JP7529448B2 - Method for detecting the mixing ratio of two-component adhesive composition - Google Patents

Description

The present invention relates to a method for detecting the mixing ratio of a two-component adhesive composition.

2. Description of the Related Art Two-part adhesive compositions having a base agent and a curing agent have conventionally been used as adhesives for use in automobile fitting (assembly) and the like.
It has also been proposed to prepare a sealant used for parts of an aircraft or the like by mixing a first material and a second material at the manufacturing site (for example, see Patent Document 1).
As a method for mixing the two-part composition as described above, for example, at the site where the two-part composition is used, first, a first container for containing the base agent and a second container for containing the hardener are prepared. The base agent is pumped out of the first container using a first pump, and the base agent is guided to the mixing device through a first conduit. Meanwhile, the hardener is pumped out of the second container using a second pump, and the hardener is guided to the mixing device through a second conduit. Then, the base agent and the hardener guided to the mixing device from each conduit are mixed in the mixing device to form a mixture, and the mixture is applied to parts or the like.

JP 2018-134630 A

When a two-component composition is mixed at the site of use, the actual mixing ratio of the base agent and the hardener may not be within the specified range due to, for example, changes in the viscosity of the base agent or hardener used, or the base agent or hardener may become clogged or difficult to flow inside the conduits connecting each container to the mixing device.
However, it has been difficult to accurately grasp the actual mixing ratio of the base resin and the hardener in real time at the site where a two-liquid composition is used.

For example, when attempting to analyze the mixture ratio of the base agent and the hardener from the hardness of the hardened product obtained by hardening the mixture of the base agent and the hardener at the site where a two-liquid composition is used, it is not possible to detect the mixture ratio of the base agent and the hardener that is continuously discharged in real time because it takes time to harden the mixture.

On the other hand, by irradiating an object with X-rays and analyzing the resulting fluorescent X-rays, it is possible to determine the types of elements that make up the object and the intensity of the fluorescent X-rays, etc.
Under these circumstances, the present inventors, referring to Patent Document 1, prepared and evaluated a two-liquid type composition containing a compound that generates fluorescent X-rays when irradiated with X-rays.
As a result, it became clear that when the main purpose of adding the above-mentioned compounds is to obtain fluorescence in response to X-ray irradiation (emission of fluorescent X-rays), such compounds may inhibit the adhesion of the two-component composition.

Therefore, an object of the present invention is to provide a detection method capable of quickly and accurately quantifying the mixture ratio of a two-component adhesive composition (base agent and curing agent) having excellent adhesive properties.
Another object of the present invention is to provide a two-component adhesive composition for use therein, and a method for producing the coated article.

As a result of intensive research conducted by the present inventors to solve the above problems,
A step 1 of using a two-component adhesive composition having a base agent and a curing agent and mixing the base agent and the curing agent to obtain a mixture;
A step 2 of irradiating the mixture with X-rays;
a step 3 of measuring the intensity of fluorescent X-rays generated from the mixture irradiated with X-rays;
and a step 4 of quantifying a mixing ratio of the base agent and the curing agent in the mixture based on the intensity of the fluorescent X-rays.
The inventors have found that in the two-component adhesive composition used in step 1, at least one or both of the base agent and the curing agent contain at least one selected from the group consisting of compounds containing calcium, silicon, or aluminum, polymers containing sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays, and that when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the contents of the same type of compound in the base agent and the curing agent are different, a desired effect can be obtained by a method for detecting the mixing ratio of a two-component adhesive composition, and have arrived at the present invention.
The present invention is based on the above findings and has the following specific configuration to solve the above problems.

[1] A step 1 of using a two-component adhesive composition having a base agent and a curing agent, and mixing the base agent and the curing agent to obtain a mixture;
A step 2 of irradiating the mixture with X-rays;
a step 3 of measuring the intensity of fluorescent X-rays generated from the mixture irradiated with X-rays;
and a step 4 of quantifying a mixing ratio of the base agent and the curing agent in the mixture from the intensity of the fluorescent X-rays.
a method for detecting a mixing ratio of a two-component adhesive composition, wherein in the two-component adhesive composition used in step 1, at least one or both of the base agent and the curing agent contain, as an X-ray detectable compound that can be detected by X-rays, at least one selected from the group consisting of a compound having calcium, silicon, or aluminum, a polymer having sulfur, and manganese dioxide, and, when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the content of the same type of compound in the base agent and the curing agent are different.
[2] The method for detecting a mixing ratio of a two-component adhesive composition according to [1], wherein the X-ray detectable compound is at least one selected from the group consisting of calcium carbonate, silica, aluminum oxide, polysulfide polymer, and manganese dioxide.
[3] Using an X-ray fluorescence analyzer in the steps 2 and 3,
the X-ray fluorescence analyzer is an energy dispersive X-ray fluorescence analyzer having an X-ray tube using Rh, W, Ag, Cr, or Fe as a target material as an X-ray excitation source, and a silicon semiconductor detector, a silicon drift detector, or a silicon PIN diode detector as a detector;
The method for detecting a mixing ratio of a two-component adhesive composition according to [1] or [2], wherein the weight of the X-ray fluorescence analyzer is less than 5 kg.
[4] The method for detecting a mixing ratio of a two-component adhesive composition according to any one of [1] to [3], further comprising a step 5 of determining whether the mixing ratio quantified in step 4 is within a predetermined range of mixing ratios, and, if the mixing ratio quantified in step 4 is outside the predetermined range of mixing ratios, adjusting the amount of the base agent and/or the curing agent so that the mixing ratio outside the predetermined range of mixing ratios becomes an appropriate mixing ratio.

[5] A method for producing a coated product, comprising the method for detecting the mixing ratio of a two-component adhesive composition described in any one of [1] to [4], and further comprising a coating step of coating the mixture on a substrate.

[6] A two-component adhesive composition used in a method for detecting a mixing ratio of the two-component adhesive composition according to any one of [1] to [4],
Contains a base agent and a hardener,
A two-component adhesive composition in which at least one or both of the base agent and the curing agent contain at least one type selected from the group consisting of a compound having calcium, silicon, or aluminum, a polymer having sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays, and when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the content of the same type of compound in the base agent and the curing agent are different.

The method for detecting the mixing ratio of a two-component adhesive composition of the present invention can rapidly and accurately quantify the mixing ratio of a two-component adhesive composition (base agent and curing agent) having excellent adhesive properties.
Furthermore, the two-component adhesive composition of the present invention used in the method for detecting the mixing ratio of the two-component adhesive composition of the present invention has excellent adhesiveness, and the mixing ratio of the base agent and the curing agent can be rapidly and accurately quantified.
According to the method for producing a coated product of the present invention, a two-component adhesive composition having excellent adhesive properties can be applied to a substrate by quickly and accurately determining the mixture ratio of the base agent and the curing agent.

FIG. 1 is a graph 1-A showing the relationship between the mixing ratio of the hardener to the base agent and the Si concentration ratio (Si/Ca) measured by fluorescent X-ray intensity for this Example 1 and Comparative Example 1. FIG. 2 is a graph 2 showing the relationship between the mixing ratio of the hardener to the base agent and hardness 1 for this Example 1 and Comparative Example 1. FIG. 3 is a graph 1-B showing the relationship between the mixing ratio of the hardener to the base agent and the Ca concentration measured by the fluorescent X-ray intensity for the present Examples 1 and 2 and Comparative Example 1. FIG. 4 is a graph 3 showing the relationship between the number of rotations of the motor of the second supply device that supplies the hardener and the average discharge amount when the base agent and the hardener are mixed and discharged using the two-component adhesive mixing and discharging device of this Example 1. FIG. 5 is an example of a chart showing the spectrum of fluorescent X-rays (Kα rays) of Ca, measured using a general fluorescent X-ray analyzer.

The present invention will be described in detail below.
In this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In this specification, unless otherwise specified, each component may be used alone or in combination of two or more substances corresponding to that component. When a component contains two or more substances, the content of the component means the total content of the two or more substances.
In this specification, the effect of the present invention may be said to be superior in at least one of the following: excellent adhesion; and the ability to rapidly and accurately quantify the mixing ratio of the two-component adhesive composition.

