JP2018145067A - Intermediate film for laminated glass, laminated glass and laminated glass system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an intermediate film for a laminated glass having both high heat generating performance capable of melting frost or ice adhered to glass and high transparency; a laminated glass using the intermediate film for a laminated glass and the laminated glass system.SOLUTION: There is provided an intermediate film 1 for a laminated glass having a conductive layer 2 composed of a laminate comprising a zinc oxide layer 21 containing zinc oxide and a silver layer 22 containing silver, an alloy of siver or a silver compound which is directly formed on the zinc oxide layer 21. Thereby, there is provided a laminated glass having high heat generating performance capable of melting frost or ice adhered to glass.SELECTED DRAWING: Figure 1

Description

The present invention relates to an interlayer film for laminated glass capable of melting frost and ice adhering to the glass and having both high heat generation performance and high transparency, a laminated glass using the interlayer film for laminated glass, and the laminated glass. About the system.

Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, it is widely used for automobiles and buildings.
In recent years, the performance required for laminated glass has also diversified, and a technique for heating a laminated glass itself to warm a frozen window glass and melting frost and ice has been studied.

As one method for heating the laminated glass itself, a method is considered in which a conductive film is formed on the glass surface of the laminated glass and the laminated glass is warmed by heat generated from resistance during energization. Laminated glass on which such a conductive film is formed is disclosed in, for example, Patent Document 1 and the like.
On the other hand, as one method of heating the laminated glass itself, a method of laminating a heat generating layer made of a conductive film on an interlayer film for laminated glass has been studied. Such an interlayer film for laminated glass is usually produced by a method of laminating a resin layer containing a thermoplastic resin such as polyvinyl acetal on the heat generating layer. An interlayer film for laminated glass having a heat generating function is expected to become a mainstream in the future because it is excellent in terms of manufacturability and cost.

However, an excellent transparency is required for the interlayer film for laminated glass in order to be widely used as glass for automobiles and buildings. The conventional interlayer film for laminated glass having a heat generation function has a problem that it is not sufficient in terms of transparency.

JP 2008-222513 A

Based on the research so far, the present inventors have used a silver layer containing silver, a silver alloy or a silver compound as a conductive layer, thereby exhibiting a high heat generation function and being excellent in transparency. It was found that an interlayer film was obtained. However, even the interlayer film for laminated glass having such a silver layer cannot exhibit the performance as designed in terms of transparency, and further improvement in transparency has been demanded.

The present inventor has developed an interlayer film for laminated glass that has both high heat generation performance and high transparency capable of melting frost and ice adhering to the glass, laminated glass using the interlayer film for laminated glass, and the laminated glass The object is to provide a glass system.

The present invention relates to a laminated glass having a conductive layer comprising a laminate of a zinc oxide layer containing zinc oxide and a silver layer containing silver, a silver alloy or a silver compound directly formed on the zinc oxide layer. It is an intermediate film for use.
The present invention is described in detail below.

The present inventors examined the cause of the decrease in transparency in an interlayer film for laminated glass having a silver layer containing silver, a silver alloy or a silver compound as a conductive layer. As a result, when a silver layer is formed on a substrate or the like by a sputtering method or the like, fine irregularities are generated on the surface of the silver layer, and light is scattered by the irregularities, thereby reducing transparency. I found out that Furthermore, as a result of intensive studies, when a zinc oxide layer containing zinc oxide is formed as the underlayer of the silver layer, and the silver layer is formed directly on the zinc oxide layer, the formation of irregularities is suppressed and high transparency is achieved. The present invention has been completed.

The interlayer film for laminated glass of the present invention has a conductive layer composed of a laminate of a zinc oxide layer containing zinc oxide and a silver layer directly formed on the zinc oxide layer.
The conductive layer generates heat by applying a voltage, warms the frozen glass, and melts frost and ice.

The conductive layer preferably has a surface resistivity of 10Ω / □ or less. A conductive layer having a surface resistivity of 10 Ω / □ or less can generate sufficient heat by applying a voltage to warm frozen glass and melt frost and ice. More preferably, it is 2.5Ω / □ or less, and still more preferably 2.0Ω / □ or less.

