Patent Application
20210046740
The present invention relates to an interlayer film for laminated glass which is used for obtaining laminated glass. Moreover, the present invention relates to a laminated glass prepared with the interlayer film for laminated glass.
Since laminated glass generates only a small amount of scattering glass fragments even when subjected to external impact and broken, laminated glass is excellent in safety. As such, the laminated glass is widely used for automobiles, railway vehicles, aircraft, ships, buildings and the like. The laminated glass is produced by sandwiching an interlayer film for laminated glass between two glass plates.
As one example of the interlayer film for laminated glass, the following Patent Document 1 discloses an interlayer film having a sound insulating layer formed of composition (A) containing at least one resin (a1) selected from a thermoplastic resin and a thermosetting resin. Tan δ that is obtained when the dynamic viscoelasticity of the sheet formed of the aforementioned composition to have a thickness of 0.8 mm is measured at a frequency of 0.3 Hz in a tensile mode has the maximum value at temperature TA (° C.). In the measurement of the dynamic viscoelasticity, TA (° C.) ranges from −50 to 50° C., and tan δ at TA (° C.) is 2.5 or more.
Patent Document 1 indicates polyvinyl acetal, polyvinyl alcohol, polyurethane, polyvinyl carboxylate, olefin-vinyl carbonate copolymer, polyurethane elastomer, polyester elastomer, styrene-diene block copolymer, and chlorinated polyolefin, as the thermoplastic resin. Patent Document 1 indicates epoxy resins, phenol resins, urethane resins, melamine resins, and unsaturated polyester resins as the thermosetting resin.
Also, Patent Document 1 indicates that the sound insulating property of the interlayer film is enhanced. In Examples of Patent Document 1, as measurement results of sound transmission loss at temperatures of 0° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C. and 40° C., the temperature at which the mean value of the sound transmission loss is the largest, and the sound transmission loss at the temperature at which the mean value of the sound transmission loss is the largest (mean value at a plurality of frequencies) are indicated.
The following Patent Document 2 discloses a film (interlayer film) having a structure of PVB/PET/acrylate/PET/PVB.
Patent Document 1: WO2017/170259A1
Patent Document 2: JP H10-177390A
A laminated glass including an interlayer film is used in various temperature environments. In a laminated glass prepared with a conventional interlayer film, it is sometimes the case that the sound insulating property cannot be enhanced over a wide range of temperature. A laminated glass having high sound insulating property at a specific one temperature can have low sound insulating property when the laminated glass is used at a temperature different from the specific one temperature.
Also, Patent Document 1 indicates that the sound insulating property of the interlayer film is enhanced. While Patent Document 1 evaluates the sound transmission loss at temperatures of 0° C., 5° C., 10° C., 15° C., 20° C., 25° C., 30° C., 35° C. and 40° C., it lacks description of results of sound transmission loss at every temperature of the plurality of temperatures. Patent Document 1 fails to indicate enhancement of the sound insulating property over a wide range of temperature by Examples.
The present invention is aimed at providing an interlayer film for laminated glass capable of enhancing the sound insulating property over a wide temperature range with width of at least 15° C. in a temperature region from 10° C. to 30° C. Moreover, the present invention is also aimed at providing laminated glass prepared with the interlayer film for laminated glass.
According to a broad aspect of the present invention, there is provided an interlayer film for laminated glass (hereinafter, also referred to as an interlayer film) having a two or more-layer structure, the interlayer film including a resin layer, the resin layer having a glass transition temperature of −10° C. or more and 0° C. or less, tan δ at the glass transition temperature of the resin layer being 2.5 or more, storage modulus G′ at −5° C. of the resin layer being 3.0×104 Pa or more and 5.0×106 Pa or less.
In a specific aspect of the interlayer film according to the present invention, the resin layer is a layer containing a cured product or a polyolefin resin, and the cured product is a cured product of a photocurable compound or a moisture-curable compound. The resin layer is a layer containing a cured product or a polyolefin resin, and the cured product may be a cured product of a curable compound having a (meth)acryloyl group.
In a specific aspect of the interlayer film according to the present invention, the cured product is a cured product of a photocurable compound.
In a specific aspect of the interlayer film according to the present invention, the resin layer contains a plasticizer.
In a specific aspect of the interlayer film according to the present invention, the resin layer is a layer other than a surface layer in the interlayer film.
In a specific aspect of the interlayer film according to the present invention, the interlayer film includes a layer containing a resin that is different from both of the cured product and the polyolefin resin.
In a specific aspect of the interlayer film according to the present invention, the interlayer film includes a layer containing a polyester resin as the layer containing a resin that is different from both of the cured product and the polyolefin resin.
In a specific aspect of the interlayer film according to the present invention, the interlayer film includes a layer containing a polyvinyl acetal resin as the layer containing a resin that is different from both of the cured product and the polyolefin resin.
