intermediate film for laminated glass and laminated glass

专利摘要:
INTERMEDIATE FILM FOR LAMINATED GLASS AND LAMINATED GLASS. The present invention relates to an intermediate layer film for laminated glass which can provide excellent heat protection properties for laminated glass and can maintain the excellent heat protection properties of laminated glass for a long period of time. Also supplied is a laminated glass that includes the middle layer film for a laminated glass. An intermediate layer film 1 for laminated glass according to the present invention includes a heat protection layer 2 and an ultraviolet protection layer 3. The heat protection layer 2 includes a thermoplastic resin, protection particles against heat and at least one component selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound. The ultraviolet protection layer 3 includes a thermoplastic resin and an ultraviolet protection agent. The laminated glass according to the present invention includes: a first laminated glass component and a second laminated glass component; and an intermediate layer film interspersed between the first and the second laminated glass components. The middle layer film is (...).
公开号:BR112012003918B1
申请号:R112012003918-0
申请日:2010-08-24
公开日:2020-12-29
发明作者:Hirofumi Kitano；Juichi Fukatani；Daizou Ii；Takazumi Okabayashi；Ryuta Tsunoda
申请人:Sekisui Chemical Co., Ltd；
IPC主号:

专利说明:

TECHNICAL FIELD
[0001] The present invention relates to an intermediate layer film for laminated glass which is used for laminated glass for vehicles, buildings or the like. More specifically, the present invention relates to an intermediate layer film for a laminated glass that allows the thermal insulation properties of the laminated glass to be increased, and a laminated glass that includes the intermediate layer film for a laminated glass. BACKGROUND TECHNIQUE
[0002] A laminated glass is a safety glass that, even when broken by the impact on the outside, splinters into some flying glass fragments. For this reason, laminated glass is widely used for cars, rail cars, aircraft, boats and ships, buildings and the like. Laminated glass is produced by sandwiching an intermediate layer film onto laminated glass between a pair of glass plates. Such laminated glass used to open parts of vehicles and buildings is desired to have high thermal insulation properties.
[0003] Infrared rays, which have a wavelength of not less than 780 nm, which is longer than that of visible light, have a small amount of energy compared to ultraviolet rays. Infrared rays, however, have a great thermal effect and are emitted as heat when absorbed by a substance. For this reason, infrared rays are commonly referred to as heat rays. Laminated glass is therefore required to be sufficiently protected from infrared rays in order to have high thermal insulation properties.
[0004] Patent Document 1 teaches how to effectively block infrared rays (heat rays), an intermediate layer film for laminated glass that contains heat protection particles, such as doped indium oxide particles. tin (ITO particles) and antimony doped tin oxide particles (ATO particles).
[0005] Patent Document 2 teaches a heat protection component that includes no less than two layers, each containing at least one selected from the phthalocyanine infrared absorbers and ultraviolet absorbers. The heat protection component is placed in such a way that the layers containing an ultraviolet absorber or the like are closer to the incident side of the heat ray than the other layers.
[0006] Patent Document 1: WO 01/25162 A1
[0007] Patent Document 2: JP 10-77360 A SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0008] In recent years, conventional intermediate layer films containing ITO particles or ATO particles are required to have even greater heat protection properties. ITO particles and ATO particles, however, do not absorb infrared rays even enough. Therefore, only when adding the ITO particles or the ATO particles to the intermediate layer film as in Patent Document 1, it is not easily allowed to greatly increase the heat protection properties of the laminated glass.
[0009] For example, in the United States, the California Air Resources Council (CARB) has proposed reducing carbon oxide discharged from cars so that greenhouse gas is reduced. The CARB considered regulating the thermal energy that passes through the laminated glass and that flows into the car, such that the fuel consumed by the air conditioner is reduced and, thus, the car's fuel economy is increased. Specifically, CARB planned to introduce the Cooled Cars Standard.
[00010] The Cooled Cars Standard was to be implemented in 2012 to require that the total solar transmittance (Tts) of laminated glass used for cars should not be more than 50%. The Chilled Car Standard should also regulate the Tts of laminated glass to be no more than 40% in 2016. The Tts is an index of the properties of protection against heat.
[00011] Laminated glass that reflects heat with a thin metal film disposed in it or laminated glass that reflects heat containing PET that reflects heat (such glass is typically referred to as heat-reflecting glass) reflects not only infrared rays, as well as communication waves in the communication wavelength range. In the case of using heat-reflective laminated glass for the windshield, the heat-reflecting part needs to be cut to allow many sensors to work. As a result, the average Tts of the entire windscreen surface including laminated glass that reflects heat with a 50% Tts is about 53%. Therefore, a laminated glass that transmits communication waves through it and that absorbs infrared rays should allow it to have a Tts of up to 53%.
[00012] In August 2010, there was still a tendency for laminated glass with a low Tts to be desired despite the fact that the Cooled Cars Standard was not introduced.
[00013] Furthermore, laminated glass is required to have a high visible transmittance, as well as high heat protection properties. For example, visible transmittance is desired so that it is not less than 70%. That is, it is required to increase the heat protection properties while maintaining a high visible transmittance.
[00014] In the case of employing an intermediate layer film for a laminated glass that contains the heat protection particles described in Patent Document 1, it is very difficult to produce a laminated glass that has both high heat protection properties and a high visible transmittance. For example, it is very difficult to produce laminated glass with both a Tts of not more than 53% and a visible transmittance of not more than 70%.
[00015] Also in the case of using at least one selected of the naphthalocyanine infrared absorbers and the ultraviolet absorbers as in Patent Document 2, it is difficult to produce a laminated glass that has both high heat protection properties and a high visible transmittance .
[00016] The present invention aims to provide an intermediate layer film for a laminated glass that can give excellent heat protection properties to a laminated glass and maintain the excellent heat protection properties of the laminated glass; and a laminated glass that includes the intermediate layer film for a laminated glass. MEANS TO SOLVE THE PROBLEMS
[00017] A broad aspect of the present invention is an intermediate layer film for laminated glass, comprising: a heat protection layer; and a first ultraviolet protection layer, wherein the heat protection layer comprises a thermoplastic resin, heat protection particles and at least one component selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound , and the first ultraviolet protection layer comprises a thermoplastic resin and an ultraviolet protection agent.
[00018] In a specific aspect of the intermediate layer film for a laminated glass in accordance with the present invention, the first ultraviolet protection layer is laminated to a surface of the heat protection layer.
[00019] In another specific aspect of the intermediate layer film for a laminated glass comprises for the present invention, the intermediate layer film which additionally comprises a second layer of protection against ultraviolet, in which the first layer of protection against ultraviolet is placed on one side of the surface of the heat protection layer, the second layer of ultraviolet protection is placed on the other side of the surface of the heat protection layer, and the second layer of ultraviolet protection comprises a thermoplastic resin and a protective agent against ultraviolet.
[00020] In yet another aspect of the intermediate layer film for a laminated glass according to the present invention, the first layer of ultraviolet protection is laminated on one surface of the heat protection layer, and the second layer of protection against ultraviolet is laminated on the other surface of the heat protection layer.
[00021] In yet another specific aspect of the intermediate layer film for laminated glass according to the present invention, an ultraviolet transmittance of the ultraviolet protection layer is no more than 0.5% at a wavelength of 360 to 390 nm, or the ultraviolet transmittance of the ultraviolet protection layer is no more than 0.8% at a wavelength of 380 to 390 nm.
[00022] In yet another specific aspect of the intermediate layer film for a laminated glass according to the present invention, the component is at least one selected from the group consisting of phthalocyanine, a phthalocyanine derivative, naphthalocyanine and a naphthalocyanine derivative .
[00023] In yet another specific aspect of the intermediate layer film for laminated glass according to the present invention, the heat protection particles are metal oxide particles.
[00024] In yet another specific aspect of the intermediate layer film for a laminated glass according to the present invention, the heat protection particles are tin doped indium oxide particles.
[00025] In yet another specific aspect of the intermediate layer film for a laminated glass according to the present invention, the thermoplastic resin is a polyvinyl acetal resin.
[00026] In yet another specific aspect of the intermediate layer film for a laminated glass according to the present invention, each of the heat protection layer and the ultraviolet protection layer additionally comprise a plasticizer.
[00027] In yet another specific aspect of the intermediate layer film for a laminated glass according to the present invention, an amount of the ultraviolet protecting agent is 0.2 to 1.0% by weight based on 100% in weight of the ultraviolet protection layer.
[00028] The laminated glass according to the present invention includes: a first laminated glass component and a second laminated glass component; and an intermediate layer film sandwiched between the first and second laminated glass components, wherein the intermediate layer film is an intermediate layer film for a laminated glass according to the present invention. EFFECT OF THE INVENTION
[00029] The intermediate layer film for a laminated glass according to the present invention can provide excellent heat protection properties to a laminated glass, because the intermediate layer film has the above heat protection layer provided with a specific composition. and the first ultraviolet protection layer above with a specific composition. The intermediate layer film can also maintain the excellent heat protection properties of the laminated glass produced for a long period of time. BRIEF DESCRIPTION OF THE DRAWINGS
[00030] Figure 1 is a partially cut cross-sectional view which schematically illustrates an example of the intermediate layer film for laminated glass according to an embodiment of the present invention.
[00031] Figure 2 is a partially sectioned cross-sectional view illustrating an example of laminated glass that includes the intermediate layer film for a laminated glass illustrated in figure 1. WAYS OF CARRYING OUT THE INVENTION
[00032] Hereinafter, the present invention is described in detail. Middle layer film for laminated glass
[00033] An example of the intermediate layer film for laminated glass according to an embodiment of the present invention is illustrated in figure 1 as a partially cut cross-sectional view.
[00034] The intermediate layer film 1 shown in Figure 1 includes a heat protection layer 2, a first ultraviolet protection layer 3 placed on the side of a surface 2a (first surface) of the heat protection layer 2, and a second ultraviolet protection layer 4 placed on the other surface 2b (second surface) of the heat protection layer 2. The first ultraviolet protection layer 3 is laminated to a surface 2a of the heat protection layer 2. The second layer ultraviolet protection layer 4 is laminated on the other surface 2b of the heat protection layer 2. The intermediate layer film 1 is used to produce laminated glass. The intermediate layer film 1 is an intermediate layer film for laminated glass.