The silver layer contains silver, a silver alloy, or a silver compound. Since silver, a silver alloy, or a silver compound has a sufficiently low electric resistivity, sufficient heat generation can be obtained when a voltage is applied.
The silver alloy is not particularly limited, and examples thereof include an alloy in which titanium, nickel, palladium, chromium, or the like is mixed with silver. Especially, since it can suppress that a silver layer aggregates, the APC alloy which mixed palladium and chromium in silver is preferable. In addition, since it can suppress that a silver layer aggregates and can improve the exothermic property of the obtained silver layer, the ratio of the metal mixed with silver in a silver alloy is 100 weight% of silver alloys, It is preferable that it is 2 weight% or less.
The silver compound is not particularly limited, and a conventionally known silver compound can be used as long as it is a silver compound having a low electrical resistivity.

The thickness of the silver layer (thickness of one silver layer) is not particularly limited, but the preferred lower limit is 15 nm and the preferred upper limit is 40 nm. By making the thickness of the silver layer within this range, it is possible to sufficiently generate heat by applying a voltage to the conductive layer, warm the frozen glass, melt frost and ice, and obtain the laminated glass obtained. The transparency of the intermediate film can be increased. The more preferable lower limit of the thickness of the silver layer is 20 nm, the more preferable upper limit is 35 nm, the still more preferable lower limit is 25 nm, and the still more preferable upper limit is 30 nm.
When two or more silver layers are present, the preferred lower limit of the total thickness of all the silver layers is 15 nm, and the preferred upper limit is 80 nm. By setting the total thickness of all the silver layers within this range, it is possible to generate heat even more sufficiently by applying a voltage to the conductive layer, warming the frozen glass and melting frost and ice. In addition, the transparency of the resulting interlayer film for laminated glass can be further enhanced. A more preferable lower limit of the total thickness of all the silver layers is 30 nm, and a more preferable upper limit is 70 nm.

The zinc oxide layer serves as an underlayer for forming the silver layer, and has a role of preventing the surface of the silver layer from having fine irregularities and reducing transparency. When a silver layer is formed on a zinc oxide layer that is an underlayer, an extremely smooth interface is formed, and therefore it is considered that unevenness is hardly generated on the surface of the silver layer. Therefore, the excellent effect of the present invention can be exhibited by forming the silver layer directly on the zinc oxide layer.
The conductive layer may have only one zinc oxide layer and one silver layer, or each may have a plurality of layers. At this time, higher transparency can be exhibited by allowing one silver layer to be sandwiched between two zinc oxide layers.

The zinc oxide layer may be composed only of zinc oxide, or may contain a metal other than zinc oxide, a compound thereof, or the like.
Although it does not specifically limit as metals other than the said zinc oxide and its compound, For example, metals, such as palladium, titanium, tin, and aluminum, its oxide, nitride, etc. are mentioned.
In addition, when the said zinc oxide layer contains metals other than zinc oxide, its compound, etc., the minimum with preferable content of the zinc oxide in the said zinc oxide layer is 80 weight%, and a more preferable minimum is 90 weight%.

The thickness of the zinc oxide layer (thickness of one zinc oxide layer) is not particularly limited, but the preferred lower limit is 2 nm and the preferred upper limit is 150 nm. By setting the thickness of the zinc oxide layer within this range, when the silver layer is formed using the zinc oxide layer as a base layer, the surface of the silver layer is surely formed with fine irregularities and the transparency is lowered. Can be prevented. A more preferable lower limit of the thickness of the zinc oxide layer is 3 nm, a more preferable upper limit is 130 nm, a still more preferable lower limit is 5 nm, and a still more preferable upper limit is 100 nm.
When two or more zinc oxide layers are present, the preferred lower limit of the total thickness of all zinc oxide layers is 4 nm, and the preferred upper limit is 300 nm. By making the total thickness of all the zinc oxide layers within this range, when the silver layer is formed using the zinc oxide layer as a base layer, fine irregularities are more reliably generated on the surface of the silver layer. Therefore, it is possible to prevent the transparency from being lowered. The more preferred lower limit of the total thickness of all the zinc oxide layers is 6 nm, the more preferred upper limit is 250 nm, the still more preferred lower limit is 10 nm, and the still more preferred upper limit is 200 nm.

The conductive layer may further include a metal oxide layer containing a metal oxide having a refractive index of 1.5 or more. By having a metal oxide layer, the transparency of the interlayer film for laminated glass obtained can be improved.
Examples of the metal oxide having a refractive index of 1.5 or more include titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), and silicon oxide (SiO ₂ ). Among these, titanium oxide is preferable because particularly high transparency can be obtained.