[Method for detecting the mixing ratio of a two-component adhesive composition]
The method for detecting the mixing ratio of the two-component adhesive composition of the present invention (the detection method of the present invention) is as follows:
A step 1 of using a two-component adhesive composition having a base agent and a curing agent and mixing the base agent and the curing agent to obtain a mixture;
A step 2 of irradiating the mixture with X-rays;
a step 3 of measuring the intensity of fluorescent X-rays generated from the mixture irradiated with X-rays;
and a step 4 of quantifying a mixing ratio of the base agent and the curing agent in the mixture based on the intensity of the fluorescent X-rays.
The method for detecting a mixing ratio of a two-component adhesive composition used in step 1 is such that at least one or both of the base agent and the curing agent contain, as an X-ray detectable compound that can be detected by X-rays, at least one selected from the group consisting of a compound containing calcium, silicon, or aluminum, a polymer containing sulfur, and manganese dioxide, and that when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the content of the same type of compound in the base agent and the curing agent are different.

<Step 1>
In the detection method of the present invention, step 1 is a step of using a two-liquid adhesive composition having a base agent and a curing agent, and mixing the base agent and the curing agent to obtain a mixture.
In step 1, the base agent and the curing agent of the two-part adhesive composition can be mixed, for example, as follows to obtain a mixture.
First, the base agent is placed in a first container, and the hardener is placed in a second container.
The base material is pumped from the first container and guided to the mixing device through a first conduit. A first supply device can be used to supply the base material to the mixing device. For example, the supply amount of the base material can be changed by changing the rotation speed of the motor of the first supply device. A first pump can be used to pump the base material from the first container.
On the other hand, the hardener is pumped from the second container and is guided to the mixing device through a second conduit. A second supply device can be used to supply the hardener to the mixing device. For example, the supply amount of the hardener can be changed by changing the rotation speed of the motor of the second supply device. A second pump can be used to pump the base material from the second container.
The base agent and the curing agent are introduced into the mixing device from their respective conduits and mixed in the mixing device to form a mixture, which may be discharged from the mixing device or applied to a substrate.

The mixing device is not particularly limited as long as it can mix the base agent and the curing agent in the manner described above. For example, a static mixer can be used.

The two-part adhesive composition used in the detection method of the present invention will be described later as the two-part adhesive composition of the present invention.

<Step 2>
In the detection method of the present invention, step 2 is a step of irradiating the mixture obtained in step 1 with X-rays.
The X-rays irradiated in step 2 include, for example, X-rays from an X-ray tube as an X-ray excitation source.
The X-ray tube used in step 2 is not particularly limited.
Examples of the target material in the X-ray tube include Rh (rhodium), W (tungsten), Ag, Cr, and Fe, with Rh, W, and Ag being preferred.

<Step 3>
In the detection method of the present invention, step 3 is a step of measuring the intensity of fluorescent X-rays generated from the mixture irradiated with X-rays in step 2.
The detector used to detect the fluorescent X-rays in step 3 may be, for example, a silicon semiconductor detector, a silicon drift detector, or a silicon PIN diode detector.

The detector is typically capable of detecting elements with atomic numbers 11 through 92.
In the present invention, at least one or both of the base agent and the curing agent of the two-component adhesive composition used contains, as an X-ray detectable compound that can be detected by X-rays, at least one selected from the group consisting of compounds containing calcium, silicon, or aluminum, polymers containing sulfur, and manganese dioxide.
For this reason, in step 3, at least one X-ray detectable element selected from the group consisting of calcium, silicon, aluminum, sulfur and manganese corresponding to the X-ray detectable compound and the fluorescent X-ray intensity (also referred to as "fluorescent X-ray intensity") of the X-ray detectable element are analyzed.

Attached Figure 5 is an example of a chart showing the fluorescence X-ray (Kα ray) spectrum of Ca measured using a general X-ray fluorescence analyzer.

When the X-ray detectable compound used in the two-component adhesive composition contains two or more elements (the above-mentioned X-ray detectable elements) that are the subject of fluorescent X-ray analysis to quantify the mixture ratio of the base agent and the curing agent, the combination is preferably a combination of silicon and calcium.

When a plurality of characteristic spectra (Kα rays, Kβ rays, etc.) are detected as fluorescent X-rays from one element, one preferred embodiment is to measure the intensity of the Kα rays as the fluorescent X-ray intensity.
The fluorescent X-ray spectrum of silicon (Kα radiation) is observed in the range of 1.5 to 2.0 keV.
The fluorescent X-ray spectrum of calcium (Kα radiation) is observed in the region of 3.5 to 3.9 keV.
The fluorescent X-ray spectrum (Kα radiation) of aluminum is observed in the range of 1.3 to 1.7 keV.
The fluorescent X-ray spectrum (Kα radiation) of sulfur is observed in the region of 2.1 to 2.5 keV.
The fluorescent X-ray spectrum (Kα radiation) of manganese is observed in the region of 5.7 to 6.1 keV.

<Fluorescent X-ray Intensity>
In the present invention, the intensity of the fluorescent X-rays of at least one X-ray detectable element selected from the group consisting of calcium, silicon, aluminum, sulfur, and manganese can be expressed by the peak area of the fluorescent X-rays of each element (when one element has multiple inherent spectra as fluorescent X-rays, it can be in the Kα ray region; the same applies below). The same applies to elements with atomic numbers 11 to 92 (excluding the above X-ray detectable elements).

<Intensity of fluorescent X-rays emitted from the mixture>
In the present invention, the intensity of the fluorescent X-rays generated from the mixture (the intensity of the fluorescent X-rays of the above-mentioned X-ray detectable elements generated from the mixture) can be expressed by the peak area of the fluorescent X-rays of each element (the above-mentioned X-ray detectable elements). The same applies to elements with atomic numbers 11 to 92 (excluding calcium, silicon, aluminum, sulfur, and manganese).

Concentration of each element in all atoms based on the fluorescent X-ray intensity of each element As described above, the detector used in step 3 can usually detect elements with atomic numbers from 11 to 92. Therefore, the device used in step 3 may have a function of, for example, automatically calculating and displaying the concentration of each element in all detected atoms based on the data on the fluorescent X-ray intensity of each detected element.
For this reason, in the present invention, the concentration of each element in all atoms (content concentration of each element, unit %) obtained in step 3 based on data on the intensity of the fluorescent X-rays of each element detected can be treated as the intensity of the fluorescent X-rays.
In other words, based on the data on the intensity of the fluorescent X-rays of each of the X-ray detectable elements, the concentration of each of the X-ray detectable elements in all atoms (content concentration of each X-ray detectable element, in % or ppm) can be treated as the "intensity of the fluorescent X-rays."

When only one of the base agent and the curing agent contains the first X-ray detectable compound When only one of the base agent and the curing agent in the two-component adhesive composition contains the first X-ray detectable compound (containing the first X-ray detectable element), in step 3, the intensity of the fluorescent X-rays originating from the first X-ray detectable element and generated from the mixture of the base agent and the curing agent can be measured.

When only one of the base agent and the curing agent contains a first X-ray detectable compound, and both the base agent and the curing agent further contain a second X-ray detectable compound When only one of the base agent and the curing agent in the two-component adhesive composition contains a first X-ray detectable compound (the first X-ray detectable compound contains a first X-ray detectable element (e.g., silicon)), and both the base agent and the curing agent further contain a second X-ray detectable compound (the second X-ray detectable compound contains a second X-ray detectable element (e.g., calcium)), in step 3, the intensities of fluorescent X-rays originating from the first and second X-ray detectable elements generated from a mixture of the base agent and the curing agent may be measured.

When the concentration of each of the X-ray detection elements in all atoms (content concentration of each X-ray detection element, unit %) is obtained based on the data on the intensity of the fluorescent X-rays of each of the X-ray detection elements, the concentration ratio of the first and second X-ray detection elements (concentration of the first X-ray detection element/concentration of the second X-ray detection element; the sum of the concentration ratio of the first X-ray detection element and the concentration ratio of the second X-ray detection element is 100) can be calculated from the concentration results of each of the X-ray detection elements.
When only one of the base agent and the curing agent contains a first X-ray detectable compound and both the base agent and the curing agent further contain a second X-ray detectable compound, from the viewpoint of achieving a superior effect of the present invention (particularly, enabling the mixing ratio of the base agent and the curing agent to be more accurately quantified), one preferred embodiment is to use the concentration ratio of the first and second X-ray detectable elements as the fluorescent X-ray intensity of each X-ray detectable element.