[00035] Each of the first ultraviolet protection layer 2 of the second ultraviolet protection layer 4 includes a thermoplastic resin and an ultraviolet protection agent. Since each of the first and second ultraviolet protection layers 3 and 4 includes an ultraviolet protection agent, they function as layers that effectively prevent the transmission of ultraviolet rays.
[00036] The first ultraviolet protection layer 3 preferably has an ultraviolet transmittance of no more than 4% at a wavelength of 360 to 400 nm, or is preferably a layer to provide an ultraviolet transmittance of no more than than 0.5% for intermediate layer film 1 at a wavelength of 360 to 400nm. Since the second ultraviolet protection layer 4 includes an ultraviolet protection agent, the second ultraviolet protection layer 4 preferably has an ultraviolet transmittance of no more than 4% at a wavelength of 360 to 400 nm , or is preferably a layer to provide an ultraviolet transmittance of no more than 0.5% for the intermediate layer film 1 at a wavelength of 360 to 400 nm. The intermediate layer film 1 preferably has an ultraviolet transmittance of not more than 0.5% at a wavelength of 360 to 400 nm. In the case where the intermediate layer film 1 has such an ultraviolet transmittance, the excellent heat protection properties of the laminated glass can be maintained for a longer period of time. The ultraviolet protection layer most preferably has an ultraviolet transmittance of not more than 3.6%, even more preferably not more than 3%, and particularly preferably not more than 2.5% at a wavelength of 360 to 400 nm. The intermediate layer film more preferably has an ultraviolet transmittance of not more than 0.45%, even more preferably not more than 0.4%, and particularly preferably not more than 0.35% at a wavelength from 360 to 400 nm. The term "ultraviolet transmittance at a wavelength of 360 to 400 nm" means the average value of the light transmittances of the laminated glass at 360 nm, 370 nm, 375 nm, 380 nm, 385 nm, 390 nm, 395 nm and 400nm.
[00037] The first ultraviolet protection layer 3 can have an ultraviolet transmittance of no more than 0.5% at a wavelength of 360 to 390 nm, or it can be a layer to provide an ultraviolet transmittance of no more than 0.05% for intermediate layer film 1 at a wavelength of 360 to 390 nm. The second ultraviolet protection layer 4 can have an ultraviolet transmittance of no more than 0.5% at a wavelength of 360 to 390 nm, or it can be a layer to provide an ultraviolet transmittance of no more than 0.05% for intermediate layer 1 film at a wavelength of 360 to 390 nm. The intermediate layer film 1 preferably has an ultraviolet transmittance of not more than 0.05% at a wavelength of 360 to 390 nm. In the event that such an ultraviolet transmittance is achieved, the excellent heat protection properties of the laminated glass can be maintained for a longer period of time. The ultraviolet protection layer most preferably has an ultraviolet transmittance of not more than 0.3%, even more preferably not more than 0.2% and particularly preferably not more than 0.1% at a wavelength from 360 to 390 nm. Intermediate layer film more preferably has an ultraviolet transmittance of not more than 0.04%, even more preferably not more than 0.02% and particularly preferably not more than 0.015% at a wavelength of 360 to 390 nm. The term "ultraviolet transmittance at a wavelength of 360 to 390 nm" means the average value of the light transmittances of the laminated glass at 360 nm, 370 nm, 375 nm, 380 nm, 385 nm and 390nm.
[00038] The first ultraviolet protection layer 3 can have an ultraviolet transmittance of no more than 0.8% at a wavelength of no more than 0.8% at a wavelength of 380 to 390 nm , or it can be a layer to provide an ultraviolet transmittance of no more than 0.1% for the intermediate layer film 1 at a wavelength of 380 to 390 nm. The second ultraviolet protection layer 4 can have an ultraviolet transmittance of no more than 0.8% at a wavelength of 380 to 390 nm, or it can be a layer to provide an ultraviolet transmittance of no more than 0.1% for intermediate layer film 1 at a wavelength of 380 to 390 nm. The intermediate layer film 1 preferably has an ultraviolet transmittance of no more than 0.1% at a wavelength of 380 to 390 nm. In the event that such an ultraviolet transmittance is achieved, the excellent heat protection properties of laminated glass can be maintained for a long period of time. The ultraviolet protection layer most preferably has an ultraviolet transmittance of not more than 0.7%, even more preferably not more than 0.66%, and particularly preferably not more than 0.2% over a length of 380 to 390 nm wave. The intermediate layer film more preferably has an ultraviolet transmittance of not more than 0.04%, even more preferably not more than 0.03%, and particularly preferably not more than 0.02% at a wavelength from 380 to 390 nm. The term "ultraviolet transmittance at a wavelength of 380 to 390 nm" means the average value of the light transmittances of the laminated glass at 380nm, 385 nm and 390 nm.
[00039] The "ultraviolet transmittance at a wavelength of 360 to 400 nm", the "ultraviolet transmittance at a wavelength of 360 to 390 nm" and "ultraviolet transmittance at a wavelength of 380 to 390 nm "can be measured using a laminated glass obtained by inserting an ultraviolet protection layer or an intermediate layer film between two 2 mm thick float glass plates according to JIS R 3202.
[00040] The heat protection layer 2 includes a thermoplastic resin, heat protection particles 5 and at least one selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound. Hereinafter, the at least one selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound can be referred to as a "component X".
[00041] In the case of using an intermediate layer film for laminated glass that contains heat protection particles, such as ITO particles, there is a problem that the heat protection properties of laminated glass are sometimes low, making it difficult to produce laminated glass with lower solar transmittance and greater visible transmittance. Solar transmittance is an index of the properties of protection against heat. Also, in the case of using an intermediate layer film for a laminated glass that contains heat protection particles, such as ITO particles, it has been very difficult to obtain a laminated glass that has both a total solar transmittance (Tts) of no more than 53% and a visible transmittance of no more than 70%, and it has been difficult to define Tts to be no more than 50%.
[00042] One of the main features of the present invention is that the heat protection layer includes heat protection particles and the specific X component above. The present inventors have found that the use of a heat protection layer that includes both heat protection particles and the specific X component results in an increase in both the heat protection properties and the visible transmittance of laminated glass.
[00043] As a result of the studies done by the present inventors, the inventors found that simply using an intermediate layer film that includes heat protection particles and the specific X component leads to a decrease in the heat protection properties if the laminated glass is used for a long period of time. The present inventors therefore carried out further studies, and then discovered the structure of the intermediate layer film for a laminated glass that makes it possible to maintain the high heat protection properties for a long period of time.
[00044] Another main feature of the present invention is the structure in which the intermediate layer film for a laminated glass includes multiple layers (not less than two layers) that include a heat protection layer and an ultraviolet protection layer. . This structure effectively protects the interlayer film particularly from ultraviolet rays among the light rays that enter the interlayer film from the side of the ultraviolet protection layer. In particular, ultraviolet rays that have a wavelength of about 360 to 400 nm are effectively blocked. Therefore, the amount of ultraviolet rays that reach the heat protection layer can be reduced, particularly the amount of ultraviolet rays that have a wavelength of 360 to 400 nm, a wavelength of 360 to 390 nm or a wavelength from 380 to 390 nm and reaching the heat protection layer. Therefore, a chemical change of component X contained in the heat protection layer and deterioration of the resin that can be caused by the chemical change of component X can be prevented. For this reason, the excellent heat protection properties can be maintained for a long period of time.
[00045] Therefore, the use of an ultraviolet protection layer together with the heat protection layer that includes component X and the heat protection particles can sufficiently increase the heat protection properties of the intermediate layer film and laminated glass, and makes it possible to produce laminated glass that has a low solar transmittance, which is an index of the heat protection properties, and a high visible transmittance. In addition, a laminated glass with a sufficiently low Tts and a sufficiently high visible transmittance can be produced.
[00046] For example, the solar transmittance (Ts2500) of laminated glass can be no more than 56% at a wavelength of 300 to 2,500 nm, and the visible transmittance of laminated glass can be no less than 65%. In addition, the solar transmittance (Ts2500) can be no more than 60%, and the visible transmittance can be no less than 70%. The Tts of laminated glass can be no more than 53%, and the visible transmittance of laminated glass can be no less than 70%. Tts can also be no more than 50%. Therefore, for example, laminated glass can be produced, which is usable under the Cooled Car Standard that the California Air Resources Council (CARB) was planning to introduce in the United States.
[00047] The properties of Tts and visible transmittance, hereinafter, refer to the properties required by the Chilled Cars Standard. Tts is measured, for example, by the measurement method specified by the Cooled Car Standard that was introduced. Visible transmittance can be measured according to JIS R 3211 (1998), for example.
[00048] The intermediate layer film for laminated glass according to the present invention can not only achieve both high heat protection properties and visible transmittance, but also maintain high heat protection properties for a long period of time. time. In order to maintain the excellent heat protection properties for a long period of time, the ultraviolet transmittance of the first ultraviolet protection layer 3 or the intermediate layer film 1 at a wavelength of 360 to 400 nm, in a a wavelength of 360 to 390 nm or a wavelength of 380 to 390 nm is preferably adjusted to be no more than a given value.
[00049] Also, the present invention makes it possible to increase transparency; for example, the opacity value can be no more than 1% and it can also be no more than 0.5%.
[00050] The intermediate layer film 1 has a three-layer structure in which the first ultraviolet protection layer 3, the heat protection layer 2 and the second ultraviolet protection layer 4 are laminated in this order. In this way, the heat protection layer is preferably placed between the first and second heat protection layers, and is more preferably sandwiched between the first and second heat protection layers. In this case, the ultraviolet rays entering the middle layer can be effectively blocked on both sides of the middle layer film by the first and second layers of heat protection.
[00051] At present, the second layer of protection against ultraviolet 4 may not necessarily be used. That is, only the first ultraviolet protection layer 3 can be laminated to a surface 2a of the heat protection layer 2. In this case, the first ultraviolet protection layer of the intermediate layer film 1 can be placed on the incident side of light beam. For example, in the case of using laminated glass that includes the middle layer film for a car, the laminated glass is placed in such a way that the first layer of ultraviolet protection is on the outside of the car and the layer of heat protection is on the inside of the car. The intermediate layer film may have a laminated structure of at least four layers. Each of the first and second ultraviolet protection layers 3 and 4 can contain the heat protection particles and the specific X component.
