JPH09178727A - Method and equipment for testing organic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To measure the deterioration of organic material quickly and accurately by providing means for generating a specific factor correlated with the aging of organic material therein, and means for analyzing the organic material containing the specific factor. SOLUTION: In a plasma generator unit 51, an organic material is set in a reaction chamber, for example, and high frequency is generated while bringing about filling gas atmosphere, in the reaction chamber under vacuum to excite the filling gas thus producing a radical compound in the organic polymer compound of organic material. A thermal decomposition unit 52 thermally decomposes the organic polymer compound containing the radical compound to produce respective compounds composing the organic polymer compound. A gas chromatograph 55 separates the composition of each constitutive compound being decomposed which is then determined by a mass spectrometer 56.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can rapidly and quantitatively test an organic polymer compound, an organic polymer compound and an organic compound, or an organic material composed of an organic polymer compound and an inorganic compound. The present invention relates to an organic material testing device and an organic material testing method using the same.

[0002]

2. Description of the Related Art Organic materials composed of organic polymer compounds or organic polymer compounds blended with organic compounds and inorganic compounds have been utilized in various industrial fields in modern times. For example, various parts that compose automobile bodies and coating films that paint them; furniture, housing materials, interior decoration,
Interior parts, exterior parts, and other housing-related parts and coatings that paint them; refrigerators, washing machines, and other home appliances and coatings that paint them; bridges, iron bridges, and other outdoor structures, and marine structures and their coatings It is used in almost all fields that are used in ordinary everyday life such as paint films.

These organic materials have the property of being essentially deteriorated by the passage of time, contact with air, high and low temperatures, mechanical shock, etc., and, for example, decrease in mechanical strength,
Discoloration, fading, loss of gloss, reduction in weight, generation of substances that adversely affect the human body, etc. appear as deterioration phenomena, and in extreme cases, the material may be disintegrated.

For example, in the field of paints, such a deterioration phenomenon is a measure for measuring weather resistance, and in the case of building exterior materials, marine structures, etc.
Long-term warranty issues such as 0-year warranty and 20-year warranty have become apparent, and the issue has become more important.

In the field of automobile painting, in addition to weather resistance, durability, etc., with the recent progress of painting technology, for example,
Light resistance related to discoloration and fading of the top coat is attracting attention as a performance directly related to the quality of automobiles. Also,
It has been a very important issue for outdoor buildings, etc., because the collapse of the buildings may cause serious loss of human life. Furthermore, in addition to the addition of high weather resistance and high functionality, in recent years, the PL Law has been enforced from the viewpoint of consumer protection,
There is an urgent need to supply products that are safer and more reliable, and the tendency toward recycling in order to protect the global environment and secure resources becomes more prominent. In any case, more fundamental evaluation of product materials and elucidation of the deterioration mechanism It was the current situation that was strictly required.

By the way, the degree and type of the deterioration phenomenon occurring in the organic material represent the degree of progress of the deterioration and represent the durability or life of the organic material. In this specification, the degree of progress of this deterioration is referred to as the degree of deterioration.

As a conventional technique for measuring the degree of deterioration of an organic material, an outdoor exposure test for examining the weatherability, light resistance, ozone resistance, etc. of the organic material by leaving it in a natural environment for many years is It has been used as the most reliable. However, in this outdoor exposure test, for example, 1
In order to measure the degree of deterioration for 0 years, a continuous test for 10 years is indispensable, and it was too inconvenient to adapt to the speed of modern research and development.

As an alternative to the above outdoor exposure test,
There is an acceleration test that examines weather resistance, light resistance, ozone resistance, etc. in a state that is similar to the natural environment and can be accelerated. As such an accelerated test, for example, "Sunshine Weather Meter Test (SW-W-) carried out according to the accelerated exposure test method for plastic building materials (JIS A 1415)
OM) "," High temperature sunshine weather meter test (H-WOM); "Due cycle weather meter test (D-D)" performed in accordance with the safety reflection sheet and tape test method (JIS Z 9117). WM) ";
Weather resistance test method for automobile parts (JIS D 0205)
"Ultraviolet carbon fade meter test (UFM)" carried out in conformity with "Xenon fade meter test (X-F-M)" carried out in accordance with ASTM G26.
M) ”;“ QUV test ”performed in accordance with ASTM G53-77; US Desert Sunshine (DSE)
T Labo. Inc. ) "EMMAQUA test" carried out in accordance with the standard of); General paint test method (JIS
"Xenon arc lamp type test" carried out in accordance with K 5400); a combined cycle test in which these are combined is known.

However, the test time for these accelerated tests is, for example, the weather resistance test method for automobile parts (JIS D).
In the "UV carbon fade meter test (UFM)" conducted according to 0205), at least 50
Usually, 1000 to 5000 hours are required, such as 0 hours, and it is not possible to sufficiently adapt to the speed of modern research and development.

In addition, although these accelerated tests realize an environment close to the natural environment, the natural conditions to which the organic material is exposed in actual use are not reproduced as they are. Therefore, these accelerated tests are simulated. It was not possible to get out of the test range, and it was not possible to accurately measure the degree of deterioration.

Conventionally, in these accelerated tests, changes in gloss, discoloration and fading, changes in image clarity, and other changes in appearance;
The degree of deterioration has been determined by measuring items such as changes in mechanical properties such as tensile strength; changes in chemical properties such as adhesive strength; changes in electrical properties such as impedance.

However, in the determination of the degree of deterioration based on the measurement result of the change in appearance, there is a problem that the reliability of the stability is not sufficient. In addition, since the factors that cause deterioration of organic materials and the mechanism of deterioration have not been sufficiently clarified, it is not possible to judge the degree of deterioration based on measurement results such as changes in mechanical properties, chemical properties, and electrical properties. Also,
No analysis has been conducted that links the deterioration phenomenon to changes in the chemical structure of the compound contained in the substance that constitutes the organic material, and at present, it can be known from, for example, IR measurement results. Only the analysis linked to the change of the chemical structure of the functional group in the range has been performed.