In a specific aspect of the interlayer film according to the present invention, the interlayer film includes a layer containing a polyester resin and a layer containing a polyvinyl acetal resin, as the layers containing a resin that is different from both of the cured product and the polyolefin resin.
In a specific aspect of the interlayer film according to the present invention, a content of a plasticizer per 100 parts by weight of the cured product or 100 parts by weight of the polyolefin resin in the layer containing a cured product or a polyolefin resin is smaller than a content of a plasticizer per 100 parts by weight of the polyvinyl acetal resin in the layer containing a polyvinyl acetal resin.
According to a broad aspect of the present invention, there is provided a laminated glass including a first lamination glass member, a second lamination glass member, and the above-described interlayer film for laminated glass, the interlayer film for laminated glass being arranged between the first lamination glass member and the second lamination glass member.
The interlayer film for laminated glass according to the present invention has a two or more-layer structure. The interlayer film for laminated glass according to the present invention includes a resin layer. In the interlayer film for laminated glass according to the present invention, the resin layer has a glass transition temperature of −10° C. or more and 0° C. or less, and tan δ at the glass transition temperature of the resin layer is 2.5 or more. In the interlayer film for laminated glass according to the present invention, storage modulus G′ at −5° C. of the resin layer is 3.0×104 Pa or more and 5.0×106 Pa or less. In the interlayer film for laminated glass according to the present invention, since the aforementioned configuration is provided, it is possible to enhance the sound insulating property over a wide temperature range with width of at least 15° C. in a temperature region from 10° C. to 30° C.
Hereinafter, the present invention will be described in detail.
The interlayer film for laminated glass according to the present invention (hereinafter, also referred to as an interlayer film) has a two or more-layer structure.
The interlayer film according to the present invention includes a resin layer. The kind of the resin in the resin layer is not particularly limited. Resins that are preferred as the resin in the resin layer will be described later.
In the interlayer film according to the present invention, the resin layer has a glass transition temperature of −10° C. or more and 0° C. or less, and tan δ at the glass transition temperature of the resin layer is 2.5 or more. In the interlayer film according to the present invention, storage modulus G′ at −5° C. of the resin layer is 3.0×104 Pa or more and 5.0×106 Pa or less.
In the interlayer film according to the present invention, since the aforementioned configuration is provided, it is possible to enhance the sound insulating property over a wide temperature range with width of at least 15° C. in a temperature region from 10° C. to 30° C. For example, it is possible to enhance the sound insulating property over a temperature region from 10° C. to 25° C. or over a temperature region from 15° C. to 30° C. Further, in the interlayer film according to the present invention, it is possible to enhance the sound insulating property over the entire temperature region from 10° C. to 30° C. Therefore, it is possible to exert high sound insulating property even when a laminated glass prepared with the interlayer film is used in various temperature environments.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the glass transition temperature of the resin layer be −7° C. or more. From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the glass transition temperature of the resin layer be −2° C. or less.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, tan δ at the glass transition temperature of the resin layer is preferably 2.8 or more, more preferably 3.0 or more. The upper limit of tan δ at the glass transition temperature is not limited. The tan δ may be 6.0 or less.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, storage modulus G′ at −5° C. of the resin layer is preferably 5.0×104 Pa or more, and more preferably 1.0×105 Pa or more. From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, storage modulus G′ at −5° C. of the resin layer is preferably 3.0×106 Pa or less, more preferably 1.0×106 Pa or less, and further preferably 9.0×105 Pa or less.
From the viewpoint of effectively enhancing the sound insulating property, it is preferred that the resin layer be a layer containing a cured product or a polyolefin resin. The resin layer may be a layer containing a cured product, or may be a layer containing a polyolefin resin. From the viewpoint of effectively enhancing the sound insulating property, it is preferred that the cured product be a cured product of a photocurable compound or a moisture-curable compound. From the viewpoint of effectively enhancing the sound insulating property, it is preferred that the cured product be a cured product of a curable compound having a (meth)acryloyl group. From the viewpoint of effectively enhancing the sound insulating property, the interlayer film according to the present invention may include a layer containing a resin that is different from both of the cured product and the polyolefin resin (hereinafter, also referred to as a layer containing a resin).
In the interlayer film according to the present invention, the curable compound may be a photocurable compound or a moisture-curable compound, or may be a curable compound having a (meth)acryloyl group. The curable compound having a (meth)acryloyl group may be a photocurable compound or may be a moisture-curable compound, or may be a curable compound that is different from both the photocurable compound and the moisture-curable compound. In general, since a curable compound having a (meth)acryloyl group has a (meth)acryloyl group, the compound cures by irradiation with light.
The glass transition temperature, the tan δ, and the storage modulus G′ are measured by viscoelasticity measurement. The viscoelasticity measurement is specifically conducted in the following manner.