[00052] The intermediate layer film for laminated glass according to the present invention can additionally include another layer other than the heat protection layer and the ultraviolet protection layer. In addition, a layer other than the heat protection layer and the ultraviolet protection layer can be sandwiched between the heat protection layer and the ultraviolet protection layer.
[00053] The thickness of the intermediate layer film is not particularly limited. The thickness of the intermediate layer film indicates the total thickness of the respective layers that make up the intermediate layer film. Therefore, in the case of the intermediate layer film, the thickness of the intermediate layer film 1 indicates the total thickness of the heat protection layer 2 and the first and second layers of ultraviolet protection 3 and 4. In terms of practicality and a sufficient increase in heat protection properties, the lower limit of the thickness of the intermediate layer film is preferably 0.1 mm, and more preferably 0.25 mm, while the upper limit of it is preferably 3 mm, and more preferably 1.5 mm . If the thickness of the intermediate layer film is very small, the resistance to penetration of the laminated glass tends to decrease.
[00054] In terms of practicality and sufficient long-term maintenance of the heat protection properties, the lower limit of the thickness of each of the first and second layers of ultraviolet protection 3 and 4 is preferably 0.001 mm, and more preferably 0 , 2 mm, while the upper limit of it is preferably 0.8 mm, and more preferably 0.6 mm.
[00055] In terms of practicality and a sufficient increase in heat protection properties, the lower limit of the thickness of the heat protection layer 1 is preferably 0.001 mm, and more preferably 0.05 mm, while the upper limit of it is preferably 0.8 mm, and more preferably 0.6 mm.
[00056] Details of the materials that constitute the heat protection layer 2 and the first and second layers of protection against ultraviolet 3 and 4 are given below. Thermoplastic resin
[00057] Each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 contain a thermoplastic resin. The thermoplastic resin can be a conventionally known thermoplastic resin. A thermoplastic resin can be used or two or more thermoplastic resins can be used in combination.
[00058] Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene vinyl acetate copolymer resin, ethylene acrylic acryl resin, polyurethane resin and polyvinyl alcohol resin. Thermoplastic resins other than these can also be used.
[00059] The thermoplastic resin contained in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is preferably a polyvinyl acetal resin. Each and every thermoplastic resin contained in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is preferably a polyvinyl acetal resin. In this case, the compatibility between the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is increased and the adhesion between the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 can be further increased.
[00060] Each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 preferably contains a plasticizer which is described below. In the case where the thermoplastic resin contained in the first and second layers of protection against ultraviolet 3 and 4 is a polyvinyl acetal resin, a use in combination of polyvinyl acetal resin and a plasticizer makes it possible to further increase the adhesion between the protective layer against heat 2 and the first and second layers of protection against ultraviolet 3 and 4.
[00061] Polyvinyl acetal resin can be produced by acetalizing polyvinyl alcohol with an aldehyde. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate, for example. Generally, the degree of saponification of polyvinyl alcohol is in the range of 80 to 99.8 mol%.
[00062] The lower limit of the degree of polymerization of polyvinyl alcohol is preferably 200, and more preferably 500, while the upper limit of it is preferably 3,000, and more preferably 2,500. If the degree of polymerization is too low, laminated glass tends to have a reduced resistance to penetration. If the degree of polymerization is too high, the formation of the intermediate layer film for laminated glass can be difficult.
[00063] Aldehyde is not particularly limited. Generally, a C1 to C10 aldehyde is suitably used as the aldehyde above. Examples of aldehyde C1 to C10 include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyl aldehyde, n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, formaldehyde, acetaldehyde and benzaldehyde. Particularly, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexyl aldehyde and n-valeraldehyde are preferred, propionaldehyde, n-butyraldehyde and isobutyraldehyde are more preferred, and n-butyraldehyde is even more preferred. One aldehyde can be used alone or two or more aldehydes can be used in combination.
[00064] In terms of further increasing the adhesion of each layer, the polyvinyl acetal resin preferably has a hydroxyl group content (amount of hydroxyl groups) of the polyvinyl acetal resin in the range of 15 to 40 mol%. The lower limit of the hydroxyl group content is more preferably 18 mol%, and the upper limit of it is more preferably 35 mol%. If the content of the hydroxyl group is very low, the adhesion of each layer may be low. If the content of the hydroxyl group is very high, the flexibility of the intermediate layer film 1 tends to be low, also causing a problem in handling the intermediate layer film 1.
[00065] The hydroxyl content of the polyvinyl acetal resin is a molar fraction (represented as a percentage) determined by dividing the amount of ethylene group that has the hydroxyl group attached to it by the total amount of the ethylene group in the main chain. The amount of ethylene group that has the hydroxyl group attached to it can be determined, for example, by measuring the amount of the ethylene group that has the hydroxyl group attached to it in polyvinyl alcohol, which is the raw material, according to JIS K 6726 "Testing Methods for polyvinyl alcohol".
[00066] The lower limit of the degree of acetylation (quantity of acetyl groups) of the polyvinyl acetal resin is 0.1 mol%, more preferably 0.3 mol% and even more preferably 0.5 mol%, while the upper limit thereof is preferably 30 mol%, more preferably 25 mol% and even more preferably 20 mol%.
[00067] If the degree of acetylation is very low, the compatibility between the polyvinyl acetal resin and the plasticizer may decrease. If the degree of acetylation is too high, the moisture resistance of the interlayer film may be low.
[00068] The degree of acetylation is a molar fraction (represented as a percentage) determined by dividing, by the total amount of ethylene group in the main chain, a value that results from subtracting the amount of ethylene group that the acetal group attached to it and the amount of ethylene group that has the hydroxyl group attached to it of the total amount of ethylene group in the main chain. The amount of ethylene group that has the acetal group attached to it can be determined according to JIS K 6728 "Testing Methods for Polyvinyl Butyral", for example.
[00069] The lower limit of the degree of acetalisation (degree of butyralization in the case of a polyvinyl butyral resin) of the polyvinyl acetal resin is 60 mol%, and more preferably 63 mol%, while the upper limit of it is preferably 85 mole%, more preferably 75 mole%, and even more preferably 70 mole%.
[00070] If the degree of acetalization is very low, the compatibility between the polyvinyl acetal resin and the plasticizer may be low. If the degree of acetalization is too high, the reaction time it takes to produce a polyvinyl acetal resin can be long.
[00071] The degree of acetalization is a molar fraction (represented as a percentage) determined by dividing the amount of ethylene grade that has the acetal group attached to it by the total amount of ethylene group in the main chain.
[00072] The degree of acetalization is calculated by first measuring the degree of acetylation (quantity of the acetyl group) and the hydroxyl content (vinyl alcohol) based on JIS K 6728 "Testing Method for Polyvinyl butyral", when calculating the fraction molar from the measured values and by subtracting the degree of acetylation and the content of hydroxyl group from 100% mol.
[00073] In the case where the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the degree of acetylation (amount of acetyl group) can be calculated from the results obtained by the method according to JIS K 6728 "Testing Method for Polyvinyl butyral". Plasticizer
[00074] In terms of further increasing the adhesion of each layer, each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 contain a plasticizer. In the case where the thermoplastic resin contained in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is a polyvinyl acetal resin, it is particularly preferable that each of the heat protection layer 2 and the first and second layers of protection against ultraviolet 3 and 4 contain a plasticizer.
[00075] The plasticizer is not particularly limited and can be a conventionally known plasticizer. A plasticizer can be used alone or two or more plasticizers can be used in combination.
[00076] Examples of the plasticizer include organic ester plasticizers, such as monobasic organic acid esters and polybasic organic acid esters, and phosphoric acid plasticizers, such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. In particular, organic ester plasticizers are preferable. The plasticizer is preferably a liquid plasticizer.
[00077] Examples of esters of monobasic organic acid include, but are not limited to, glycol esters obtained by the reaction between a glycol and a monobasic organic acid, and esters of triethylene glycol or tripropylene glycol and a monobasic organic acid. Examples of glycol include triethylene glycol, tetraethylene glycol and tripropylene glycol. Examples of monobasic organic acid include butyric acid, isobutyric acid, caprylic acid, 2-ethylbutyl acid, heptyl acid, n-octyl acid, 2-ethylhexyl acid, n-nonyl acid and decyl acid.
[00078] Examples of polybasic organic acid esters include, but are not limited to, straight or branched polybasic acid ester compounds and C4 to C8 alcohols. Examples of polybasic organic acid include adipic acid, sebacic acid and azelaic acid.
[00079] Examples of the organic ester plasticizer include, but are not limited to, triethylene glycol, di-2-ethyl butyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol tipprilate, triethylene glycol di-n-octanoate , triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctylazelate, dibutylcarbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-2-ethyl butyrate propylene glycol, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethyl butyrate, di-2- triethylene glycol ethyl pentanoate, tetraethylene glycol di-ethyl butyrate, diethylene glycol tippriate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, adipate diisononyl, adipate heptilnonil adipate, dibutyl sebacate, m-alkyl sebacate odified by oil and a mixture of phosphate and adipate. Organic ester plasticizers other than these can also be used.
[00080] Examples of the organic phosphoric acid plasticizer include, but are not limited to, tributoxyethyl phosphate, isodecyl phenyl phosphate and triisopropyl phosphate.
[00081] The plasticizer is preferably at least one selected from triethylene glycol di-and-ethylhexanoate (3GO) and triethylene glycol di-ethylbutyrate (3GH) and more preferably triethylene glycol di-2-ethylhexanoate.
[00082] The amount of the plasticizer in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not particularly limited. For every 100 parts by weight of the thermoplastic resin, the lower limit of the amount of the plasticizer is preferably 25 parts by weight, and more preferably 30 parts by weight, while the upper limit is preferably 60 parts by weight, and more preferably 50 parts by weight . If the amount of the plasticizer meets the preferable lower limit, the resistance to penetration of the laminated glass can be further increased. If the amount of the plasticizer meets the preferred upper limit, the transparency of the intermediate layer film 1 can be further increased.