Further, in these accelerated tests, in order to measure the degree of deterioration, it is necessary to use a large-sized test apparatus, a large number of test specimens, or a certain shape. There were also problems such as becoming.

Journal of Coatings T
technology), Volume 722, March issue (1985)
Year), pages 37 and below, electron spin resonance (ESR)
A technique for analyzing a coating film and predicting the durability by utilizing is disclosed. However, this technique is different from the idea of predicting the deterioration phenomenon of the sample to be measured, which is merely irradiating light to see the ESR measurement result.

Therefore, as an essential problem, the factors causing the deterioration of the organic material, the deterioration mechanism, etc. are clarified, and the deterioration phenomenon and the change in the chemical structure of the compound contained in the substance constituting the organic material are linked. Until now, there has been no technology for measuring the degree of deterioration. Furthermore, deterioration phenomena include deterioration of mechanical strength, discoloration, fading, loss of gloss, weight loss, generation of substances that have a harmful effect on the human body, and other changes that occur gradually over time, as well as sudden changes in the coating surface. It is known that there are collapse phenomena that occur suddenly, such as cracks,
Until now, there has been no technique capable of simultaneously measuring such a change with time and a collapse phenomenon.

[0016]

In view of the above situation, the present invention makes it possible to predict the deterioration degree of an organic material in the future by measuring the deterioration degree of the organic material very quickly and accurately with a small amount of sample. It is an object of the present invention to provide a test apparatus and a test method therefor, and a test apparatus and a test method therefor for determining the degree of deterioration of an organic material whose age is unknown.

[0017]

The apparatus for testing an organic material according to the present invention comprises means for generating a specific factor in the organic material that correlates with a change with time of the organic material, and the organic material containing the generated specific factor. And a means for analyzing the material. In the present invention, a device for generating a specific factor that correlates with a change with time of the organic material in the organic material and a device for analyzing the organic material containing the generated specific factor are separate devices. , But in a more preferred form, these two means are integrated in the same device. Hereinafter, the present invention will be described in detail.

The first component of the apparatus for testing an organic material of the present invention is a means for producing a specific factor in the organic material which correlates with the change with time of the organic material (hereinafter also referred to as "first means"). ). The specific factor is not particularly limited as long as it correlates with the change with time of the organic material. It is the gist of the present invention to utilize the above-mentioned specific factor as a parameter to understand the change with time of the organic material. The specific factor that correlates with the change over time of the organic material is an index of the degree of deterioration of the organic material, and the generation of the specific factor in the organic material is long-term under normal use conditions. It means that the deterioration of the organic material is promoted in a short period of time by promoting the deterioration of the organic material.

As the first means, for example, a plasma generator can be cited. In this case, the specific factor may be, for example, a radical compound of an organic polymer compound that constitutes an organic material.

The plasma generator is not particularly limited as long as it produces a radical compound in an organic material from a gas or monomers in a plasma state. For example, in addition to an oxygen plasma generator filled with oxygen, argon, Examples thereof include a plasma generator filled with helium, tetrafluoromethane and the like. The plasma excitation source in the plasma generator is not particularly limited,
For example, radio waves, high frequencies, microwaves, etc. may be mentioned, and further, helicon waves, electron cyclotron resonance waves, etc. may be used, but high frequencies are preferable. In the plasma generator, for example, after the organic material to be measured is placed in the reaction chamber, a plasma excitation source is generated while the reaction chamber is under vacuum to have a filling gas atmosphere to excite the filling gas in the reaction chamber. The radical compound can be generated in the organic polymer compound in the organic material by maintaining the radical state in the reaction chamber.

In the present specification, a radical means a state in which one electron constituting a bond electron pair is lost and an unpaired electron is generated, for example, a carbon radical generated by a radical at a carbon atom, The nitrogen radical etc. which the radical generated in the nitrogen atom can be mentioned. In the present specification, the radical compound refers to a compound in which a part of the organic polymer compound forming the organic material loses one electron forming the bond electron pair and has an unpaired electron.

The above-mentioned radical compound is usually generated in the chain compound constituting the organic polymer compound in the organic polymer compound in the organic material. The chain compound may form the skeleton part of the organic polymer compound or may form the cross-linking part. The radical compound may be present in the chain compound, may be in a free radical state, and may be added for the purpose of imparting weather resistance or the like to the organic polymer compound. HALS present in organic polymer compounds
It may occur in additives such as (hindered amine-based weather resistance imparting agent and ultraviolet absorber). The radicals present in the above organic polymer compound are usually C generated at a carbon atom.
・ (Carbon radical). The radicals generated in the additive present in the organic polymer compound are N. (Nitrogen radicals) generated in the nitrogen atoms constituting the additive.
In the present specification, the radical compound is a generic term for these.

The above-mentioned deterioration of the organic material is essentially caused by chaining of hydrogen abstraction reaction due to light, heat, oxygen, water, etc. in the organic polymer compound constituting the organic material due to long-term aging. It is considered that this is a phenomenon in which the radical compound is gradually excited and gradually increases. In some cases, the increased carbon radicals in the radical compound may be transferred to organic nitrogen atoms present in HALS or the like present as an additive in the coating material to generate nitrogen radicals. Such a phenomenon in which a radical moves between atoms and focuses on a specific atom is called a radical trap, and the nitrogen atom is also called a radical trapper.

When the radical trap does not occur or when the radical trapping phenomenon occurs due to the radical trap, the chain of the organic polymer compound is cleaved at the increased radical compound generation site or accumulation site, and the organic polymer compound is It becomes impossible to maintain the higher-order structure,
As a deterioration phenomenon, a change in composition / structure of the organic material occurs. In addition, a discoloration or fading phenomenon occurs. at least,
As will be described later, there is a correlation between the increase of the radical compound and the progress of the deterioration degree of the organic material. Therefore, the increase in the above-mentioned radical compounds and the resulting composition / structure change are
It is suitable as a specific factor that correlates with the aging of the organic material according to the present invention.