The thickness of the metal oxide layer (thickness of one metal oxide layer) is not particularly limited, but a preferred lower limit is 10 nm and a preferred upper limit is 150 nm. By setting the thickness of the metal oxide layer within this range, high transparency can be imparted while exhibiting a sufficient heat generation function. The more preferable lower limit of the thickness of the metal oxide layer is 15 nm, the more preferable upper limit is 130 nm, the still more preferable lower limit is 30 nm, and the still more preferable upper limit is 100 nm.
When two or more metal oxide layers are present, the preferable lower limit of the total thickness of all the metal oxide layers is 20 nm, and the preferable upper limit is 300 nm. By setting the total thickness of all the metal oxide layers within this range, high transparency can be imparted while exhibiting a more sufficient heat generation function. The more preferable lower limit of the total thickness of all the metal oxide layers is 25 nm, the more preferable upper limit is 250 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 200 nm.

The conductive layer may further have a transparent conductive layer. Examples of the transparent conductive layer include those made of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), etc., because of its transparency and low electrical resistivity. It is done.

The conductive layer may be formed on a substrate. When the conductive layer is formed on the substrate, a uniform conductive layer can be formed by sputtering or the like.
It is preferable that the base material has a heat shrinkage ratio after heat treatment at 150 ° C. for 30 minutes measured in accordance with JIS C2151 of 1.0 to 3.5% in both MD and TD directions. By using a base material having such a heat shrinkage rate, a uniform conductive layer can be formed by sputtering or the like, and it is formed on the surface of the conductive layer and the conductive layer due to the difference in heat shrinkage rate during the production of laminated glass. It is possible to improve the adhesion between the heat generating layer and the resin layer by preventing the surface of the resin layer from being displaced. A more preferable lower limit of the heat shrinkage rate is 1.5%, and a more preferable upper limit is 3.0%.
In addition, in this specification, MD direction (Machine Direction) means the extrusion direction at the time of extruding a base material in a sheet form, and TD direction (Transverse Direction) means a direction perpendicular to the MD direction.

The base material preferably has a Young's modulus of 1 GPa or more. By using a base material having a Young's modulus of 1 GPa or more, adhesion with the resin layer formed on the surface of the conductive layer can be further improved. The Young's modulus of the substrate is more preferably 1.5 GPa or more, and further preferably 2 GPa or more. A preferable upper limit of the Young's modulus of the substrate is 10 GPa.
The Young's modulus is obtained by obtaining a strain-stress curve at 23 ° C. by a tensile test based on JIS K7127, and is indicated by the slope of the linear portion of the strain-stress curve.
In addition, it is preferable that the Young's modulus of the resin layer mentioned later is generally less than 1 GPa.

The base material preferably contains a thermoplastic resin. Examples of the thermoplastic resin contained in the substrate include chain polyolefins such as polyethylene, polypropylene, poly (4-methylpentene-1), and polyacetal, ring-opening metathesis polymers or addition polymers of norbornenes, and norbornenes. Alicyclic polyolefins such as addition copolymers with other olefins, biodegradable polymers such as polylactic acid and polybutyl succinate, polyamides such as nylon 6, nylon 11, nylon 12 and nylon 66, and aramid And polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene copolymerized polymethyl methacrylate, polycarbonate, polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene Polyester such as 1,6-naphthalate, polyether sulfone, polyether ether ketone, modified polyphenylene ether, polyphenylene sulfide, polyether imide, polyimide, polyarylate, tetrafluoroethylene resin, 3 Examples thereof include a fluorinated ethylene resin, a trifluorinated ethylene resin, a tetrafluoroethylene-6 fluorinated propylene copolymer, and polyvinylidene fluoride. These thermoplastic resins are adjusted singly or in combination of two or more so that the heat shrinkage rate and Young's modulus are within the expected ranges.

The said base material may contain conventionally well-known additives, such as a ultraviolet-ray shielding agent and antioxidant, as needed.
Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, and an ultraviolet shielding agent having a triazine structure. Conventionally known ultraviolet shielding agents such as an ultraviolet shielding agent having a malonic ester structure, an ultraviolet shielding agent having an oxalic acid anilide structure, and an ultraviolet shielding agent having a benzoate structure can be used.
As said antioxidant, conventionally well-known antioxidants, such as antioxidant which has a phenol structure, antioxidant containing sulfur, antioxidant containing phosphorus, can be used, for example.

The thickness of the said base material is not specifically limited, A preferable minimum is 10 micrometers and a preferable upper limit is 200 micrometers. When the thickness of the substrate is within this range, a uniform conductive layer can be formed using a sputtering method or the like, and the conductive layer and the resin layer formed on the surface of the conductive layer at the time of manufacturing laminated glass It is possible to prevent a deviation from occurring on the surface and further improve the adhesion between the conductive layer and the resin layer. The minimum with more preferable thickness of the said base material is 20 micrometers, and a more preferable upper limit is 150 micrometers.