[00083] The quantity of the plasticizer in the heat protection layer 2 may be different from the quantity of the plasticizer in each of the first and second layers of protection against ultraviolet 3 and 4. For example, in the case where the quantity of the plasticizer of hair at least one of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not less than 55 parts by weight for every 100 parts by weight of the thermoplastic resin, the sound insulation of the laminated glass can be increased . Ultraviolet protection agent
[00084] Each of the first and second layers of ultraviolet protection 3 and 4 contains an ultraviolet protection agent. The ultraviolet protection agent contains an ultraviolet absorber. The ultraviolet protection agent is preferably an ultraviolet absorber.
[00085] Examples of a conventional and widely known ultraviolet protection agent include metal ultraviolet protection agents, metal oxide ultraviolet protection agents, benzotriazole ultraviolet protection agents, benzophenone ultraviolet protection agents , triazine ultraviolet protection agents and benzoate ultraviolet protection agents.
[00086] Examples of metal ultraviolet absorbers include platinum particles, particles obtained by coating the surfaces of platinum particles with silica, particles of palladium and particles obtained by coating the surfaces of palladium particles with silica. The ultraviolet protection agent is preferably not heat protection particles. The ultraviolet protection agent is preferably a benzotriazole ultraviolet protection agent, a benzophenone ultraviolet protection agent, a triazine ultraviolet protection agent or a benzoate ultraviolet protection agent, and more preferably a benzotriazole ultraviolet.
[00087] Examples of the metal oxide ultraviolet absorber include zinc oxide, titanium oxide and cerium oxide. The surface of the metal oxide ultraviolet absorber can be coated. The coating material for the surface of the metal oxide ultraviolet absorber can be, for example, an insulating metal oxide, a hydrolyzable organic silicon compound or a silicone compound.
[00088] Examples of insulating metal oxide include silicon, alumina and zirconia. Insulating metal oxide has a range energy of not less than 5.0 eV, for example.
[00089] Examples of the benzotriazole ultraviolet absorber include benzotriazole ultraviolet absorbers, such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole ("Tinuvin P" produced by BASF AG), 2- (2 '-hydroxy-3', 5'-di-t-butylphenyl) benzotriazole ("Tinuvin 320" produced by BASF AG), 2- (2'-hydroxy-3'-t-butyl- 5-methylphenyl) -5- chlorobenzotriazole ("Tinuvin 326" produced by BASF AG) and 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazlo ("Tinuvin 328" produced by BASF AG). The ultraviolet protection agent is preferably a benzotriazole ultraviolet absorber that contains a halogen atom for the excellent ability to absorb ultraviolet rays, and more preferably a benzotriazole ultraviolet absorber that contains a chlorine atom.
[00090] Examples of the benzophenone ultraviolet absorber include octabenzone ("Chimassorb 81" produced by BASF A. G.). Examples of the triazine ultraviolet absorber include 2- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) 5- [(hexyl) oxy] -phenol ("Tinuvin 1577FF" produced by BASF AG) .
[00091] Examples of the benzoate ultraviolet absorber include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxy benzoate ("Tinuvin 120" produced by BASF A. G.).
[00092] The ultraviolet protection agent contained in each of the first and second layers of ultraviolet protection 3 and 4 is suitably selected such that the ultraviolet transmittance of each of the first and second layers of ultraviolet protection 3 and 4 or of the intermediate layer film 1 is within a preferable range. The ultraviolet protection agent contained in the first and second layers of ultraviolet protection 3 and 4 is preferable and appropriately selected such that the ultraviolet transmittance of the first and second layers of ultraviolet protection 3 and 4 u of the intermediate layer film 1 it is no more than the value described above at a wavelength of 360 to 400 nm, a wavelength of 360 to 390 nm or a wavelength of 380 to 390 nm.
[00093] The heat protection layer 2 may or may not contain the ultraviolet protection agent 3. The heat protection layer 2 preferably contains an ultraviolet protection agent in terms of further decreasing the ultraviolet transmittance of the film. intermediate layer 1 at a wavelength of 360 to 400 nm, a wavelength of 360 to 390 nm or a wavelength of 380 to 390 nm.
[00094] In terms of further decreasing the ultraviolet transmittance of the first and second ultraviolet protection layers 3 and 4 or of the intermediate layer film 1, the ultraviolet protection agent is preferably 2- (2'-hydroxy-3 '-t-butyl-5-methylphenyl) -5-chlorobenzotriazole ("Tinuvin 326" produced by BASF AG) or 2- (2'-hydroxy-3', 5'-di-amylphenyl) benzotriazole ("Tinuvin 328" produced by BASF AG) and more preferably 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzoriazole.
[00095] The amount of the ultraviolet protection agent in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not particularly limited. In terms of further increasing the heat protection properties at the initial stage and after a period of time, the lower limit of the amount of the ultraviolet protection agent is preferably 0.3 part by weight, more preferably 0.4 part per weight, and even more preferably 0.5 part by weight for every 100 parts by weight of the thermoplastic resin, while the upper limit of it is preferably 3 parts by weight, more preferably 2.5 parts by weight, and even more preferably 2 parts by weight for every 100 parts by weight of the thermoplastic resin.
[00096] In terms of further increasing the heat protection properties at the initial stage and after a period of time, the amount of the AGU based on 100% by weight of the ultraviolet protection layer is preferably no less than 0 , 1% by weight, more preferably not less than 0.2% by weight, still more preferably not less than 0.3% by weight and particularly and preferably not less than 0.5% by weight, while the amount it is preferably not more than 2.5% by weight, more preferably not more than 2% by weight, still more preferably not more than 1% by weight, and particularly and preferably not more than 0.8% by weight . Particularly, if the AGU amount is not less than 0.2% by weight based on 100% by weight of the UV protection layer, a decrease in the heat protection properties of the laminated glass after an interval of time can be greatly prevented.
[00097] In terms of further increasing the heat protection properties at the initial stage and after a period of time, the amount of AGU based on 100% by weight of the heat protection layer is preferably not less than 0 , 1% by weight, more preferably not less than 0.2% by weight, still more preferably not less than 0.3% by weight, and particularly and preferably not less than 0.5% by weight, while amount is preferably not more than 2.5% by weight, more preferably not more than 2% by weight, still more preferably not more than 1% by weight, and particularly and preferably not more than 0.8% by weight Weight. Particularly, in the case where the amount of the ultraviolet protection agent is not less than 0.3% by weight based on 100% by weight of the heat protection layer, a decrease in the heat protection properties of the laminated glass after a period of time it can be greatly prevented. Heat protection particles
[00098] Heat protection layer 2 contains heat protection particles. Each of the first and second layers of ultraviolet protection 3 and 4 may or may not contain particles that protect against heat. In terms of further increasing the heat protection properties of laminated glass, each of the first and second layers of ultraviolet protection 3 and 4 preferably contains particles of heat protection.
[00099] Heat protection particles are preferably particles formed from metal oxides. One type of heat protection particles can be used alone or two or more types of heat protection particles can be used in combination.
[000100] Infrared rays with a wavelength of not less than 780 nm, which is longer than that of visible light, have a small amount of energy compared to ultraviolet rays. Infrared rays, however, have a great thermal effect and are emitted as heat once absorbed by a substance. For this reason, infrared rays are commonly referred to as heat rays. The use of heat protection particles makes it possible to effectively block infrared rays (heat rays). The term "heat protection particles" means particles that can absorb infrared rays.
[000101] Specific examples of heat protection particles include metal oxide particles, such as tin oxide particles with aluminum, tin oxide particles with indium, tin oxide particles with antimony (particles of aluminum). ATO), gallium doped zinc oxide particles (GZO particles), indium doped zinc oxide particles (IZO particles), aluminum doped zinc oxide particles (AZO particles), titanium oxide particles doped niobium particles, sodium doped tungsten oxide particles, cesium doped tungsten oxide particles, thallium doped tungsten oxide particles, rubidium doped tungsten oxide particles, particles of tin doped indium oxide (particles of ITO), tin-doped zinc oxide particles and silicon-doped zinc oxide particles; and particles of lanthanum hexaboride (LaB6). Heat protection particles other than these can also be used. For the high heat protection properties, the heat protection particles are preferably metal oxide particles, more preferably ATO particles, GZO particles, IZO particles, ITO particles or cesium doped tungsten oxide particles. , and even more preferably ITO particles.
[000102] Particularly, tin-doped indium oxide particles (ITO particles) are preferable because they have high heat protection properties and are readily available.
[000103] The lower limit of the average particle size of the heat protection particles is 0.01 μm, and more preferably 0.02 μm, and the upper limit of it is 0.1 μm, and more preferably 0.05 μm . If the average particle size meets the preferable lower limit, the heat protection properties can be sufficiently increased. If the average particle size meets the preferable upper limit, the dispersibility of the heat protection particles can be increased.
[000104] The "average particle size" above means an average particle size per volume. The average particle size can be measured using a particle size distribution measuring device ("UPA-EX 150" produced by Nikkiso Co., Ltd) or the like.
[000105] The quantity of the heat protection particles in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not particularly limited. For every 100 parts by weight of the thermoplastic resin, the lower limit of the amount of heat-protective particles is preferably 0.01 parts by weight, and more preferably 0.1 part by weight, while the upper limit of it is preferably 3 parts by weight, and more preferably 2 parts by weight. If the amount of heat protection particles in each heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is above the preferable range, the heat protection particles can be sufficiently increased , the sole transmittance (Ts2500) can be sufficiently decreased, the Tts can be sufficiently decreased and the visible transmittance can be sufficiently increased. For example, the Tts above can be no more than 50%, and the visible transmittance can be no less than 70%.
[000106] The quantity of the heat protection particles in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not particularly limited. The amount of the heat protection particles based on 100% by weight of the heat protection layer and the first and second ultraviolet protection layers is preferably not less than 0.01% by weight, more preferably not less than than 0.1% by weight, even more preferably not less than 1% by weight and particularly preferably not less than 1.5% by weight, while the amount is preferably not more than 6% by weight, more preferably not more than 5.5% by weight, even more preferably not more than 4% by weight, particularly preferably not more than 3.5% by weight, and most preferably not more than 3.0% by weight. If the quantity of the heat protection particles in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is in the preferable range above, the heat protection properties can be sufficiently increased, the solar transmittance (Ts2500) can be sufficiently decreased, the Tts can be sufficiently decreased and the visible transmittance can be sufficiently increased. For example, the visible transmittance of a laminated glass that includes the intermediate layer film to a laminated glass according to the present invention can be not less than 70%. Component X