The test piece is stored for 12 hours in an environment of 23±2° C. temperature, 25±5% humidity. Then, viscoelasticity was measured using a viscoelasticity measuring device “ARES-G2” available from TA Instruments. A parallel plate with a diameter of 8 mm is used as a jig, and the measurement is performed in a shearing mode under the condition in which the temperature is decreased from 100° C. to −20° C. at a temperature decreasing rate of 3° C./minute and under the condition of a frequency of 1 Hz and a strain of 1%.
The viscoelasticity measurement may be conducted using an interlayer film itself. In this case, a peak of tan δ derived from the resin layer, or a peak of tan δ derived from the layer containing a resin may be read. For an interlayer film having a two or more-layer structure, the layers may be delaminated, and the glass transition temperature of the layer to be measured may be measured. In the case of a laminated glass, after cooling the laminated glass with liquid nitrogen or the like, the lamination glass member and the interlayer film are delaminated, and the viscoelasticity measurement may be conducted using the delaminated interlayer film.
For example, when the thickness of the resin layer is 0.5 mm or more and 2 mm or less, it is possible to easily measure the viscoelasticity by directly using the resin layer as a test piece. When the thickness of the resin layer is less than 0.5 mm, the viscoelasticity may be measured using a test piece having a thickness of 0.5 mm or more and 2 mm or less by stacking a plurality of the resin layers, or separately preparing a resin layer in which only the thickness is adjusted. When the thickness of the resin layer is more than 2 mm, the viscoelasticity may be measured using a test piece having a thickness of 0.5 mm or more and 2 mm or less by slicing the resin layer, or separately preparing a resin layer in which only the thickness is adjusted.
From the viewpoint of enhancing the uniformity of curing of the layer containing a cured product and further enhancing the sound insulating property over a wide range of temperature, the curable compound is preferably a photocurable compound, and preferably a curable compound having a (meth)acryloyl group. From the viewpoint of enhancing the uniformity of curing of the layer containing a cured product and further enhancing the sound insulating property over a wide range of temperature, the cured product is preferably a (meth)acrylic polymer.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the interlayer film include a layer containing a resin that is different from both of the cured product and the polyolefin resin (layer containing a resin). It is preferred that the resin contained in the layer containing a resin be a cured product of a thermosetting compound or a thermoplastic resin. When the resin is a cured product of a curable compound, it is preferred that the curable compound be a thermosetting compound.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the interlayer film include a layer containing a polyester resin as the layer containing a resin that is different from both of the cured product and the polyolefin resin. From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the polyester resin be polyethylene terephthalate. In particular, when the interlayer film contains a plasticizer, migration of the plasticizer is effectively prevented by the use of the layer containing a polyester resin, so that high sound insulating property can be stably exerted.
When degassing is insufficient at the time of preparation of a laminated glass, foaming can occur. From the viewpoint of suppressing foaming, it is preferred that the interlayer film include a layer containing a polyester resin as the layer containing a resin that is different from both of the cured product and the polyolefin resin. From the viewpoint of further suppressing foaming, it is preferred that the polyester resin be polyethylene terephthalate. Use of the layer containing a polyester resin effectively suppresses diffusion of the air, so that high foaming suppressing performance can be exerted.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is preferred that the interlayer film include a layer containing a polyvinyl acetal resin as the layer containing a resin that is different from both of the cured product and the polyolefin resin.
From the viewpoint of further enhancing the sound insulating property over a wide range of temperature, it is more preferred that the interlayer film include a layer containing a polyester resin and a layer containing a polyvinyl acetal resin, as the layers containing a resin that is different from both of the cured product and the polyolefin resin.
The interlayer film according to the present invention may have a two-layer structure, a two or more-layer structure, a three-layer structure, a three or more-layer structure, a four-layer structure, a four or more-layer structure, a five-layer structure, or a five or more-layer structure.
The interlayer film according to the present invention may include, a first layer, and a second layer arranged on a first surface side of the first layer. In this case, it is preferred that the first layer be the layer containing a cured product or a polyolefin resin.
From the viewpoint of effectively enhancing the sound insulating property and adhesivity between layers, the interlayer film according to the present invention may include a first layer, and a second layer arranged on a first surface side of the first layer, and may further include a third layer arranged on a second surface side opposite to the first surface side of the first layer. In this case, it is preferred that the first layer be the resin layer, and be the layer containing a cured product or a polyolefin resin.
From the viewpoint of effectively enhancing the sound insulating property and adhesivity between layers, the interlayer film according to the present invention may further include a fourth layer arranged on a side opposite to the first layer side of the second layer, and may further include a fifth layer arranged on a side opposite to the first layer side of the third layer. In this case, it is preferred that the first layer, the second layer or the third layer be the resin layer, and be the layer containing a cured product or a polyolefin resin. It is more preferred that the first layer be the resin layer, and it is more preferred that the first layer be the layer containing a cured product or a polyolefin resin.
