JP5937407B2 - Film for external glass bonding and method for producing the same - Google Patents

Description

  The present invention relates to a film for attaching to an outside glass to be adhered to a glass surface on the outdoor side, and more specifically, ultraviolet absorption characteristics, heat ray absorption characteristics, scratch resistance, scattering prevention, transparency, weather resistance, and coating film adhesion. The present invention relates to a film for externally attaching glass.

Conventionally, in order to prevent ultraviolet rays contained in sunlight and infrared rays that are heat sources from entering indoors, the glass has a function of shielding ultraviolet rays and infrared rays, and the glass surface has a function of shielding ultraviolet rays and infrared rays. Techniques such as constructing a film are employed.
For example, Patent Document 1 below discloses a polyester film in which an ultraviolet absorber is kneaded into a resin component.
By the way, when a film as described above is applied to the glass surface, the film is generally adhered to the glass surface on the indoor side. This is because, when the film is applied on the outdoor side, the film is very quickly deteriorated as compared with the indoor side because the film directly receives sunlight.

  However, when trying to construct the film on the glass surface on the indoor side, a work space is required indoors, and it is necessary to move indoor items, and there are cases where the construction work is restricted. There is a growing demand for construction on the glass surface on the outdoor side. Moreover, when attaching this film on the outdoor side, higher scratch resistance is also required.

Patent Document 2 listed below is a protective film that is adhered to the glass surface on the outdoor side, and is provided with a heat ray blocking layer and a hard coat layer on one surface of a resin film made of polyester or polycarbonate, and on the other surface. In addition to providing a pressure-sensitive adhesive layer for adhering to the protective film, the hard coat layer and the pressure-sensitive adhesive layer disclose a protective film containing an ultraviolet absorber.
Moreover, the product which vapor-deposited the heat ray blocking material on one side of the resin film, provided the hard coat layer thereon, and provided the adhesive layer for adhering to the glass surface on the other side is also commercially available.

  However, the film for external glass pasting in the prior art does not show the expected ultraviolet absorption effect and heat ray absorption effect, and also has scratch resistance, scattering prevention, transparency, weather resistance, and coating film adhesion. There was room for improvement.

JP 2005-153441 A JP 2003-213230 A

  Accordingly, the object of the present invention is to solve the conventional problems as described above, and to provide a film for externally attaching a glass excellent in ultraviolet absorption characteristics, heat ray absorption characteristics, scratch resistance, transparency, weather resistance, and coating film adhesion, and It is in providing the manufacturing method.

  As a result of intensive studies, the inventor laminated an anchor coat layer and a hard coat layer on one surface of a polyethylene terephthalate film, and laminated a back coat layer and an adhesive layer containing a heat ray absorbent on the other surface, The polyethylene terephthalate film, the anchor coat layer, and the hard coat layer are all mixed with an ultraviolet absorber, and the maximum absorption wavelength of the ultraviolet absorber of the anchor coat layer and the hard coat layer is set to a specific range in each layer, and the hard coat layer is hardened. The inventors have found that the above problems can be solved by combining the ultraviolet absorber in the coat layer with the resin component, and have completed the present invention.