The method for forming the conductive layer on the substrate is not particularly limited, and conventionally known methods such as a sputtering method, an ion plating method, a plasma CVD method, a vapor deposition method, a coating method, and a dip method can be used. . Among these, the sputtering method is preferable because a uniform conductive layer can be formed.
More specifically, for example, the zinc oxide layer is formed on the substrate by sputtering. Next, a silver layer is formed on the zinc oxide layer by sputtering. By forming each layer in this order, it is possible to prevent the surface of the silver layer from having fine irregularities and lowering the transparency.

When the conductive layer is formed on a base material, the heat shrinkage rate after heat treatment at 150 ° C. for 30 minutes measured according to JIS C2151 of the resin layer in direct contact with the base material, and JIS C2151 of the base material. It is preferable that the absolute value of the difference from the heat shrinkage ratio after heat treatment for 30 minutes at 150 ° C. measured in accordance with the above is 10% or less in both MD and TD directions. By making the absolute value of the difference in thermal shrinkage between the resin layer and the substrate in direct contact with each other to 10% or less, it is possible to prevent deviation between the resin layer and the conductive layer during the production of laminated glass. And the resin layer can be further improved in adhesion. The absolute value of the difference in thermal shrinkage between the resin layer and the substrate is more preferably 8% or less.
In addition, the heat shrinkage rate of the resin layer described later can be adjusted by the annealing treatment conditions as well as the type of thermoplastic resin constituting the resin layer, the type and blending amount of the plasticizer.

The interlayer film for laminated glass of the present invention preferably has a resin layer on one side or both sides of the conductive layer (hereinafter referred to as “first resin layer” in the case of having a resin layer on both sides). And the other is also referred to as a “second resin layer”). By having a resin layer, the adhesiveness with glass can be improved and the basic performances required for the interlayer film for laminated glass, such as penetration resistance, can be exhibited.
The first resin layer and the second resin layer may be the same or different.

The resin layer preferably contains a thermoplastic resin. Examples of the thermoplastic resin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoride ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyether, Polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, ethylene-vinyl acetate copolymer, polyoxymethylene (or polyacetal) resin, acetoacetal resin, polyvinylbenzyl acetal resin, A polyvinyl cumin acetal resin etc. are mentioned. Especially, it is preferable that the said resin layer contains a polyvinyl acetal or an ethylene-vinyl acetate copolymer, and it is more preferable to contain a polyvinyl acetal.

The polyvinyl acetal is not particularly limited as long as it is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol with an aldehyde, but polyvinyl butyral is preferable. Moreover, you may use together 2 or more types of polyvinyl acetal as needed.

The preferable lower limit of the degree of acetalization of the polyvinyl acetal is 40 mol%, the preferable upper limit is 85 mol%, the more preferable lower limit is 60 mol%, and the more preferable upper limit is 75 mol%.
The polyvinyl acetal has a preferred lower limit of the hydroxyl group content of 15 mol% and a preferred upper limit of 35 mol%. Adhesiveness between the interlayer film for laminated glass and the glass is increased when the amount of the hydroxyl group is 15 mol% or more. When the hydroxyl group amount is 35 mol% or less, handling of the interlayer film for laminated glass becomes easy.
The degree of acetalization and the amount of hydroxyl groups can be measured in accordance with, for example, JIS K6728 “Testing method for polyvinyl butyral”.

The polyvinyl acetal can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 70 to 99.8 mol% is generally used. The saponification degree of the polyvinyl alcohol is preferably 80 to 99.8 mol%.
The preferable lower limit of the polymerization degree of the polyvinyl alcohol is 500, and the preferable upper limit is 4000. When the polymerization degree of the polyvinyl alcohol is 500 or more, the penetration resistance of the obtained laminated glass is increased. When the polymerization degree of the polyvinyl alcohol is 4000 or less, the interlayer film for laminated glass can be easily molded. The minimum with a more preferable polymerization degree of the said polyvinyl alcohol is 1000, and a more preferable upper limit is 3600.

The aldehyde is not particularly limited, but generally an aldehyde having 1 to 10 carbon atoms is preferably used. The aldehyde having 1 to 10 carbon atoms is not particularly limited. For example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde N-decyl aldehyde, formaldehyde, acetaldehyde, benzaldehyde, polyvinyl benzyl aldehyde, polyvinyl cumin aldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable. These aldehydes may be used alone or in combination of two or more.

