JP3470891B2 - Infrared blocking film - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared ray shielding film which is particularly useful when it is used by being attached to various window glasses such as window glass for automobiles, window glass for buildings and houses, and particularly adhesion, The present invention relates to an infrared ray shielding film having excellent transparency, weather resistance, heat resistance, moisture resistance, and infrared ray shielding property.

[0002]

2. Description of the Related Art As an infrared ray blocking film which is used by being stuck on a window glass of an automobile, a window glass of a building or a house, etc., a conventional plastic film contains infrared ray blocking metal fine particles on one side thereof and has an infrared ray blocking property having a hard coat property. Infrared blocking films with layers are known.
The infrared ray blocking film is generally used by forming an adhesive layer on the other side of the plastic film and bonding it to a window glass or the like, so that the infrared ray blocking layer is an infrared ray blocking film. Since it is formed on the outermost layer of the film, hard coat property is required.

For example, in Japanese Unexamined Patent Publication No. 9-108621, fine particles of an inorganic metal (tin oxide, ATO (antimony-doped tin oxide), IT, etc.) having a heat ray absorbing ability are formed on a film.
A heat ray-shielding resin composition having scratch resistance and curable by ultraviolet rays, which is composed of O (tin-doped indium oxide) or the like and an active energy ray-polymerizable polyfunctional (meth) acrylate having a (meth) acryloyl group, is coated. The film is described.

[0004]

However, the coating film described in the above publication has the following drawbacks. There is a problem that the adhesive force between the coating film formed by coating the heat ray-shielding resin composition on the film and the film and the water-resistant adhesive force (adhesive force when peeling with water interposed on the coating film surface) are poor. It was Therefore, there is a problem that the coating film peels off when water is condensed on the window or when water is used for the window attachment. Further, since it is poor in weather resistance, heat resistance, and humidity resistance, particularly under conditions of high temperature and high humidity, the adhesive strength, the water resistant adhesive strength, and the haze value decrease, that is, the transparency decreases remarkably over time. There was a problem. Therefore, there is a problem in that the coating film is easily peeled off because the adhesive strength and the water resistant adhesive strength are deteriorated with time, and the scratch resistance of the coating film, that is, the hard coat property is significantly deteriorated. . From the above, there is a problem that the infrared ray blocking property of the coating film is consequently lowered.

The present invention eliminates all of the above-mentioned drawbacks, and an object of the present invention is to provide an infrared shielding film having excellent adhesion, transparency, weather resistance, heat resistance, moisture resistance, and infrared shielding property. To do.

[0006]

SUMMARY OF THE INVENTION (1) The present invention provides an infrared shielding film having a hard coat infrared shielding layer containing infrared shielding metal fine particles on one side of a plastic film, which is a plastic film. Between the infrared blocking layer, linear saturated polyester resin,
Xylene diisocyanate resin, and a functional resin layer consisting of hexamethylene diisocyanate resin is formed,
Further, it is an infrared shielding film having weather resistance, heat resistance and moisture resistance, which satisfies the following conditions. The cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The water resistant cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The haze value of the infrared shielding film is (2) The present invention is a weather resistance test (after irradiation with ultraviolet rays for 8 hours,
In each of the test of conducting dew condensation for 4 hours as one cycle, 83 cycles), the heat resistance test (80 ° C., 1000 hours), and the humidity resistance test (40 ° C. × 95%, 1000 hours), the following conditions after the test: The infrared shielding film according to (1) above, which satisfies the above condition. The cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The water resistant cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The haze value of the infrared shielding film is (3) The present invention is the infrared shielding film according to the above (1) or (2), wherein the infrared shielding metal fine particles are antimony trioxide-doped tin oxide fine particles.