The second constituent element of the organic material testing apparatus of the present invention is means for analyzing the organic material containing the specific factor produced by the first constituent element (hereinafter referred to as "second means"). Also called). The analysis means is not particularly limited as long as it can analyze the constitution of the organic material containing the specific factor. Such means may be one that does not destroy the analysis target, and examples thereof include means for testing an organic material containing the specific factor to analyze its composition. Further, such means may be one that destroys and analyzes the analysis object. If the analyte is unlikely to be reused to perform its function after analysis, the advantage is that even if the analyte is destroyed and analyzed, the amount of the analyte is small. Those having are preferred.

The apparatus applicable to the second means is not particularly limited as long as it can analyze the specific factor existing in the organic material, and the amount and the kind of the specific factor. It is more preferable if and can be simultaneously measured. As an apparatus that can be applied to the second means, for example, an electron spin resonance apparatus (ESR), an X-ray photoelectron spectroscopy analyzer (XPS), and the like can be preferably mentioned. In addition to these, for example, a gas chromatograph. Examples thereof include a tograph, a mass spectrometer, a pyrolysis device and a combination device thereof, and a pyrolysis device and a gas combustion / concentration device and a combination device thereof.

The thermal decomposition apparatus decomposes the organic material, which is the object of analysis, by heat of, for example, about 500 ° C. to form each constituent of the organic material. Such thermal decomposition
It is essential for analyzing the constituents of organic materials.

The above-mentioned gas chromatograph is suitable as an apparatus for separating components of constituents produced by decomposition by a thermal decomposition apparatus. The constituents are separated according to the difference in their molecular weight, and the retention time (retention
It is possible to separate and identify by the difference in time).

The mass spectrometer is suitable as a device for identifying what each of the constituents separated by the gas chromatograph is. The type and amount of the constituents are analyzed by the mass spectrometer.

The second means may comprise a thermal decomposition device, a gas combustion / concentration device, a gas chromatograph, and a mass spectrometer. This one is
Among the above-mentioned constitutions, a gas combustion / concentration device is inserted between the thermal decomposition device and the gas chromatograph.
The gas combustion / concentration device further decomposes the components generated by the thermal decomposition device into a gas state at a high temperature of about 1000 ° C. The decomposed products in the gas state are
It is concentrated by a concentrator and captured. Then, it is separated and identified by the same steps as above by a gas chromatograph and a mass spectrometer.

The gas combustion / concentration device is suitable as a device for analyzing the expanded state of the deterioration mechanism that cannot be analyzed without the gas combustion / concentration device. Usually, the radical compound generated in the organic polymer compound excites a chain reaction, and after a certain period of time, causes chain cleavage of the organic polymer compound. As a result, the organic polymer compound cannot retain its higher-order structure, resulting in a deterioration phenomenon. However, among the radical compounds generated in the organic polymer compound, some radical compounds themselves take up the generated radicals to stop the chain reaction and do not cause chain cleavage even after a certain period of time. is there. The characteristics of the radical compound that retains such an uncleaved state are as follows depending on the analysis means that does not have the gas combustion / concentration device.
I can't figure it out.

The radical compound which retains the above-mentioned uncleaved state is suddenly cleaved when the number of radicals reaches a certain threshold value. Such a phenomenon appears as a sudden collapse of the organic material. In the analysis means having the gas combustion / concentration device, it is possible to detect the influence of the presence of the radical compound that holds the uncleaved state, so that the sudden collapse phenomenon can be known. It is a thing.

In the organic material testing apparatus of the present invention,
The means for analyzing the produced organic material containing a specific factor is a device comprising a pyrolysis device, a gas chromatograph, and a mass spectrometer, and a pyrolysis device, a gas combustion / concentration device, a gas chromatograph, and a mass spectrometer. It can be combined with a device consisting of. With the combination device, the degree of deterioration can be measured, and at the same time, a sudden collapse phenomenon can be predicted.

The application material of the organic material test apparatus of the present invention is not particularly limited as long as it is an organic polymer compound, an organic polymer compound and an organic compound, or an organic polymer compound and an inorganic compound. However, examples thereof include paints, films, coating materials, and adhesives. More specifically, for example, various parts that compose an automobile body and a coating film that coats them; furniture-related parts such as furniture, housing building materials, interior / exterior interior parts, interior parts, and exterior parts, and a coating film that coats them; a refrigerator; Home appliances such as washing machines and coating films for coating them; outdoor structures such as bridges and iron bridges, marine structures and coating films for coating them. More specifically, examples of the coating film for coating automobile bodies include a coating film for base coat and a coating film for top coat.

The organic material testing apparatus of the present invention can be used in a test method for testing the above various organic materials. Examples of the test method include a paint design method. In the development of ordinary new paints, properties of paints such as transparency, viscosity, density and dispersibility; storage stability such as low temperature stability and skin tension; coating film such as drying time, slackness and easy polishing Forming function; visual angle characteristics such as appearance, color and diffuse reflectance; coating resistance such as impact resistance, adhesion, tensile strength and elongation, abrasion resistance, etc. can be measured in a relatively short period of time. After the coating properties that can be obtained are investigated, the coating properties that require a long measurement period, such as moisture resistance, light resistance, and weather resistance, are investigated.

However, if the long-term test such as the weather resistance test fails, all the tests conducted up to that point are wasted. Moreover, since the long-term test lasts for a long period of 5 years, 10 years, etc., it is not suitable for the recent development speed in which new technologies are successively generated in 1 or 2 years. According to the test method using the organic material test apparatus of the present invention,
Since the above weather resistance test can be carried out in a few minutes,
The above paint design method can be completed in a very short period of time.