The resin layer preferably contains a plasticizer. The plasticizer is not particularly limited, and examples thereof include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers, and the like. Is mentioned. The plasticizer is preferably a liquid plasticizer.

The monobasic organic acid ester is not particularly limited. For example, glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, and n-octyl Examples thereof include glycol esters obtained by reaction with monobasic organic acids such as acid, 2-ethylhexyl acid, pelargonic acid (n-nonyl acid), and decyl acid. Of these, triethylene glycol dicaproate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-octylate, triethylene glycol di-2-ethylhexylate and the like are preferable.

Although the said polybasic organic acid ester is not specifically limited, For example, ester compound of polybasic organic acid, such as adipic acid, sebacic acid, azelaic acid, and the alcohol which has a C4-C8 linear or branched structure Is mentioned. Of these, dibutyl sebacic acid ester, dioctyl azelaic acid ester, dibutyl carbitol adipic acid ester and the like are preferable.

The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl Butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di- -Ethyl hexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicapryate, dihexyl adipate, adipine Dioctyl acid, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified sebacic acid alkyd, a mixture of phosphate ester and adipic acid ester, adipic acid ester, alkyl alcohol having 4 to 9 carbon atoms and Examples thereof include mixed adipic acid esters prepared from cyclic alcohols having 4 to 9 carbon atoms and adipic acid esters having 6 to 8 carbon atoms such as hexyl adipate.

The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

Furthermore, since it is difficult to cause hydrolysis as the plasticizer, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), tetraethylene glycol di-2- It preferably contains ethyl hexanoate (4GO) and dihexyl adipate (DHA), and tetraethylene glycol di-2-ethylhexanoate (4GO) and triethylene glycol di-2-ethylhexanoate (3GO). More preferably, it contains triethylene glycol di-2-ethylhexanoate (3GO).

The content of the plasticizer in the resin layer is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the polyvinyl acetal is 30 parts by weight, and a preferable upper limit is 90 parts by weight. When the content of the plasticizer is 30 parts by weight or more, the melt viscosity of the laminated glass interlayer film is lowered, and the degassing property when the laminated glass is produced using this laminated glass interlayer film is increased. When the content of the plasticizer is 90 parts by weight or less, the transparency of the interlayer film for laminated glass increases. The minimum with more preferable content of the said plasticizer is 35 weight part, a more preferable upper limit is 70 weight part, and a still more preferable upper limit is 63 weight part.
In addition, when content of the said plasticizer shall be 55 weight part or more, the sound insulation excellent in this resin layer can be provided.
The content of the plasticizer may be the same or different between the first resin layer and the second resin layer.

The resin layer preferably contains an adhesive strength modifier. By containing the adhesive strength adjusting agent, the adhesive strength to glass can be adjusted, and a laminated glass excellent in penetration resistance can be obtained.
As said adhesive force regulator, at least 1 sort (s) selected from the group which consists of an alkali metal salt, alkaline-earth metal salt, and magnesium salt, for example is used suitably. As said adhesive force regulator, salts, such as potassium, sodium, magnesium, are mentioned, for example.
Examples of the acid constituting the salt include organic acids of carboxylic acids such as octylic acid, hexylic acid, 2-ethylbutyric acid, butyric acid, acetic acid, formic acid, and inorganic acids such as hydrochloric acid and nitric acid.

When heat shielding properties are required for the interlayer film for laminated glass of the present invention, the resin layer may contain a heat ray absorbent.
Although the said heat ray absorber is not specifically limited if it has the performance which shields infrared rays, A cesium dope tungsten oxide (CWO) particle | grain, a tin dope indium oxide (ITO) particle | grain, an antimony dope tin oxide (ATO) particle | grain, an aluminum dope zinc oxide At least one selected from the group consisting of (AZO) particles, indium-doped zinc oxide (IZO) particles, tin-doped zinc oxide particles, silicon-doped zinc oxide particles, lanthanum hexaboride particles and cerium hexaboride particles is preferred. .

If necessary, the resin layer may be a modified silicone oil, a flame retardant, an antistatic agent, a moisture resistant agent, a heat ray reflective agent, a heat ray absorbent, an anti-UV shielding agent, an antioxidant, a light stabilizer, or an adhesive strength modifier. You may contain conventionally well-known additives, such as a coloring agent which consists of a blocking agent, a pigment, or dye.