- When the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound (however, in the present invention, in the above case, the content of the same type of compound in the base agent and the curing agent is different).
When the base agent and the curing agent of the two-component adhesive composition contain only compounds of the same type as the X-ray detectable compound, that is, when both the base agent and the curing agent each contain only a first X-ray detectable compound (the first X-ray detectable compound contains a first X-ray detectable element (e.g., calcium)) as the X-ray detectable compound (however, in the present invention, in the above case, the contents of the same type of compound (first X-ray detectable compound) in the base agent and the curing agent are different), in step 3, the intensity (total amount) of fluorescent X-rays generated from a mixture of the base agent and the curing agent and originating from the X-ray detectable element contained in the same type of compound (the first X-ray detectable element contained in the first X-ray detectable compound) can be measured.

From the viewpoint of obtaining superior effects of the present invention (particularly, being able to more accurately determine the mixing ratio of the base agent and the curing agent), it is preferred that in the above-mentioned two-component adhesive composition, only one of the base agent and the curing agent contains the first X-ray detection compound, and both the base agent and the curing agent each further contain the second X-ray detection compound.

In the present invention, an apparatus in which the X-ray tube used in step 2 and the detector used in step 3 are integrated can be used.
The above-mentioned device may be, for example, an X-ray fluorescence analyzer, and among these, an energy dispersive X-ray fluorescence analyzer is preferred.
One preferred embodiment of an X-ray fluorescence analyzer is one that can measure the types of elements constituting a sample and the concentration (content concentration) of each element in all detected atoms by irradiating a sample with X-rays and detecting and analyzing the fluorescent X-rays emitted by the sample and their intensity.
The X-ray fluorescence analyzer may have a screen that displays the type of elements as a result of the analysis of the sample, and the fluorescent X-ray intensity of each element or the concentration (content concentration) of each element (expressed in %) or PPM.

Examples of the X-ray fluorescence analyzer include a tabletop (fixed) type (a sample is brought to the location of the analyzer) and a handy type (the analyzer can be carried and measurements can be made at the location). From the viewpoint of being able to be used at the site where the two-component adhesive composition is used, the X-ray fluorescence analyzer is preferably a handy type.
The weight of the above-mentioned X-ray fluorescence analyzer is preferably less than 5 kg so that it can be used at the site where the two-component adhesive composition is used and is convenient to carry.

In the present invention, by using the above-mentioned X-ray fluorescence analyzer, steps 2 and 3 can be carried out almost simultaneously.
Furthermore, steps 2 and 3 can be carried out on the mixture immediately after mixing the base agent and the curing agent.
Steps 2 and 3 may be carried out, for example, on the mixture that is continuously applied to the substrate.

An example of a commercially available X-ray fluorescence analyzer is the VANTA series manufactured by Olympus Corporation.

<Step 4>
In the detection method of the present invention, step 4 is a step of quantifying the mixture ratio of the base agent and the curing agent in the mixture from the intensity of the fluorescent X-rays generated from the mixture measured in step 3.
The intensity of the fluorescent X-rays generated from the mixture and used in step 4 may be the measured intensity of the fluorescent X-rays themselves, or, as described above, may be the concentration of each of the X-ray detectable elements in all atoms, or the ratio of the concentrations of the first and second X-ray detectable elements, which is obtained based on data on the intensity of the fluorescent X-rays of each of the X-ray detectable elements.

When the data used in step 4 is the intensity of fluorescent X-rays generated from the mixture itself, the procedure in step 4 can be roughly described as follows: draw a calibration curve of the fluorescent X-ray intensity results and the base agent/curing agent ratio, measure the fluorescent X-ray intensity of the measurement sample, and apply the measurement results to the calibration curve to determine the base agent/curing agent mixture ratio of the measurement sample.
When the data used in step 4 is the concentration of each of the X-ray detectable elements in all atoms as described above, a calibration curve of the concentration of each of the X-ray detectable elements in all atoms and the ratio of base agent/hardener can be drawn to obtain the concentration of each of the X-ray detectable elements in all atoms of the measurement sample, and the result is applied to the calibration curve to determine the mixing ratio of base agent/hardener of the measurement sample.
The same applies when the data used in step 4 is the ratio of the concentrations of the first and second X-ray detection elements.

(Calibration curve)
The following describes the creation of the calibration curve, taking as an example a case where the data used in step 4 is the intensity of the fluorescent X-rays generated from the mixture itself as is. The same applies to a case where the data used in step 4 is the concentration of each of the X-ray detection elements in all atoms, or the ratio of the concentrations of the first and second X-ray detection elements.

First, in step 4, the fluorescent X-ray intensity of a mixture in which the amount of curing agent relative to the base agent of a two-component adhesive composition is actually measured in advance and varied is measured, and a calibration curve is created based on the results.
The measurement of the fluorescent X-ray intensity of the above mixture for preparing the calibration curve can be carried out in the same manner as in steps 2 and 3 of the detection method of the present invention.

(Measurement of fluorescent X-ray intensity and preparation of calibration curve)
When only one of the base agent and the curing agent contains the first X-ray detectable compound When only one of the base agent and the curing agent in the two-component adhesive composition contains the first X-ray detectable compound (containing the first X-ray detectable element), the intensity of the fluorescent X-rays generated from the mixture of the base agent and the curing agent and originating from the first X-ray detectable element can be measured in accordance with step 3 of the detection method of the present invention.
In the above case, the calibration curve is created as a relationship between the ratio of the curing agent to the base agent of the two-component adhesive composition and the intensity of the fluorescent X-rays derived from the first X-ray detectable element.

When only one of the base agent and the curing agent contains a first X-ray detectable compound, and both the base agent and the curing agent further contain a second X-ray detectable compound When only one of the base agent and the curing agent in the two-component adhesive composition contains a first X-ray detectable compound (the first X-ray detectable compound contains a first X-ray detectable element (e.g., silicon)), and both the base agent and the curing agent further contain a second X-ray detectable compound (the second X-ray detectable compound contains a second X-ray detectable element (e.g., calcium)), the intensities of fluorescent X-rays originating from the first and second X-ray detectable elements generated from a mixture of the base agent and the curing agent can be measured in accordance with step 3 of the detection method of the present invention.

- When the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound (however, in the present invention, in the above case, the content of the same type of compound in the base agent and the curing agent is different).
When the base agent and the curing agent of the two-component adhesive composition contain only compounds of the same type as the X-ray detectable compound, that is, when both the base agent and the curing agent each contain only a first X-ray detectable compound (the first X-ray detectable compound contains a first X-ray detectable element (e.g., calcium)) as the X-ray detectable compound (however, in the present invention, in the above case, the contents of the same type of compound (first X-ray detectable compound) in the base agent and the curing agent are different), in step 3, the intensity (total amount) of fluorescent X-rays generated from a mixture of the base agent and the curing agent and originating from the X-ray detectable element contained in the same type of compound (the first X-ray detectable element contained in the first X-ray detectable compound) can be measured.
In the above case, the calibration curve is created as the relationship between the ratio of the curing agent to the base agent in the two-component adhesive composition and the intensity (total amount) of fluorescent X-rays originating from an X-ray detectable element contained in a compound of the same type (the first X-ray detectable element contained in the first X-ray detectable compound).

(Actual Mix Ratio)
Next, the intensity of the fluorescent X-rays generated from the mixture obtained in step 1 and measured in step 3 is applied to the calibration curve, so that the mixing ratio of the base agent to the curing agent in the mixture whose fluorescent X-rays were measured in step 3 can be quantified.

As described above, the detection method of the present invention makes it possible to quickly and accurately detect (quantify) the mixture ratio of the base agent and the curing agent in a two-component adhesive composition.

The detection method of the present invention preferably further comprises step 5.
Step 5 is a step of determining whether the mixing ratio quantified in step 4 falls within a predetermined range of mixing ratios, and if the mixing ratio quantified in step 4 falls outside the predetermined range of mixing ratios, adjusting the amount of the base agent and/or the curing agent so that the mixing ratio outside the predetermined range of mixing ratios becomes an appropriate mixing ratio.

The above-mentioned range of the specified mixing ratio can be determined appropriately, for example, according to a quality-guaranteed mixing ratio.

If the result of the above judgment is that the mixture ratio quantified in step 4 is within the range of the predetermined mixture ratio, mixing in step 1 can be continued as is.

On the other hand, if the result of the above judgment is that the mixing ratio quantified in step 4 is outside the range of the predetermined mixing ratios, the amount of the base agent and/or the curing agent is adjusted so that the mixing ratio outside the range of the predetermined mixing ratios becomes an appropriate mixing ratio.
For example, depending on whether the mixture is outside the predetermined range, the amount of base agent per unit of measurement may be increased or decreased, or the amount of hardener per unit of measurement may be increased or decreased.

