easy to estimate the degree of hardening of the ultraviolet curable resin to the maximum degree of hardening. Thereby, it is possible to avoid a situation in which the curing reaction of the ultraviolet curable resin is insufficient due to insufficient irradiation time of the ultraviolet rays for curing. In particular, the ultraviolet curable resin is deteriorated in properties due to deterioration due to temperature or long-term use, and according to this method, a hardening reaction can be produced at an optimum irradiation time in each treatment time point. (3) Estimation of the degree of hardening based on the absolute value of the fluorescence intensity It is considered that the intensity of the emitted fluorescence changes depending on the degree of progress of the hardening reaction of the ultraviolet curable resin. Therefore, based on the absolute value of the fluorescence intensity in the temporal change of the measured fluorescence intensity, the time point at which the degree of hardening of the ultraviolet curable resin reaches a specific degree of hardening is estimated. As an example, it can be found that the degree of hardening of the ultraviolet curable resin reaches a specific degree of hardening after the measured fluorescence intensity exceeds a predetermined threshold. As in the above case, the specific degree of hardening may be any degree of hardening or a degree of hardening less than the maximum degree of hardening. The state of hardening degree can be estimated based on the absolute value of the fluorescence intensity, and the time point at which the hardening degree of the ultraviolet curable resin reaches the maximum degree of hardening can be easily estimated. Thereby, it is possible to avoid a situation in which the curing reaction of the ultraviolet curable resin is insufficient due to insufficient irradiation time of the ultraviolet rays for curing. According to this method, when the hardening operation is repeated under relatively stable conditions, the hardening reaction is generated at the optimum irradiation time in each of the 145989.doc • 18-201031907 time points. (4) Estimation of the state of the ultraviolet curable resin by comparison with the temporal change as a standard. The production line or the like is subjected to hardening treatment of the same type of ultraviolet curable resin under substantially the same irradiation conditions. Therefore, it is practical and effective to obtain a representative temporal change in fluorescence intensity in accordance with the type of the ultraviolet curable resin, and to make a representative temporal change in the fluorescence intensity as a temporal change in the reference φ, by The state of the rabbit external hardening resin was estimated by comparing the temporal changes of the standard. Furthermore, in comparison with the temporal change of the acquired fluorescence intensity and the temporal change as a reference, not only the fluorescence intensity (absolute value) at a certain time point but also the use from a certain time point can be extracted. Characteristic changes in glory intensity during a specific period. The state of the ultraviolet curable resin relative to the temporal change as a reference can be easily estimated based on the state estimation of the ultraviolet curable resin by comparison with the reference temporal change. Further, it is possible to detect an abnormality such as an ultraviolet curable resin at an early stage by monitoring the presence or absence of a deviation from the temporal change of the standard. 'According to the state estimation of the ultraviolet curing resin required for the specific time-dependent change based on the above-mentioned fluorescence intensity, the time required to generate a specific temporal change in the fluorescence intensity can be performed with the reference value. Comparing, and discovering the abnormality of the ultraviolet curing resin. As a result, a large amount of defective products can be suppressed, and the production yield can be improved. (5) Ultraviolet light based on the time required for the fluorescence intensity to be generated at a specific time. 145989.doc 201031907 The state of the wire-hardening resin is estimated to be the same as the above-described state estimation method. 'Under the same irradiation conditions, the same type is repeatedly processed. In the case of an ultraviolet curable resin, it is practical and effective to 'pre-acquire the temporal change of the glory intensity of a representative sample, and estimate the state of the ultraviolet curable resin by comparing with the temporal change of the light intensity. . As an example, in the temporal change of the fluorescence intensity, 'when the specific time-varying change is required (5), and the required time is compared with a preset reference value, thereby estimating the ultraviolet curing resin State. (6) The state of the ultraviolet curable resin before and after the irradiation with ultraviolet rays is estimated in a production line or the like, and the state of the ultraviolet curable resin can be estimated before and after the irradiation of the ultraviolet rays for curing (at the end of the irradiation). With or without anomalies, manufacturing can be performed more efficiently. In other words, it is found that the type of the ultraviolet curable resin is wrong, the amount of the ultraviolet curable resin is wrong, the quality of the ultraviolet curable resin is changed, and the curing reaction is expected to be performed in the storage of the ultraviolet curable resin. In addition, after irradiation with ultraviolet rays for curing (at the end of irradiation), it is found that the type of the ultraviolet curing resin is wrong, the amount of the ultraviolet curing resin is wrong, the quality of the ultraviolet curing resin is changed, and the ultraviolet light for curing is insufficient or excessively irradiated. . As an example, the state of the ultraviolet curable resin is estimated based on the measured fluorescence intensity before irradiation of ultraviolet rays for curing to cure the ultraviolet curable resin. According to the state of the ultraviolet curable resin before the ultraviolet irradiation by the hardening, it is estimated that the ultraviolet curable resin can be inspected before the hardening reaction occurs. 145989.doc -20· 201031907 As a result, it is not necessary to irradiate the ultraviolet rays for curing with an abnormal ultraviolet curable resin. Therefore, the production efficiency of the production line or the like can be improved. In the same manner, it is possible to detect the presence or absence of abnormality of the ultraviolet curable resin after the completion of the curing reaction, based on the state of the ultraviolet curable resin after the irradiation of the ultraviolet rays for curing (at the end of the irradiation). As a result, it is possible to find an ultraviolet curable resin which does not conform to specifications such as insufficient irradiation of ultraviolet rays by curing or excessive irradiation. As an example, after the irradiation of the ultraviolet rays for curing the ultraviolet curable resin, the state of the ultraviolet curable resin is estimated based on the measured fluorescence intensity. (State Estimation Apparatus) The state estimation apparatus which realizes one embodiment of the state estimation method of the present invention will be described below. The state estimation device includes a state estimation unit, a central processing unit, a display unit, and an irradiation warning unit. The state estimation unit includes a CPU operation unit, a memory unit, and a CPU that emits an illumination signal for the fluorescence measurement probe unit based on an operation instruction from