The thickness of the resin layer (thickness of one resin layer) is not particularly limited, but a preferable lower limit is 100 μm and a preferable upper limit is 1000 μm. When the thickness of the resin layer is within this range, sufficient durability can be obtained, and basic qualities such as transparency and anti-penetration of the obtained laminated glass are satisfied. A more preferable lower limit of the thickness of the resin layer is 380 μm, and a more preferable upper limit is 900 μm.
When two or more resin layers are present, the preferable lower limit of the total thickness of all the resin layers is 200 μm, and the preferable upper limit is 2000 μm. By setting the total thickness of all the resin layers within this range, sufficient durability can be obtained, and basic qualities such as transparency and penetrability of the obtained laminated glass are satisfied. The more preferable lower limit of the total thickness of all the resin layers is 500 μm, the more preferable upper limit is 1800 μm, the still more preferable lower limit is 760 μm, and the still more preferable upper limit is 1200 μm.

Since the interlayer film for laminated glass of the present invention has the conductive layer having the above-described configuration, both high heat generation performance capable of melting frost and ice attached to the glass and high transparency can be achieved. That is, a laminated glass in which an interlayer film for laminated glass is laminated between a pair of clear glasses having a thickness of 2.5 mm, which was difficult with a conventional interlayer film for laminated glass having a heat generation function, was measured by a method based on JIS R 3208. It can be achieved that the visible light transmittance is 70% or more.

In FIG. 1, the schematic diagram which shows an example of the cross section of the thickness direction of the intermediate film for laminated glasses of this invention was shown.
In FIG. 1, an interlayer film 1 for laminated glass includes a conductive layer 2 formed on a substrate 3, a first resin layer 4 laminated on one surface side of the conductive layer 2, and the conductive layer 2. It consists of the 2nd resin layer 5 laminated | stacked on the other surface side. The conductive layer 2 further comprises a laminate in which a zinc oxide layer 21 and a silver layer 22 are laminated in this order.

The interlayer film for laminated glass of the present invention may have a wedge-shaped cross section. If the cross-sectional shape of the interlayer film for laminated glass is wedge-shaped, by adjusting the wedge angle θ of the wedge-shaped according to the mounting angle of the laminated glass, the driver can simultaneously view the front field of view and instrument display without lowering the line of sight. Generation of a double image or a ghost image can be prevented when used in a head-up display that can be visually recognized. From the viewpoint of further suppressing double images, the preferable lower limit of the wedge angle θ is 0.1 mrad, the more preferable lower limit is 0.2 mrad, the still more preferable lower limit is 0.3 mrad, the preferable upper limit is 1 mrad, and the more preferable upper limit is 0.9 mrad.
For example, when an interlayer film for laminated glass having a wedge-shaped cross section is manufactured by a method of extruding a resin composition using an extruder, a slightly inner region (specifically, from one end on the thin side) , Where X is the distance between one end and the other end, and has a minimum thickness in the range from 0X to 0.2X inward from one end on the thin side, and one end on the thick side The maximum thickness in a slightly inner region (specifically, a region having a distance of 0X to 0.2X inward from one end on the thick side when the distance between one end and the other end is X) It may become the shape which has. In the present specification, such a shape is also included in the wedge shape. The distance X between the one end and the other end of the interlayer film for laminated glass is preferably 3 m or less, more preferably 2 m or less, particularly preferably 1.5 m or less, preferably 0.5 m or more, more preferably 0.8 m or more, particularly preferably 1 m or more.

When the cross-sectional shape of the interlayer film for laminated glass of the present invention is a wedge shape, for example, the thickness of the heat generating layer is set within a certain range, and the shape of the first resin layer and / or the second resin layer is adjusted. Thereby, it can adjust so that the cross-sectional shape as the whole intermediate film for laminated glasses may become a wedge shape which is a fixed wedge angle.

The method for producing the interlayer film for laminated glass of the present invention is not particularly limited, but a method of thermocompression bonding a laminate in which the first resin layer, the conductive layer, and the second resin layer are laminated in this order is preferable. It is. Among them, each layer was unwound from a rolled body and laminated, and the obtained laminated body was thermocompression bonded through a heated press roll to obtain an interlayer film for laminated glass, and then obtained. A so-called roll-to-roll method in which the interlayer film for laminated glass is wound into a roll shape is suitable.