[Method of manufacturing the coating material]
The method for producing the coated product of the present invention (the method for producing the coated product of the present invention) comprises the steps of:
A method for producing a coated article includes the method for detecting the mixing ratio of the two-component adhesive composition of the present invention, and further includes a coating step of coating the mixture onto a substrate.

Detection method
The detection method in the production method of the present invention is not particularly limited as long as it is a detection method of the present invention.

<Coating process>
The production method of the present invention further comprises a coating step of coating the mixture onto a substrate, in addition to the steps of the detection method of the present invention.
In the coating step, the mixture can be coated onto a substrate to obtain a coating.
The mixture in the coating step may be a mixture obtained by mixing a base agent and a curing agent contained in a two-component adhesive composition.
The coating step in the manufacturing method of the present invention may be performed at any timing with respect to the detection method. For example, the coating step may be performed in parallel with the detection method. Also, for example, the coating step may be stopped during steps 2 to 4 (or steps 2 to 5) in the detection method, and may be resumed together with step 1 after step 4 (or step 5) is completed.

The coating method in the coating step is not particularly limited. For example, it may be discharged from the static mixer.

The conditions for curing the mixture are not particularly limited.
The mixture is preferably curable by the action of moisture and/or heat.

There is no particular limitation on the substrate to which the mixture can be applied.
Substrates to which the mixture can be applied include, for example, plastics, glass, rubber, metals, etc. Suitable substrates include substrates containing plastics. The plastics may be, for example, homopolymers, copolymers, or hydrogenated products. The same is true for rubbers.

Examples of the plastics include polyolefins such as polypropylene, polyethylene, ethylene-propylene copolymers, COP (cycloolefin polymer), and COC (cycloolefin copolymer);
Polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT);
Examples of the resin include polymethyl methacrylate resin (PMMA resin); polycarbonate resin; polystyrene resin; acrylonitrile-styrene copolymer resin; polyvinyl chloride resin; acetate resin; ABS resin (acrylonitrile butadiene styrene resin); and polyamide resin.
The COC may, for example, be a cycloolefin copolymer such as a copolymer of tetracyclododecene and an olefin such as ethylene.
Examples of the COP include cycloolefin polymers such as polymers obtained by ring-opening polymerization of norbornenes and hydrogenation.
The plastic may be a poorly adhesive resin.

The substrate may be surface-treated. Examples of surface treatments include flame treatment, corona treatment, itro treatment, and plasma treatment. There are no particular limitations on the method of each of the above surface treatments. For example, conventionally known methods may be used.

The substrate is preferably a substrate containing polyolefin, and more preferably a substrate containing polypropylene.
The substrate may further contain, in addition to the above-mentioned plastic (eg, polyolefin) or rubber, for example, a filler.
Examples of the filler include carbon fiber;
Glass, such as glass filler;
Examples include talc, calcium carbonate, and alumina.

After the coating step, another substrate may be laminated or bonded to the coating obtained in the coating step to form a laminate. The other substrate is not particularly limited. Examples of the substrate are the same as the substrates to which the mixture can be applied, as described above.

[Two-component adhesive composition]
The two-component adhesive composition of the present invention (the composition of the present invention) is
A two-component adhesive composition used in the method for detecting a mixing ratio of a two-component adhesive composition of the present invention,
Contains a base agent and a hardener,
This is a two-component adhesive composition in which at least one or both of the base agent and the curing agent contain at least one type selected from the group consisting of compounds containing calcium, silicon, or aluminum, polymers containing sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays, with the proviso that when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the content of the same type of compound in the base agent and the curing agent are different.

The two-component adhesive composition used in the above-mentioned method for detecting the mixing ratio of a two-component adhesive composition of the present invention (step 1) is the same as the two-component adhesive composition of the present invention.

The two-part adhesive composition of the present invention has a base agent and a curing agent.

In the two-component adhesive composition of the present invention, the combination of the base agent and the curing agent is not particularly limited. Examples of the two-component adhesive composition include a urethane adhesive composition (wherein the base agent contains, for example, a polyisocyanate and the curing agent contains an active hydrogen-containing compound), an epoxy adhesive composition, an acrylic adhesive composition, a modified silicone adhesive composition, and a polysulfide adhesive composition.
One of the preferred embodiments of the two-component adhesive composition of the present invention is a urethane-based adhesive composition.
Each component contained in the composition of the present invention will be described below.

<Main ingredient>
The base agent of the composition of the present invention may include, for example, polyisocyanates. The polyisocyanates are not particularly limited as long as they are compounds having a plurality of isocyanate groups. Examples of polyisocyanates include urethane prepolymers and low molecular weight polyisocyanate compounds. The polyisocyanate compounds may be used to form urethane prepolymers.

Examples of the polyisocyanate compound include aromatic polyisocyanate compounds such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and triphenylmethane triisocyanate;
Aliphatic (the aliphatic is a concept including linear, branched and alicyclic) polyisocyanates, such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (H ₆ XDI), and dicyclohexylmethane diisocyanate (H ₁₂ MDI);
These modified polyisocyanates include:

One preferred embodiment of the polyisocyanate is a urethane prepolymer.

The active hydrogen-containing compound capable of forming the urethane prepolymer together with the polyisocyanate compound is not particularly limited as long as it is a compound having active hydrogen.
Examples of the active hydrogen-containing compound include polyols, polyamines, and polythiols. Among these, polyols are preferred, polyether polyols are more preferred, and difunctional polyether polyols and/or trifunctional polyether polyols are even more preferred.

Examples of polyether polyols include polyoxyethylene diol (polyethylene glycol), polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, ethylene oxide/propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and polytetraethylene glycol.
Of the polyether polyols, polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, and ethylene oxide/propylene oxide copolymers are preferred.

The weight average molecular weight of the polyether polyol is preferably 500 to 20,000. In the present invention, the weight average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) (solvent: tetrahydrofuran (THF)).

From the viewpoint of achieving superior predetermined adhesiveness and excellent curing properties, the urethane prepolymer is preferably a urethane prepolymer obtained by reacting a polyether polyol with an aromatic polyisocyanate compound.
The urethane prepolymers may be used alone or in combination of two or more kinds.

The method for producing the urethane prepolymer is not particularly limited. For example, a polyisocyanate compound is used so that 1.5 to 2.5 moles of isocyanate groups react with 1 mole of active hydrogen-containing groups (e.g., hydroxyl groups) of the active hydrogen-containing compound, and the urethane prepolymer can be produced by mixing and reacting them.
The urethane prepolymers may be used alone or in combination of two or more kinds.

<Curing Agent>
The curing agent contained in the composition of the present invention may be any agent that at least contains a curing agent (curing agent in the narrow sense) as a substantial curing component. Hereinafter, the curing agent contained in the composition of the present invention may be referred to as a "curing agent in the broad sense", and the curing agent as a substantial curing component may be referred to as a "curing agent in the narrow sense".

The curing agent in the narrow sense is not particularly limited as long as it is a compound containing a plurality of groups having active hydrogen (active hydrogen-containing compound).
The curing agent in the narrow sense includes, for example, a compound having at least two functional groups selected from the group consisting of a hydroxy group, an amino group, an imino group, a thiol group, and a carboxy group.
Specific examples of the curing agent in the narrow sense include polyols, polyamines, and polythiols. Among them, polyols are preferred, polyether polyols and polyols represented by the following formula (4) are more preferred, and trifunctional polyether polyols, tetrafunctional polyether polyols, and polyols represented by the following formula (4) are even more preferred.

In formula (4), R ₆ to R ₉ each independently represent a propylene group, R ₁₀ represents an ethylene group, and a to d each independently represent 1 to 10.

Examples of polyether polyols include polyoxyethylene diol (polyethylene glycol), polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, ethylene oxide/propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and polytetraethylene glycol.
Of the polyether polyols, polyoxypropylene diol (polypropylene glycol: PPG), polyoxypropylene triol, and ethylene oxide/propylene oxide copolymers are preferred.

The weight-average molecular weight of the polyether polyol is preferably 500 to 20,000, from the viewpoint that the viscosity of the reaction product obtained by the reaction with the polyisocyanates contained in the base resin has an appropriate fluidity at room temperature. In the present invention, the weight-average molecular weight is a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) method (solvent: tetrahydrofuran (THF)).