[000107] Heat protection layer 2 contains component X. Component X is at least one component selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound.
[000108] Component X is not particularly limited. Compound X can be a phthalocyanine compound, naphthalocyanine compound or conventionally known anthracyanine compound. One type of compound X can be used alone or two or more types of compound X can be used in combination.
[000109] The use in combination of the particles of protection against the heat and the compound X allows to block sufficiently the infrared rays (rays of heat). The use in combination of the metal oxide particles and the X component makes it possible to block infrared rays more effectively. The combination of the ITO particles and the X component makes it possible to block the infrared rays even more effectively.
[000110] Examples of component X include phthalocyanine, a phthalocyanine derivative, naphthalocyanine, a naphthalocyanine derivative, anthracyanine and an anthracyanine derivative. Each of the phthalocyanine compound and the phthalocyanine derivative preferably has a phthalocyanine backbone. Each of the naphthalocyanine compound and the naphthalocyanine derivative preferably has a naphthalocyanine backbone. Each of the anthracyanine compound and the anthracyanine derivative preferably has an anthracyanin backbone.
[000111] In terms of further increasing the heat protection properties, sufficiently decreasing the solar transmittance (Ts2500), sufficiently decreasing the Tts and sufficiently increasing the visible transmittance with respect to the intermediate layer film and laminated glass, component X it is preferably at least one selected from the group consisting of phthalocyanine, a phthalocyanine derivative, naphthalocyanine and a naphthalocyanine derivative.
[000112] In terms of effectively increasing the heat protection properties and maintaining visible transmittance at an even higher level for a long period of time, component X preferably contains vanadium atoms or copper atoms, and more preferably contains atoms vanadium. Component X is preferably at least one selected from a phthalocyanine derivative that contains vanadium atoms or copper atoms and a naphthalocyanine derivative that contains vanadium atoms or copper atoms. In terms of further enhancing the heat protection properties of the intermediate layer film and laminated glass, component X preferably has a structure in which the vanadium atoms are contained.
[000113] The amount of component X in each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 is not particularly limited. For every 100 parts by weight of the thermoplastic resin, the lower limit of the amount of compound X is preferably 0.0005 part by weight, and more preferably 0.003 part by weight, while the upper limit of it is preferably 0.1 part by weight, and more preferably 0.05 part by weight. If the amount of component X in the heat protection layer 2 is in the preferable range above, the heat protection properties can be sufficiently increased, the solar transmittance (Ts2500) can be sufficiently decreased, the Tts can be sufficiently decreased and the transmittance can be sufficiently increased. For example, Tts can be no more than 50% and the visible transmittance can be no less than 70%.
[000114] The amount of component X based on 100% by weight of the heat protection layer and the first and second ultraviolet protection layers is preferably not less than 0.001% by weight, more preferably not less than 0.005% by weight, even more preferably not less than 0.05% by weight, and particularly preferably not less than 0.1% by weight, while the amount is preferably not more than 0.2% by weight, more preferably not more than 0.18% by weight, even more preferably not more than 0.16% by weight, and particularly preferably not more than 0.15% by weight. If the amount of component X in the first heat protection layer is in the range from the lower limit up to the upper limit above, the heat protection properties can be sufficiently increased, the solar transmittance (Ts2500) can be sufficiently decreased, at Tts it can be sufficiently decreased and the visible transmittance can be sufficiently increased. For example, the visible transmittance can be no less than 70%. Other components
[000115] Each of the heat protection layer 2 and the first and second ultraviolet protection layers 3 and 4 can optionally contain additives, such as an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion adjuster, a moisture resistant agent, a fluorescent whitener and an infrared absorber. Each of the additives can be used alone or two or more of these can be used in combination. Laminated glass
[000116] The intermediate layer film for a laminated glass according to the present invention is used to produce a laminated glass.
[000117] Figure 2 illustrates a laminated glass that includes the intermediate layer film 1 shown in Figure 1.
[000118] A laminated glass 11 illustrated in Figure 2 includes the intermediate layer film 1 and the first and second laminated glass components 12 and 13. The intermediate layer film 1 is an intermediate layer film for a laminated glass. The intermediate layer film 1 is sandwiched between the first and second laminated glass components 12 and 13. Therefore, laminated glass 11 has the first laminated glass component 12, the intermediate layer film 1 and the second laminated glass component. 13 rolled in this order. The first laminated glass component 12 is laminated on a surface 3a on the outer side of the first ultraviolet protection layer 3. The second laminated glass component 13 is laminated on a surface 4a on the outer side of the second ultraviolet protection layer 4.
[000119] Examples of the first and second laminated glass components 12 and 13 include glass plates and PET (polyethylene terephthalate) films. Laminated glass 11 includes not only laminated glass provided with an intermediate layer film interspersed between two glass plates on it, but also laminated glass provided with an intermediate layer film interspersed between a glass plate and a PET film or the like in him. Laminated glass 11 is a laminated product that contains a glass plate, and preferably includes at least one glass plate.
[000120] Examples of the glass plate include inorganic glass plates and organic glass plates. Examples of inorganic glass include float flat glass, heat absorbing glass, heat reflecting glass, polished flat glass, molded flat glass, flat mesh glass, wired flat glass and green glass. Inorganic glass is heat absorbing glass. Heat-absorbing glass is defined under JIS R 3208. Organic glass is synthetic resin glass replaced by inorganic glass. Examples of organic glass include polycarbonate plates and poly (meth) acrylate resin plates. Examples of poly (meth) acrylate resin plates include polymethyl (meth) acrylate resin plates.
[000121] The thickness of each of the first and second laminated glass components 12 and 13 is preferably not less than 1 mm, while the thickness is preferably not more than 5 mm, and more preferably not more than 3 mm. In the case where the laminated glass components 12 and 13 are glass plates, the thickness of each glass plate is preferably not less than 1 mm, while the thickness is preferably not more than 5 mm, and more preferably not more than 3 mm. In the case where the laminated glass components 12 and 13 are PET films, the thickness of each of the PET films is preferably in the range of 0.03 to 0.5 mm.
[000122] The method of producing laminated glass 1 is not particularly limited. For example, the intermediate layer film 1 is interspersed between the first and the second laminated glass components 12 and 13, and the resulting product is pressed by a pressing roller or vacuum under reduced pressure in a rubber bag so that the air remaining between the first and second laminated glass components 12 and 13 and the intermediate layer film 1 is removed. Thereafter, a laminated product is obtained by means of preliminary adhesion at about 70 ° C to 110 ° C. Then, a laminated product is placed in an autoclave or is pressed, and the laminated product is pressure bonded at about 120 ° C to 150 ° C under a pressure of 1 to 1.5 MPa. In this way, laminated glass 11 can be obtained.
[000123] Laminated glass 11 can be used for cars, rail cars, aircraft, boats and ships and buildings. Laminated glass 11 can be used for windshields, side windows, rear windows or car roof windows. Laminated glass 11 can be used for applications other than these applications. Since laminated glass 11 has high heat protection properties, low solar transmittance (Ts2500), low Tts and high visible transmittance, laminated glass 11 is used appropriately for cars.
[000124] In terms of obtaining laminated glass having better heat protection properties, the Tts of laminated glass 11 is preferably not more than 53%, preferably not more than 50%, and preferably not more than 40% .
[000125] In terms of obtaining a laminated glass having an even better transparency, the visible transmittance of the laminated glass 11 is preferably not less than 65%, and more preferably not less than 70%. The visible transmittance of laminated glass can be measured in accordance with JIS R 3211 (1998). The visible transmittance of a laminated glass obtained by interleaving the intermediate layer film into a laminated glass according to the present invention between the two 2 mm thick float glass plates according to JIS R 3202 is preferably no less than 70%.
[000126] The solar transmittance (Ts2500) of the laminated glass is preferably not more than 65%, and more preferably not more than 50%. The solar transmittance of laminated glass can be measured according to JIS R 3106 (1998). The solar transmittance of a laminated glass obtained by interleaving the intermediate layer film to a laminated glass according to the present invention between the two 2 mm thick float glass plates according to JIS R 3202 is preferably no more than 65%, more preferably not more than 60%, and even more preferably not more than 50%.
[000127] The opacity value of a laminated glass is preferably not more than 2%, more preferably not more than 1%, even more preferably not more than 0.5%, and particularly preferably not more than 0, 4%. Since the intermediate layer film for a laminated glass according to the present invention includes a heat protection layer and an ultraviolet protection layer, the intermediate layer film contributes to a decrease in the opacity value of the laminated glass. The opacity value of laminated glass can be measured according to JIS K 6714.
[000128] Hereinafter, the present invention is described in more detail based on the examples. The present invention is not limited to the following examples.
[000129] In the examples and comparative examples, the following materials were used.
[000130] Thermoplastic resin: PVB1 (polyvinyl butyral resin acetalized with n-butyraldehyde, average degree of polymerization: 2,300, hydroxyl group content: 22% by mol, degree of acetylation: 12% by mol, degree of butyralization: 66 mol%) PVB2 (polyvinyl butyral resin acetalized with n-butyraldehyde, average degree of polymerization: 1,700, hydroxyl group content: 30.5% by mol, degree of acetylation: 1% by mol, degree of butyralization: 68 , 5 mol%)
[000131] Plasticizer: 3GO (triethylene glycol di-2-ethylhexanoate)
[000132] Heat protection particles: ITO (ITO particles, product of Mitsubishi Materials Corporation) ATO (ATO particles, "SN-100P" produced by Ishihara Sangyo Kaisha, Ltd., BET value: 70 m2 / g) GZO (GZO particles, "FINEX-50" produced by Sakai Chemical Industry Co., Ltd., BET value: 50m2 / g)
[000133] Component X: IR-906 (vanadyl phthalocyanine compound containing vanadium atoms and oxygen atoms, "EXCOLOR 906" produced by NIPPON SHOKUBAI Co., Ltd.) IR-915 (vanadyl phthalocyanine compound containing atoms vanadium, "EXCOLOR 915" produced by NIPPON SHOKUBAI Co., Ltd.) IRSORB 203 (naphthalocyanine copper compound produced by FUJIFILM Corporation)
[000134] Ultraviolet protection agent: Tinuvin 326 (2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) - chlorobenzotriazole, "Tinuvin 326" produced by BASF A. G.) Example 1 (1) Production of heat protection layer
[000135] Triethylene glycol di-2-ethylhexanoate (3GO) (60 parts by weight), Tinuvin 326 (0.625% by weight based on 100% by weight of the heat protection layer to be obtained), ITO (1.52% by weight based on 100% by weight of the heat protection layer to be obtained) and IR-906 (0.122% by weight based on 100% by weight of the heat protection layer to be obtained) . To the mixture, a phosphate ester compound was added as a dispersant. The resulting mixture was mixed in a horizontal microgranule mill, so that a dispersion was obtained. The average particle size per volume of the ITO particles in the dispersion was 35 nm. The amount of the phosphate ester compound was adjusted to be 1/10 of the amount of the heat protection particles.