From the viewpoint of effectively enhancing the sound insulating property and adhesivity between the interlayer film and the glass plates, it is preferred that the resin layer be not a surface layer in the interlayer film, and it is preferred that the resin layer be an intermediate layer in the interlayer film. It is to be noted that the resin layer may be a surface layer in the interlayer film. From the viewpoint of effectively enhancing the sound insulating property and adhesivity between the interlayer film and glass plates, it is preferred that the layer containing a cured product or a polyolefin resin be not a surface layer in the interlayer film, and be an intermediate layer in the interlayer film. It is to be noted that the layer containing a cured product or a polyolefin resin may be a surface layer in the interlayer film.
From the viewpoint of enhancing the transparency of the laminated glass, the visible light transmittance of the interlayer film is preferably 70% or more, more preferably 80% or more, further preferably 85% or more.
The visible light transmittance is measured at a wavelength ranging from 380 to 780 nm by using a spectrophotometer (“U-4100” available from Hitachi High-Tech Corporation) in conformity with JIS R3211:1998.
The visible light transmittance of the interlayer film may be measured while the interlayer film is arranged between two sheets of clear glass. It is preferred that the clear glass have a thickness of 2.0 mm.
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
An interlayer film 11 shown in
In the interlayer film 11, it is preferred that the first layer 1 be the resin layer, and be the layer containing a cured product or a polyolefin resin. The second layer 2 may be the resin layer, or may be the layer containing a cured product or a polyolefin resin. The third layer 3 may be the resin layer, or may be the layer containing a cured product or a polyolefin resin.
In this connection, other layers may be arranged between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively. It is preferred that the second layer 2 and the first layer 1, and the first layer 1 and the third layer 3 be directly layered. As the other layer, an adhesive layer can be recited.
An interlayer film 11A shown in
In the interlayer film 11A, it is preferred that the first layer 1A, the second layer 2A or the third layer 3A be the resin layer, and be the layer containing a cured product or a polyolefin resin, and it is more preferred that the first layer 1A be the resin layer, and be the layer containing a cured product or a polyolefin resin. The fourth layer 4A may be the resin layer, or may be the layer containing a cured product or a polyolefin resin. The fifth layer 5A may be the resin layer, or may be the layer containing a cured product or a polyolefin resin.
Between the fourth layer 4A and the second layer 2A, between the second layer 2A and the first layer 1A, between the first layer 1A and the third layer 3A, and between the third layer 3A and the fifth layer 5A, respectively, other layer may be arranged. It is preferred that the fourth layer 4A and the second layer 2A, the second layer 2A and the first layer 1A, the first layer 1A and the third layer 3A, and the third layer 3A and the fifth layer 5A, respectively be layered directly. As the other layer, an adhesive layer can be recited.
Hereinafter, the details of the interlayer film according to the present invention, the resin layer, the layer containing a cured product or a polyolefin resin, the layer containing a resin, the first layer, the second layer, the third layer, the fourth layer, and the fifth layer, and the details of ingredients used in the interlayer film will be described.
The interlayer film includes a resin layer.
The resin layer contains a resin. Examples of the resin include a cured resin (cured product), a polyolefin resin, a vinyl acetate resin, an ethylene-vinyl acetate resin, a polyester resin, modified resins of these resins, and the like. The cured resin is a cured product of a curable compound. Examples of the curable compound include a photocurable compound, a moisture-curable compound, a thermosetting compound, and the like. The resin may be a cured product of a photocurable compound or a moisture-curable compound. The cured product of a photocurable compound or a moisture-curable compound can be a thermoplastic resin. Thermoplastic resins other than these may be used.
It is preferred that the interlayer film include a layer containing a resin that is different from both of the cured product and the polyolefin resin.
Examples of the resin include cured products of thermosetting compounds, thermoplastic resins, and the like. Examples of the thermoplastic resin include a polyvinyl acetal resin, a polyester resin, an aliphatic polyolefin, polystyrene, an ethylene-vinyl acetate copolymer resin, an ethylene-acrylic acid copolymer resin, a polyurethane resin, an ionomer resin, a polyvinyl alcohol resin, a polyvinyl acetate resin, and the like. Thermoplastic resins other than these may be used. The polyoxymethylene (or polyacetal) resin is included in the polyvinyl acetal resin. Thermoplastic resins other than these may be used. The thermoplastic resin may be a thermoplastic elastomer.
The thermoplastic resin means a resin that softens and exhibits plasticity when it is heated, and hardens when it is cooled to room temperature. Among the thermoplastic resins, especially the thermoplastic elastomer means a resin that softens and exhibits plasticity when it is heated, and hardens to exhibits rubber elasticity when it is cooled to room temperature (25° C.)
The thermoplastic resins exemplified above can be a thermoplastic elastomer by adjusting the molecular structure, the polymerization degree and the like of the resin.
