JPH0726906B2 - Weather resistance test method and device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention is directed to quality deterioration such as gloss change and discoloration of chemical products such as coating films and synthetic resin products that are exposed to sunlight for a long time. The present invention relates to an accelerated weathering test method for simulating a laboratory in a short period of time and an apparatus used therefor.

[Prior Art] Conventionally, as this type of accelerated weathering test method, a chemical product is used as an artificial light source, such as carbon arc, xenon arc, or light emitted from an ultraviolet fluorescent lamp, with or without passing through a filter. Irradiating the sample.

However, the test results obtained by the conventional test method do not always match the results actually used in the natural world, and it cannot be said that they have a high correlation with the actual use results.

The present inventor has studied the quality deterioration of chemical products due to light, and has found that the degree of quality deterioration largely depends on the wavelength of light received by the chemical product. For example, five types of coating films (A to E) having different vehicles were irradiated with light dispersed under the same conditions for light of each wavelength, and the gloss reduction rate of the coating film with respect to the light of each wavelength was measured. The results are shown in FIG. It can be seen from FIG. 7 that the gloss reduction rates of the five types of coating films (AE) increase exponentially as the wavelength of light is shortened from about 350 nm. That is, the deterioration of the quality of chemical products due to light has a wavelength dependence that varies depending on the type of chemical product.
It has a strong dependence on light having a wavelength of 0 nm or less, particularly light having a wavelength of 295 nm or less.

Next, the present inventor investigated the spectral distribution of the artificial light source used in the conventional accelerated weathering test method. As a typical example, FIG. 1 shows the spectral distribution of the sunshine carbon arc lamp and sunlight.

The spectral distribution of the sunshine carbon arc lamp is as shown by the characteristic curve A shown by the solid line in FIG. 1, and even when the optical filter used in the conventional accelerated weathering test method is used, its spectral distribution is Is as shown by the characteristic curve B shown by the broken line in FIG. 1, and the spectral distribution of 350 nm or less is significantly different from the spectral distribution of sunlight (shown by the dashed-dotted characteristic curve C in FIG. 1). In particular, there is light of 295 nm or less that is not in sunlight and has a great influence on the deterioration of chemical products, as shown by characteristic curves A and B in FIG. Therefore, in the conventional test method, it is recognized that the test results do not match the results of use in the natural world.

Further, the conventional glass optical filter for weather resistance test device is easily deteriorated during use, and in order to irradiate the sample with light having a uniform spectral distribution, an expensive glass filter must be replaced in a short time. However, it was disadvantageous in terms of cost and time for replacement.

Therefore, the present applicant has developed a test method according to Japanese Patent Laid-Open No. 58-71439 in order to irradiate a sample with artificial light whose spectral distribution of light having a wavelength of 350 nm or less is very similar to that of sunlight.

However, in the test method according to Japanese Patent Laid-Open No. 58-71439, the ratio of the amount of light having a wavelength of 310 nm to the amount of light having a wavelength of 320 nm is I320nm / I310nm = 2 ± 0.1, and I330nm / I310nm = 3.
It is set to be ± 0.15. Here, I320 nm represents the light intensity at 320 nm of the wavelength of light. However, the actual spectral composition of sunlight is I320nm / I310nm = 3-5, I330n
Since m / I310nm = 5 to 8, the test result of the above-mentioned Japanese Patent Laid-Open No. 58-71439 cannot sufficiently simulate the use result in the natural world.

[Problems to be Solved by the Invention] The present invention eliminates the above-mentioned conventional drawbacks and provides an accelerated weathering test method and an apparatus used for the same that improve the correlation with the actual outdoor use result. The purpose is to provide.