In addition to the above, examples of the test method using the organic material test apparatus of the present invention include the existing coating material diagnosis method and the like. Until now, diagnosis of offshore structures, bridges, iron bridges, etc., whose ages after construction are unknown or whose durability is unknown, could only be made by inference. In the existing coating material diagnosis method of the present invention, first, a part of the coating film of such a building is sampled and obtained, and the composition resulting from the radical compound is applied to the organic material test apparatus of the present invention. Structural changes, if desired, are also analyzed for the effects of uncleaved radical compounds after gas combustion and concentration. On the other hand, for a paint having the same composition as the coating film, a calibration curve showing the correlation between the amount of a specific factor that correlates with the composition / structure change caused by a radical compound and the degree of deterioration is determined by the organic material testing apparatus of the present invention. I draw it. By comparing the two, it is possible to diagnose the degree of deterioration of the paint obtained by sampling and, if desired, the point of sudden collapse.

It should be noted that the coating composition of the coating film to be diagnosed can be known from the material of the building if it exists, and even if such material does not exist, the coating composition of the coating film can be known. It can be known by separately analyzing the composition of. Further, according to the above-mentioned existing coating object means method, since the sampling amount is several to several tens of mg of the coating film, there is no possibility of damaging the existing coating object.

As a method of testing the organic material of the present invention, for example, by applying a sample whose age is known to the second means, the age and the measurement result in the second means are applied. And the step (1) for obtaining the calibration curve (i) from the relationship, and applying the sample of which the number of years has elapsed to the organic material testing device including the first means and the second means. By doing so, the specific factor amount correlated with the composition / structure change caused by the radical compound in the first means, and the measurement result of the second means are obtained, and the specific factor amount and the measurement result are By applying the step (2) of obtaining the calibration curve (ii) showing the correlation and the sample whose age is unknown to the second means, the sample is correlated with the composition / structure change caused by the radical compound of the sample. specific The step (3) of measuring the quantity of offspring and determining the age of the sample by applying this to the calibration curve (i) and the calibration curve (ii) (3), resulting in the number of years elapsed Examples thereof include a method of determining the age of an unknown sample and its degree of deterioration. According to this method, it is possible to predict in the future how the existing sampled object will be deteriorated thereafter.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of an organic material testing apparatus of the present invention will be described with reference to the drawings. In FIG.
The means 101 for generating in the organic material a specific factor that correlates with the change with time of the organic material is constituted by the plasma generator 51. Further, the means 102 for analyzing the generated organic material containing the specific factor is configured by the thermal decomposition device 52, the gas combustion device 53, the gas concentrator 54, the gas chromatograph 55, and the mass spectrometer 56. . The first means 101 and the second means 102 may be incorporated in the same device, or may be incorporated in different devices and exist. As far as possible, it is preferable that they are incorporated in the same device for operability, convenience, and high reproducibility.

In the organic material testing apparatus of the present invention,
A test device in which the gas combustion device 53 and the gas concentrator 54 drawn by dotted lines do not exist (hereinafter referred to as “device 1 of the present invention”)
And an existing test device (hereinafter referred to as “device 2 of the present invention”)
As described above, there are three types of test devices: a test device in which a nonexistent test device and an existing test device are combined (hereinafter referred to as “invention device 3”).

When the plasma generator 51 is a plasma generator in which the filling gas is oxygen and the excitation source is high frequency, as shown in detail in FIG. 2, a high frequency generator, a vacuum system controller, a high pressure oxygen cylinder, and It consists of a reaction chamber. In the figure, 1
Represents a high frequency power supply, 2 represents a matching unit, 3 represents a vacuum pump, 4 represents a vacuum gauge,
5 represents a high pressure oxygen cylinder, 6 represents an auxiliary cylinder, 7 represents a reaction chamber, 8 represents a flow meter, and 9 represents
Represents a valve.

The high frequency generating section is preferably
The output can be continuously variable from 0 to 500 W. The oscillation frequency of the high frequency generator is preferably 13.56 MHz. As the above-mentioned vacuum system control unit, preferably, there can be mentioned one having an automatic decompression device, an automatic leak valve and the like. The reaction chamber is preferably made of quartz because plasma is less likely to disappear.

In the plasma generator 51, for example, after an organic material is placed in the reaction chamber, a high frequency is generated while the reaction chamber is filled with a filled gas atmosphere under vacuum to excite the filled gas in the reaction chamber. A radical compound can be generated in the organic polymer compound in the organic material.

The thermal decomposition apparatus 52 decomposes the organic polymer compound containing the radical compound generated as described above by heat to generate each constituent compound constituting the organic polymer compound. As the thermal decomposition device, for example, "Curie Point Pyrolyzer" manufactured by Japan Analytical Industry Co., Ltd.,
"Double Shot Pyrolyzer" made by Frontier Lab
And the like.

The gas chromatograph 55 separates the composition of each decomposed constituent compound. Further, the mass spectrometer 56 identifies each of the separated constituent compounds. Examples of the apparatus composed of the gas chromatograph and the mass spectrometer include "M-80B system" manufactured by Hitachi Ltd. and "Automa" manufactured by JEOL Ltd.
ss150 system ”and the like.

An example of the gas combustion device 53 and the gas concentrator 54 is shown in FIG. In the figure, 10 represents a high frequency coil, and 1
1 represents a combustion chamber, 12 represents a combustion heater,
13 represents an oven heater, 14 represents a bifoil, 15 represents a sample, 16 represents a sample introducing rod, 17 represents an air inlet, 18 represents an O-ring, and 19 represents , Represents a filter, 20 represents an adsorption chamber, and 21 represents a liquid nitrogen inlet.

Examples of the gas concentrator include “Headspace Sampler” manufactured by Nippon Analytical Industry Co., Ltd., “Purge & Trap” manufactured by Takumer Co., Ltd., and the like.

The process of measuring the degree of deterioration of the organic material in the organic material testing apparatus of the present invention will be described. For example,
The organic polymer compound constituting the organic material is a coating film having a skeleton made of an epoxy resin and a cross-linking portion made of a urethane resin (hereinafter referred to as "Ep / BI-based coating film"). In the case of deterioration, in the organic polymer compound constituting the organic material, first, cleavage of the cross-linking portion of the organic polymer compound constituting the organic material occurs, and then the organic polymer compound Cleavage of the skeleton has occurs.