It is preferred that the surface layer in the interlayer film contain a thermoplastic resin. It is preferred that each of the second layer and the third layer in the interlayer film having a second layer/first layer/third layer structure contain a thermoplastic resin. It is preferred that each of the fourth layer and the fifth layer in the interlayer film having a fourth layer/second layer/first layer/third layer/fifth layer structure contain a thermoplastic resin.
It is preferred that each of the second layer and the third layer in the interlayer film having a fourth layer/second layer/first layer/third layer/fifth layer structure contain a thermoplastic resin.
The photocurable compound or the moisture-curable compound is preferably a curable compound having a (meth)acryloyl group, and is more preferably a (meth)acrylic polymer. The resin is preferably a curable compound having a (meth)acryloyl group, and is more preferably a (meth)acrylic polymer.
It is preferred that the (meth)acrylic polymer be a polymer of a polymerizable composition containing a curable compound having a (meth)acryloyl group. The polymerizable composition contains a polymerizable component. In order to effectively form the cured product in the layer containing the cured product, the polymerizable composition may contain a photoreaction initiator. The polymerizable composition may contain an auxiliary for accelerating the curing reaction together with the photoreaction initiator. Representatives of the curable compound having a (meth)acryloyl group include (meth)acrylic ester. It is preferred that the (meth)acrylic polymer be a poly(meth)acrylic ester.
For effectively obtaining the effect of the present invention, it is preferred that the polymerizable component include a (meth)acrylic ester having a cyclic ether structure, a (meth)acrylic ester having an aromatic ring, a (meth)acrylic ester having a polar group, or an acyclic (meth)acrylic ester having 6 or less carbon atoms in the side chain. By using such a preferred (meth)acrylic ester, it is possible to enhance both the sound insulating property and the ability to prevent foaming in good balance.
Examples of the (meth)acrylic ester having a cyclic ether structure include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, 5-hydroxypentyl (meth)acrylate glycidyl, 6-hydroxyhexyl (meth)acrylate glycidyl ether; (3-methyloxetan-3-yl)methyl (meth) acrylate, (3-propyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, (3-butyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)ethyl (meth)acrylate, (3-ethyloxetan-3-yl)propyl (meth) acrylate, (3-ethyloxetan-3-yl)butyl (meth)acrylate, (3-ethyloxetan-3-yl)pentyl (meth)acrylate, (3-ethyloxetan-3-yl)hexyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-methyl-2-isobutyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-cyclohexyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, tetrahydrofurfuryl alcohol acrylic acid multimer ester; tetrahydro-2H-pyran-2-yl-(meth)acrylate, 2-{1-[(tetrahydro-2H-pyran-2-yl)oxy]-2-methylpropyl}(meth)acrylate, cyclic trimethylol propane formal acrylate, (meth)acryloyl morpholine, and the like. From the viewpoint of effectively obtaining the effect of the present invention, tetrahydrofurfuryl (meth)acrylate, or cyclic trimethylol propane formal acrylate is especially preferred.
Examples of the (meth)acrylic ester having an aromatic ring include benzyl acrylate, phenoxypolyethyleneglycol acrylate, and the like.
Examples of the (meth)acrylic ester having a polar group include (meth)acrylic esters having a hydroxyl group, an amide group, an amino group, an isocyanate group, a carboxyl group or the like as the polar group.
Examples of the (meth)acrylic ester having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and the like.
Examples of the (meth)acrylic ester having an amide group include N,N-dimethylaminopropyl (meth) acrylamide, N,N-dimethyl (meth)acrylamide, (meth)acryloyl morpholine, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth)acrylamide, and the like.
Examples of the (meth)acrylic ester having an amide group or an amino group include N-dialkylaminoalkyl (meth)acrylamide, N,N-dialkylaminoalkyl (meth)acrylamide, and the like.
Examples of the (meth)acrylic ester having an isocyanate group include triallylisocyanurate, derivatives thereof, and the like.
Examples of the (meth)acrylic ester having a carboxyl group include acrylic acid, o-carboxy-polycaprolactone monoacrylate, 2-acryloyloxyethylsuccinic acid, and the like.
The above-described (meth)acrylic ester may be a polycarboxylic ester having a (meth)acryloyl group. Examples of the polycarboxylic ester having a (meth)acryloyl group include 2-acryloyloxyethyl succinate, and the like.
From the viewpoint of effectively obtaining the effect of the present invention, a (meth)acrylic ester having a hydroxyl group is preferred, and 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or 4 hydroxybutyl (meth)acrylate is especially preferred.
Examples of the acyclic (meth)acrylic ester having 6 or less carbon atoms in the side chain include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and the like.
For effectively obtaining the effect of the present invention, it is preferred that the content of the acyclic (meth)acrylic ester having 8 or more carbon atoms in the side chain in 100% by weight of the polymerizable component be less than 20% by weight.