The laminated glass in which the interlayer film for laminated glass of the present invention is laminated between a pair of glass plates is also one aspect of the present invention.
The said glass plate can use the transparent plate glass generally used. Examples thereof include inorganic glass such as float plate glass, polished plate glass, template glass, netted glass, wire-containing plate glass, colored plate glass, heat ray absorbing glass, heat ray reflecting glass, and green glass. Further, an ultraviolet shielding glass having an ultraviolet shielding coating layer on the glass surface can also be used. Furthermore, organic plastics plates such as polyethylene terephthalate, polycarbonate, and polyacrylate can also be used.
Two or more types of glass plates may be used as the glass plate. For example, the laminated glass which laminated | stacked the intermediate film for laminated glasses of this invention between transparent float plate glass and colored glass plates like green glass is mentioned. Moreover, you may use the glass plate from which 2 or more types of thickness differs as said glass plate.
It does not specifically limit as a manufacturing method of the laminated glass of this invention, A conventionally well-known manufacturing method can be used.

The laminated glass system provided with the laminated glass of this invention and the voltage supply part for applying a voltage to the conductive layer of the intermediate film for laminated glasses in this laminated glass is also one of this invention.

According to the present invention, an interlayer film for laminated glass that achieves both high heat generation performance and high transparency capable of melting frost and ice adhering to glass, laminated glass using the interlayer film for laminated glass, and the A laminated glass system can be provided.

It is a schematic diagram which shows an example of the cross section of the thickness direction of the intermediate film for laminated glasses of this invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Preparation of conductive layer A film having a thickness of 50 μm made of polyethylene terephthalate (PET) was used as a base material.
Sputtering was performed on the base material using zinc as a target. Sputtering power is medium wave (MF) 1500 W, argon gas is used as atmosphere gas, gas flow rate is 225 sccm, oxygen gas gas flow rate is 26 sccm, sputtering pressure is 0.170 Pa, and a 35 nm thick zinc oxide layer is formed of zinc oxide. did.
Next, sputtering was performed on the zinc oxide layer with a target of silver. The sputtering power was direct current (DC) 1150 W, the atmosphere gas was argon, the gas flow rate was 225 sccm, the sputtering pressure was 0.28 Pa, and a silver layer having a thickness of 15 nm was formed of silver.

Except for changing the thickness of each layer to be sputtered, the conditions for sputtering the zinc oxide layer and the silver layer are the same as those described above, and the same method is repeated, so that the zinc oxide layer ( A conductive layer in which 35 nm) / silver layer (15 nm) / zinc oxide layer (90 nm) / silver layer (15 nm) / zinc oxide layer (35 nm) were laminated in this order was formed.
The surface resistivity of the obtained conductive layer was 2.0Ω / □.

(2) Preparation of resin layer Polyethylene butyral (content of hydroxyl group: 30 mol%, degree of acetylation: 1 mol%, degree of butyralization: 69 mol%, average degree of polymerization: 1700) per 100 parts by weight of triethylene glycol diethylene as a plasticizer 2-ethylhexanoate (3GO) 40 parts by weight and 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF Corporation) as an ultraviolet shielding agent Tinuvin 326 ") 0.5 parts by weight and 2,6-di-t-butyl-p-cresol (BHT) 0.5 parts by weight as an antioxidant were added. This was sufficiently kneaded with a mixing roll to obtain a composition. The obtained composition was extruded by an extruder to obtain a single layer resin film having a thickness of 380 μm made of polyvinyl butyral (PVB1).

(3) Manufacture of laminated glass interlayer film and laminated glass A base material on which a conductive layer is formed is sandwiched between two obtained resin layers, and the first resin layer / conductive layer / base material / An interlayer film for laminated glass having a laminated structure of the second resin layer was produced. Thermocompression bonding is performed using a thermocompression laminator (“MCK Model Y” manufactured by MCK Corporation) under the conditions of a heating temperature of 75 ° C., a linear pressure of 1.0 kN during crimping, and a tension of 20 N during conveyance. The two-roll method was used. For thermocompression bonding, a laminate roll in which the upper and lower rolls are both made of rubber was used.
The obtained interlayer film for laminated glass was cut into a size of 320 mm long × 300 mm wide and sandwiched between two transparent clear glasses (length 300 mm × width 300 mm × thickness 2.5 mm) to obtain a laminate. At that time, the interlayer film for laminated glass protruded by 10 mm from the edge of the float glass. The first resin layer of the interlayer film for laminated glass protruding from the glass was cut out to expose the heat generating layer. A single-sided copper foil tape (STS-CU42S (manufactured by Sekisui Techno Corporation West Japan)) is attached as an electrode so that the exposed heat generation layer and the copper foil of the copper foil tape are in contact with each other, and a heat resistant tape (Niftron 973UL-S (Nitto Denko) )). The obtained laminated body was temporarily press-bonded using a 230 ° C. heating roll. Then, the laminated body temporarily crimped | bonded for 20 minutes on the conditions of 135 degreeC and the pressure of 1.2 MPa using the autoclave by the heating roll method, and the laminated glass was manufactured. Then, the heat-resistant tape was removed, and the copper foil tape was fixed by attaching a turn clip from above the single-sided copper foil tape.