the operation unit and an irradiation state signal from the curing ultraviolet irradiation device. Instructions. The cpu causes the illumination warning portion to be lit or blinked, so that the protection is not irradiated with ultraviolet light for fluorescence measurement emitted from the probe portion for fluorescence measurement according to the instruction for ultraviolet irradiation of the fluorescence measurement for the probe portion for fluorescence measurement. Then, the CPU receives the state of the ultraviolet curable resin as the target of the work intensity measured by the fluorescence measuring probe unit, and outputs the estimated result or the like to the display unit. At the same time, the CPU outputs a signal (analog, digit) of the fluorescence intensity measured by the probe unit for fluorescence measurement, such as the external device 145989.doc -21 - 201031907. Further, the CPU reads various kinds of pre-stored data from the memory unit, and stores the measured data and the like in the memory unit. The display unit includes, for example, an LCD (Liquid Crystal Display) or a CRT (Cathode-Ray tube). A display such as a ray tube displays a graph of changes in fluorescence intensity received from the CPU. The operation unit includes various switches and the like, accepts an operation from the user, and outputs an operation instruction corresponding to the operation to the CPU. The irradiation warning unit includes, for example, an LED (Light Emitting Diode) or a lamp tube, and displays the ultraviolet light for fluorescence measurement for the user or the like located at a position close to the state estimation device. The memory unit includes, for example, an EEPROM (Electrically Erasable and Programmable Read Only Memory), and stores measurement data or various materials corresponding to the type of the ultraviolet curable resin. The probe unit for fluorescence measurement includes a light projection drive circuit, a light projection element, a half mirror, a filter, a light receiving element, an HPF (High Pass Filter), an amplifier circuit, and S/H (Sample and Hold, Sample-and-hold) and Analog-to-Digital Converter 'ADC. The light projection drive circuit applies a pulsed voltage to the light projection element at a specific cycle in accordance with an irradiation instruction of ultraviolet light for fluorescence measurement received from the CPU. The light projection element includes, for example, an ultraviolet LED, which generates and emits ultraviolet light for fluorescence measurement according to a pulse voltage applied by a light projection drive 145989.doc -22-201031907. In the embodiment of the invention, the light projection element emits ultraviolet light for fluorescence measurement having a main emission peak of 365 nm. The half mirror is disposed on the same optical axis as the light projection element, and transmits ultraviolet light for fluorescence measurement emitted from the light projection element, and changes the fluorescence emitted by the ultraviolet curing resin to be measured. The transfer path is used to guide the ultraviolet light for fluorescence measurement to the filter. For example, the reflecting surface of the half mirror is formed by metal evaporation. The filter is disposed to remove ambient light such as ultraviolet rays for fluorescence measurement irradiated from the light projection element, and is configured to attenuate light in the ultraviolet region to transmit light in the visible light region. In the embodiment of the present invention, the filter is a filter for passing through a dielectric multilayer film having a wavelength of 410 nm or more. As an example, the light-emitting element includes a photodiode, generates a current corresponding to the intensity of the fluorescent light incident through the filter, and outputs the current to the HPF. The HPF system removes a component having a specific frequency or higher by removing a DC component and a low-frequency component in the fluorescence intensity signal received from the light-receiving element, and extracting a component generated by ultraviolet light for fluorescence measurement. The amplifying circuit amplifies the signal through the HpF to the S/Η circuit with a specific gain (current voltage conversion rate). The S/Η circuit samples the received light intensity L number in synchronization with the light-emitting timing of the light projection element, and maintains the sampled signal value until the next sampling, thereby taking place in each specific period of the pulsed light projection. The maximum amplitude value of the signal in each period of 145989.doc •23- 201031907 is measured and the amplitude value is large. The analogous digital conversion unit measured by the side (10) converts the voltage signal (analog signal) that has been rotated from the S/H circuit into a digital value, and outputs it to the CPU. The following is a summary of the optical system of the probe unit for fluorescence measurement. The probe unit for fluorescence measurement further includes a focus lens. Further, the probe unit for fluorescence measurement is configured such that the light projection element, the half mirror, the focus lens, and the target external line hardening resin are disposed on the same straight line, and the ultraviolet light for fluorescence measurement irradiated from the light projection element is focused. The lens is focused on a specific range of diameters on the UV curable resin. Then, the fluorescent light emitted from the ultraviolet curable resin is reversely transmitted in the same path as the ultraviolet light for fluorescence measurement, and is reflected by the half mirror to change the transmission path. Further, the fluorescent light is incident on the light receiving element via the filter. Further, the distance from the irradiation surface of the light projection element to the focus lens is substantially the same as the distance from the self-focusing lens to the ultraviolet curable resin. The fluorescent intensity measuring device (for example, 〇L3〇1; manufactured by SENTEC Co., Ltd.) may have a light projection element (for example, an LED having an ultraviolet ray irradiation wavelength characteristic) as described below, and the light projection element has the above The intensity of the fluorescent light emitted from the material contained in the substrate does not exceed the irradiation wavelength of the ultraviolet light for fluorescence measurement from the intensity of the fluorescent light emitted from the photopolymerization initiator. In the above-described fluorescence intensity measuring apparatus, the fluorescent intensity measuring unit may include a filter (for example, a cut filter) as described below, and the filter removes the following wavelengths, and the wavelength is received. The fluorescent measurement in the above-mentioned irradiation step 145989.doc -24-201031907 is irradiated with ultraviolet rays so that both the fluorescent light emitted from the material contained in the substrate and the fluorescent light emitted from the photopolymerization initiator are contained. The latter is wavelength determined by preference or selectivity. _ (Improvement of state of ultraviolet curable resin) For example, the state of the ultraviolet curable resin is estimated by the following treatment. Hereinafter, four patterns of the patterns A to D will be described in order. Further, such state estimation is described in Patent No. 4185939 except that a polyester resin is used as the substrate. ❿ (Pattern A) First, the CPU judges whether or not the irradiation of the ultraviolet rays for curing is started (hereinafter referred to as step 11). If the irradiation with ultraviolet rays for curing is not started for a long time, the