Examples of the (meth)acrylic ester include besides the compounds as recited above, diethyleneglycol monoethylether (meth)acrylate, isobornyl (meth)acrylate, 3-methoxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxypropylphthalate, 2-acryloyloxyethyl-2-hydroxylpropylphthalate, cyclohexyl (meth) acrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexane diol di(meth)acrylate, 1,9-nonane diol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2,2-bis[4-(acryloxyethoxy)phenyl]propane di(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(2-acryloyloxyethyl)phosphate, tetramethylol methane tri(meth)acrylate, tetramethylol propane tetra(meth)acrylate, derivatives thereof, and the like.
One kind of the (meth)acrylic ester may be used alone, and two or more kinds thereof may be used in combination. The above-described (meth)acrylic polymer may be a homopolymer of the above-described (meth)acrylic ester, or may be a copolymer of a polymerizable component containing the above-described (meth)acrylic ester.
Concrete examples of the photoreaction initiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzene methanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthon-9-one methochloride, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenylmethylium tetrakis(pentafluorophenyl) borate, and the like. Only one kind of the photoreaction initiator may be used, and two or more kinds thereof may be used in combination.
Examples of the auxiliary include triethanol amine, triisopropanol amine, 4,4′-dimethylaminobenzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethyl benzoate, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like. One kind of the auxiliary may be used alone and two or more kinds thereof may be used in combination.
It is preferred that the auxiliary be benzyldimethylketal, 1-hydroxycyclohexylphenyl ketone, benzoylisopropyl ether, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or triphenylmethylium tetrakis(pentafluorophenyl) borate.
In 100% by weight of the polymerizable composition, the content of the photoreaction initiator is preferably 0.01% by weight or more, more preferably 0.1% by weight or more and is preferably 10% by weight or less, more preferably 5% by weight or less. When the content of the photoreaction initiator is in the range from the above-described lower limit to the above-described upper limit, the photocurability and the storage stability further increase.
When the curable compound for forming the cured product in the layer containing a cured product is a photocurable compound such as a photocurable compound having a (meth)acryloyl group, it is preferred that a photocuring device such as an ultraviolet irradiation device be used to cure the photocurable compound. Examples of the ultraviolet irradiation device include a box-type ultraviolet irradiation device, a belt-conveyer-type ultraviolet irradiation device, and the like. Examples of the ultraviolet lamp installed in the ultraviolet irradiation device include a superhigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a chemical lamp, a metal halide lamp, an excimer lamp, a UV-LED, and the like. The ultraviolet lamp is preferably a chemical lamp or a UV-LED.
When the photocurable compound is irradiated with ultraviolet rays so as to obtain the cured product, the ultraviolet dose (cumulative dose) is preferably 500 mJ or more, more preferably 1000 mJ or more, further preferably 1500 mJ or more, and especially preferably 2000 mJ or more. The ultraviolet dose (cumulative dose) is preferably 20000 mJ or less, more preferably 10000 mJ or less, and further preferably 8000 mJ or less. When the ultraviolet dose (cumulative dose) is the above lower limit or more, it is possible to reduce the unreacted monomers. When the ultraviolet dose (cumulative dose) is the above upper limit or less, the storage stability of the resin increases. The irradiation intensity of the ultraviolet irradiation is preferably 0.1 mW or more, more preferably 0.5 mW or more, further preferably 1 mW or more, and especially preferably 2 mW or more.
It is preferred that the polyvinyl acetate be a polymer of a polymerizable composition containing vinyl acetate and a monomer having the above-described functional group because excellent effect of the present invention is achieved.
Examples of the monomer having the above-described functional group include 3-methyl-3-buten-1-ol, ethylene glycol monovinyl ether, isopropylacrylamide, and the like.
From the viewpoint of effectively enhancing the sound insulating property, the weight average molecular weight of the polyvinyl acetate is preferably 250000 or more, more preferably 300000 or more, further preferably 400000 or more, especially preferably 500000 or more. From the viewpoint of enhancing the interlayer adhesion, the weight average molecular weight of the polyvinyl acetate is preferably 1200000 or less, more preferably 900000 or less.
The weight average molecular weight refers to a weight average molecular weight, calculated on the polystyrene equivalent basis, measured by gel permeation chromatography (GPC).
The method for polymerizing the polymerizable composition to synthesize the polyvinyl acetate is not particularly limited. Examples of the synthesizing method include a solution polymerization, suspension polymerization, UV polymerization, and the like.
From the viewpoint of increasing the transparency of the interlayer film, and effectively enhancing the sound insulating property and the interlayer adhesion in the interlayer film having increased transparency, the synthesizing method of the polyvinyl acetate is preferably solution polymerization.
From the viewpoint of further enhancing the penetration resistance, it is preferred that the thermoplastic resin be a polyvinyl acetal resin, an ionomer resin or an ethylene-vinyl acetate copolymer resin. From the viewpoint of further enhancing the penetration resistance, it is more preferred that the thermoplastic resin be a polyvinyl acetal resin.
Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, and the like.