[Means for Solving Problems] Therefore, the present inventor provides a weather resistance test method having an extremely high correlation with the outdoor use results of chemical products,
The spectral distribution of the light of the following wavelength is very close to that of sunlight, that is, the light of the wavelength of 300 nm or less does not include the light of the wavelength of 295 nm or less. % Or less, I320nm / I310nm = 2.1 to 4, I330nm / I310nm =
Various studies were conducted on an artificial light source and an optical filter capable of irradiating a sample with artificial light having a light intensity distribution of 5-10.3 and I340nm / I310nm = 6.4-13. As a result, 31
If the amount of light with a wavelength of 0 nm is 1, the amount of light with a wavelength of 290 nm is 0.5 or less, and the amount of light with a wavelength of 300 nm is 4 or less, 320 nm
The amount of light of the wavelength of 0.7 to 2.4, the amount of light of the wavelength of 330 nm
An artificial light source with a light amount of 1.1 to 4.6 and a wavelength of 340 nm of 0.9 to 5.4 is used, and further, by weight%, SiO ₂ 70 ± 1%, Fe ₂
O ₃ 0.03 ± 0.02, Na ₂ O 7.5 ± 1%, K ₂ O 7 ± 1%, CaO 7.
5 ± 1%, BaO 2 ± 0.5%, ZnO 4 ± 0.5% and other than Al ₂
O _3, MgO, contain Sb ₂ O _3, TiO ₂ oxide, the thickness 2~4m
I found that I could use an optical filter made of m glass. The present invention has been completed based on this discovery.

The spectral distribution of artificial light applied to a sample by the test method according to the present invention has a great influence on the quality deterioration of chemical products.
Since the light having a wavelength of 0 nm or less is closer to that of sunlight than the spectral distribution of conventional artificial light, the test result of the present invention has a higher correlation with the actual use result than the conventional test result.

The test apparatus according to the present invention includes a test tank that forms a test chamber that stores a sample, an artificial light source that emits light toward the sample that is stored in the test chamber, and an intervening device between the artificial light source and the test tank. A test device comprising a glass optical filter that
The optical filter is composed of SiO ₂ 70 ± 1% and Fe ₂ O ₃ 0.03 ±% by weight.
0.02%, Na ₂ O 7.5 ± 1%, K ₂ O 7 ± 1%, CaO 7.5 ± 1
%, BaO 2 ± 0.5%, ZnO 4 ± 0.5%, and Al
_It contains oxides of ₂ O ₃ , MgO, Sb ₂ O ₃ and TiO ₂ and has a thickness of 2 to 4 mm. The artificial light source has a wavelength of 290 nm at a wavelength of 310 nm, if the amount of light is 310 nm. The amount of light is 0.5 or less, the amount of light of 300 nm wavelength is 4 or less, and the amount of light of 320 nm wavelength is 0.7 to 2.
4, the amount of light having a wavelength of 330 nm is 1.1 to 4.6, and the amount of light having a wavelength of 340 nm is 0.9 to 5.4.

The test tank according to the present invention can be essentially the same as the test tank of the conventional test apparatus, and is usually a box-shaped body constituting the test chamber, a door for inserting and removing the sample, It has ventilation holes and exhaust holes.

The artificial light source according to the present invention has the above spectral distribution, and a sunshine carbon arc lamp is typical. The sunshine arc lamp has a spectral distribution shown by a characteristic curve A in FIG. Sunshine arc lamp is 310m
If the amount of light of wavelength m is 1, the amount of light of wavelength 290 nm is
0.36 ± 0.05, the amount of light with a wavelength of 300 nm is 0.51 ± 0.05, 3
The amount of light with a wavelength of 20nm is 1.24 ± 0.05, the amount of light with a wavelength of 330nm is 2.33 ± 0.05, the amount of light with a wavelength of 340nm is 2.36 ± 0.0.
It emits light with a distribution of 5. The artificial light source according to the present invention is not limited to the sunshine carbon arc lamp, and the spectral distribution has a light amount of 310 nm wavelength of 1 and a light amount of 290 nm wavelength of 0.5. Below 300n
The amount of light of wavelength m is 4 or less, and the amount of light of wavelength 320nm is 0.
Any light source may be used as long as it has a wavelength of 7 to 2.4, a wavelength of 330 nm of 1.1 to 4.6, and a wavelength of 340 nm of 0.9 to 5.4.