acquired fluorescence intensity is set to the previous fluorescence intensity, and the process returns to step 11. In step 11, when it is determined that the irradiation of the ultraviolet rays for curing is not started, the CPU determines whether or not the fluorescence intensity has started to increase. • In addition, the brightness of the fluorescent light has started to increase, which means that in the following step 12, the CPU determines that the fluorescence speed starts to increase. When it is not the case that the fluorescence intensity has started to increase, the CPU calculates the rate of change based on the difference between the fluorescence intensity obtained this time and the intensity of the four times of fluorescence. Then, the CPU judges whether the calculated rate of change is greater than zero. When the calculated rate of change is greater than zero, CI>U determines that the fluorescence intensity starts to increase (hereinafter referred to as step 12)' and stores the fluorescence intensity at this point in time as the ground fluorescence intensity and returns to the original deal with. On the other hand, when the calculated change speed is not greater than zero, the CPU returns to the original processing. 145989.doc •25- 201031907 In addition, the value used to determine the increase in glory speed can also be positively determined in advance of zero. When the fluorescence intensity has started to increase, the CPU determines whether the amount of change in the fluorescence intensity relative to the reference fluorescence intensity exceeds a predetermined threshold. Specifically, the CPU determines whether the difference between the fluorescence intensity obtained this time and the reference fluorescence intensity exceeds the threshold value, or the fluorescence intensity obtained this time is relative to the reference fluorescence intensity. Whether the ratio exceeds the threshold. The user can also pre-specify which criteria to use. Then, when the amount of change in the light intensity with respect to the reference glare intensity exceeds a predetermined threshold value, the CPU considers that the hardening degree of each of the external hardening resins reaches the maximum degree of hardening, and returns to the original process (step 11). On the other hand, when the amount of change in the fluorescence intensity with respect to the reference fluorescence intensity does not exceed the preset threshold value, the CPU returns to the original processing (step 11). (Pattern B) The CPU determines whether or not the ultraviolet rays for curing start irradiation based on the irradiation state signal from the curing ultraviolet irradiation device. When the irradiation of the ultraviolet light for curing is not started, the CPU returns to the start time point (hereinafter referred to as step 21). When the irradiation for the curing and the external line start, the cpu emits the fluorescent light to the probe portion for the fluorescence measurement. An irradiation instruction for ultraviolet light for light measurement (hereinafter referred to as step 22). Then, the fluorescent measuring probe unit irradiates the ultraviolet curable resin to be irradiated with ultraviolet light for fluorescence measurement. Then, the cpu is obtained from the probe portion for fluorescence measurement, and the fluorescence intensity of the fluorescent light emitted from the photopolymerization initiator contained in the ultraviolet light 145989.doc -26- 201031907 . Then, the CPU stores the acquired fluorescence intensity in the memory unit, and determines whether or not a specific number or more of the fluorescence intensity data is stored in the memory unit. When there is no specific number of pieces of fluorescence intensity data stored, the CPU returns to step 22. When a specific number or more of the fluorescence intensity data is stored, the cPU reads a specific number of fluorescence intensity data from the 3 memory portion, performs an averaging process φ (moving average), and calculates the fluorescence intensity at the time point. . Further, the CPU performs a state estimation process of the ultraviolet curable resin based on the calculated fluorescence intensity (hereinafter referred to as step 23). Specifically, the CPU calls the subroutine including the following processing flow and executes it. Then, the CPU pair It is determined whether or not the measurement end condition is satisfied by the result of the output state estimation process such as the display unit, etc. As the measurement end condition, the following conditions can be appropriately employed: a specific time e from the start of irradiation of ultraviolet rays for curing and a step at step 23 For example, it is determined that the hard ❿ degree of the ultraviolet curable resin reaches a specific result of the maximum degree of hardening. When 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. From the start time point (step 21 (pattern C), the information of the material hardening resin and the irradiation condition # which is input by the user or the like is obtained, and based on the acquired information, it is read from the memory unit or the like as a reference. a specific temporal change and time f. Then, the CPU determines whether a specific temporal change occurs in the acquired fluorescence intensity. ° 145989.doc -27- 201031907 when the time changes,

On the other hand, when the difference is equal to or greater than the preset threshold value, the CPU estimates that the CPU calculates the fluorescence intensity acquired, and the CPU calculates the start of the irradiation of the ultraviolet light for curing. In the calculation of the required time, the CPU estimates the ultraviolet curable resin which is the normal time calculated by the target ultraviolet curable resin and the time required for the reference. Then, the CPU returns to the original processing. Also, when a specific temporal change is not generated in the acquired fluorescence intensity, the CPU returns to the original processing. (Pattern D) The following is a flow chart for estimating the state of the ultraviolet curable resin before and after the irradiation of ultraviolet rays for curing. The CPU determines whether or not it is before or after the irradiation of the ultraviolet rays for curing based on the irradiation state 彳S of the ultraviolet rays for curing from the ultraviolet irradiation device for curing. The user can also pre-specify which criteria to use. The CPU waits until it is hardened before or after irradiation with ultraviolet rays before or after irradiation with ultraviolet rays. When the right is before or after the irradiation with ultraviolet rays, the cpu acquires specific information such as the ultraviolet curing resin and the irradiation conditions before or after the irradiation with ultraviolet rays, and based on the specific information acquired. The fluorescence intensity as a reference is read in the memory unit or the like (step 4丨). Then, 'CI> U issues an irradiation command to the probe unit for fluorescence measurement (step 42). 1459S9.doc -28 - 201031907 The fluorescent probe is irradiated with the ultraviolet curable resin as the target. Then, the CPU obtains the fluorescence intensity of the fluorescent light emitted from the photopolymerization initiator contained in the ultraviolet curable resin by the probe portion obtained by the glory measurement. Then, the CPU stores the acquired fluorescence intensity in the memory unit, and judges whether or not a specific number or more of the fluorescence intensity data is stored in the Z memory portion (step 42). In the case where the glory intensity data of a specific number or more is not stored • When the CPU repeatedly performs steps 41 to 42.