The present invention is as follows.
1. It is a film for attaching to the outside of the glass to be attached to the glass surface on the outdoor side,
On one side of a polyethylene terephthalate film containing a UV absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4- Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone and 2,2 ′, An anchor coat layer containing at least one ultraviolet absorber selected from 4,4′-tetrahydroxy-benzophenone, and a hard coat layer containing an ultraviolet absorber having a maximum absorption wavelength of 200 nm or more and less than 360 nm and a resin component Laminated in this order, the polyester On the other side of the styrene terephthalate film, a back coat layer containing a heat ray absorbent and an adhesive layer are laminated in this order,
The ultraviolet absorbent in the hard coat layer, Ri Na bound to the resin component, and
A film for external glass application, wherein the resin component in the hard coat layer is an organic-inorganic composite .
2 . 2. The glass outer paste according to 1 above, wherein the heat ray absorbent contained in the back coat layer is at least one selected from antimony-doped tin oxide, tin-doped indium oxide, antimony-doped zinc oxide and tungsten oxide. Film.
3 . A method for producing a film for external glass sticking to the glass surface on the outdoor side,
(1) On one side of a polyethylene terephthalate film containing an ultraviolet absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy -4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone and 2, Applying an anchor coat layer-forming paint containing at least one ultraviolet absorber selected from 2 ′, 4,4′-tetrahydroxy-benzophenone , drying and curing, and forming an anchor coat layer;
(2) After the step (1), a hard coat layer-forming coating material containing a UV absorber and a resin component having a maximum absorption wavelength of 200 nm or more and less than 360 nm is applied on the formed anchor coat layer, and UV irradiation is performed. Performing a hard coat layer,
(3) After the step (2), a step of forming a back surface coating layer by applying a coating material for forming a back surface coating layer containing a heat ray absorbent to the other surface of the polyethylene terephthalate film, and irradiating with ultraviolet rays. 4) After the step (3), forming a pressure-sensitive adhesive layer on the back coat layer with a pressure-sensitive adhesive layer-forming coating,
Have
The ultraviolet absorbent in the hard coat layer, Ri Na bound to the resin component, and
The method for producing a film for external glass bonding, wherein a resin component in the hard coat layer is an organic-inorganic composite .

  The film for external glass application of the present invention has an anchor coat layer and a hard coat layer laminated on one side of a polyethylene terephthalate film, and a back coat layer and an adhesive layer containing a heat ray absorbent are laminated on the other side. A UV absorber is added to all of the terephthalate film, the anchor coat layer, and the hard coat layer, and the maximum absorption wavelength of the UV absorber of the anchor coat layer and the hard coat layer is set to a specific range in each layer, and the hard coat is added. Since the UV absorber in the layer is combined with the resin component, it is a film for external application to glass that excels in UV absorption properties, heat ray absorption properties, scratch resistance, scattering prevention, transparency, weather resistance, and coating film adhesion Can be obtained.

It is sectional drawing of one Embodiment of the film for glass outer pasting of this invention.

Hereinafter, the film for external glass bonding of the present invention will be further described with reference to the drawings.
FIG. 1 is a cross-sectional view of one embodiment of the film for external glass pasting of the present invention.

In FIG. 1, an outer glass film 10 according to the present invention has an anchor coat layer 104 and a hard coat layer 106 laminated in this order on one surface of a polyethylene terephthalate film 102 containing an ultraviolet absorber. The back coat layer 108 and the adhesive layer 109 are laminated in this order on the other surface of the adhesive layer 112 via the easy-adhesion layer 112, and a peeling means 114 is provided on the surface of the adhesive layer 109.
The film 10 for glass outer pasting of this invention is further equipped with the following requirements (1)-(4).
(1) The polyethylene terephthalate film 102 contains an ultraviolet absorber;
(2) Anchor coat layer 104 comprises 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2 -Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone and 2,2 ', 4,4'- Including at least one ultraviolet absorber selected from tetrahydroxy-benzophenone (hereinafter sometimes referred to as an ultraviolet absorber for an anchor coat layer) ;
(3) The hard coat layer 106 includes an ultraviolet absorber having a maximum absorption wavelength of 200 nm or more and less than 360 nm and a resin component, and the ultraviolet absorber in the hard coat layer 106 is bonded to the resin component; 4) The back surface coating layer 108 contains a heat ray absorbent.
Hereinafter, each layer will be described.