<X-ray detection compound>
In the composition of the present invention, at least one or both of the base agent and the curing agent contain at least one selected from the group consisting of compounds containing calcium, silicon, or aluminum, polymers containing sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays. However, when the base agent and the curing agent contain only the same type of compound as the X-ray detectable compound, the content of the same type of compound in the base agent and the curing agent is different.

The X-ray detection compound is capable of producing fluorescent X-rays when irradiated with X-rays.
The X-ray detecting compound has an X-ray detecting element (an element that can be detected by fluorescent X-rays generated by irradiating with X-rays), and the X-ray detecting element includes calcium, silicon, aluminum, sulfur, or manganese.
In the case where a compound containing calcium is used as the X-ray detection element, one preferred embodiment is to use only one type of compound containing calcium (e.g., calcium carbonate). The same applies to compounds containing silicon or aluminum.
The X-ray detecting compound is preferably capable of contributing to, for example, the adhesiveness, strength, etc., of the adhesive obtained from the composition of the present invention. On the other hand, the X-ray detecting compound is preferably one that does not inhibit the adhesiveness, etc.

The compound containing calcium, silicon, or aluminum is preferably an inorganic filler.

The calcium-containing compound as the X-ray detection compound is preferably calcium carbonate. The calcium carbonate is not particularly limited. The calcium carbonate may contain silicon as an impurity.
The silicon-containing compound is preferably silica. The silica is not particularly limited.
The aluminum-containing compound is preferably aluminum oxide. The aluminum oxide is not particularly limited.
The sulfur-containing polymer is preferably a polysulfide polymer. The polysulfide polymer has, in the main chain,
₍ A ₎ -( _{C2H4OCH2OC2H4} - _Sx )- (where x is an integer from 1 _to 5.)
and at the terminal
(a) There are no particular limitations as long as it has a thiol group represented by --C ₂ H ₄ OCH ₂ OC ₂ H ₄ --SH.
The manganese dioxide is not particularly limited.

From the viewpoint of achieving superior effects of the present invention, the X-ray detection compound preferably contains at least one selected from the group consisting of calcium carbonate, silica, aluminum oxide, polysulfide polymer, and manganese dioxide, more preferably contains at least one selected from the group consisting of calcium carbonate, silica, and aluminum oxide, and even more preferably contains calcium carbonate and/or silica.

In the composition of the present invention, at least one or both of the base agent and the curing agent contain the X-ray detection compound.

The X-ray detection compound may be added to the base agent or the curing agent, for example.
When only one of the base agent and the curing agent contains a first X-ray detecting compound (in the above case, the remaining one may optionally contain a second X-ray detecting compound. Note that when only one of the base agent and the curing agent contains a first X-ray detecting compound, this does not include the case described below where only one of the base agent and the curing agent contains a first X-ray detecting compound and both the base agent and the curing agent further contain a second X-ray detecting compound),
When only one of the base agent and the curing agent contains a first X-ray detecting compound (e.g., a compound containing silicon), and both the base agent and the curing agent further contain a second X-ray detecting compound (e.g., a compound containing calcium) (in the above case, the contents of the second X-ray detecting compound in the base agent and the curing agent may be the same or different, but from the viewpoint of obtaining a superior effect of the present invention, it is preferable that the contents of the second X-ray detecting compound in the base agent and the curing agent are different).
Examples of the X-ray detecting compound include a case where the base agent and the curing agent contain only the same type of compound, that is, a case where both the base agent and the curing agent each contain only a first X-ray detecting compound (e.g., a compound having calcium) as the X-ray detecting compound (however, in the present invention, in the above case, the content of the same type of compound (first X-ray detecting compound) in the base agent and the curing agent is different).

However, in the composition of the present invention, when the base agent and the hardener contain only the same type of compound as the X-ray detecting compound (when both the base agent and the hardener contain, for example, only calcium carbonate as the first X-ray detecting compound), the content of the same type of compound in the base agent and the hardener is different (in the above example, the concentration of the calcium carbonate compound in the base agent and the concentration of the calcium carbonate compound in the hardener are different).
The above "same kind of compound as X-ray detection compound" means that the compound is the same at the level of the compound name. Examples of the level of the above "same kind of compound as X-ray detection compound" include calcium carbonate, silica, aluminum oxide, polysulfide polymer, and manganese dioxide. When the base agent and the hardener contain only the same kind of compound as the X-ray detection compound, if the same kind of compound is, for example, calcium carbonate, the base agent and the hardener may each contain only calcium carbonate as the X-ray detection compound.
When the base agent and the curing agent contain only the same type of compound as the X-ray detecting compound, the different contents of the same type of compound in the base agent and the curing agent mean that the base agent contains only a first X-ray detecting compound, the curing agent contains only a first X-ray detecting compound, and the content (mass %) of the first X-ray detecting compound in the base agent is greater or smaller than the content (mass %) of the first X-ray detecting compound in the curing agent.
In the above case, one aspect in which the content (mass %) of the first X-ray detecting compound in the base agent is greater than the content (mass %) of the first X-ray detecting compound in the curing agent is mentioned.

When the composition of the present invention contains multiple types of X-ray detection compounds as the X-ray detection compounds, one preferred embodiment is that the X-ray detection elements of each X-ray detection compound are different elements. When, for example, a first X-ray detection compound and a second X-ray detection compound are used as the X-ray detection compounds, it is preferred that the X-ray detection elements of the first X-ray detection compound and the second X-ray detection compound are different elements.

As for the addition of the X-ray detection compound to the base agent or the hardener, from the viewpoint of obtaining a superior effect of the present invention (particularly, being able to more accurately determine the mixing ratio of the base agent and the hardener), it is preferable that in the composition of the present invention, only one of the base agent and the hardener contains a first X-ray detection compound (e.g., a compound containing silicon) and both the base agent and the hardener contain a second X-ray detection compound (e.g., a compound containing calcium), and it is more preferable that only the hardener contains a first X-ray detection compound (e.g., a compound containing silicon) and both the base agent and the hardener contain a second X-ray detection compound (e.g., a compound containing calcium).

(Content of X-ray detectable compound)
The content A of the X-ray detectable compound in the base material is preferably 0 to 30 parts by mass, and more preferably 10 to 25 parts by mass, per 100 parts by mass of the base material, from the viewpoint of obtaining a superior effect of the present invention.
When the base material contains a compound having calcium as the X-ray detectable compound, the content of the calcium-containing compound is preferably 10 to 25 parts by mass in 100 parts by mass of the base material.

From the viewpoint of obtaining superior effects of the present invention, the content B of the X-ray detectable compound in the curing agent is preferably 0 to 50 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, in 100 parts by mass of the curing agent (in a broad sense).
However, in the present invention, the total amount of the content A of the X-ray detectable compound and the content B of the X-ray detectable compound is more than 0 mass % in the composition of the present invention.

When the curing agent contains at least a compound having calcium as the X-ray detectable compound, the content of the calcium-containing compound is preferably 10 to 45 parts by mass in 100 parts by mass of the curing agent (in a broad sense).
When the curing agent contains a calcium-containing compound and a silicon-containing compound as X-ray detecting compounds, the content of the silicon-containing compound is preferably 1 to 5 parts by mass in 100 parts by mass of the curing agent (broad definition). In the above case, the content of the calcium-containing compound is preferably 10 to 45 parts by mass in 100 parts by mass of the curing agent (broad definition).

(Additive)
The composition of the present invention may further contain additives such as carbon black, plasticizers, and curing catalysts in addition to the X-ray detecting compound.
The additives may be included in the base agent and/or the curing agent as appropriate.

The method for preparing the base agent and the curing agent of the composition of the present invention is not particularly limited. For example, a conventionally known method may be used.

The present invention will be specifically explained below with reference to examples. However, the present invention is not limited to these.

<Production of two-component adhesive composition>
The components in Table 1 below were mixed in the amounts (parts by mass) shown in the table to produce the base agent and curing agent of a two-component adhesive composition.

Details of each component shown in Table 1 are as follows.
<Main ingredient>
Urethane prepolymer: A urethane prepolymer produced by mixing 70 parts by mass of polyoxypropylene diol (product name: Sannix PP2000, manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight: 2,000), polyoxypropylene triol (product name: Sannix GP3000, manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight: 3,000) and MDI (product name: Sumidur 44S, manufactured by Sumika Bayer Urethane Co., Ltd.), and reacting the mixture at 80° C. for 5 hours. NCO content: 1.48% by mass.