When a specific number or more of the fluorescence intensity data is stored, the CPU reads a specific number of fluorescence intensity data from the memory unit, and performs an averaging process 'calculating the fluorescence intensity at that time point. Further, the CPU determines whether or not the difference between the calculated fluorescence intensity at the time point and the fluorescence intensity as the reference read in step 41 is equal to or greater than a preset threshold value. When the calculated fluorescence intensity at the time point is not a predetermined threshold value or more, the cpu estimates that the ultraviolet curable resin before and after the irradiation with ultraviolet rays is normal. On the other hand, when the calculated deviation of the fluorescence intensity at the time point from the reference fluorescence intensity is equal to or greater than the preset threshold value, the CPU estimates the ultraviolet curing resin abnormality before or after the irradiation. Then, the CPU ends the processing. Further, the adhesion between the substrate and the ultraviolet curable resin can be evaluated based on the measurement results of the fluorescence intensity obtained above. The method for evaluating the adhesion of the substrate and the ultraviolet curable resin includes a reference selection step and an evaluation step. (Base selection step) 145989.doc • 29- 201031907 The benchmark selection step is a step of selecting a reference for determining the adhesion of the same type of sample (substrate and ultraviolet curable resin). For example, first, a plurality of samples of the same type of reference are selected, and the fluorescence intensity is measured in the above manner, and then the adhesion of the sample is evaluated by a known adhesion evaluation method. The sample for the same type of reference is the same as the type of the substrate and the ultraviolet curable resin, and the substrate and the ultraviolet curable resin have the same film thickness. As a known adhesion evaluation method, for example, a peeling test such as a cutter test or a peeling test can be mentioned. According to the fluorescence intensity measurement result and the known adhesion evaluation method, if the fluorescence intensity is higher than a certain fixed intensity, the fluorescence intensity as a reference can be estimated for the same type of sample. Value (reference value). (Evaluation Step) The evaluation step is an evaluation step for evaluating the purity of the substrate and the ultraviolet curable resin based on the reference value selected in the reference selection step. For example, the sample selected for the reference and the sample for evaluation of the same kind can be used to measure the fluorescence intensity. If the fluorescence intensity is higher than the reference value 基准 in the reference selection step, the adhesion of the sample can be estimated to be good. Further, the fluorescence intensity is measured for the sample selected for the reference and the sample of the same type, and the #fluorescence intensity is lower than the reference value in the reference selection step, and the adhesion of the sample can be estimated to be poor. The same type of sample can be evaluated for adhesion in such a manner that it is not used in tests such as peeling tests with sample damage. This adhesion evaluation can be carried out continuously. The state of the ultraviolet curable resin of H5989.doc -30-201031907 can be estimated by combining the method for evaluating the adhesion between the ultraviolet curable resin and the substrate, and the method for estimating the state of the ultraviolet curable resin of the present invention. The adhesion between the resin and the substrate was evaluated. Finally, a method for producing a cured resin obtained by containing at least one selected from the group consisting of a monomer and a polymer and irradiated by ultraviolet irradiation will be described. The ultraviolet curable resin of the fluorescent photopolymerization initiator produces hardening. The present manufacturing method has the following steps: Φ (A) A substrate which is made of a material containing a material which emits fluorescence by ultraviolet irradiation and an ultraviolet curable resin, and which is prepared to coexist with a substrate containing a material which emits fluorescence by ultraviolet irradiation. (B) irradiating the prepared ultraviolet curable resin with ultraviolet rays for curing to cure the ultraviolet curable resin; (C) irradiating the cured ultraviolet curable resin with the intensity of the fluorescent light emitted from the material not exceeding The ultraviolet light of the wavelength of the intensity of the fluorescent light emitted by the photopolymerization initiator; (D) the ultraviolet light irradiated by the ultraviolet light in the above step (C), and the fluorescence emitted from the material and the photopolymerization start The latter of the fluorescent light in the agent is determined by the fluorescence intensity of the fluorescent wavelength of the preferential or selective measurement; (E) the hardened intensity is estimated based on the fluorescence intensity measured in the above step (D) The state of the ultraviolet curable resin determines whether the quality of the ultraviolet curable resin is good or bad. According to this manufacturing method, it is easier and faster to judge the ultraviolet hardening tree without extracting and inspecting the product containing the ultraviolet curable resin produced. 145989.doc •31 · 201031907 The quality of the fat is good or bad. Moreover, since the quality of the ultraviolet curable resin can be judged more quickly, when the judgment result is that the quality is poor, the product can be found to be defective at an early stage, and as a result, the manufacture of the product which does not conform to the specification can be reduced, and The manufacturing conditions of the product (for example, the amount of irradiation of ultraviolet rays for curing) are changed in the early stage. In particular, the manufacturing method is suitable for the case of continuously manufacturing a product. As such a product, a polarizing film is mentioned. In the step (A), a substrate containing a material which emits fluorescence by ultraviolet irradiation and an ultraviolet curable resin are used to prepare an ultraviolet curable resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation. Specifically, a step of applying the ultraviolet curable resin to the base