The optical filter made of glass, which features the test apparatus according to the present invention, is interposed between the artificial light source and the test tank, and its composition is SiO ₂ 70 ± 1% by weight% and Fe ₂ O ₃ 0.03 ±. 0.02%, N
a ₂ O 7.5 ± 1%, K ₂ O 7 ± 1%, CaO 7.5 ± 1%, BaO 2 ±
0.5%, ZnO 4 ± 0.5%, Al ₂ O ₃ , MgO, Sb
_It contains ₂ O ₃ and TiO ₂ . The thickness of the optical filter is 2 to 4 mm because it affects the spectral characteristics as will be shown in Examples and Comparative Examples described later.

The test tank preferably has an adjusting device for adjusting the distance between the artificial light source and the sample. Using such an adjusting device is advantageous because the distance between the artificial light source such as a sunshine carbon arc lamp and the sample can be adjusted in size.

That is, when the optical filter according to the present invention is used, since there is no light of 295 nm or less that easily deteriorates the sample that is a chemical product, the acceleration factor for quality deterioration tends to be low. This is because the distance to the sample can be shortened and the reduction in acceleration factor can not be compensated. If the optical filter according to the present invention is used in combination with an artificial light source such as a sunshine carbon arc lamp having the spectral characteristic shown in FIG.
The spectral characteristics of the light with which the sample is irradiated are very similar to the spectral characteristics of sunlight. That is, it closely approximates within a range of 350 nm or less, does not include light of a wavelength of 295 nm or less, and the amount of light of a wavelength of 300 nm or less is 5% or less of the amount of light of a wavelength of 300 to 320 nm. If the amount of light of the wavelength is 1, the amount of light of the wavelength of 320 nm is 2.1 to 4, and the amount of light of the wavelength of 330 nm is 5 to 10.3.
Thus, light having a spectral distribution in which the amount of light having a wavelength of 340 nm is 6.4 to 13 is obtained.

[Effects of the Invention] According to the test method of the present invention, the spectral distribution of the artificial light with which the sample is irradiated is the same as that of the conventional artificial light with respect to light having a wavelength of 350 nm or less, which greatly affects the quality deterioration of the chemical product. Since the spectral distribution is closer to that of sunlight, the test result of the present invention has a higher correlation with the actual use result than the conventional test result.

Moreover, according to the test apparatus of the present invention, the above-described test method can be implemented.

Also, since the optical filter used in the conventional weather resistance test method is easily deteriorated during the test, the initial spectral distribution shown by the characteristic curve G shown by the solid line in FIG. Then, the spectral distribution of light largely changes as shown by the characteristic curve F shown by the broken line in FIG. On the other hand, when the optical filter according to the present invention is used, the initial spectral distribution is shown by the characteristic curve E in FIG. 3, but after the use for 1500 hours, Third spectral distribution
As shown by the characteristic curve P in the figure, only a slight amount changes, and therefore light having a very stable spectral characteristic can be irradiated on the sample for a long time. Therefore, by using the optical filter according to the present invention, it is possible to reduce the frequency of filter replacement, for example, 1/10 or less of the case of using a conventional filter, which requires a long time for optical filter replacement. This is a great advantage as it requires almost no manpower for filter replacement in the required test equipment.

Example 1 A weather resistance test apparatus having a structure shown in FIG.
A test tank 2 that is provided in the base body 1 and forms a test chamber 20 in which the sample S is housed, a sunshine carbon arc lamp 3 as an artificial light source that emits light toward the sample S housed in the test chamber 20, and a sunshine carbon An optical filter 4 made of glass is provided between the arc lamp 3 and the test tank 2.
Here, the base 1 is a switchboard 10, an air regulating valve 11, a transformer 1
2. Has a blower 13. Sunshine carbon arc light 3
Is a carbon body 30 that is provided a predetermined distance apart and discharges when energized, and a case that houses the carbon body 30.
It consists of 31 and. When the carbon body 30 is consumed due to discharge,
The holder 30a that holds the carbon body 30 moves up and down, and the spacing between the carbon bodies 30 is kept constant. The test tank 2 includes a holder 23 for holding the sample S, a rotary frame 21 for rotating the holder 23 around a carbon arc lamp, and a black panel thermometer 22.
With and.