In the infrared ray shielding film of the present invention, since the functional resin layer is formed between the plastic film and the infrared ray shielding layer, the cross-cut adhesive force and the water resistant cross-cut adhesive force between the plastic film and the infrared ray shielding layer. Is 80/100 to 100/100, and the adhesiveness is excellent. Here, the cross-cut adhesion is JI.
It is the adhesive force measured according to SK-5400-1990, and, for example, if the value is 100/100, it indicates that there is no peeling at all and completely adheres,
On the contrary, if the value is 0/100, it means that there is no close contact. What is the water resistant cross cut adhesion?
It is the cross-cut adhesion when peeled with water interposed on the surface of the infrared blocking layer, and the value has the same meaning as the cross-cut adhesion. If the cross-cut adhesion between the plastic film and the infrared shielding layer and the water resistant cross-cut adhesion are both 80/100 or more, there is no practical problem as an infrared shielding film for window sticking. Furthermore, since the haze value of the infrared ray shielding film of the present invention is less than 2, it has excellent transparency. When the haze value of the infrared ray blocking film is less than 2, there is no practical problem as an infrared ray blocking film for attaching a window.

Further, since the infrared ray blocking film of the present invention has the above-mentioned functional resin layer formed thereon, it has a weather resistance test (a cycle of irradiation of ultraviolet rays for 8 hours and then dew condensation for 4 hours is defined as one cycle, which is 83 cycles). ), Heat resistance test (80
℃, 1000 hours), and humidity resistance test (40 ℃ × 95
%, 1000 hours), the cross-cut adhesion between the plastic film and the infrared ray blocking layer and the water-resistant cross-cut adhesion are both 80/100 to 80% after the test.
It is 100/100 and maintains excellent adhesion, and the infrared ray shielding film has a haze value of less than 2 and also maintains transparency. As described above, the infrared shielding film of the present invention is excellent in weather resistance, heat resistance, and moisture resistance, and therefore, particularly under high temperature and high humidity conditions, the cross-cut adhesive strength, the water-resistant cloth, and the like. Since the cut adhesion and the haze value are very little reduced, the plastic film and the infrared ray shielding layer are not easily peeled off, and therefore the scratch resistance and transparency of the infrared ray shielding film are not deteriorated. Also, the infrared ray blocking property does not deteriorate.

In particular, if the functional resin layer of the infrared ray shielding film of the present invention is formed of a linear saturated polyester resin, a xylene diisocyanate resin, and a hexamethylene diisocyanate resin, adhesion, transparency, weather resistance and heat resistance will be improved. Since it is possible to obtain an infrared ray shielding film having further excellent properties and moisture resistance, it is more complete.

Further, when the infrared ray shielding metal fine particles contained in the infrared ray shielding layer of the infrared ray shielding film of the present invention are antimony trioxide-doped tin oxide fine particles, the infrared ray shielding property, transparency and economy are excellent. It becomes an infrared ray blocking film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The plastic film used in the infrared ray shielding film of the present invention is not particularly limited as long as it has such transparency that the haze value of the infrared ray shielding film is less than 2. For example, various transparent plastic films such as polyesters such as polyethylene terephthalate, polyethylene, polypropylene, polystyrene, acrylic, polycarbonate, nylon, vinyl chloride, etc., which have been used for infrared shielding films for pasting windows, can be used.

The infrared ray blocking layer containing the infrared ray blocking metal fine particles and having a hard coat property, which is formed on the infrared ray blocking film of the present invention, is formed on the functional resin layer to be described later. Adheres closely and blocks infrared rays,
It has transparency to the extent that the haze value of the infrared shielding film is less than 2, and has a hard coat property of 2H or more in pencil hardness. The infrared blocking layer has a structure in which infrared blocking metallic fine particles having an infrared blocking property are dispersed in a resin having a hard coat property.

The resin used for the infrared ray blocking layer is not particularly limited as long as it is in close contact with the functional resin layer and has a hard coat property of 2H or more in pencil hardness. From the viewpoint of dispersibility of the infrared ray blocking metal fine particles, an ultraviolet curable acrylic resin is preferable.