(Examples 2-5, Comparative Examples 1-3)
An interlayer film for laminated glass and laminated glass were produced in the same manner as in Example 1 except that the configuration of the conductive layer was as shown in Table 1.
Table 1 shows the stacking order of each layer.
In Table 1, “TiO ₂ ” means titanium oxide, the target is titanium, the sputtering power is medium wave (MF) 1500 W, the atmosphere gas is argon gas with a gas flow rate of 225 sccm, and oxygen gas with a gas flow rate of 58 sccm, during sputtering. It was formed by sputtering under conditions where the pressure was 0.177 Pa.
In Table 1, “ZnO.Ti” means a mixture containing 10% by weight of titanium oxide (TiO ₂ ) in zinc oxide, the target is ZnO—Ti, the sputtering power is medium wave (MF) 1500 W, As the atmosphere gas, argon gas was formed by sputtering under the conditions of a gas flow rate of 225 sccm, an oxygen gas flow rate of 18 sccm, and a sputtering pressure of 0.165 Pa.
Furthermore, in Table 1, “Ag · Pd” means a silver-palladium alloy containing 1% by weight of palladium, the target is Ag—Pd, the sputtering power is direct current (DC) 1100 W, the atmospheric gas is argon, gas It was formed by sputtering under the conditions of a flow rate of 225 sccm and a sputtering pressure of 0.28 Pa.

(Evaluation)
About the laminated glass obtained by the Example and the comparative example, it evaluated by the following method.
The results are shown in Table 1.

(1) Evaluation of visible light transmittance The visible light transmittance of the obtained laminated glass was measured by a method based on JIS R 3208 using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech).

(2) Evaluation of heat generation performance Alligator cable and DC power supply device PWR800L (manufactured by KIKUSUI) were connected, a voltage of 14V was applied for 7 minutes under an atmosphere of 25 ° C, and after 7 minutes using a contact thermometer The heat generation temperature (surface temperature) at the center of the laminated glass surface was measured, and the heat generation performance was evaluated according to the following criteria.
○: Heat generation temperature is 45 ° C or more ×: Heat generation temperature is less than 45 ° C

According to the present invention, an interlayer film for laminated glass that achieves both high heat generation performance and high transparency capable of melting frost and ice adhering to glass, laminated glass using the interlayer film for laminated glass, and the A laminated glass system can be provided.

DESCRIPTION OF SYMBOLS 1 Intermediate film 2 for laminated glass Conductive layer 21 Zinc oxide layer 22 Silver layer 3 Base material 4 1st resin layer 5 2nd resin layer

Claims (9)

A conductive layer comprising a laminate of a zinc oxide layer containing zinc oxide and a silver layer containing silver, a silver alloy or a silver compound directly formed on the zinc oxide layer. Intermediate film for glass. The interlayer film for laminated glass according to claim 1, wherein one silver layer is sandwiched between two zinc oxide layers. The interlayer film for laminated glass according to claim 1 or 2, wherein the zinc oxide layer has a thickness of 2 to 150 nm. The interlayer film for laminated glass according to claim 1, 2 or 3, further comprising a metal oxide layer containing a metal oxide having a refractive index of 1.5 or more. The interlayer film for laminated glass according to claim 4, wherein the metal oxide having a refractive index of 1.5 or more is titanium oxide. The interlayer film for laminated glass according to claim 1, 2, 3, 4, or 5, wherein a resin layer is provided on one surface or both surfaces of the conductive layer. The visible light transmittance measured by a method in accordance with JIS R 3208 for a laminated glass in which an interlayer film for laminated glass is laminated between a pair of clear glasses having a thickness of 2.5 mm is 70% or more. The interlayer film for laminated glass according to 2, 3, 4, 5 or 6. A laminated glass, wherein the interlayer film for laminated glass according to claim 1, 2, 3, 4, 5, 6, or 7 is laminated between a pair of glass plates. A laminated glass system comprising: the laminated glass according to claim 8; and a voltage supply unit for applying a voltage to the conductive layer of the interlayer film for laminated glass in the laminated glass.

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