The optical filter 4 made of glass has a weight percentage of SiO ₂ 70 ± 1%, F
e ₂ O ₃ 0.03 ± 0.02%, Na ₂ O 7.5 ± 1%, K ₂ O 7 ± 1%, Ca
Contains O 7.5 ± 1%, BaO 2 ± 0.5%, ZnO 4 ± 0.5%,
Furthermore, it contains oxides such as Al ₂ O ₃ , MgO, Sb ₂ O ₃ and TiO ₂ ,
It is characterized by having a thickness of mm.

Now, the carbon body 30 is energized to discharge the carbon body 30 to cause the sunshine carbon arc lamp 3 to emit light, and the light is passed through the optical filter 4. Then, the characteristic curve D shown by the solid line in FIG.
The light having the spectral characteristics as described above is applied to the sample S housed in the test chamber 20. The light irradiated on the sample S is
The spectral characteristics of sunlight having characteristics such as the characteristic curve C shown by the one-dot chain line in Fig. 2 and the characteristics at the low wavelength near 300 nm, which have a great influence on the deterioration of chemical products, match very well, and especially There is no light having a wavelength of 295 nm or less, which is not present in sunlight, which is present when a conventional optical filter is used. Therefore, in the present embodiment, it is possible to obtain a result in which the color difference and the gloss are very well matched with the result of the outdoor exposure.

Further, when the optical filter 4 according to the present embodiment is combined with the sunshine carbon arc lamp 3, the spectral characteristics on the sample S surface after use for 1500 hours are as shown by the characteristic curve P in FIG. The deterioration of 4 is very small.

Comparative Example 1 The optical filter according to Comparative Example 1 was used in the same test apparatus as in Example 1. This optical filter is SiO ₂ 67.
9%, B ₂ O ₃ 17.3%, K ₂ O 7.15%, Na ₂ O 4.0%, Al ₂ O ₃ 3.
A glass filter having a thickness of 2.5 mm and a composition containing 24%, Li ₂ O 0.80%, and several other oxides generally used as glass constituent elements selected from CaO, Fe ₂ O ₃ , MgO, etc. Is. In this comparative example 1, the light having the spectral characteristic shown by the characteristic curve H in FIG. 4 is irradiated onto the sample S, which means that light having a wavelength of 295 nm or less, which is not found in sunlight, is considerably emitted as shown in FIG. In addition to having the amount, the spectral characteristics are different from sunlight. Therefore, in Comparative Example 1, when the weather resistance test of the chemical product was performed, the results of which the color difference and the gloss were different from the results of the outdoor exposure were obtained.

[Comparative Example 2] The optical filter according to Comparative Example 2 was used in the same test apparatus as in Example 1. This optical filter is made of SiO ₂ 6
7.3%, Al ₂ O ₃ 1.68%, Fe ₂ O ₃ 0.023%, Na ₂ O 21.6%, B
₂ O 7.37%, Sb ₂ O ₃ 1.13%, and a composition containing several kinds of oxides commonly used as glass components,
A filter made of glass with a thickness of 0.85 mm. Comparative example 2
Optical filter and sunshine carbon arc lamp 3
When combined with, the sample S is irradiated with the light having the spectral characteristic shown by the characteristic curve I in FIG. In Comparative Example 2 as well, there is a considerable amount of wavelengths of 295 nm or less, which is not found in sunlight, and the spectral characteristics of wavelengths near 300 nm are significantly different from the spectral characteristics of sunlight. Therefore, in Comparative Example 2 as well, results different from the results of outdoor exposure in color difference and gloss were obtained.