Carbon black 1: Product name Niteron #200, manufactured by Shin-Nichika Carbon Co., Ltd.

X-ray detection compound 1 (calcium carbonate 1): trade name Super S, manufactured by Maruo Calcium Co., Ltd.
X-ray detection compound 2 (calcium carbonate 2): calcium carbonate surface-treated with fatty acid. Product name: Calfine 200, manufactured by Maruo Calcium Co., Ltd.

Plasticizer: DINP: diisononyl phthalate, manufactured by J-Plus Corporation. Curing catalyst: DMDEE: dimorpholinodiethyl ether, product name UCAT-660M, manufactured by San-Apro Corporation.

<Curing Agent>
Polyol 1: Polyoxypropylene triol, trade name Preminol 7001K, manufactured by AGC Co., Ltd. This corresponds to a hardener in the narrow sense.
Polyol 2: Trade name EXCENOL 450ED, manufactured by AGC. Corresponding to a hardener in the narrow sense. A compound having four hydroxyl groups in one molecule and represented by the following formula (4). (Hydroxyl value = 450 mg KOH/g)
In formula (4), R ₆ to R ₉ each independently represent a propylene group, R ₁₀ represents an ethylene group, and a to d each independently represent 1 to 10.

X-ray detection compound 3 (silica): fumed silica, product name QS-102S, manufactured by Tokuyama Corporation.
X-ray detection compound 4 (calcium carbonate 2): calcium carbonate surface-treated with fatty acid. Kalfain 200, manufactured by Maruo Calcium Co., Ltd.

Curing catalyst: DMDEE: dimorpholinodiethyl ether, product name UCAT-660M, manufactured by San-Apro Co., Ltd. Carbon black 1: product name Niteron #200, manufactured by Shin-Nichika Carbon Co., Ltd.

Fluorescent agent: 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) (structure below). Trade name: Tinopal OB CO (manufactured by BASF). Emits fluorescence when irradiated with ultraviolet light.

<Rating: 1-1>
((Creating a calibration curve))
The base agent and curing agent produced as described above were weighed and mixed to obtain a mixture in the mixing ratio (mass ratio) shown in Table 2 (part 1) below. In addition, in Evaluation 1-1, the two-liquid adhesive mixing and discharging device (static mixer) described later was not used.

(Column A-1 of Table 2: Ca, Si concentration ratio based on fluorescent X-ray intensity)
Preparation of Laminate Two identical polyethylene terephthalate films were prepared, the mixture obtained as described above was applied onto the first polyethylene terephthalate film, and another polyethylene terephthalate film was placed on top of the mixture applied as described above. The mixture was then pressure-molded to a thickness of 2 cm (a circle having a diameter of 4 cm) to form a laminate.
When placing another polyethylene terephthalate film on the applied mixture, care is taken to avoid trapping air bubbles.
In this embodiment, the substrate used when applying the mixture is the same polyethylene terephthalate film as above.

Analysis by X-ray fluorescence analyzer One of the polyethylene terephthalate films of the laminate produced as described above was irradiated with X-rays using an X-ray fluorescence analyzer (VANTA C series manufactured by Olympus Corporation. X-ray tube: 4W X-ray tube, target material: Rh, Ag, W, detector: high-sensitivity silicon drift detector. The same applies below), and the intensity of the fluorescent X-rays emitted by the mixture was measured with the above-mentioned X-ray fluorescence analyzer. The above-mentioned X-ray fluorescence analyzer measures the intensity of the fluorescent X-rays of each X-ray detection element, and based on the data, the concentration of each of the above-mentioned X-ray detection elements in all atoms (content concentration of each X-ray detection element. Unit: % or ppm) can be automatically calculated and displayed.
When measuring the fluorescent X-rays with the above-mentioned X-ray fluorescence analyzer, the measurement surface of the X-ray fluorescence analyzer was pressed against the above-mentioned polyethylene terephthalate film (the same applies below).

The Ca,Si concentration ratio based on the fluorescent X-ray intensity in column A-1 of Table 2 (part 1) is the concentration ratio of calcium and silicon calculated by measuring the fluorescent X-ray intensity of calcium and silicon in each mixture using the fluorescent X-ray analyzer, and automatically calculating and displaying the concentration of each of the X-ray detection elements (calcium and silicon content concentration, unit: %) in all atoms detected in each mixture by the fluorescent X-ray analyzer based on the data, and using the displayed concentrations of each of the X-ray detection elements (calcium and silicon), the total of the concentrations of calcium and silicon is set to 100.

(Column A-2 of Table 2: Hardness 1* of cured adhesive)
The mixture obtained as described above was heated at 60° C. for 30 minutes and then allowed to cool at room temperature for 10 minutes. After that, the hardness 1 of the cured mixture (cured adhesive product) was measured at room temperature using a JIS-A hardness tester.

The results are shown in Table 2 (part 1) above and in the accompanying drawings (Figs. 1 and 2).
In Table 2 (part 1), in the case of Comparative Example 1 where the mixing ratio of base agent/curing agent was 10/0.0, the result of hardness 1 of the adhesive cured product "unmeasurable" means that the adhesive did not cure and therefore the hardness could not be measured. The same applies to "unmeasurable" in Example 1.
In addition, in the Example 1 column of Table 2 (Part 1), the case where the base agent/curing agent mixing ratio was 10/0.0 is included in the Example 1 column for convenience.

FIG. 1 is a graph 1-A showing the relationship between the mixing ratio of the hardener to the base agent and the Si concentration ratio (Si/Ca) measured by fluorescent X-ray intensity for this Example 1 and Comparative Example 1.
FIG. 1 was created based on the data on the Si concentration ratio in the Ca, Si concentration ratio based on fluorescent X-ray intensity in column A-1 of Table 2 (part 1).
From the results of Graph 1-A, it can be said that there is a proportional relationship between the mixing ratio of the hardener to the base agent in Example 1 and the Si concentration ratio based on the fluorescent X-ray intensity.
From the above results, it can be said that Example 1 has a responsiveness of fluorescent X-ray intensity to the variation of the curing agent, while Comparative Example 1 does not have the responsiveness (see Table 1 "Responsiveness of fluorescent X-ray intensity to the variation of the curing agent"). In Comparative Example 1, the base agent and the curing agent contain only calcium carbonate as the X-ray detection compound, and the calcium carbonate contents in both the base agent and the curing agent are the same, 19.3% by mass.

From the results of Example 1 in Graph 1-A, an approximate formula (the following formula (1)) was obtained that expresses the relationship between the mixing ratio of the hardener to the base agent and the Si concentration ratio based on the fluorescent X-ray intensity of silicon. Note that ^R2 (coefficient of determination; R is a correlation function) of the following formula (1) was 0.9973.
y=1.5029x+1.3241 (1)
The straight line of Example 1 in Graph 1-A (the straight line represented by the above formula (1)) was used as a calibration curve showing the relationship between the mixing ratio of the base agent and the curing agent and the Si concentration ratio based on the fluorescent X-ray intensity of silicon in <Evaluation 2> described later.
The intercept (1.3241) in the above formula (1) is presumed to be derived from silicon contained as an impurity in the calcium carbonate 1 used in Example 1.

FIG. 2 is a graph 2 showing the relationship between the mixing ratio of the hardener to the base agent and hardness 1 for this Example 1 and Comparative Example 1.
The curve in this Example 1 is gentle and rises to the right. The curve in Comparative Example 1 is almost the same as that in Example 1.

<Rating 1-2>
The base agent and curing agent produced as described above were weighed and mixed to obtain a mixture in the mixing ratio (mass ratio) shown in Table 2 (part 2) below. In addition, in evaluation 1-2, the two-liquid adhesive mixing and discharging device (static mixer) described later was not used.

(Column A-3 of Table 2: Ca concentration based on fluorescent X-ray intensity)
Using the mixture obtained as described above, a laminate was produced in the same manner as in "Column A-1 of Table 2: Ca, Si concentration ratio based on fluorescent X-ray intensity - production of laminate" described above. One of the polyethylene terephthalate films of the laminate produced as described above was irradiated with X-rays using an X-ray fluorescence analyzer (similar to the above), and the intensity of the fluorescent X-rays derived from Ca emitted by the mixture was measured using the above X-ray fluorescence analyzer.

The Ca concentration based on the fluorescent X-ray intensity in column A-3 of Table 2 (part 2) is the concentration (%) of the calcium in all atoms detected in each mixture by the fluorescent X-ray analyzer.