The infrared ray blocking metal fine particles dispersed in the resin used in the infrared ray blocking layer are not particularly limited as long as they are infrared ray blocking metal particles, and examples thereof include antimony trioxide-doped tin oxide particles and ITO (tin-doped). Although metal fine particles such as indium oxide) fine particles, tin oxide fine particles, and zinc oxide fine particles can be used, tin oxide fine particles and zinc oxide fine particles are slightly inferior in infrared ray blocking performance and transparency, and IT
Since O is slightly expensive, it is more complete if antimony trioxide-doped tin oxide fine particles are used from the viewpoints of infrared ray blocking property, transparency, and economical efficiency.

The content of the infrared ray blocking metal fine particles in the infrared ray blocking layer is preferably 50 to 500 PHR. Here, PHR is the content of the infrared ray blocking metal fine particles with respect to the resin solid content in the infrared ray blocking layer, which is expressed by weight%. The content of the infrared ray blocking metal fine particles is 50 PH
If it is less than R, the infrared ray blocking property is deteriorated, which is not preferable. The content of infrared ray blocking metal fine particles is 500 PHR
If it is more than the above range, the haze value of the infrared ray blocking layer becomes high, and as a result, the transparency of the infrared ray blocking film is lowered, and the scratch resistance of the infrared ray blocking layer is lowered to deteriorate the hard coat property, which is not preferable. Therefore, the content of the infrared ray blocking metal fine particles in the infrared ray blocking layer is preferably 50 to 500 PHR from the viewpoint of infrared ray blocking property, transparency and hard coat property.

As the method for forming the infrared ray blocking layer, conventionally known coating methods such as a gravure coating method, a reverse coating method and a die coating method are used by using a coating material in which infrared ray blocking metal fine particles are dispersed in a resin having a hard coating property. Can be used.

The functional resin layer formed on the infrared ray shielding film of the present invention is located between the plastic film and the infrared ray shielding layer to improve the adhesion between the plastic film and the infrared ray shielding layer, and also has weather resistance and heat resistance. sex,
It also has the function of improving the moisture resistance.

In the infrared ray blocking film of the present invention, the functional resin layer is formed between the plastic film and the infrared ray blocking layer, so that the cross-cut adhesion between the plastic film and the infrared ray blocking layer and the water resistant cross-cut layer are formed. Both the adhesion is 80/100 to 100/100,
It has excellent adhesion. Furthermore, a weather resistance test (83 cycles with a test of irradiation of ultraviolet rays for 8 hours and then condensation for 4 hours as one cycle), heat resistance test (80 ° C., 1 cycle)
000 hours), and humidity resistance test (40 ° C x 95%, 10
After the test, the cross-cut adhesion between the plastic film and the infrared shielding layer and the water-resistant cross-cut adhesion were both 80/100 to 100 /.
The haze value of the infrared ray-shielding film is 100, and the transparency is maintained. In addition, the haze value before and after each of the above-mentioned tests of the infrared ray shielding film of the present invention is 0.1 or more because of the constitution of the infrared ray shielding film of the present invention.

The resin used in the functional resin layer formed in the infrared ray shielding film of the present invention is the crosscut adhesion and the water resistant crosscut adhesion described above, or the weather resistance test and heat resistance test described above. And, after the moisture resistance test, there is no particular limitation as long as it satisfies the cross-cut adhesion, the water-resistant cross-cut adhesion, and the haze value, and for example, polyester resin, acrylic resin, urethane resin or the like can be used, It is preferable to use a thermosetting resin in which these resins and isocyanate are combined.
Above all, if it is formed from a resin that is a combination of three types of linear saturated polyester resin, xylene diisocyanate resin, and hexamethylene diisocyanate resin,
It is particularly perfect in terms of weather resistance, heat resistance, and humidity resistance.