[Comparative Example 3] The following optical filter was used in the same test apparatus as in Example 1. This optical filter is SiO ₂ 69.9%, Al ₂ O ₃
1.83%, Fe ₂ O ₃ 0.008%, Na ₂ O 16.3%, K ₂ O 1.87%, C
It is a filter made of glass having a thickness of 2 mm and having a composition containing aO 5.91%, MgO 2.89%, B ₂ O ₃ 1.07% and several kinds of oxides generally used as glass constituent elements.
When the optical filter and the sunshine carbon arc lamp 3 are combined, the sample S is irradiated with the light having the spectral characteristic shown by the characteristic curve J in FIG. In Comparative Example 3 as well, a considerable amount of light having a wavelength of 295 nm or less, which is not found in sunlight, is included, and 3
The spectral characteristics of wavelengths near 00 nm are very different from the spectral characteristics of sunlight. Therefore, also in Comparative Example 3, results different from the results of outdoor exposure in color difference and gloss were obtained.

[Example 2] An optical filter having the same composition as in Example 1 was used in the same test apparatus as in Example 1. However, in the case of Example 2, the thickness of the glass of the optical filter was 2 mm. In the second embodiment, the spectral characteristic of the light with which the sample S is irradiated is as shown by the characteristic curve K in FIG. Therefore, similar to the characteristic curve D showing the spectral characteristics of Example 1, the spectral characteristics of the sunlight were in good agreement. Therefore, also in Example 2, it is possible to obtain a result in which the color difference and gloss are very well matched with the result of outdoor exposure.

[Comparative Example 4] In Example 2, the thickness of the optical filter was set to 1.4 mm,
After that, the test was performed under the same conditions as in Example 2. In this case, the spectral characteristic shown by the characteristic curve L shown in FIG. 5 was obtained. This spectral characteristic is that the light of wavelength 295 nm or less, which is not found in sunlight, is applied to the sample, and I320nm / I310nm = 1.
6, I330nm / I310nm = 3.5, I340nm / I310nm = 3.7,
This is the spectral characteristics of sunlight (I320nm / I310nm = 3-5, I33
0nm / I310nm = 5-8, I340nm / I310nm = 5-11). Therefore, in Comparative Example 3, the color difference and the gloss were different from the results of the outdoor exposure.

Example 3 An optical filter having the same composition as in Example 1 was used in the same test apparatus as shown in Example 1. However, the thickness of the glass of the optical filter was set to 4 mm, and thereafter the test was performed under the same conditions as in Example 1. In this case, the sample S is irradiated with the light having the spectral characteristic shown by the characteristic curve M in FIG.
In this case, I320nm / I310nm = 3.4, I330nm / I310nm = 10.
3, I340nm / I310nm = 12.6. This is in good agreement with the spectral characteristics of sunlight. Therefore, test results are obtained that are in good agreement with the results of outdoor exposure.

[Comparative Example 5] An optical filter having the same composition as in Example 1 was used by using the same test apparatus as that shown in Example 1. However, the glass thickness of the optical filter was 5 mm. After that, the test was performed under the same conditions as in Example 1. In this case, the sample S is irradiated with light having the spectral characteristic shown by the characteristic curve N in FIG. In this case, I320nm / I310nm = 5.7, I330nm / I310nm = 15.7, I340n
m / I 310nm = 20.3. This is very different from the spectral characteristics of sunlight. Therefore, different results are obtained in terms of color difference and gloss from the results of outdoor exposure.