(Polyethylene terephthalate film)
The polyethylene terephthalate film 102 is preferably a biaxially stretched polyethylene terephthalate film from the viewpoint of imparting strength to the film. Further, the ultraviolet absorber contained in the polyethylene terephthalate film 102 is not particularly limited, but from the viewpoint of the effect of the present invention, particularly from the viewpoint of ultraviolet absorption characteristics and weather resistance, a cyclic imino ester is preferable, and bisbenzoxazinone is used. Further preferred. By using the ultraviolet absorber, it is possible to achieve that the transmittance of light at a wavelength of 380 nm is 25% or less, the transmittance of light at 390 nm is 60% or more, and the transmittance of light at 400 nm is 80% or more. . Since these compounds have low solubility in general solvents and are difficult to coat as paints, they are contained in the polyethylene terephthalate film 102. The polyethylene terephthalate film 102 containing such an ultraviolet absorber is publicly known and described in Patent Document 1 above, and is commercially available from Teijin DuPont Films Ltd. under the trade name Tetron HB3.
The thickness of the polyethylene terephthalate film 102 is preferably 25 μm to 200 μm, more preferably 30 μm to 150 m. When the thickness is less than 25 μm, the weather resistance and scattering prevention properties decrease, and when it exceeds 200 μm, the workability decreases. In addition, in order to ensure scattering prevention property, it is preferable that thickness is 50 micrometers or more.

(Anchor coat layer)
The anchor coat layer 104 is a coat layer including the anchor coat layer ultraviolet absorber .
As the ultraviolet absorber for the anchor coat layer, 2, 4-dihydroxy - benzophenone, 2-hydroxy-4-methoxy - benzophenone, 2-hydroxy -4-n-octoxy - benzophenone, 2-hydroxy-4-dodecyloxy - benzophenone 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4 '- include benzophenone emissions - tetrahydroxy.
The resin component that forms the anchor coat layer 104 is not particularly limited as long as it can secure adhesion and adhesion to the polyethylene terephthalate film 102 and the hard coat layer 106 and does not impair the weather resistance. System, polyester system, etc. can be used.
As addition amount of a ultraviolet absorber, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of resin components, and 0.5 mass part-8 mass parts are more preferable. By setting the amount within this range, a product having a balanced ultraviolet absorption property, weather resistance, and adhesion can be obtained.
The thickness of the anchor coat layer 104 is preferably 0.5 μm to 5 μm, and more preferably 1 μm to 4 μm. When the thickness is less than 0.5 μm, adhesion and adhesiveness are lowered, and transparency exceeding 5 μm is lowered.

(Hard coat layer)
The hard coat layer 106 is a coat layer that includes an ultraviolet absorber having a maximum absorption wavelength of 200 nm or more and less than 360 nm and a resin component, and the ultraviolet absorber is bonded to the resin component.
The resin component is preferably an organic-inorganic composite from the viewpoint of scratch resistance, scattering prevention, weather resistance, and the like. Organic-inorganic composites are also known as organic-inorganic hybrid polymers. In the present invention, an organic-inorganic composite of a type in which an inorganic component and an ultraviolet absorber are bonded to an organic skeleton by copolymerization, grafting, or the like and cured by ultraviolet rays is more preferable. Examples of the organic skeleton include acrylic, epoxy, and urethane, and examples of the inorganic component include polysiloxane and zinc oxide. Since the ultraviolet absorber is bonded to the organic skeleton, detachment and decomposition are suppressed and weather resistance and long-term stability are excellent as compared with the type in which the ultraviolet absorber is simply added. Further, since the inorganic component is bonded to the organic skeleton, the hardness becomes high, and the scratch resistance and durability are excellent.
The ultraviolet absorber may be appropriately selected from those having a maximum absorption wavelength of 200 nm or more and less than 360 nm. Examples thereof include known benzophenone series, benzotriazole series, phenyl salicylate series, and the like. In order to be able to react with the organic skeleton, it is preferable to use an ultraviolet absorber as a reactive monomer and copolymerize with an organic skeleton.
An organic-inorganic composite of a type in which an inorganic component and an ultraviolet absorber are bonded to the organic skeleton and is cured by ultraviolet rays is known and commercially available, for example, a product name manufactured by China Paint Co., Ltd. Forse Seed No. 460C type is mentioned.
The thickness of the hard coat layer 106 is preferably 3 μm to 10 μm, and more preferably 4 μm to 8 μm. When the thickness is less than 3 μm, the weather resistance and scratch resistance are reduced, and when it exceeds 10 μm, curling and cracks in the coating film are likely to occur.