For example, the polyvinyl acetal resin can be produced by acetalizing polyvinyl alcohol (PVA) with an aldehyde. It is preferred that the polyvinyl acetal resin be an acetalized product of polyvinyl alcohol. For example, the polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol generally lies within the range of 70 to 99.9% by mole.
The average polymerization degree of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, further preferably 1600 or more, and is preferably 5000 or less, more preferably 4000 or less, further preferably 3500 or less, especially preferably 3000 or less. When the average polymerization degree is the above lower limit or more, the penetration resistance of laminated glass is further enhanced. When the average polymerization degree is the above upper limit or less, formation of an interlayer film is facilitated.
The average polymerization degree of the polyvinyl alcohol is determined by a method in accordance with JIS K6726 “Testing methods for polyvinyl alcohol”.
The number of carbon atoms of the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used at the time of producing the polyvinyl acetal resin is not particularly limited. It is preferred that the number of carbon atoms of the acetal group in the polyvinyl acetal resin fall within the range of 3 to 5 and it is more preferred that the number of carbon atoms of the acetal group be 3 or 4. When the number of carbon atoms of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the interlayer film is sufficiently lowered.
The aldehyde is not particularly limited. In general, an aldehyde with 1 to 10 carbon atoms is preferably used. Examples of the aldehyde with 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde, and the like. Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde, or n-valeraldehyde is preferred, propionaldehyde, n-butyraldehyde, or isobutyraldehyde is more preferred, and n-butyraldehyde is further preferred. One kind of the aldehyde may be used alone, and two or more kinds thereof may be used in combination.
The content of the hydroxyl group (the amount of hydroxyl groups) of the polyvinyl acetal resin is preferably 15% by mole or more, more preferably 18% by mole or more, and preferably 40% by mole or less, and more preferably 35% by mole or less. When the content of the hydroxyl group is the above lower limit or more, the adhesive force of the interlayer film is further enhanced. Moreover, when the content of the hydroxyl group is the above upper limit or less, the flexibility of the interlayer film is enhanced and the handling of the interlayer film is facilitated.
The content of the hydroxyl group of the polyvinyl acetal resin is a mole fraction, represented in percentage, obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain. For example, the amount of ethylene groups to which the hydroxyl group is bonded can be determined in conformity with JIS K6728 “Testing methods for polyvinyl butyral”.
The acetylation degree of the polyvinyl acetal resin is preferably 0.01% by mole or more, more preferably 0.5% by mole or more, and preferably 10% by mole or less, and more preferably 2% by mole or less. When the acetylation degree is the above lower limit or more, the compatibility between the polyvinyl acetal resin and a plasticizer is enhanced. When the acetylation degree is the above upper limit or less, with regard to the interlayer film and laminated glass, the moisture resistance thereof is enhanced.
The acetylation degree is a mole fraction, represented in percentage, obtained by dividing the amount of ethylene groups to which the acetyl group is bonded by the total amount of ethylene groups in the main chain. For example, the amount of ethylene groups to which the acetyl group is bonded can be determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”.
The acetalization degree of the polyvinyl acetal resin (the butyralization degree in the case of a polyvinyl butyral resin) is preferably 55% by mole or more, more preferably 60% by mole or more and is preferably 75% by mole or less, and more preferably 71% by mole or less. When the acetalization degree is the above lower limit or more, the compatibility between the polyvinyl acetal resin and a plasticizer is enhanced. When the acetalization degree is the above upper limit or less, the reaction time required for producing the polyvinyl acetal resin is shortened.
The acetalization degree is determined in the following manner. From the total amount of the ethylene group in the main chain, the amount of the ethylene group to which the hydroxyl group is bonded and the amount of the ethylene group to which the acetyl group is bonded are subtracted. The obtained value is divided by the total amount of the ethylene group in the main chain to obtain a mole fraction. The mole fraction represented in percentage is the acetalization degree.
In this connection, it is preferred that the content of the hydroxyl group (the amount of hydroxyl groups), the acetalization degree (the butyralization degree) and the acetylation degree be calculated from the results determined by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. In this context, a method in accordance with ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the content of the hydroxyl group (the amount of hydroxyl groups), the acetalization degree (the butyralization degree) and the acetylation degree can be calculated from the results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”.
In 100% by weight of the composition for forming a first layer, the content of the resin is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, and especially preferably 80% by weight or more. When the content of the resin is the above lower limit or more, it is possible to further exert the effect of the present invention. When the content of the resin is the above upper limit or less, the amount of the additive other than the resin is small, so that it is possible to prevent the additive from bleeding out on the surface of the interlayer film.
It is preferred that the interlayer film contain a tackifier resin. It is preferred that the layer containing a cured product contain a tackifier resin. It is preferred that the layer containing a resin contain a tackifier resin. It is preferred that the first layer contain a tackifier resin. One kind of the tackifier resin may be used alone and two or more kinds thereof may be used in combination.