The thickness of the functional resin layer is from 0.01 μm to
It is preferably less than 0.3 μm. The thickness of the functional resin layer is
If the thickness is 0.01 μm or less, the adhesion between the plastic film and the infrared ray blocking layer is deteriorated, which is not preferable. When the thickness of the functional resin layer exceeds 0.3 μm, the adhesion between the plastic film and the infrared ray blocking layer is deteriorated, and the weather resistance, heat resistance, and moisture resistance are deteriorated, which is not preferable.

As the method for forming the functional resin layer, conventionally known methods such as a gravure coating method, a reverse coating method and a die coating method can be used.

[0022]

[Example] On one side of a 25 μm thick polyethylene terephthalate film (Lumirror T60 manufactured by Toray), 10 parts by weight of a linear saturated polyester resin (Aronmelt PES370 manufactured by Toagosei Co., Ltd.) and xylene diisocyanate resin (Takenate D manufactured by Takeda Pharmaceutical Co., Ltd.) -110 N) 1 part by weight, hexamethylene diisocyanate resin (Coronate HK manufactured by Nippon Polyurethane Co., Ltd.) 5 parts by weight, tin catalyst (Orestar M8 manufactured by Mitsui Chemicals, Inc.) 0.24 parts by weight are diluted with a solvent (toluene / MEK). The prepared coating material was coated by a gravure coating method to form a functional resin layer having a thickness of 0.2 μm. Next, UV curable acrylic resin (Kayanova FOP1700 manufactured by Nippon Kayaku Co., Ltd.) was diluted with a solvent, and antimony trioxide-doped tin oxide (manufactured by Ishihara Sangyo)
SN-10M100P) is added to 100 PHR and the dispersed coating material is coated by the die coating method,
An infrared ray blocking film of the present invention was obtained by forming an infrared ray blocking layer having a thickness of 3 μm.

[0023]

Comparative Example 1 An infrared shielding film having an infrared shielding layer formed directly on a polyethylene terephthalate film was obtained in the same manner as in Example 1 except that a functional resin layer having a thickness of 0.2 μm was not formed. It was

[0024]

Comparative Example 2 An infrared shielding film was obtained in the same manner as in Example 1 except that 5 parts by weight of hexamethylene diisocyanate resin was not added to the coating material for forming the functional resin layer.

The infrared ray shielding films obtained in Examples, Comparative Examples 1 and 2 were subjected to the following weather resistance test, heat resistance test and moisture resistance test, and the following physical properties were measured and compared. did.

1. Weather resistance test (test sample) For the infrared ray-shielding films obtained in Examples, Comparative Example 1 and Comparative Example 2, three pieces each cut into a rectangle of 5 cm × 7 cm were prepared, and for performance comparison. Of the sample. (Test method) Using a weathering acceleration tester (Yubucon UC-1 manufactured by Toyo Seiki Seisakusho Co., Ltd.), ultraviolet rays (lamp: FS)
40 cycles, wavelength 313 nm) for 8 hours and then condensed for 4 hours. One cycle is 83 cycles (about 1 cycle).
000 hours) was tested.

2. Heat resistance test (test sample) Regarding the infrared ray blocking films obtained in Examples, Comparative Example 1 and Comparative Example 2, three sheets each cut into a rectangle of 5 cm × 7 cm were prepared for performance comparison. Of the sample. (Test method) Using a dryer, the sample was left to stand in an environment of a temperature of 80 ° C. for 1000 hours.

3. Moisture resistance test (test sample) Regarding the infrared ray blocking films obtained in Examples, Comparative Examples 1 and 2, three pieces each cut into a rectangle having a size of 5 cm × 7 cm were prepared for performance comparison. Of the sample. (Test method) Using a wet-dryer, it was left for 1000 hours in an environment of a temperature of 40 ° C. and a humidity of 95%.