The results are shown in Table 2 (part 2) above and in the attached drawing (Figure 3).
For the sake of convenience, the case where the mixing ratio of the base agent/curing agent was 10/0.0 is included in the Example 1 column of Table 2. The same applies to Example 2.

FIG. 3 is a graph 1-B showing the relationship between the mixing ratio of the hardener to the base agent and the Ca concentration measured by the fluorescent X-ray intensity for the present Examples 1 and 2 and Comparative Example 1.
From the results of Graph 1-B, it can be said that there is a proportional relationship between the mixing ratio of the hardener to the base agent in Examples 1 and 2 and the Ca concentration measured by the fluorescent X-ray intensity of calcium.
From the results of Examples 1 and 2 in Graph 1-B, an approximate formula (the following formula (2)) was obtained that represents the relationship between the mixing ratio of the hardener to the base agent and the Ca concentration determined by the fluorescent X-ray intensity of calcium.
y=0.5543x+7.5895 (2)
From the results of Example 2, it can be said that there is a responsiveness of the fluorescent X-ray intensity to the variation of the curing agent in Example 2. Even if the base agent and the curing agent of the two-component adhesive composition contain only the same type of compound (calcium carbonate in the case of Example 2) as the X-ray detectable compound, it is considered that the mixing ratio of a two-component adhesive composition having excellent adhesive properties can be rapidly and accurately quantified if the contents of the same type of compound in the base agent and the curing agent are different.

(Adhesion evaluation in Table 1)
Preparation of two-component adhesive compositions Each two-component adhesive composition was prepared by weighing and mixing the base agent and curing agent in Table 1 above at a mass ratio of 10 (base agent):1 (curing agent). Note that a two-component adhesive mixing and discharging device was not used in the adhesion evaluation in Table 1.

Preparation of Samples Two adherends were prepared, each of which was a substrate (width: 25 mm, length: 120 mm, thickness: 3 mm) made of polypropylene resin (product name: Noblen, manufactured by Sumitomo Chemical Co., Ltd.) and had one side subjected to frame treatment.
After each adherend was subjected to frame treatment, a mixture for wet tension testing (manufactured by Wako Pure Chemical Industries, Ltd.) was used to confirm that the wettability of the resin surface was 50.0 mN/m or more.
Next, each of the two-component adhesive compositions (in the form of a mixture) prepared as described above was applied to the surface of one of the adherends (the surface that had been subjected to the frame treatment) to a width of 25 mm, length of 10 mm and thickness of 5 mm, and then this was bonded to the surface of the other adherend (the surface that had been subjected to the frame treatment) to obtain a sample.

- Aging of Samples Each sample obtained as described above was placed under conditions of 25°C and a relative humidity of 50% RH for 3 days to obtain an aged sample.

Tensile shear test: Each cured sample was subjected to a tensile shear test (tensile speed 50 mm/min, in an environment of 20° C.) in accordance with JIS K6850:1999 to measure the shear strength (MPa) and observe the state of failure.
When the shear strength measured as described above was 2.5 MPa or more and the failure state was cohesive failure, the two-component adhesive composition was evaluated as having excellent adhesiveness and was indicated with a rating of "Good."
On the other hand, if the shear strength was less than 2.5 MPa, or if the failure state was other than cohesive failure (for example, peeling at the adhesive interface was observed), the adhesion of the two-component adhesive composition was evaluated as poor, and this was indicated by "X".
The results are shown in the "Adhesion" column of Table 1.
Comparative Example 2, which contained a low molecular weight compound having a sulfur atom as a fluorescent agent that emits fluorescence when irradiated with ultraviolet light, had poor adhesion. This is thought to be because the fluorescent agent, which is intended mainly to emit fluorescence when irradiated with ultraviolet light and is not involved in adhesion, inhibited the adhesion of the two-component adhesive composition.
On the other hand, the adhesive properties of the two-component adhesive composition used in the present invention were good.

<Evaluation 2> Evaluation using a mixing and discharging device The base agent and curing agent of Example 1 produced as described above were mixed under the conditions shown below using a two-liquid adhesive mixing and discharging device (Static Mixer 161-230, manufactured by Yokohama Giken Co., Ltd.) to obtain a mixture.
In detail, first, the base material was placed in a first container, and the hardener was placed in a second container.
The base agent was pumped out from the first container and guided to the static mixer through a first conduit. A first supply device was used to supply the base agent from the first conduit to the static mixer. The supply amount of the base agent can be changed by changing the rotation speed of the motor of the first supply device (the rotation speed of the base agent side).
Meanwhile, the hardener was pumped out from the second container and led to the static mixer through the second conduit. A second supply device was used to supply the hardener from the second conduit to the static mixer. The supply amount of the hardener was changed by changing the rotation speed of the motor (hardener side rotation speed) of the second supply device that supplies the hardener to the static mixer as follows.
The base agent and the curing agent introduced from the respective conduits into the static mixer were mixed in the static mixer to form a mixture, and the mixture was discharged from the static mixer onto a polyethylene terephthalate film.

<Test conditions>
[Static mixer] 30 elements [Base material side rotation speed] 150 rpm
[Main agent side pre-pressure] 12.8-13.0MPa
[Hardening agent side rotation speed] 70, 83, 107, 131 rpm
[Hardening agent side pre-pressure] 5.8-6.0 MPa

[Base agent side reserve pressure] represents the pressure in the first supply device when the base agent is supplied to the static mixer. [Hardening agent side reserve pressure] represents the pressure in the second supply device when the hardener is supplied to the static mixer.

The amount of the mixture discharged from the two-component adhesive mixing and discharging device in a fixed time (10 seconds) under the above test conditions was measured and shown in the column of average discharge amount in Table 4 (unit: g).
The average discharge amount shown in Table 4 indicates the total amount of the base agent and the hardener discharged in the above-mentioned fixed time period. The same applies to the vertical axis (average discharge amount) in FIG.

Mass ratio of base agent to hardener in evaluation 2 (theoretical value)
FIG. 4 is a graph 3 showing the relationship between the motor rotation speed of the second supply device that supplies the hardener and the average discharge amount when the base agent and hardener of this Example 1 are mixed and discharged using the two-component adhesive mixing and discharging device as described above.
From the results of graph 3, it can be seen that the rotation speed and the average discharge amount are in a proportional relationship.
From the results of Graph 3, an approximation (the following formula (3)) of the relationship between the rotation speed of the motor of the second supply device that supplies the hardener and the average discharge amount was obtained.
y=0.0679x+68.006 (3)
From the above approximation formula, it was found that under the above conditions, the amount of base agent discharged (theoretical value) in each average discharge amount was approximately 68 g.
In addition, from the above approximation formula, the amount of hardener discharged (theoretical value) in each average discharge amount under the above conditions could be calculated.
The mass ratio of the base agent to the curing agent (grams of the curing agent per 10 g of the base agent) was calculated from the base agent discharged amount (theoretical value) and the curing agent discharged amount (theoretical value) in each average discharge amount obtained as described above. The results are shown in column B-3 of Tables 4 and 5.

Measurement of Si concentration ratio of Ca,Si concentration by fluorescent X-ray intensity The base agent and the curing agent of this Example 1 were mixed under the conditions shown in Table 4 using a two-liquid adhesive mixing and discharging device, and discharged onto the polyethylene terephthalate film. A laminate was formed in the same manner as in "Column A-1 of Table 2: Ca,Si concentration ratio by fluorescent X-ray intensity - Preparation of laminate" described above.
One of the polyethylene terephthalate films of the obtained laminate was irradiated with X-rays using an X-ray fluorescence analyzer (similar to the above), and the Si concentration ratio of Ca and Si concentrations based on the X-ray fluorescence intensity was obtained in the same manner as in "Column A-1 of Table 2: Ca, Si concentration ratio based on X-ray fluorescence intensity - Analysis by X-ray fluorescence analyzer" described above.

Mixture hardness 2
The mixture (mixture after mixing) was heated at 60° C. for 30 minutes and allowed to cool at room temperature for 10 minutes, after which the hardness 2 of the mixture was measured at room temperature using a JIS-A hardness tester.
The results are shown in column B-1 (Ca, Si concentration ratio of Si concentration by fluorescent X-ray intensity) and column B-2 (hardness 2 of cured adhesive) of Table 4.