material or the like can be mentioned. The substrate may also contain a material that does not emit fluorescence due to ultraviolet irradiation. For example, the ultraviolet curable resin is used, and a film containing a material that emits fluorescence by ultraviolet irradiation and a film containing a material that does not emit fluorescence by ultraviolet irradiation are bonded, and ultraviolet curing is provided between the films. A laminated film of a resin layer. The step (B) is a step of irradiating the ultraviolet curable resin prepared in the above step (A) with ultraviolet rays for curing to cure the upper ultraviolet curable resin. The wavelength of the ultraviolet light for curing or the irradiation time is appropriately selected by the type of the ultraviolet curing resin or the like. In the step (C), the cured ultraviolet curable resin is irradiated with ultraviolet rays having a wavelength from which the intensity of the fluorescent light emitted from the material does not exceed the intensity of the fluorescence emitted from the photopolymerization initiator (for fluorescence measurement). The step of 'ultraviolet rays' is carried out in the same manner as the "irradiation step" of the above-described state estimation method of the present invention by the step of "curing the ultraviolet curable resin obtained in the above step" 145989.doc - 32 - 201031907. For example, the ultraviolet light for fluorescence measurement may be irradiated at predetermined intervals such as a fixed time, or may be continuously irradiated. It is preferred to continuously irradiate ultraviolet rays for fluorescence measurement, and to continuously measure the fluorescence intensity in the following step (D) by continuously irradiating ultraviolet rays, and as a result, it is possible to judge not only the quality of the ultraviolet curable resin but also the quality of the ultraviolet curable resin. Moreover, information on subtle changes in quality can be obtained, so that abnormal quality can be found more quickly, and the ultraviolet curable resin can be more stably produced. The step (D) is carried out by preferentially or selectively determining both of the fluorescence emitted from the material and the light emitted from the photopolymerization initiator by ultraviolet irradiation in the above step (C). The fluorescence intensity in the wavelength of the fluorescence is measured, and the same operation as the "measurement step" of the state estimation method of the present invention described above is performed. Step (E) is a step of estimating the state of the cured ultraviolet curable resin based on the fluorescence intensity measured in the above step (D), determining the quality of the ultraviolet curable resin, and performing the above-described invention The same operation of the "estimation step" of the state estimation method, and the step (8) green evaluation of the state of the cured ultraviolet curing resin and judging the quality of the predetermined ultraviolet curing resin and the above state, determining the ultraviolet rays Whether the quality of the hardened resin is good or bad, that is, whether the hardening reaction of the ultraviolet curing resin is substantially knotted. For example, if the above steps (the fluorescence intensity of 咐敎 is more than the characteristic value, and the hardening reaction of the ultraviolet ray hardening resin is substantially finished), and a good product is produced, on the other hand, in the above step () When the fluorescence intensity of bismuth is lower than a specific value, it is judged that the hardening reaction of the ultraviolet ray hardening resin is not finished (4), so the product is defective. I45989.doc • 33 · 201031907 : 2: If the product is in a bad condition, then For example, the production is stopped, and it is confirmed whether or not the manufacturing = (for example, the amount of irradiation of ultraviolet rays for curing), the type of the substrate, and the like, and the manufacturing conditions are changed, and the production is resumed. EXAMPLES Hereinafter, the ultraviolet curable resin is realized according to the embodiment of the present invention. An outline of an embodiment of the state estimation method. The method for estimating the state of the ultraviolet curable resin according to the embodiment of the present invention is to estimate the ultraviolet curable resin disposed on the sample stage using the state estimation device and the ultraviolet irradiation device for curing. State of the state. Then, the state estimation device applies ultraviolet rays for curing by the ultraviolet irradiation device for curing The state of the ultraviolet curable resin which causes the hardening reaction is estimated. The state estimation device includes a fluorescent measurement head and a state estimation unit. The probe portion for the camping light measurement is based on the fluorescence measurement received from the state estimation unit. In the ultraviolet ray-curable resin, the ultraviolet ray-curable resin is irradiated with ultraviolet ray for measuring luminescence, and the state estimation unit outputs the fluorescence intensity measured by the fluorescence emitted from the ultraviolet ray-curable resin. The estimation unit emits an irradiation instruction for ultraviolet light for fluorescence measurement on the probe portion for fluorescence measurement based on the irradiation state signal of the ultraviolet light for curing from the curing ultraviolet irradiation device. Then, the state estimation unit is based on the probe portion for fluorescence measurement. In the ultraviolet ray irradiation device, the ultraviolet ray irradiation probe unit and the irradiation control unit are included. The ultraviolet ray irradiation probe unit is illuminating the ultraviolet ray according to the ultraviolet ray irradiation instruction from the irradiation control unit. The hardened resin is cured by ultraviolet rays. 145989.doc •34- 201031907 The radiation control unit emits an ultraviolet light irradiation instruction to the ultraviolet irradiation probe unit in response to an instruction from the outside of the user, and outputs an irradiation state signal of the ultraviolet light for curing to the state estimation unit in synchronization with the irradiation instruction. An example of the method of selecting and determining the wavelength of the ultraviolet light to be irradiated in the step and the wavelength of the fluorescent light measured in the measurement step. Weighing epoxy