[000136] The entire amount of the dispersion was added to 100 parts by weight of a polyvinyl butyral resin (PVB1), and the mixture was sufficiently kneaded on a mixing roller. In this way, a first composition was obtained. (2) Production of ultraviolet protection layer
[000137] Triethylene glycol di-2-ethylhexanoate (3GO) (40 parts by weight) and Tinuvin 326 (0.571% by weight based on 100% by weight of the ultraviolet protection layer to be obtained) were mixed in one horizontal microgranule mill, so that a dispersion was obtained.
[000138] The entire amount of the dispersion obtained was added to 100 parts by weight of a polyvinyl butyral resin (PVB2), and the mixture was sufficiently kneaded on a mixing roller. In this way, a second composition was obtained. (3) Production of intermediate layer film for laminated glass
[000139] The first composition and the second composition obtained were co-extruded using an extruder, and a laminated product provided with a three-layer structure of the ultraviolet protection layer / heat protection layer / ultraviolet protection layer was gotten. The thickness of the ultraviolet protection layer was 330 μm and the thickness of the heat protection layer was 100 μm. For this reason, an intermediate layer film with a thick three-layer structure with 760 μm was obtained. (4) Production of laminated glass
[000140] The obtained intermediate layer film was cut to a size of 30 cm in length x 30 cm in width. then, two float glass plates (30 cm in length x 30 cm in width x 2 mm in thickness) according to JIS R 3202 were prepared. The obtained intermediate layer film was sandwiched between these two float glass plates. The resulting product was retained in a vacuum laminator at 90 ° C for 30 minutes and then pressed under vacuum, so that a laminated product was obtained. The part of the intermediate layer film that protrudes from the glass plates was cut, by means of which a laminated glass was obtained. Examples 2 to 10
[000141] A heat protection layer and an ultraviolet protection layer were produced in the same way as in Example 1, except that the types and amounts of the thermoplastic resin, the plasticizer, the heat protection particles, the component X, and the ultraviolet protection agent have been changed to those shown in Table 1 below. Using the heat protection layer and the ultraviolet protection layer obtained, a laminated glass that includes an intermediate layer film with a three-layer structure was produced in the same way as in Example 1. Also in Examples 2 a 10, the amount of the phosphate ester has been adjusted to be 1/10 of the amount of the heat protection particles in the production of a heat protection layer. Example 11 (1) Production of heat protection layer
[000142] Triethylene glycol di-2-ethylhexanoate (3GO) (40 parts by weight), Tinuvin 326 (0.571% by weight based on 100% by weight of the heat protection layer to be obtained), ITO (3.04% by weight based on 100% by weight of the heat protection layer to be obtained) and IR-915 (0.129% by weight based on 100% by weight of the heat protection layer to be obtained) . To the mixture, a phosphate ester compound was added as a dispersant. The resulting mixture was mixed in a horizontal microgranule mill, so that a dispersion was obtained. The average particle size per volume of the ITO particles in the dispersion was 35 nm. The amount of the phosphate ester compound was adjusted to be 1/10 of the amount of the heat protection particles.
[000143] The entire amount of the dispersion obtained was added to 100 parts by weight of a polyvinyl butyral resin (PVB 2), and the mixture was sufficiently kneaded on a mixing roller. In this way, a first composition was obtained. (2) Production of ultraviolet protection layer
[000144] Triethylene glycol di-2-ethylhexanoate (3GO) (40 parts by weight) and Tinuvin 326 (0.714% by weight based on 100% by weight of the ultraviolet protection layer to be obtained) were mixed in one horizontal microgranule mill, so that a dispersion was obtained.
[000145] The entire amount of the dispersion obtained was added to 100 parts by weight of a polyvinyl butyral resin (PVB2), and the mixture was sufficiently kneaded on a mixing roller. In this way, a second composition was obtained. (3) Production of intermediate layer film for laminated glass
[000146] The first composition and the second composition obtained were co-extruded using an extruder, and a laminated product provided with a two-layer structure of the ultraviolet protection layer / heat protection layer was obtained. The thickness of the ultraviolet protection layer was 660 μm and the thickness of the heat protection layer was 100 μm. Therefore, an intermediate layer with a structure of two layers with a thickness of 760 μm was obtained. (4) Production of laminated glass
[000147] A laminated glass was obtained in the same way as in Example 1, except that the obtained intermediate layer film was used. Example 12
[000148] A heat protection layer and an ultraviolet protection layer were produced in the same way as in Example 11, except that the thickness of each of the heat protection layer and the ultraviolet protection layer was changed to value shown in Table 1 below. Also in Example 12, the amount of the phosphate ester was adjusted to be 1/10 of the amount of the heat protection particles in the production of a heat protection layer.
[000149] An intermediate layer film with a two-layer structure and laminated glass were obtained in the same manner as in Example 11, except that the obtained heat protection layer and the ultraviolet protection layer were used. Reference Example 1
[000150] Triethylene glycol di-2-ethylhexanoate (3GO) (40 parts by weight), ITO (0.20% by weight based on 100% by weight of the intermediate layer film to be obtained), Tinuvin were mixed 326 (0.625% by weight based on 100% by weight of the intermediate layer film to be obtained) and IR-906 (0.016% by weight based on 100% by weight of the intermediate layer film to be obtained). To the mixture, a phosphate ester compound was added as a dispersant. The resulting mixture was mixed in a horizontal microgranule mill, so that a dispersion was obtained. The amount of the phosphate ester compound was adjusted to be 1/10 of the amount of the heat protection particles.
[000151] The entire amount of the dispersion obtained was added to 100 parts by weight of a polyvinyl butyral resin (PVB2) and the mixture was sufficiently kneaded on a mixing roller. In this way, a composition was obtained.
[000152] The obtained composition was extruded to provide a single layer intermediate layer film with a thickness of 760 μm. using the obtained intermediate layer film, a laminated glass that includes a single layer intermediate layer film was obtained in the same manner as in Example 1. Reference Examples 2 to 4, Comparative Examples 1 to 7 and Reference Example 5
[000153] An intermediate layer film was produced in the same way as in Reference Example 1, except that the types and amounts of the thermoplastic resin, plasticizer, heat protection particles, ultraviolet protection agent and component X have been changed to those shown in Table 2 below. Using the intermediate layer film, a laminated glass that includes a single layer intermediate layer film was obtained.
[000154] The amount of the phosphate ester compound has been adjusted to be 1/10 of the amount of the heat protection particles also in Reference Examples 2 to 4, Comparative Examples 6 to 7 and Reference Example 5. No compound of phosphate ester was used in Comparative Examples 1 to 5.
[000155] In Reference Examples 1 to 5, the heat protection particles and component X were contained in the same layer (intermediate layer film). In Comparative Examples 1 to 4, no heat protection particles were used and component X was mixed. In Comparative Example 5, neither the heat protection particles nor the X component was mixed. In Comparative Examples 6 and 7, the heat protection particles were mixed, but component X was not mixed. Evaluation (1) Measurement of ultraviolet transmittance (360 to 400 nm), (360 to 390 nm) and (380 to 390 nm)
[000156] The ultraviolet protection layer (a layer) used to obtain the intermediate layer film of each of the examples was produced. Also, the intermediate layer film was prepared for each of the examples and the comparative examples. The ultraviolet transmittance of each of the ultraviolet protection layer and the intermediate layer film at a wavelength of 360 to 400 nm, a wavelength of 360 to 390 nm, and a wavelength of 380 to 390 nm was measured using a spectrophotometer ("U-4100" produced by Hitachi High-Technologies Corporation) according to JIS R 3211 (1998). (2) Measurement of visible transmittance (Y value of light A, initial A-Y (380 to 780 nm))
[000157] The visible transmittance of the laminated glass obtained at a wavelength of 380 to 780 nm was measured using a spectrometer ("U-4100" produced by Hitachi High-Technologies Corporation) according to JIS R 3211 (1998 ). (3) Measurement of solar transmittance (initial Ts2500 (300 to 2,500 nm))
[000158] The solar transmittance Ts (Ts2500) of the laminated glass obtained at a wavelength of 300 to 2,500 nm was measured using a spectrometer ("U-4100" produced by Hitachi High-Technologies Corporation) according to JIS R 3106 (1998). (4) Measurement of light transmission (initial T850 (850 nm), initial T900 (900 nm) and initial T950 (950 nm))
[000159] The light transmittances (T850 (850 nm), T900 (900 nm) and T950 (950 nm)) of the laminated glass obtained at a wavelength of 850 nm, 900 nm and 950 nm were measured using a spectrometer ("U-4100" produced by Hitachi High-Technologies Corporation) according to JIS R 3106 (1998). (5) Yellow measurement (YI of light C: yellow index)
[000160] The yellow (yellow index) of the laminated glass obtained was measured using a spectrometer ("U-4100" produced by Hitachi High-Technologies Corporation) using a transmission method in accordance with JIS K 7105. (6) Measurement of the opacity value
[000161] The opacity value of the laminated glass obtained was measured using an opacity meter ("TC-HIIIDPK" by Tokyo Denshoku Co., Ltd.) according to JIS K 6714. (7) Long-term stability (resistance to light)
[000162] Using an ultraviolet lamp ("HLG-25" produced by Suga Test Instruments Co., Ltd.) or similar, the laminated glass was irradiated with ultraviolet rays (mercury lamp with quartz glass (750 W)) for 500 hours and 100 hours according to JIS R 3205. AY, Ts2500, T850, T900, T950 and YI of light C after irradiation for 500 hours and irradiation for 1,000 hours were measured by the above methods. In Examples 11 and 12, ultraviolet rays were irradiated from the first side of the ultraviolet protection layer.
[000163] From the measurement values obtained, ΔA-Y ((AY after ultraviolet irradiation) - (initial AY)), ΔTs2500 (Ts2500 after ultraviolet irradiation - initial Ts2500), ΔT850 (T850 after irradiation of ultraviolet - initial T850), ΔT900 (T900 after ultraviolet irradiation - initial T900), ΔT950 (T950 after ultraviolet irradiation - initial T950) and ΔYI of light C (YI of light C after ultraviolet irradiation - YI of light Initial C) were calculated.
[000164] Tables 1 and 2 below show the compositions of the intermediate layer films and the following Tables 3 to 5 show the results of the evaluation. The amount of plasticizer composition in Tables 1 and 2 indicates the amount (parts by weight) of the plasticizer for every 100 parts by weight of the thermoplastic resin. The amount of composition for each of the heat protection particles, component X and the ultraviolet protection agent in Table 1 indicates the amount (% by weight) of each of the heat protection particles, component X and the ultraviolet protection agent based on 100% by weight of the heat protection layer or the ultraviolet protection layer. The amount of composition for each of the heat protection particles, component X and the ultraviolet protection agent in Table 2 indicates the amount of each of the heat protection particles, component X and the protection agent against ultraviolet based on 100% by weight of the intermediate layer film. In Tables 1 and 2, the amount of the phosphate ester compound is omitted.