4. Cross-cut Adhesion (Measurement Sample) The infrared blocking films obtained in Examples, Comparative Examples 1 and 2 were each cut into a rectangle of 5 cm × 7 cm, and three pieces were prepared (before the test). Sample), and one sample after the weather resistance test, the heat resistance test, and the moisture resistance test were performed for Examples, Comparative Example 1, and Comparative Example 2, respectively, to prepare samples for performance comparison. (Test method) A polypropylene adhesive tape is attached to the surface of the infrared ray blocking layer of each sample according to JIS-K-5400-199.
Adhesion was measured according to 0. (Measurement result) Table 1

5. Water-Resistant Cross-Cut Adhesion (Measurement Sample) Each of the infrared ray blocking films obtained in Examples, Comparative Examples 1 and 2 was cut into a rectangle of 5 cm × 7 cm, and three sheets were prepared (test). Pre-sample), and one sample after the weather resistance test, the heat resistance test, and the moisture resistance test for Examples, Comparative Example 1, and Comparative Example 2 were prepared and used as samples for performance comparison. (Test method) After spraying water evenly over the entire surface of the adhesive side of the polypropylene adhesive tape with a mist, the adhesive tape was applied to the surface of the infrared ray blocking layer of each sample and left for 5 minutes, followed by JIS-K- Adhesion was measured according to 5400-1990. (Measurement result) Table 1

6. Haze value (measurement sample) The infrared shielding films obtained in Examples, Comparative Examples 1 and 2 were each cut into a rectangle of 5 cm × 7 cm, and three pieces were prepared (sample before test). , And Example, Comparative Example 1, and Comparative Example 2, one sample after the weather resistance test, the heat resistance test, and the moisture resistance test was prepared, and used as a sample for performance comparison. (Test method) Haze meter (Nippon Denshoku NDH-3
00A) and was measured according to JIS-K-7105. (Measurement result) Table 1

[0032]

[Table 1]

As is apparent from Table 1, there was a large difference in performance between the infrared ray blocking film of Example, the infrared ray blocking film of Comparative Example 1 and the infrared ray blocking film of Comparative Example 2. The infrared cut film of the example has both a cross-cut adhesion before the test and a water-resistant cross-cut adhesion of 100/100 and a haze value of 0.81, which is excellent in both adhesion and transparency. You can see that Here, the haze value before the test of the infrared shielding film of the example is lower than the haze value (1.26) of the infrared shielding film of the comparative example 1 before the test is that the functional resin layer The surface of the plastic film on the functional resin layer side is made smoother by suppressing the irregular reflection of light, and by forming the functional resin layer, the effect of improving transparency can be obtained. Shows. In addition, the infrared blocking film of the example has a cross-cut adhesive strength and a water-resistant cross-cut adhesive strength of 10 after both the weather resistance test, the heat resistance test, and the moisture resistance test.
It was 0/100, the respective adhesive strength before the test was not reduced at all, and the haze value after the test was hardly reduced, and the adhesiveness and transparency were maintained, and the weather resistance was improved. It can be seen that it has excellent heat resistance and moisture resistance. On the other hand, the infrared shielding film of Comparative Example 1 in which the functional resin layer is not formed is excellent in transparency because the haze value before the test is 1.26, but the cross-cut adhesion before the test. The strength and the water resistant crosscut adhesion are 70/100 and 60/100, respectively, and the adhesion is poor. In each of the weather resistance test, heat resistance test, and moisture resistance test, the cross-cut adhesion and the water-resistant cross-cut adhesion after the test were both 0/100, and the plastic film and the infrared ray blocking layer were completely adhered. Not
It can be seen that the adhesiveness after each test is drastically lowered, and the haze value after the test is also lowered, and that the infrared shielding film of Comparative Example 1 is extremely inferior in weather resistance, heat resistance and moisture resistance. The infrared cut-off film of Comparative Example 2 had a cross-cut adhesion and a water-resistant cross-cut adhesion before the tests of 60/100 and 30/100, respectively, and was inferior in adhesion, and had a weather resistance test, a heat resistance test, and a moisture resistance. In all of the tests, a decrease in the crosscut adhesion and the water resistant crosscut adhesion after the test are observed. Furthermore, the haze value after each test exceeds 2, and it can be seen that the haze value is extremely lowered, and the infrared shielding film of Comparative Example 2 is also inferior in weather resistance, heat resistance and moisture resistance. As described above, the infrared ray shielding films of the examples are excellent in adhesion, transparency, weather resistance, heat resistance and moisture resistance.