resin (EPik〇te YX8000; manufactured by japan Epoxy Resins) 10 g and ultraviolet rays 4 g of a photocationic polymerization initiator (SP-500; manufactured by ADEKA Co., Ltd.) which is irradiated and irradiated with fluorescence, and placed in a brown spiral tube for mixing to prepare an ultraviolet curable resin using polytrimethylene terephthalate A film of ethylene glycol (hereinafter referred to as pET (Polyethylene Terephthalate)) is a material which emits fluorescence by ultraviolet irradiation. A film comprising polyvinyl alcohol (hereinafter abbreviated as pvA (polyvinyl alcohol)) and a film containing a cycloolefin polymer (hereinafter referred to as COP (Ring 〇iefin P〇lymer)) are used as radiation which is not irradiated by ultraviolet rays. material. These films are used as a substrate. The ultraviolet curable resin X was placed on the film containing PVA and the film containing COP. Using a film bonding machine (LPA3301; manufactured by FUJIPLA Co., Ltd.), a film containing pvA on which a film comprising PET is placed with an ultraviolet curing resin, and a film containing C〇P on which an ultraviolet curing resin X is placed are adhered thereto. A film comprising PET, a film containing PVA, and a film containing c〇p are sequentially laminated to form a film having an ultraviolet-curable resin ruthenium layer between the films. In this manner, "an ultraviolet curable resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation" is prepared. The film is placed in an exposure machine (cv-11 〇〇_G; manufactured by Fusion UV Systems Japan) which is previously set to illuminate a specific wavelength of 145989.doc • 35- 201031907 Ultraviolet-irradiated model sample is prepared by arbitrarily accumulating the amount of light (specifically, 〇mJ/cm2, 750 mJ/cm, 1050 mJ/cm2) by passing it through the exposure machine at any fixed speed. . In this manner, three kinds of model samples in which the ultraviolet curing resin X is in a hardening stage different from the hardening state to the fully hardened state are prepared. Next, a fluorescent spectrum analyzer (Fluor·Max-3; manufactured by Horiba, Ltd.) was used for the three types of model samples prepared, and the fluorescence emitted by ultraviolet irradiation by fluorescence measurement was measured by the apparatus. The intensity is used as the fluorescence spectrum, and the wavelength of the ultraviolet light for the measurement of the fluorescence to be irradiated (see Fig. 1 to Fig. 3, Fig. 1: 2 5 0 nm, Fig. 2: 300 nm, Fig. 3: 350 nm) ), the cumulative amount of ultraviolet light for the hardening ultraviolet light to be irradiated (that is, the reference to the parameter categories in each of FIGS. 1 to 3, parameter A: 0 mJ/cm2, parameter b ··75〇mJ/cm2) , parameter c : 1〇5〇mj/cm2), obtain the fluorescence spectrum (horizontal axis: the wavelength of the fluorescent light measured by the fluorescence spectrum analyzer, and the vertical axis: the intensity of the fluorescent light emitted from the model sample) . In Fig. 1 (250 nm) and Fig. 3 (35 〇 nm), there is no tens of light amount for the hardening and external lines to be irradiated (parameter A: 〇mj/em2, parameter b: 750 mJ/cm, In the parameter C: 1〇5〇mj/cm2), the waveform of the fluorescence spectrum has a difference. In other words, it has been found that there is no hardening stage corresponding to the ultraviolet curable resin, and the intensity of the fluorescent light emitted from the model sample has a change waveform "the wavelength of the ultraviolet light to be irradiated for fluorescence measurement". On the other hand, in Fig. 2 (300 nm), the cumulative amount of light for the hardened ultraviolet light 145989.doc -36- 201031907 (parameter A: 0 mJ/cm2, parameter B: 750 mJ/cm2, parameter C: In the 1050 mJ/cm2), the waveform of the fluorescence spectrum is different. Therefore, it has been found that there is a hardening stage corresponding to the ultraviolet curable resin, and the intensity of the fluorescent light emitted from the model sample has a varying waveform. The wavelength of ultraviolet light." Based on the above results, 300 nm was selected as the wavelength of the ultraviolet light for fluorescence measurement of the irradiation. Furthermore, 'according to Fig. 2 (300 nm)', the cumulative amount of ultraviolet light (the parameter A: 0 mJ/cm2, parameter B: 750 mJ/cm2, parameter C: 1050 mJ/cm2) of the ultraviolet light for curing is determined. In the waveform of the fluorescence spectrum, a difference in the intensity of the fluorescence is exhibited in a wavelength region of 450 nm or more. From the above results, '450 nm or more' was selected as the wavelength of fluorescence measured by a fluorescence spectrometer. According to the above method, the wavelength of the ultraviolet light for fluorescence measurement irradiated in the irradiation step can be determined for each of the ultraviolet curable resins (that is, the intensity of the fluorescent light emitted from the material contained in the substrate does not exceed The wavelength of the intensity of the fluorescent light emitted from the photopolymerization initiator, and the wavelength of the fluorescent light measured in the measurement step (that is, the fluorescence emitted from the material contained in the substrate and the photopolymerization from the above) The wavelength of the latter of the emitted fluorescence in the initiator is preferentially or selectively determined). Next, a test example for demonstrating the state estimation method of the ultraviolet curable resin of the present invention will be disclosed. Weighing 10% of oxygen resin (Epikote YX8000; manufactured by Japan Epoxy Resins Co., Ltd.) 10 g and photopolymerization initiator fluorescing by ultraviolet irradiation 145989.doc •37· 201031907 Photocationic polymerization initiator (SP-500) ; 4 g, manufactured by ADEKA, and placed in a brown spiral tube for mixing to prepare an ultraviolet curable resin Y. The ultraviolet curable resin Y contains the same monomer and photopolymerization initiator as the ultraviolet curable resin X. A film containing PET is used as a material that emits fluorescence by ultraviolet irradiation, and a film containing PVA and a film containing COP are used as a material that does not emit fluorescence by irradiation with ultraviolet rays. These films are used as a substrate. The ultraviolet curable resin Y was placed on the film containing PVA and the film containing COP, respectively. Using a film bonding machine (LPA3301; manufactured by FUJIPLA Co., Ltd.), a film