Actually, from the IR measurement performed after naturally degrading the Ep / BI type coating film, the SiO contained in the pigment was found.
₂ to (1050 cm ^-1), a urethane bond constituting the bridge portions C = O of the epoxy resin constituting the absorption intensity and the skeleton of the ^{(1730cm -1) C = C (} 1510cm -1)
It has been confirmed that the absorption intensity of is less than the value before deterioration.

Further, from the thermal analysis of the Ep / BI-based coating film after deterioration, among the two glass transition points existing, the glass transition point on the high temperature side due to the change in the structure of the skeleton part shows the deterioration. It was confirmed that the glass transition point on the low temperature side due to the change in the structure of the cross-linking portion was decreased while the temperature was increased along with the progress. Among the existing thermal decomposition points, the amount of decomposition at the low temperature side thermal decomposition point, which can be attributed to the cleavage of the skeleton, increases relatively with the progress of deterioration and may be attributed to the cleavage of the crosslinked portion. It has been confirmed that the amount of decomposition at the thermal decomposition point on the high temperature side that can be formed decreases as the deterioration progresses.

In the present invention, the above Ep / BI coating film is applied to a plasma generator 51, a thermal decomposition device 52, a gas chromatograph 55 and a mass spectrometer 56,
(Amount of TDI) / (amount of phenol) [hereinafter, this value is referred to as "A value"] is measured.

FIG. 4 is a graph showing how the A value changes depending on the amount decomposed by the thermal decomposition apparatus (ratio (%) to the whole organic material to be tested). In the figure, the vertical axis represents the A value, and the horizontal axis represents the decomposition amount (%) at the thermal decomposition point. □ indicates the result of the device 1 of the present invention,
The ∘ mark represents the result of the device 2 of the present invention. As shown in FIG. 4, A measured by the device 1 of the present invention and the device 2 of the present invention
The value increases as the amount of thermal decomposition increases, and a reliable calibration curve is obtained.

FIG. 7 is a graph showing changes in the A value depending on the radical compound generation time by the plasma generator 51, using the device 2 of the present invention, as will be described in detail in a later example. It can be seen that the A value sharply rises after the reaction for about 3 minutes after the deterioration from the cross-linking portion, and a sudden deterioration phenomenon of the skeleton portion occurs.

FIG. 8 shows a further preferred embodiment of the organic material testing apparatus of the present invention. In FIG. 8, the apparatus for testing an organic material of the present invention is composed of a first means 101 composed of a plasma generator 51 and a second means 102 composed of an ESR 57 (hereinafter, “invention apparatus 4”). That). In this case, XPS can be used instead of ESR. The device 4 of the present invention is simpler than the devices 1 and 2 of the present invention described above, and can be said to be a more advantageous embodiment in that a reliable result can be obtained. The first means 101 and the second means 102 may be incorporated in the same device, or may be incorporated in different devices and exist. As far as possible, it is preferable that they are incorporated in the same device for operability, convenience, and high reproducibility. As an example in which the above two means are incorporated in the same apparatus, an apparatus in which a plasma generating mechanism is added inside the ESR can be cited.

In the device 4 of the present invention, the ESR is
For example, it is preferable to use the sample tube with a cooling device. In the XPS, for example, it is preferable that the XPS is set so that a stable binding state of the radical compound can be measured. In ESR, by measuring the spin number (spin / g or spin / mol), the correlation with the number of radicals will be seen. Such a spin number has a stable correlation with the number of radicals of the object to be measured, and a definite calibration curve can be drawn.
One of the ESR measurement conditions is expressed as a g value.
For example, in the case of carbon radicals, as shown in Table 1,
It has been found that certain carbon radicals have a certain g-value, and nitrogen radicals have a g-value of 2.0050. Therefore, the measurement condition of the second means in the device 4 of the present invention can be determined by determining the g value depending on the sample to be measured.

[0057]

Embedded image

For example, a paint used as a top coat of a car body coating comprises two main components, an acid anhydride group-containing maleic acrylic polymer and a glycidyl group-containing acrylic polymer, and has HALS and ultraviolet absorption. Although the composition is formed by adding an agent and other additives, the amount of nitrogen radicals can be measured by subjecting the coating material to ESR and measuring it with a g value of 2.0050. The amount of nitrogen radicals measured in this way and the irradiation time in the radical generator, which is the first means in the device 4 of the present invention, have an excellent correlation, as will be seen in the examples described later. ing. Furthermore, when the relationship between the color difference (ΔE) indicating the degree of discoloration or fading of the paint and the irradiation time is examined, this also has an excellent correlation.

Therefore, for a certain specific paint (for example, paint A), the number of spins at a specific g value in the second means is measured for a sample whose age is zero, and the number of years elapsed is separately determined by an exposure test or the like. A calibration curve can be obtained by measuring the number of spins at a specific g value in the second means for the sample being tested, and taking the number of years of aging on the horizontal axis and the number of spins on the vertical axis (step (1)). ). Then, the sample made of the paint A is applied to the device 4 of the present invention, and the relationship between the plasma irradiation time in the first means and the spin number in the second means is obtained (step (2)).

Then, by measuring the sample of the paint A whose aging is unknown by using only the second means, the aging of the sample whose aging is unknown can be known from the calibration curve (step (3)). The calibration curve used here is a calibration curve showing the relationship between the number of years elapsed and the spin number obtained in the above step (1), the above step (2).
2 is a calibration curve showing the relationship between the irradiation time of the first means and the spin number of the second means obtained in 1. By skillfully using these two calibration curves, it is possible to finally know the age of the sample whose age is unknown and whose composition is known.

By utilizing the measurement conditions of the second means thus determined, a test method other than the above can be carried out. For example, for the paint A, since the relationship between the spin number and the irradiation time has already been obtained by the above test method, a calibration curve with the spin number on the vertical axis and the irradiation time on the horizontal axis must be obtained. Becomes Therefore, in the case of designing to improve the paint A to obtain a paint B having better weather resistance and light resistance, after designing the composition of the paint B, the composition is applied to the device 4 of the present invention, and the spin number is set. And the irradiation time are measured. When the relationship lies sideways from the calibration curve, the paint B has better weather resistance than the paint A, and when standing vertically from the calibration curve, The paint B is inferior in weather resistance and the like to the paint A, and the comprehensive judgment of these makes it possible to judge the quality of the design without a performance test of the paint B.