(Back coat layer)
The back coat layer 108 is a coat layer containing a heat ray absorbent.
As the heat absorber, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), antimony-doped zinc oxide (AZO) and tungsten oxide are preferable, and antimony-doped tin oxide (ATO) is particularly preferable.
As the resin component forming the back coat layer 108, an ultraviolet curable polyfunctional urethane acrylate is preferable.
As addition amount of a heat ray absorber, 100 mass parts-300 mass parts are preferable with respect to 100 mass parts of resin components, and 120 mass parts-250 mass parts are more preferable.
The thickness of the back coat layer 108 is preferably 2 μm to 8 μm, and more preferably 3 μm to 6 μm. When the thickness is less than 2 μm, the heat ray absorbability decreases, and when it exceeds 8 μm, curling and cracks in the coating film are likely to occur.

(Adhesive layer)
The adhesive layer 109 is not particularly limited as long as it has suitable adhesiveness and weather resistance and is transparent, and examples thereof include acrylic, polyester, and urethane adhesives.
The adhesive layer 109 can further contain an ultraviolet absorber. As addition amount of a ultraviolet absorber, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of resin components, and 0.5 mass part-8 mass parts are more preferable.
The thickness of the adhesive layer 109 is preferably 15 μm to 40 μm, and more preferably 20 μm to 25 μm. When the thickness is less than 15 μm, the adhesive strength is reduced, and when it exceeds 40 μm, a problem in appearance occurs.
In addition, a peeling means 114 (for example, a release paper or a release sheet) is usually installed on the surface of the adhesive layer 109.

  The film 10 for glass outer pasting of this invention can be manufactured through the following (1)-(4) process, for example.

(1) In the step, the anchor coat layer forming paint containing the UV absorber for the anchor coat layer is applied to one surface of the polyethylene terephthalate film 102 containing the UV absorber , dried and cured, and the anchor coat layer 104 is formed. It is a process of forming.
Examples of the paint for forming the anchor coat layer include a paint obtained by dissolving the resin component and the ultraviolet absorber in a solvent. The obtained coating material is applied to one surface of the polyethylene terephthalate film 102 using a known coater, and dried and cured, whereby the anchor coat layer 104 can be formed.

In the step (2), after the step (1), a hard coat layer-forming coating material containing an ultraviolet absorber having a maximum absorption wavelength of 200 nm or more and less than 360 nm and a resin component is applied onto the formed anchor coat layer 104. In this step, the hard coat layer 106 is formed by performing ultraviolet irradiation.
As the hard coat layer-forming coating material, for example, a coating material in which an inorganic component and an ultraviolet absorber are bonded to the organic skeleton, and an organic-inorganic composite of a type that is cured by ultraviolet rays and a photoinitiator are dissolved in a solvent is suitable. is there. The obtained paint can be applied onto the anchor coat layer 104 using a known coater and irradiated with ultraviolet rays to form the hard coat layer 106. By selecting a photoinitiator that initiates the reaction at 360 to 400 nm, the maximum absorption wavelength contained in the hard coat layer 106 is not inhibited by the ultraviolet absorber that is 200 nm or more and less than 360 nm, and is cured by ultraviolet irradiation. Is made. Accordingly, productivity is improved.

In the step (3), after the step (2), the other surface of the polyethylene terephthalate film 102 is coated with a coating material for forming a back surface coating layer containing a heat ray absorbent, and irradiated with ultraviolet rays to form the back surface coating layer 108. It is a process.
Examples of the back coat layer forming coating material include a coating material in which the resin component and the heat ray absorbent are dissolved and dispersed in a solvent. The obtained coating material can be applied to the other surface of the polyethylene terephthalate film 102 using a known coater and cured by ultraviolet irradiation to form the back coat layer 108.

The step (4) is a step of forming the adhesive layer 109 with the adhesive layer forming paint on the back coat layer 108 after the step (3).
Examples of the adhesive layer-forming coating material include a coating material in which the resin component is dissolved in a solvent. The obtained paint can be applied on the back coat layer 108 or the peeling means 114 using a known coater to form the adhesive layer 109.