containing PET, a film containing PVA on which the ultraviolet curable resin Y is placed, and a film containing COP on which the ultraviolet curable resin Y is placed are adhered to each other, thereby including A film of PET, a film containing PVA, and a film containing COP are sequentially laminated to form a film having an ultraviolet curable resin Y layer between the films. In this way, "an ultraviolet curable resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation" is prepared. Next, the produced film is placed in an exposure machine (CV-1 l〇〇-G; manufactured by Fusion UV Systems Japan Co., Ltd.) which is previously set to irradiate ultraviolet rays having a specific wavelength, by any fixed speed Passing through the exposure machine, and using any accumulated light amount (specifically, 0 mJ/cm2, 50 mJ/cm2, 100 mJ/em2, mJ/cm2, 600 mJ/cm2, 1000 mJ/cm2) Samples for demonstration of ultraviolet radiation. In this manner, six kinds of argument samples for the hardening stage in the hardening stage of the ultraviolet curable resin Y from the unhardened state to the fully hardened state were prepared. Next, in the fluorescent intensity measuring device (OL301; manufactured by SENTEC Co., Ltd.) 145989.doc -38 - 201031907, the light source is changed to an LED lamp (output wavelength characteristic is 310 nm), and then cut off for fluorescence measurement. A galvanometer with a wavelength below 45 nm. Then, with respect to the six kinds of argument samples prepared above, the intensity of the fluorescence emitted by the ultraviolet light for fluorescence measurement was measured by the apparatus. The results obtained are shown in Fig. 4 (horizontal axis: cumulative light amount of the ultraviolet rays for curing of the sample for irradiation demonstration, and vertical axis: intensity of fluorescence emitted from the self-certified sample measured by the fluorescence intensity measuring device). As can be seen from Fig. 4, the cumulative amount of ultraviolet light for the curing of the sample for irradiation is increased, and the intensity of the fluorescent light emitted from the self-exploratory sample measured by the fluorescence intensity measuring device is increased, and the correlation is proportionally proportional. Sex. In addition, according to the analysis result of the hardening behavior of the "ultraviolet-curing resin to be used" which is analyzed by infrared spectroscopy, it is determined that the cumulative amount of ultraviolet light for curing is 2 〇〇mJ/cm 2 or more. The hardening reaction of the hardened resin is substantially completed. In addition to the above-mentioned knowledge, the results of the above-mentioned test results are as follows. If the intensity of the fluorescent light emitted from the self-certified sample measured by the fluorescence intensity measuring device reaches 0.4 V or more, the ultraviolet curable resin can be estimated. The hardening reaction is substantially completed (that is, the state of the ultraviolet curable resin). UV-curing was prepared by mixing a ring-shaped latex resin (Epikote YX8000; manufactured by Japan Epoxy Resins Co., Ltd.) with a photopolymerization initiator (SP-500; manufactured by ADEKA Co., Ltd.) which is a photopolymerization initiator which emits fluorescence by ultraviolet irradiation. Resin. The above-prepared ultraviolet curable resin was applied to the surface of the film containing PET which was in contact with PVA and the film containing COP, and the film prepared by using the film bonding machine of 145989.doc -39-201031907 (LPA3301; FUJIPLA) (manufactured by the company), a film containing PET coated with an ultraviolet curing resin, a film containing PVA, and a film containing COP coated with an ultraviolet curing resin are continuously adhered to each other so that a film containing PET, a film containing PVA, and a film containing COP are included. The film was sequentially laminated, and a film having an ultraviolet curable resin layer between the films was continuously produced. The film to be produced is placed in an exposure machine (匸乂-1100-G; manufactured by Fusion UV Systems Japan Co., Ltd.) which is previously set to irradiate ultraviolet rays having a specific wavelength, and is passed through the exposure machine at a fixed speed. The film which is irradiated with ultraviolet rays is produced by a specific amount of light, and the film is produced by continuously irradiating ultraviolet light for fluorescence measurement with a fluorescence intensity measuring device (OL301; manufactured by SENTEC Co., Ltd.), and continuously measuring the fluorescence. The intensity of the fluorescent light emitted by the ultraviolet ray irradiation is checked, and it is checked whether or not the intensity value of the measured fluorescent light is a predetermined value or more, and the specific value of the state in which the curing reaction of the ultraviolet curable resin is substantially completed is determined. Thereby, it can be more easily judged whether or not a film of good quality is continuously produced. A film comprising polycarbonate, a film containing PVA, and a film containing COP may be sequentially laminated in the same manner as described above except that a film containing polycarbonate is used instead of the film containing PET. A film having an ultraviolet curable resin layer is subjected to the same steps as described above for the film to be formed, and the state of the ultraviolet curable resin is estimated. A film comprising a polyether oxime, a film containing PVA, and a film containing COP are sequentially laminated in the same manner as described above except that a film containing polyethersulfone is used instead of the film containing PET. The film of the ultraviolet curable resin layer was subjected to the same steps as described above for the film thus formed, and the state of the ultraviolet curable resin was estimated to be 145989.doc -40·201031907. The film containing pET, the film containing the film, and the film containing PET may be sequentially laminated in the same manner as described above except that the film containing PET is used instead of the film containing c〇p, and the outer film is hardened between the films. The film of the resin layer 'and the state of the ultraviolet curable resin is estimated by performing the same steps as described above on the formed film. [Industrial Applicability] ♦ According to the present invention, it is applicable to an ultraviolet curable resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation, and is based on the characteristics of a photopolymerization initiator. A method of estimating the state of the ultraviolet curable resin, and the like. [Simple description of the map]