Further, the test apparatus of the present invention can be used more skillfully to carry out a test method other than the above.
For example, as detailed above, for a particular sample:
It is known that an established calibration curve can be drawn for the relationship between the spin number and the irradiation time obtained by the combination of the first means and the second means of the present invention. Therefore, a plurality of organic materials of unknown composition (for example, organic material X
And the organic material Y), the irradiation time is first specified for the organic material X, and the first means is applied, and then the second means is applied to measure the spin number, and the same organic material X is irradiated differently. The spin number is measured by applying the first means with time and then the second means, and by repeating this, the relationship between the spin number and the irradiation time for the organic material X of unknown composition is obtained. Thus, a graph in which the vertical axis represents the spin number and the horizontal axis represents the irradiation time is obtained. Separately, the same graph is obtained for the organic material Y. If the graph for organic material X lies sideways than the graph for organic material Y, then organic material X
Has better weather resistance than the organic material Y. According to such a method, it is possible to carry out a comparative examination of weather resistance of a plurality of organic materials, not only for a sample having a known composition but also for a sample having a completely unknown composition.

[0063]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 As a plasma generator, "Plasm" manufactured by Yamato Scientific Co., Ltd.
a Reactor PR-41 ", an Ep / BI coating film to be measured is placed in the reaction chamber 7, an oxygen gas inflow rate of 50 ml / min, a high frequency output of 100 to 500 W,
Oxygen plasma is generated under conditions of an oscillation frequency of 13.56 MHz and a pressure of 1.0 Torr to change the residual gloss ratio of the Ep / BI-based coating film, and the composition of the radical compound generated from the Ep / BI-based coating film. Was observed.

The gloss remaining rate of the Ep / BI coating film was measured by using "Digital variable angle gloss meter UGD-5D" manufactured by Suga Test Instruments Co., Ltd. The results are shown in FIG. The vertical axis represents the residual gloss ratio (%), and the horizontal axis represents the plasma irradiation time (minutes). The gloss remaining rate of the Ep / BI coating film reached a saturation level with the elapse of the plasma irradiation time, and the same phenomenon as the reduction of the gloss remaining rate in natural exposure was obtained.

The compound after the composition / structure change due to the radical compound generated from the Ep / BI type coating film was prepared as "Headspace Sampler JHS-10" manufactured by Nippon Analytical Industry Co., Ltd.
A value = (amount of TDI produced from the cross-linking portion) / (amount of phenol produced from the skeleton) was calculated by Hitachi "M-80B". The results are shown in FIG. The vertical axis represents the A value, and the horizontal axis represents the plasma irradiation time (minutes). The above A value decreased with the elapse of plasma irradiation time, and a phenomenon was observed in which the cleavage of the crosslinked portion of the organic polymer compound constituting the Ep / BI coating film proceeded.

The plasma irradiation time is about 20 minutes until the reduction of the residual gloss ratio reaches saturation, and the measured value after 20 minutes of the above A value is equipped on an automobile that has run 100,000 to 130,000 km. Since it was the same as the A value obtained from the 8-year-old coating film of the existing fuel neck tube,
It was found that the 20-minute deterioration acceleration test using the oxygen plasma generator reproduces the same deterioration phenomenon as natural exposure for 8 years.

Example 2 A radical compound was produced by the oxygen plasma generator used in Example 1, and in the gas combustion apparatus shown in FIG. 3, the above Ep / containing the produced radical compound was produced.
A pyrolysis gas of the BI-based coating film was generated, and the pyrolysis gas was burned to generate a combustion gas. As the above-mentioned apparatus gas combustion apparatus, a “combustion gas sampler CG” manufactured by Nippon Analytical Industry Co., Ltd.
-77 type "was used. The combustion gas is similarly concentrated,
The A value was determined. The results are shown in Fig. 7. The vertical axis represents the A value, and the horizontal axis represents the plasma irradiation time (minutes).

The above A value had an inflection point near the plasma irradiation time of 3 minutes. When ESR measurement was performed, phenoxy radicals, which were hardly detected before the plasma irradiation time of 3 minutes, increased and were detected after the plasma irradiation time of 3 minutes. A more detailed analysis was conducted. Before the plasma irradiation time of 3 minutes, the phenoxy radicals generated from the skeleton, which was promoting the stable bond with bisphenol A and the like constituting the epoxy resin in the system, were generated after the plasma irradiation time of 3 minutes. It was found that the phenoxy radical scavenging of bisphenol A exceeded the limit amount and was liberated into the system, causing a sudden cleavage phenomenon.

Example 3 Using the device 1 of the present invention and the device 2 of the present invention, deterioration measurement with time and prediction of life of a highly elastic coating film for building exterior were performed.

Device 1 of the present invention Oxygen plasma generator Oxygen gas inflow rate: 50 ml / min High frequency output: 150 W Oscillation frequency: 13.56 MHz Pressure: 500 mTorr Radical compound composition measurement conditions Pyrolysis temperature: 500 ° C. × 5 sec / He Gas chromatograph: Column DB-5 (0.25φ × 30 mm) Column temperature 50 ° C. to 300 ° C. (10 ° C./min) Mass spectrometer: Ionization / EI, 70 eV Temperature 160 ° C.

Under the above-mentioned conditions, the composition after the reaction of irradiating the high-elasticity coating film for building exterior, which is the object of measurement, with plasma to promote the formation of radical compounds was (amount of butene) / (n
-Amount of butyl acrylate) [hereinafter referred to as "B value"] was measured.