In the thus-prepared glass outer film 10 according to the present invention, ultraviolet rays having a wavelength of 200 nm or more and less than 360 nm contained in sunlight are well absorbed by the hard coat layer 106. As described above, the ultraviolet absorber contained in the hard coat layer 106 does not inhibit curing by ultraviolet irradiation when the hard coat layer 106 is formed, and is excellent in productivity . Hand, ultraviolet rays pass through the hard coat layer 106 and the anchor coat layer 104 is further absorbed by the ultraviolet absorber contained in the polyethylene terephthalate film 102. Further, infrared rays, which are heat rays contained in sunlight, are favorably absorbed by the back coat layer 108. In addition, since the back surface coating layer 108 that absorbs heat rays is provided on the opposite side of the polyethylene terephthalate film 102 that is a base material with respect to the layer that absorbs ultraviolet rays, the film 10 for external glass pasting of the present invention has a back surface. It can suppress that the resin component contained in the coat layer 108 is deteriorated by ultraviolet rays, and has excellent heat ray absorption characteristics and weather resistance. Further, since the back coat layer 108 is not formed using a vapor deposition method as in the prior art, it can provide high transparency. Further, in the form in which an ultraviolet absorber is added to the adhesive layer 109, the ultraviolet absorption characteristics can be improved more favorably.
The film 10 for external glass application according to the present invention is excellent in ultraviolet absorption characteristics, heat ray absorption characteristics, scratch resistance, scattering prevention, transparency, weather resistance, and coating film adhesion. Especially suitable for construction.

  EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.

  In the following examples and comparative examples, one of the following paints was used.

Anchor coat layer forming paint 1:
Amorphous polyester polyol (Toyobo Co., Ltd. Byron 103) 100 parts by mass hexamethylene diisocyanate (Japan Polyurethane Industry Co., Ltd. Coronate HX)
18 parts by mass Benzophenone-based UV absorber (Sipro Kasei Co., Ltd. Seesorb 106) 12 parts by mass Ethyl acetate (solvent) 300 parts by mass

Anchor coat layer forming paint 2:
In the paint 1 for forming an anchor coat layer, a paint in which the benzophenone ultraviolet absorber (Seesorb 106 manufactured by Sipro Kasei Co., Ltd.) is changed to 6 parts by mass.

Anchor coat layer forming paint 3:
A paint that does not use a benzophenone-based ultraviolet absorber (Seeprob 106 manufactured by Sipro Kasei Co., Ltd.) in the anchor coat layer forming paint 1.

Hard coat layer forming paint 1:
Organic-inorganic composite (Forseed No. 460C made by China Paint Co., Ltd., solid content 50%)
100 parts by weight alkylphenone photoinitiator (Irgacure 127 manufactured by BASF) 2 parts by weight methyl ethyl ketone (solvent) 20 parts by weight

Hard coat layer forming paint 2:
Dipentaerythritol hexaacrylate (DPHA) 100 parts by mass Benzotriazole-based UV absorber (TINUV 384-2 manufactured by BASF) 3 parts by mass Alkylphenone photoinitiator (Irgacure 127 manufactured by BASF) 4 parts by mass methyl ethyl ketone (solvent) 120 Parts by mass

Back coat layer forming coating 1:
ATO-dispersed UV curable acrylate resin (SHI-60, Sumitomo Osaka Cement Co., Ltd., photoinitiator internal addition, solid content 50%)

Back surface coating layer forming paint 2:
ATO dispersion type UV curable acrylate resin (SHI-60, Sumitomo Osaka Cement Co., Ltd., photoinitiator internal addition, solid content 50%) 100 parts by mass dipentaerythritol hexaacrylate (DPHA) 50 parts by mass alkylphenone photoinitiator (Irgacure 184 manufactured by BASF) 3.5 parts by mass Methyl ethyl ketone (solvent) 50 parts by mass

Paint 3 for forming the back coat layer:
A coating that does not use an ATO-dispersed UV-curable acrylate resin (SHI-60 manufactured by Sumitomo Osaka Cement Co., Ltd., photoinitiator added, solid content 50%) in the coating 2 for forming the back coat layer.