Fig. 1 is a graph showing the cumulative amount of ultraviolet light for curing when the wavelength of the ultraviolet light to be irradiated is 25 〇 11111 (parameter A: 0 mJ/cm2, > 75 〇mJ/cm, parameter ς; : the relationship between the wavelength of the fluorescence (horizontal axis) measured by the fluorescence spectrum analyzer and the intensity of the fluorescence emitted by the Φ from the model sample (vertical axis) in 1〇5〇mJ/cm2), that is, A map of the fluorescence spectrum. Fig. 2 is a graph showing the amount of light accumulated for each ultraviolet light to be irradiated when the wavelength of the ultraviolet light for measurement is 3 Å (parameter A: 0 mJ/cm2, number B' 750 mJ/cm2, parameter c: The relationship between the wavelength of the fluorescence measured by the fluorescence spectrometer (horizontal axis) and the intensity of the fluorescence emitted from the model sample (vertical axis) in 1050 mj/cm 2 ), that is, the spectrum of the fluorescence spectrum . Fig. 3 is a graph showing the cumulative amount of ultraviolet light for curing when the wavelength of the ultraviolet light for measurement is 35 〇 nm (parameter A: 〇mj/cm2, parameter B. 750 mJ/cm2, parameter c: 1) 〇5〇mJ/cm2) The relationship between the wavelength of Ai Xian (horizontal axis) and the intensity of fluorescence from the model sample (vertical axis) measured by the fluorescence 145989.doc •41 · 201031907 spectrum analyzer Fig. 4 is a diagram showing the cumulative amount of light (horizontal axis) of the outer line of the squeezing line for the illuminating test material and the firefly emitted by the self-discipline sample measured by the fluorescence intensity measuring device. A diagram showing the correlation of the intensity of light (vertical axis). 145989.doc 42-

Claims (1)

201031907 VII. Patent application scope: 1. A state estimation method for ultraviolet curing resin, which comprises at least one main component selected from the group consisting of monomers and oligomers, and emitted by ultraviolet irradiation. The method for estimating the state of the ultraviolet curable resin of the fluorescent photopolymerization initiator, wherein the ultraviolet curable resin is coexisted with a substrate containing a material that emits fluorescence by ultraviolet irradiation, and the method for estimating the state of the ultraviolet curable resin The method comprising the steps of: irradiating the ultraviolet curable resin with an ultraviolet ray having a wavelength from which the intensity of the camping light emitted from the material does not exceed the intensity of the glare emitted from the photopolymerization initiator; The ultraviolet light is irradiated from both the fluorescent material emitted from the material and the fluorescent light emitted from the photopolymerization initiator, and the fluorescent wavelength t is measured in such a manner that the latter is preferentially or selectively measured. The step of measuring the light intensity; • & the fluorescence intensity measured in the above measurement step, estimating the purple The estimation step of the state of the external hardening resin. 2. The method for estimating the state of the ultraviolet curable resin of the requester, wherein the above-mentioned estimation step (4) is based on the hardening of the outer line for the hardening of the ultraviolet curing resin, and the hardening of the hardening resin The step of estimating the state of the ultraviolet curable resin by the temporal change of the strength of the reaction. 3. In the method of estimating the state of the ultraviolet curable resin of claim 2, the above-mentioned estimation step is based on the temporality of the ray change of the fluorescence intensity of the warp and the preset value of 145989.doc 201031907. The step of describing the state of the ultraviolet curable resin is described. Compare, to estimate the above 4. 5. 6. The method for estimating the state of the ultraviolet curable resin of item 2, wherein the upper=estimating step takes time to obtain a temporal change of the fluorescence intensity characteristic from a specific reference time point, and the required time is obtained The green 曰 曰 之 之 之 之 之 之 基准 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The step of estimating the state of the ultraviolet curable resin by the fluorescence intensity measured before the irradiation with ultraviolet rays, and the method for estimating the state of the ultraviolet curable resin according to claim 1, wherein the estimation step is based on a step of estimating the state of the ultraviolet curable resin by measuring the fluorescence intensity of the ultraviolet curable resin after the curing by the curing of the ultraviolet curable resin. The method for producing the ultraviolet curable resin is selected from the group consisting of a main agent of at least one of a group consisting of a body and an oligomer, and irradiated by ultraviolet rays A method for producing a cured resin obtained by curing an ultraviolet curable resin which emits a fluorescent photopolymerization initiator, comprising the steps of: (Α) a substrate comprising a material which emits fluorescence by ultraviolet irradiation and ultraviolet rays The cured resin 'prepares an ultraviolet curable resin which coexists with a substrate containing a material which emits fluorescence by ultraviolet irradiation; (Β) irradiates the prepared ultraviolet curable resin with ultraviolet rays for curing, and 145989.doc 201031907 hardens the above ultraviolet curing resin (c) irradiating the cured ultraviolet curable resin with ultraviolet rays having a wavelength from which the intensity of the fluorescent light emitted from the material does not exceed the intensity of the fluorescent light emitted from the photopolymerization initiator; In the above step (C), in the ultraviolet light irradiation, the fluorescence emitted from the material and the fluorescence emitted from the photopolymerization initiator are the latter, and the fluorescence wavelength is determined by preferential or selective measurement. The intensity of the fluorescence in the middle; and (E) based on the fluorescence intensity measured in the above step (D), the hardened ultraviolet light is estimated State of the resin, the column off the brake ^ ^ ultraviolet hardening resin or bad-quality "❿ 145989.doc