Furthermore, the "Sunshine weather meter test (S-W-O) according to the conventional JIS A 1415 is used.
-M) "B value of the above-mentioned highly elastic coating film for building exterior after 1500 hours, and" Due cycle weather meter test (D
-W-M) "The B value of the high-elasticity coating film for building exterior after 400 hours was measured. As a result, as shown in FIG. 9, the deterioration promoting method of the present invention and the conventional S-W-O-M method were used.
It was confirmed that there is a correlation between the deterioration promoting method in D.M.A. and the deterioration promoting method in DW-M, and in the measurement of the deterioration degree of the highly elastic coating film for building exterior, the B value indicates the deterioration degree. It turned out to be an appropriate index to represent.

Further, by plasma irradiation for about 20 minutes,
It is possible to reproduce deterioration acceleration by S-W-O-M for about 600 hours, and about 10 minutes by plasma irradiation for about 30 minutes.
Since it was possible to reproduce the deterioration promotion by S-W-O-M for 00 hours, it was found from FIG. 9 that the life and the like can be quantitatively predicted.

Further, from the decrease of B value with the increase of plasma irradiation time, it was found that the butene content in the above-mentioned highly elastic paint was decreased and the elastic modulus was decreased with the progress of deterioration.

Inventive device 2 In the same manner as in the inventive device 1, the B value of another high-elasticity coating film sample was measured. The results are shown in FIG. By the plasma irradiation, the deterioration phenomenon of 6 years of outdoor exposure could be reproduced in about 20 minutes. It was also found that the B value of the coating film increased with the increase of the plasma irradiation time, so that the butene content increased and the elastic modulus increased with the progress of deterioration.

Example 4 Using the device 4 of the present invention, the relationship between the irradiation time in the plasma generator and the spin number in ESR was determined. As the ESR, "EMX" manufactured by Bruker Japan Ltd. was used. As a plasma generator, "Plasma Reactor PR-" manufactured by Yamato Scientific Co., Ltd.
41 ”(oxygen plasma generator) was used. Oxygen plasma generator conditions Oxygen gas inflow rate: 50 ml / min High frequency output: 150 W Oscillation frequency: 13.56 MHz Pressure: 1000 mTorr Measurement conditions for radical compound composition X-band: Field; 327.4 ± 5 mT Temperature; -100 ° C spin std: CuSO ₄

The relationship between the irradiation time (minutes) of the oxygen plasma generator and the spin number of the ESR was examined for each sample. Sample 1 Maleic acrylic polymer having an acid anhydride group (monomer composition: styrene, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, maleic anhydride) 5
2 parts by weight, 45 parts by weight of an acrylic polymer having a glycidyl group (monomer composition: styrene, 2-ethylhexyl acrylate, caprolactone-modified acrylic ester, glycidyl methacrylate), HALS
(Tinuvin 1130: Sanol LS-400 = 1:
1), Tinuvin 900, and Irganox 1010 were each mixed in an amount of 1 part by weight. FIG. 11 shows the results.
It was shown to. It was found that the relationship between the number of spins and the irradiation time became an excellent linear shape and constituted a calibration curve.

Composition of Sample 2 22 parts by weight of acrylic polymer (monomer composition: styrene, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methacrylic acid, maleic anhydride), acrylic polymer (monomer composition: styrene, methacrylic acid 2 -Ethylhexyl, n-butyl methacrylic acid, methacrylic acid modified acrylic monomer, 4-hydroxybutyl acrylate) To a resin obtained by adding 29 parts by weight of a butyl modified amino resin to HALS (Tinuvin 1130: Sanol). LS-400 = 1: 1), Tinuvin 900, and Irganox 1010 were each mixed in an amount of 1 part by weight. The results are shown in FIG.
It was found that the relationship between the number of spins and the irradiation time became an excellent linear shape and constituted a calibration curve.

Example 5 Using the device 4 of the present invention, sample 1 (black colored triangles), sample 2
The relationship between the irradiation time and the color difference of (□) and Sample 3 (◯) was obtained. Composition of Sample 3 Maleated acrylic polymer having acid anhydride group (monomer composition: styrene, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, maleic anhydride) 5
2 parts by weight, 45 parts by weight of an acrylic polymer having a glycidyl group (monomer composition: styrene, 2-ethylhexyl acrylate, caprolactone-modified acrylic ester, glycidyl methacrylate), HALS
(Tinuvin 1130: Sanol LS-400 = 1:
1), Tinuvin 900, and Irganox 1010 were each mixed in an amount of 1 part by weight, and the crosslinking degree of Sample 1 was increased. The color difference is represented by the difference (ΔE) between the value before and after the application to the device 4 of the present invention. FIG. 13 shows the results.
It was shown to. It has been found that there is a certain relationship between irradiation time and color difference. Separately from the above, with respect to Sample 1 (black-painted Δ) and Sample 2 (□), each sample was coated with clear coat (top coat) 40 μm, intermediate coat 40 μm, undercoat 15 μm.
Film thickness of 100mm x 140 ° C for 20 minutes
A 300 mm steel plate was coated to form a coating film, which was exposed to wind and rain at an experimental site in Okinawa for 0 to 50 months (exposure test). The relationship between the number of months of exposure and the color difference (ΔE) was determined, and the results are shown in FIG. By comparing FIG. 13 and FIG. 14, it was found that there is a correlation between the actual exposure test and the result of the device 4 of the present invention also in the color difference (change in hue).

[0080]

Since the organic material testing apparatus of the present invention has the above-mentioned structure, the required sample is 0.1 to several meters.
Since a small amount such as g is sufficient and the shape of the sample does not matter, the organic material can be tested extremely quickly and accurately, and the deterioration degree can be determined by the chemistry of the organic polymer compound constituting the organic material. It is possible to analyze quantitatively what kind of deterioration phenomenon may occur in the future, since it can be analyzed by linking to the change of the structural structure.

With the organic material testing apparatus of the present invention, for example, it is possible to easily predict the durability of a coating applied via an adhesive and control the quality of films etc. be able to.

[Brief description of the drawings]

FIG. 1 is a system diagram showing an organic material testing apparatus of the present invention.