The Si concentration ratio of the Ca, Si concentration by fluorescent X-ray intensity in column B-1 of Table 4 is calculated by measuring the fluorescent X-ray intensity of calcium and silicon in each mixture using the fluorescent X-ray analyzer, and based on that data, automatically calculating and displaying the concentration of each of the X-ray detection elements (calcium and silicon content concentration, unit: %) in all atoms detected in each mixture by the fluorescent X-ray analyzer, and using the displayed concentrations of each of the X-ray detection elements (calcium and silicon), the total of the calcium and silicon concentrations is expressed as 100, which is the concentration ratio of calcium and silicon.

Referring to Table 4 summarizing the above results, first, column B-3 in Table 4 is the ratio (mass ratio) of the hardener to 10 parts by mass of the base agent, calculated from the approximate formula of the weight change in Graph 3, as described above.
Column B-4 in Table 4 shows the ratio (mass ratio) of the curing agent to 10 parts by mass of the base agent, calculated by applying the Si concentration ratio of the Ca and Si concentrations by fluorescent X-rays in Column B-1 to the approximate formula (formula (1) as a calibration curve) of Example 1 in Graph 1-A.

In Table 4, when columns B-3 and B-4 are compared, the mass ratio of the base agent to the curing agent obtained using the two-component adhesive mixing and discharging device (column B-3) was almost identical to the mass ratio of the base agent to the curing agent (column B-4) calculated by applying the Si concentration ratio of the Ca, Si concentration of the mixture based on the fluorescent X-ray Si intensity (column B-1) to the approximation formula of Example 1 in Graph 1-A (formula (1) as a calibration curve).
From the above results, it can be said that even when a two-component adhesive mixing and discharging device is used, the mixing ratio of the base agent and the curing agent in the mixture can be quantified from the fluorescent X-ray intensity of the obtained mixture.

<Evaluation 3>
Using the base agent and curing agent of Example 1 produced as described above, one of the two-component adhesive mixing and dispensing devices was attached to a six-axis robot, and mixing was carried out under the conditions shown below, and the mixture was continuously discharged onto a substrate (the above-mentioned polyethylene terephthalate film).
Another polyethylene terephthalate film was placed on top of the mixture discharged from the two-component adhesive mixing and discharging device in a manner to prevent air bubbles from being trapped, and the mixture was spread out so that the thickness of the mixture between the two polyethylene terephthalate films was 3 to 10 mm. The width of the mixture after spreading out may be larger than the window for collecting fluorescent X-rays in the fluorescent X-ray analyzer.

<Test conditions>
[Static mixer] 30 elements [Base material side rotation speed] 150 rpm
[Main agent side pre-pressure] 12.8-13.0MPa
[Hardening agent side rotation speed] 107 rpm
[Hardening agent side pre-pressure] 5.8-6.0 MPa

In the mixture obtained by continuous extrusion, X-rays were irradiated from above the polyethylene terephthalate film on the mixture at each position of the distance from the extrusion start point (the portion where the mixture was initially extruded onto the substrate) shown in Table 6 using the fluorescent X-ray analyzer (similar to the above), and the fluorescent X-ray intensity emitted by the mixture was measured, and the Si concentration ratio of Ca,Si concentration by fluorescent X-ray intensity (similar to the Si concentration ratio of Ca,Si concentration by fluorescent X-ray intensity in column B-1 of Table 4) was obtained in the same manner as in "Column A-1 of Table 2: Ca,Si concentration ratio by fluorescent X-ray intensity - Analysis by fluorescent X-ray analyzer" above. The results are shown in Table 6.
The ratio (mass ratio) of the curing agent to 10 parts by mass of the base agent was calculated by applying the Ca and Si concentrations of the Si concentrations obtained by the fluorescent X-ray intensity obtained as described above to the approximate formula (formula (1) as a calibration curve) of Example 1 in Graph 1-A (FIG. 1).
The mixture was heated at 60° C. for 30 minutes and then allowed to cool at room temperature for 10 minutes, after which the hardness 3 of the mixture was measured at room temperature using a JIS-A hardness tester.

As shown in the results in Table 6, by applying the Si concentration ratio of the Ca and Si concentrations of the mixture obtained based on the fluorescent X-ray intensity to the above approximation formula (the calibration curve represented by formula (1)), the mixing ratio of the base agent and the hardener could be rapidly and accurately quantified and monitored in real time.
Furthermore, the above results make clear that it is quicker to quantify the mixture ratio of the base agent and the curing agent in the mixture from the fluorescent X-ray intensity of the obtained mixture than to determine the mass ratio of the base agent and the curing agent from the hardness of the cured adhesive.
Furthermore, the hardness 3 results of the obtained cured adhesive products were approximately constant, so that the detection method of the present invention makes it possible to rapidly and accurately determine the mixture ratio of the base agent and the curing agent.
Furthermore, according to the method for producing a coating material using the detection method of the present invention, the mixing ratio of the base agent and the curing agent can be quickly and accurately quantified, making it possible to produce a coating material with stable adhesion.

Claims (6)

A step 1 of using a two-component adhesive composition having a base agent and a curing agent and mixing the base agent and the curing agent to obtain a mixture;
A step 2 of irradiating the mixture with X-rays;
a step 3 of measuring the intensity of fluorescent X-rays generated from the mixture irradiated with X-rays;
and a step 4 of quantifying a mixing ratio of the base agent and the curing agent in the mixture from the intensity of the fluorescent X-rays.
In the two-component adhesive composition used in step 1, at least one or both of the base agent and the curing agent contain at least one type selected from the group consisting of compounds containing calcium, silicon, or aluminum, polymers containing sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays, provided that when the base agent and the curing agent substantially contain only the same type of compound as the X-ray detectable compound, the contents of the same type of compound in the base agent and the curing agent differ to an extent that an approximation formula expressing the relationship between the contents of the same type of compound in the mixture measured by an X-ray fluorescence analyzer and the proportion of the curing agent in the mixture can be obtained,
The method for detecting a mixing ratio of a two-component adhesive composition , wherein the sulfur-containing polymer is a polysulfide polymer . the X-ray detection compound is at least one selected from the group consisting of calcium carbonate, silica, aluminum oxide, polysulfide polymer, and manganese dioxide;
2. The method for detecting a mixing ratio of a two-component adhesive composition according to claim 1, wherein, when the base agent and the curing agent substantially contain only compounds of the same type as the X-ray detection compound, a difference between the content (mass %) of the same type of compound relative to 100 mass % of the base agent and the content (mass %) of the same type of compound relative to 100 mass % of the curing agent is 13.7 mass % or more. In the steps 2 and 3, an X-ray fluorescence analyzer is used,
the X-ray fluorescence analyzer is an energy dispersive X-ray fluorescence analyzer having an X-ray tube using Rh, W, Ag, Cr, or Fe as a target material as an X-ray excitation source, and a silicon semiconductor detector, a silicon drift detector, or a silicon PIN diode detector as a detector;
3. The method for detecting a mixing ratio of a two-component adhesive composition according to claim 1, wherein the weight of the X-ray fluorescence analyzer is less than 5 kg. The method for detecting the mixing ratio of a two-component adhesive composition according to any one of claims 1 to 3 further comprises a step 5 of determining whether the mixing ratio quantified in step 4 is within a predetermined range of mixing ratios, and, if the mixing ratio quantified in step 4 is outside the range of the predetermined mixing ratios, adjusting the amount of the base agent and/or the curing agent so that the mixing ratio outside the range of the predetermined mixing ratios becomes an appropriate mixing ratio. A method for producing a coated product, comprising the method for detecting the mixing ratio of a two-component adhesive composition according to any one of claims 1 to 4, and further comprising a coating step of coating the mixture on a substrate. A two-component adhesive composition used in a method for detecting a mixing ratio of the two-component adhesive composition according to any one of claims 1 to 4,
Contains a base agent and a hardener,
At least one or both of the base agent and the curing agent contain at least one selected from the group consisting of a compound having calcium, silicon, or aluminum, a polymer having sulfur, and manganese dioxide as an X-ray detectable compound that can be detected by X-rays, provided that when the base agent and the curing agent substantially contain only the same type of compound as the X-ray detectable compound , the contents of the same type of compound in the base agent and the curing agent differ to such an extent that an approximation formula expressing the relationship between the contents of the same type of compound in the mixture measured by an X-ray fluorescence analyzer and the proportion of the curing agent in the mixture can be obtained;
A two-component adhesive composition, wherein the sulfur-containing polymer is a polysulfide polymer .