[Brief description of drawings]

FIG. 1 is a graph showing the spectral characteristics of sunlight, the spectral characteristics of a sunshine carbon arc lamp, and the spectral characteristics of a combination of a sunshine carbon arc lamp and a conventional optical filter. FIG. 2 is a graph showing the sunshine carbon. FIG. 3 is a graph showing a spectral characteristic when an arc lamp and an optical filter according to the present invention are combined, and FIG. 3 is a graph showing a spectral characteristic change of light irradiated on a sample due to deterioration of the optical filter. FIG. 4 is a graph showing the spectral characteristics of the light radiated to the sample by the optical filter having a changed glass composition and the sunshine carbon arc lamp, and FIG. 5 is a graph showing the changes in the spectral characteristics due to the change in the thickness of the optical filter. And
FIG. 6 is an explanatory view showing the inside of the test apparatus used in this example. FIG. 7 is a graph showing the relationship between the wavelength of light and the gloss reduction rate. In the figure, 1 is a substrate, 2 is a test tank, 20 is a test chamber, 3 is a sunshine carbon arc lamp, and 4 is an optical filter.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Koyama, Nagachite-cho, Aichi-gun, Aichi Prefecture 1-41 Yokomichi, Toyota Central Research Institute Co., Ltd. (72) Inventor Takeshi Narita Nagakute-cho, Aichi-gun, Nagachite-machi 1 in 41 Chuo-dori, Toyota Central Research Institute Co., Ltd. (72) Inventor Tomi Aragaga, Nagakute-cho, Aichi-gun, Aichi Prefecture 1-chome, 1 in 42 Toyota Chuo Research Laboratory (72) Inventor Shoichi Suzuki Akita Prefecture, Aichi District, Nagakute-machi, Oita, Nagatoji, 41, Yokomichi, Toyota Central Research Institute Co., Ltd. (72) Inventor, Hiroshi Hattori, Toyota-City, Toyota City, Aichi Prefecture, Toyota Town, Ltd. (72) Inventor, Aoki Kikuo Aichi 100 Kanayama, Ichiriyama-cho, Kariya city, Toyota Auto Body Co., Ltd. (72) Inventor, Koichiro Itagaki, Mugen, Tauraminato-cho, Yokosuka-shi, Kanagawa Kanto Automobile Industry Co., Ltd. (56) Reference JP-A-58-71439 (JP, A) JP-A-60-15544 (JP, A)

Claims (3)

[Claims] 1. A combination of an artificial light source and an optical filter,
Does not include light with a wavelength of 5 nm or less, and the amount of light with a wavelength of 300 nm or less is 5% or less of the amount of light with a wavelength of 300 to 320 nm.
If the amount of light of wavelength is 1, the amount of light of wavelength of 320nm is
2.1 ~ 4, the amount of light with wavelength of 330nm is 5-10.3, 340nm
A method for accelerated weathering test, characterized in that light having a spectral distribution in which the amount of light of the wavelength is 6.4 to 13 is generated and the sample is irradiated with the light. 2. A test tank that forms a test chamber in which a sample is housed, an artificial light source that emits light toward the sample housed in the test chamber, and an intervening device between the artificial light source and the test tank. A test device comprising a glass optical filter, wherein the optical filter comprises SiO ₂ 70 ± 1% by weight and Fe ₂ O ₃ 0.03.
± 0.02%, Na ₂ O 7.5 ± 1%, K ₂ O 7 ± 1%, CaO 7.5 ± 1
%, BaO 2 ± 0.5%, ZnO 4 ± 0.5%, and Al
_It contains oxides of ₂ O ₃ , MgO, Sb ₂ O ₃ and TiO ₂ , has a thickness of 2 to 4 mm, and the artificial light source has an amount of light of 310 nm of 1 is 290
The amount of light of wavelength of nm is 0.5 or less, the amount of light of wavelength of 300 nm is 4 or less, the amount of light of wavelength of 320 nm is 0.7 to 2.4, the amount of light of wavelength of 330 nm is 1.1 to 4.6, The amount of light with a wavelength of 340 nm is 0.9
Test equipment characterized by being ~ 5.4. 3. The test apparatus according to claim 2, wherein the test tank has an adjusting device for adjusting the distance between the artificial light source and the sample.