[000165] The intermediate layer films for laminated glass in Reference Examples 1 to 5 had sufficiently high initial heat protection properties. SYMBOLS EXPLANATION 1 - intermediate layer film for laminated glass 2 - heat protection layer 2a - first surface 2b - second surface 3 - first ultraviolet protection layer 3a - external surface 4 - second ultraviolet protection layer 4a - surface external 5 - heat protection particles 11 - laminated glass 12 - first laminated glass component 13 - second laminated glass component

权利要求:
Claims (10)
[0001]
1. Intermediate layer film for laminated glass (1), characterized by the fact that it comprises: a heat protection layer (2); and a first ultraviolet protection layer (3), wherein the heat protection layer (2) comprises a thermoplastic resin, which is a polyvinyl acetal resin, heat protection particles and at least one component selected from a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound, the first ultraviolet protection layer (3) comprises a thermoplastic resin, which is an acetal polyvinyl resin and an ultraviolet protection agent, and an amount of ultraviolet protection is 0.2 to 1.0% by weight based on the 100% by weight of the ultraviolet protection layer (3).
[0002]
2. Intermediate layer film for laminated glass (1) according to claim 1, characterized by the fact that the first ultraviolet protection layer (3) is laminated on a surface of the heat protection layer (2) .
[0003]
3. Intermediate layer film for laminated glass (1), according to claim 1, characterized in that it additionally comprises a second layer of protection against ultraviolet (4), in which the first layer of protection against ultraviolet (1 ) is placed on one side of the surface of the heat protection layer (2), the second layer of ultraviolet protection (4) is placed on the other side of the surface of the heat protection layer (2), and the second layer of ultraviolet protection (4) comprises a thermoplastic resin, which is a polyvinyl acetal resin, and an ultraviolet protection agent.
[0004]
4. Intermediate layer film for laminated glass (1), according to claim 3, characterized by the fact that the first ultraviolet protection layer (3) is laminated on a surface of the heat protection layer (2) , and the second ultraviolet protection layer (4) is laminated to the other surface of the heat protection layer (2).
[0005]
5. Intermediate layer film for laminated glass (1) according to any one of claims 1 to 4, characterized in that the ultraviolet transmittance of the ultraviolet protection layer is not more than 0.8% in one wavelength from 380 to 390 nm.
[0006]
6. Intermediate layer film for laminated glass (1) according to any one of claims 1 to 4, characterized in that the component is at least one selected from the group consisting of phthalocyanine, a phthalocyanine derivative, naphthalocyanine and a naphthalocyanine derivative.
[0007]
7. Intermediate layer film for laminated glass (1) according to any one of claims 1 to 4, characterized in that the heat protection particles are metal oxide particles.
[0008]
8. Intermediate layer film for laminated glass, according to claim 7, characterized by the fact that the heat protection particles are tin doped indium oxide particles.
[0009]
9. Intermediate layer film for laminated glass (1) according to any one of claims 1 to 4, characterized by the fact that each of the heat protection layer (2) and the first ultraviolet protection layer ( 3) additionally comprises a plasticizer.
[0010]
10. Laminated glass (11), characterized by the fact that it comprises: a first laminated glass component (12) and a second laminated glass component (13); and an intermediate layer film interspersed between the first laminated glass component (11) and the second laminated glass component (12), wherein the intermediate layer film is an intermediate layer film for a laminated glass (1) as defined in any of claims 1 to 4.