Adhesive layer forming paint 1:
Acrylic adhesive (BPS5896 manufactured by Toyochem Co., Ltd.) 100 parts by mass hexamethylene diisocyanate (Duranate 21S-75E manufactured by Asahi Kasei Chemicals Corporation)
0.25 parts by mass Benzophenone-based UV absorber (Sipro Kasei Co., Ltd. Seesorb 106) 1 part by mass ethyl acetate (solvent) 20 parts by mass

Example 1
As shown in FIG. 1, a film 10 for attaching to glass was prepared.
As the polyethylene terephthalate film 102, Tetron HB3 manufactured by Teijin DuPont Films Co., Ltd. having an easy-adhesion layer 112 on one side was used. Tetron HB3 is a film in which an ultraviolet absorber is kneaded into a resin component, and has a thickness of 50 μm.
The anchor coat layer forming paint shown in Table 1 was applied to one surface of the polyethylene terephthalate film 102, dried and cured to form an anchor coat layer 104 having a thickness of 2 μm.
Next, the hard coat layer-forming paint shown in Table 1 was applied on the anchor coat layer 104, dried, and irradiated with ultraviolet rays having a wavelength of 250 to 400 nm to form a hard coat layer 106 having a thickness of 6 μm.
Subsequently, the other surface of the polyethylene terephthalate film 102 was coated with the coating material for forming the back surface coating layer shown in Table 1, dried, irradiated with ultraviolet rays having a wavelength of 250 to 400 nm, and the back surface coating layer 108 having a thickness of 5 μm was formed. Formed.
Next, the adhesive layer forming paint shown in Table 1 is applied on the back coat layer 108 and dried to form an adhesive layer having a thickness of 25 μm, and the surface thereof is protected by the peeling means (release paper) 114, The film 10 for glass outer pasting of Example 1 was created.

The following evaluation was performed with respect to the obtained film 10 for glass outer pasting.
<Film appearance>
The prepared glass outer film 10 was visually observed with transmitted light at a position 50 cm or more away from the fluorescent lamp, and the state of dirt, streaks and cloudiness was confirmed by five people.
○: No dirt, streaks, or cloudiness is observed, and five people judge that the appearance is good.
Δ: 3 or 4 people judged that the appearance was good without dirt, streaks, or cloudiness,
×: No more than two people judged that the appearance was good with no dirt, streaks, or cloudiness.
As evaluated.

<Visible light transmittance>
It measured according to JIS A5759 with the spectrophotometer.
○: 75% or more
Δ: 65% or more, less than 75%,
X: less than 65%,
As evaluated.

<Ultraviolet transmittance>
It measured according to JIS A5759 with the spectrophotometer.
However, it evaluated by the structure of only a hard-coat layer, a polyethylene terephthalate film layer, and an anchor coat layer.
○: Less than 1%
Δ: 1% or more, less than 3%,
X: 3% or more
As evaluated.

<Solar absorption rate>
It measured according to JIS A5759 with the spectrophotometer.
○: 40% or more
Δ: 25% or more, less than 40%,
X: Less than 25%,
As evaluated.

<Weather resistance>
After conducting an 8-cycle accelerated test with a weathering accelerated metal weather manufactured by Suga Test Instruments Co., Ltd., it was confirmed by five persons whether or not each of the above test items was different from the initial state.
○: It is judged that there is no difference in all five people.
Δ: 3 or 4 people judged that there was no difference,
×: 2 or less people judged that there was no difference,
As evaluated.
Test conditions: 1 cycle / irradiation 20 hours Temperature = 53 ° C. Humidity = 50% Irradiation intensity = 70 W / cm ²
・ Condensation 4 hours Temperature = 30 ℃ Humidity = 98% Irradiation intensity = No irradiation

<Coating film adhesion>
Adhesion was confirmed according to a cross cut test of JIS K5400.
○: After the peel test, the coating film residual ratio is 90/100 or more,
(Triangle | delta): After a peeling test, coating film residual rate 80/100 or more, less than 90/100,
X: After the peel test, the coating film remaining rate is less than 80/100,
As evaluated.
The results are shown in Table 1.