[0034]

EFFECT OF THE INVENTION Since the infrared ray blocking film of the present invention has the functional resin layer formed between the plastic film and the infrared ray blocking layer, the cross cut adhesion between the plastic film and the infrared ray blocking layer, and the water resistant cross cut layer. The adhesion is both 80/100 to 100/100, and the adhesion is excellent. Furthermore, since the haze value of the infrared ray shielding film of the present invention is less than 2, it has excellent transparency.

Further, since the infrared ray blocking film of the present invention has the above-mentioned functional resin layer formed thereon, it has a weather resistance test (a cycle of irradiation of ultraviolet rays for 8 hours and then dew condensation for 4 hours is defined as 1 cycle, and 83 cycles are included). ), Heat resistance test (80
℃, 1000 hours), and humidity resistance test (40 ℃ × 95
%, 1000 hours), the cross-cut adhesion between the plastic film and the infrared ray blocking layer and the water-resistant cross-cut adhesion are both 80/100 to 80% after the test.
It is 100/100 and maintains excellent adhesion, and the infrared ray shielding film has a haze value of less than 2 and also maintains transparency. As described above, the infrared shielding film of the present invention is excellent in weather resistance, heat resistance, and moisture resistance, and therefore, particularly under high temperature and high humidity conditions, the cross-cut adhesive strength, the water-resistant cloth, and the like. Since the cut adhesion and the haze value are very little reduced, the plastic film and the infrared ray shielding layer are not easily peeled off, and therefore the scratch resistance and transparency of the infrared ray shielding film are not deteriorated. Also, the infrared ray blocking property does not deteriorate.

In particular, if the functional resin layer of the infrared ray shielding film of the present invention is formed of a linear saturated polyester resin, a xylene diisocyanate resin, and a hexamethylene diisocyanate resin, adhesion, transparency, weather resistance and heat resistance will be improved. Since it is possible to obtain an infrared ray shielding film having further excellent properties and moisture resistance, it is more complete.

Further, when the infrared ray blocking metal fine particles contained in the infrared ray blocking layer of the infrared ray blocking film of the present invention are antimony trioxide-doped tin oxide fine particles, the infrared ray blocking property, transparency and economy are excellent. It becomes an infrared ray blocking film.

Claims (3)

(57) [Claims] 1. An infrared blocking film comprising an infrared blocking layer having a hard coat property, containing infrared blocking metal fine particles on one surface of a plastic film, wherein a linear saturation is formed between the plastic film and the infrared blocking layer. An infrared shielding film having weather resistance, heat resistance, and moisture resistance, which is characterized in that a functional resin layer composed of a polyester resin, a xylene diisocyanate resin, and a hexamethylene diisocyanate resin is formed and satisfies the following conditions. The cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The water resistant cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The haze value of the infrared shielding film is Is less than 2 2. A weather resistance test (83 cycles, with a cycle of irradiation of ultraviolet rays of 8 hours and dew condensation of 4 hours as one cycle), heat resistance test (80 ° C., 1000 hours), and humidity resistance test (40 ° C. × 40 ° C.) 95%, 1000 hours), the infrared shielding film according to claim 1, which satisfies the following conditions after the test. The cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The water resistant cross cut adhesion between the plastic film and the infrared shielding layer is 80/100 to 100/100. The haze value of the infrared shielding film is Is less than 2 3. The infrared shielding film according to claim 1, wherein the infrared shielding metal fine particles are antimony trioxide-doped tin oxide fine particles.