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同族专利:

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JP2015171989A|2015-10-01|

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JP2012106931A|2012-06-07|

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RU2540569C2|2015-02-10|

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CN102625786B|2015-04-15|

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JP6374914B2|2018-08-15|

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JP2016193826A|2016-11-17|

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BR112012003918A2|2016-03-29|

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JPWO2011024788A1|2013-01-31|

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EP2471762A4|2013-02-13|

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JP5695585B2|2015-04-08|

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EP2471762B1|2016-04-13|

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WO2011024788A1|2011-03-03|

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RU2012111220A|2013-10-10|

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EP2471762A1|2012-07-04|

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MX2012001804A|2012-05-08|

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KR20120066007A|2012-06-21|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-11-06| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|Free format text: O DEPOSITANTE DEVE RESPONDER A EXIGENCIA FORMULADA NESTE PARECER POR MEIO DO SERVICO DE CODIGO 206 EM ATE 60 (SESSENTA) DIAS, A PARTIR DA DATA DE PUBLICACAO NA RPI, SOB PENA DO ARQUIVAMENTO DO PEDIDO, DE ACORDO COM O ART. 34 DA LPI.PUBLIQUE-SE A EXIGENCIA (6.20). |

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2020-03-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-07-07| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-10-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-29| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 29/12/2020, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2009193721|2009-08-24|

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JP2009-193721|2009-08-24|

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PCT/JP2010/064247|WO2011024788A1|2009-08-24|2010-08-24|Intermediate film for laminated glass, and laminated glass|

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