FIG. 2 is a diagram showing an oxygen plasma generator that constitutes an organic material testing apparatus of the present invention.

FIG. 3 is a diagram showing a gas combustion device which is included in the organic material testing device of the present invention.

FIG. 4 is a diagram showing a thermal decomposition amount by a thermal decomposition device and an amount ratio of a radical compound produced in the organic material testing device of the present invention.

5 is a graph showing the relationship between the residual gloss ratio and the oxygen plasma irradiation time in Example 1. FIG.

FIG. 6 is a diagram showing the results of Example 1.

FIG. 7 is a diagram showing the results of Example 2.

FIG. 8 is a system diagram showing the device 4 of the present invention.

FIG. 9 is a diagram showing a result of the device 1 of the present invention in Example 3;

FIG. 10 is a diagram showing a result of the device 2 of the present invention in Example 3;

FIG. 11 is a diagram showing the results of Sample 1 of Example 4. The vertical axis represents the spin number and the horizontal axis represents the irradiation time.

FIG. 12 is a diagram showing the results of Sample 2 of Example 4. The vertical axis represents the spin number and the horizontal axis represents the irradiation time.

13 is a diagram showing the results of the device 4 of the present invention in Example 5. FIG. The vertical axis represents color difference (ΔE), and the horizontal axis represents irradiation time (minutes). The black solid Δ indicates sample 1, □ indicates sample 2, and ◯ indicates sample 3.

FIG. 14 is a view showing a result of the device 4 of the present invention of Example 5. The vertical axis represents color difference (ΔE), and the horizontal axis represents irradiation time (minutes). Black-colored triangles represent sample 1, and squares represent sample 2.

[Explanation of symbols]

 1 High Frequency Power Supply 2 Matching Unit 3 Vacuum Pump 4 Vacuum Gauge 5 High Pressure Oxygen Cylinder 7 Reaction Chamber 10 High Frequency Coil 11 Combustion Chamber 12 Combustion Heater 13 Oven Heater 14 Virofoils 15 Sample 20 Adsorption Chamber

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G01N 33/32 C09B 67/00 // C09B 67/00 G01N 24/10 510S

Claims (19)

[Claims] 1. An organic material comprising means for generating a specific factor in the organic material, which correlates with a change with time of the organic material, and means for analyzing the organic material containing the generated specific factor. Material testing equipment. 2. A device for generating a specific factor that correlates with a change with time of the organic material in the organic material, and a device for analyzing the organic material containing the generated specific factor are in the same apparatus. The apparatus for testing an organic material according to claim 1, which is incorporated in a. 3. An apparatus incorporating a means for generating a specific factor in the organic material that correlates with a change with time of the organic material, and a means for analyzing the organic material containing the generated specific factor. The apparatus for testing an organic material according to claim 1, which comprises an incorporated device. 4. The apparatus for testing an organic material according to claim 2 or 3, wherein the means for generating a specific factor in the organic material that correlates with a change with time of the organic material is a plasma generator. Is a radical compound of an organic polymer compound that constitutes the organic material. 5. A means for analyzing the produced organic material containing the specific factor is an electron spin resonance apparatus (ES).
R) is the organic material testing device according to claim 4. 6. An X-ray photoelectron spectroscopic analyzer (X
PS) The organic material testing device according to claim 4. 7. The apparatus for testing an organic material according to claim 4, wherein the means for analyzing the produced organic material containing the specific factor comprises a thermal decomposition apparatus, a gas chromatograph, and a mass spectrometer. 8. The means for analyzing the produced organic material containing the specific factor comprises a thermal decomposition device, a gas combustion / concentration device, a gas chromatograph, and a mass spectrometer. Testing equipment for organic materials. 9. An apparatus comprising a pyrolysis apparatus, a gas chromatograph, and a mass spectrometer, for analyzing the produced organic material containing the specific factor,
The organic material testing apparatus according to claim 4, which is a combination of a pyrolysis apparatus, a gas combustion / concentration apparatus, a gas chromatograph, and an apparatus including a mass spectrometer. 10. The organic material comprises an organic polymer compound, an organic polymer compound and an organic compound, or an organic polymer compound and an inorganic compound. , 8 or 9 organic material testing device. 11. The apparatus for testing an organic material according to claim 10, wherein the organic material is a paint, a film, a coating material or an adhesive. 12. A method for testing an organic material, comprising using the apparatus for testing an organic material according to claim 10. 13. The method for testing an organic material according to claim 12, wherein the method for testing an organic material predicts the degree of deterioration of a new organic material. 14. The method for testing an organic material according to claim 12, wherein the method for testing the organic material measures the weather resistance of the novel organic material. 15. The method for testing an organic material compares the weather resistance of a plurality of organic materials of unknown composition.
Test methods for the described organic materials. 16. A paint designing method, characterized in that the method for testing an organic material according to claim 13, 14 or 15 is applied. 17. The amount of a specific factor that correlates with a composition / structure change caused by a radical compound in the sample is measured by applying a sample whose age is known to a means for analyzing an organic material. A step (1) of obtaining a calibration curve (i) representing a correlation between the amount and the number of years of aging of the sample, by applying a sample of which the number of years of aging is known to the organic material testing apparatus according to claim , Obtaining two of the analysis result in the means for analyzing the organic material containing the specific factor produced and the amount of the specific factor in the means for analyzing the organic material, and showing the correlation between the amount of the specific factor and the analysis result. The step (2) of obtaining the calibration curve (ii) represented, and the sample by applying the sample of which the age is unknown to the means for analyzing the produced organic material containing the specific factor Of the organic material, which comprises the step (3) of obtaining the analysis result of 1. and obtaining the age of the sample by combining the two calibration curves of the calibration curve (i) and the calibration curve (ii). Test method. 18. The test method for an organic material according to claim 17, wherein the test method for the organic material is a method for measuring a degree of deterioration of an existing organic material. 19. A method for diagnosing an existing article to which the test method for an organic material according to claim 18 is applied.