Examples 2 and 3, Comparative Examples 1, 2, 3, and 5
Example 1 was repeated except that the various paints shown in Table 1 were used. The results are shown in Table 1.

Comparative Example 4
As the polyethylene terephthalate film 102, except that a biaxial polyethylene terephthalate film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., a film having a thickness of 50 μm not including an ultraviolet absorber) provided with an easy-adhesion layer 112 on one side was used. Example 1 was repeated.

Comparative Example 6
A commercially available film for attaching glass outside, in which an aluminum metal vapor deposition layer and a hard coat layer were provided in this order on one side of the resin film, and an adhesive layer for adhering to the glass surface on the other side was used. . The configuration of the commercially available glass film for external application is hard coat layer (thickness 10 μm) / metal vapor deposition layer / polyethylene terephthalate film (thickness 50 μm) / adhesion layer (thickness 10 μm). The results are shown in Table 1.

  From the results shown in Table 1, the film for external application to glass of the Examples has an anchor coat layer and a hard coat layer laminated on one side of a polyethylene terephthalate film, and a back coat layer and an adhesive layer containing a heat ray absorbent on the other side. And blending the polyethylene terephthalate film, the anchor coat layer, and the hard coat layer with an ultraviolet absorber, and setting the maximum absorption wavelength of the ultraviolet absorber of the anchor coat layer and the hard coat layer to a specific range in each layer. In addition, since the ultraviolet absorber in the hard coat layer is combined with the resin component, compared with each comparative example, ultraviolet absorption characteristics, heat ray absorption characteristics, scratch resistance, scattering prevention, transparency, weather resistance It was proved to be excellent in adhesion and coating film adhesion.

DESCRIPTION OF SYMBOLS 10 Outer glass film 102 Polyethylene terephthalate film 104 Anchor coating layer 106 Hard coating layer 108 Back surface coating layer 109 Adhesive layer 112 Easy adhesion layer 114 Peeling means

Claims (3)

It is a film for attaching to the outside of the glass to be attached to the glass surface on the outdoor side,
On one side of a polyethylene terephthalate film containing a UV absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4- Dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone and 2,2 ′, An anchor coat layer containing at least one ultraviolet absorber selected from 4,4′-tetrahydroxy-benzophenone, and a hard coat layer containing an ultraviolet absorber having a maximum absorption wavelength of 200 nm or more and less than 360 nm and a resin component Laminated in this order, the polyester On the other side of the styrene terephthalate film, a back coat layer containing a heat ray absorbent and an adhesive layer are laminated in this order,
The ultraviolet absorbent in the hard coat layer, Ri Na bound to the resin component, and
A film for external glass application, wherein the resin component in the hard coat layer is an organic-inorganic composite . 2. The glass exterior according to claim 1 , wherein the heat ray absorbent contained in the back coat layer is at least one selected from antimony-doped tin oxide, tin-doped indium oxide, antimony-doped zinc oxide, and tungsten oxide. Film for pasting. A method for producing a film for external glass sticking to the glass surface on the outdoor side,
(1) On one side of a polyethylene terephthalate film containing an ultraviolet absorber, 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy -4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone and 2, Applying an anchor coat layer-forming paint containing at least one ultraviolet absorber selected from 2 ′, 4,4′-tetrahydroxy-benzophenone , drying and curing, and forming an anchor coat layer;
(2) After the step (1), a hard coat layer-forming coating material containing a UV absorber and a resin component having a maximum absorption wavelength of 200 nm or more and less than 360 nm is applied on the formed anchor coat layer, and UV irradiation is performed. Performing a hard coat layer,
(3) After the step (2), a step of forming a back surface coating layer by applying a coating material for forming a back surface coating layer containing a heat ray absorbent to the other surface of the polyethylene terephthalate film, and irradiating with ultraviolet rays. 4) After the step (3), forming a pressure-sensitive adhesive layer on the back coat layer with a pressure-sensitive adhesive layer-forming coating,
Have
The ultraviolet absorbent in the hard coat layer, Ri Na bound to the resin component, and
The method for producing a film for external glass bonding, wherein a resin component in the hard coat layer is an organic-inorganic composite .

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