Examples of the tackifier resin include a styrene resin, a terpene resin, a rosin resin, and the like. From the viewpoint of enhancing the sound insulating property over a wide range of temperature while keeping haze satisfactorily, the tackifier resin is preferably a styrene resin. It is preferred that the styrene resin be an oligomer of styrene. One exemplary commercially available product of the oligomer of styrene is “YS resin SX100” available from YASUHARA CHEMICAL CO., LTD.
In the layer containing a tackifier resin, the content of the tackifier resin per 100 parts by weight of the resin excluding the tackifier resin contained in the layer is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, further preferably 30 parts by weight or more, and is preferably 150 parts by weight or less, more preferably 100 parts by weight or less. When the content of the tackifier resin is the above lower limit or more, it is possible to enhance the sound insulating property over a wide range of temperature while keeping haze satisfactorily.
It is preferred that the interlayer film contain a plasticizer. From the viewpoint of effectively enhancing the sound insulating property, it is preferred that the resin layer contain a plasticizer. It is preferred that the layer containing a resin contain a plasticizer. It is preferred that each of the first, second, third, fourth, and fifth layers contain a plasticizer. By using the plasticizer, adhesive force between layers tends to be further increased. One kind of the plasticizer may be used alone and two or more kinds thereof may be used in combination.
Examples of the plasticizer include paraffin oil, a benzoic ester plasticizer, an organic ester plasticizer, an organic phosphate plasticizer, and the like. Examples of the organic ester plasticizer include a monobasic organic acid ester, a polybasic organic acid ester, and the like. Examples of the phosphate plasticizer include an organic phosphate plasticizer, an organic phosphite plasticizer, and the like. It is preferred that the plasticizer be a liquid plasticizer.
Examples of the paraffin oil include naphthenic process oil, white mineral oil, mineral oil, paraffin wax, liquid paraffin, and the like.
Examples of commercially available paraffin oil include “Diana process oil PW-90” available from Idemitsu Kosan Co., Ltd., “Diana process oil PW-100” available from Idemitsu Kosan Co., Ltd., “Diana process oil PW-32” available from Idemitsu Kosan Co., Ltd., and the like.
Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, 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, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dibutyl maleate, bis(2-butoxyethyl) adipate, dibutyl adipate, diisobutyl adipate, 2,2-butoxyethoxyethyl adipate, benzoic acid glycol ester, adipic acid 1,3-butyleneglycol polyester, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, tributyl citrate, tributyl acetylcitrate, diethyl carbonate, dibutyl sebacate, oil-modified sebacic alkyds, a mixture of a phosphoric acid ester and an adipic acid ester, and the like. Organic ester plasticizers other than these may be used. Other adipic acid esters other than the above-described adipic acid esters may be used.
Examples of the organic ester plasticizer include a diester plasticizer represented by the following structural formula (1).
In the foregoing formula (1), R1 and R2 each represent an organic group with 2 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. It is preferred that R1 and R2 in the foregoing formula (1) each be an organic group with 5 to 10 carbon atoms, and it is more preferred that R1 and R2 each be an organic group with 6 to 10 carbon atoms.
It is preferred that the plasticizer include triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate. It is more preferred that the plasticizer include triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and it is further preferred that the plasticizer include triethylene glycol di-2-ethylhexanoate.
In the layer containing a cured product or a polyolefin resin, the content of the plasticizer per 100 parts by weight of the cured product or per 100 parts by weight of the polyolefin resin is referred to as a content (1). The content (1) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 20 parts by weight or more, and especially preferably 25 parts by weight or more, and is preferably 60 parts by weight or less, more preferably 55 parts by weight or less, and further preferably 50 parts by weight or less. When the content (1) is the above lower limit or more, it is possible to effectively enhance the sound insulating property. When the content (1) is the above upper limit or less, the penetration resistance of laminated glass is further enhanced.
In the layer containing a resin that is different from both of the cured product and the polyolefin resin (layer containing a resin), the content of the plasticizer per 100 parts by weight of the resin is referred to as a content (2). The content (2) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 20 parts by weight or more, and is preferably 60 parts by weight or less, more preferably 55 parts by weight or less, further preferably 50 parts by weight or less. When the content (2) is the above lower limit or more, it is possible to effectively enhance the sound insulating property. When the content of the plasticizer is the above upper limit or less, the penetration resistance of laminated glass is further enhanced.
When a layer containing a polyvinyl acetal resin is provided as the layer containing a resin that is different from both of the cured product and the polyolefin resin (layer containing a resin), the content of the plasticizer per 100 parts by weight of the polyvinyl acetal resin in the layer containing a polyvinyl acetal resin is referred to as a content (2′). It is preferred that the content (1) be smaller than the content (2′).
The interlayer film may contain a heat shielding substance. The resin layer may contain a heat shielding substance. The layer containing a resin may contain a heat shielding substance. Each of the first, second, third, fourth, and fifth layers may contain a heat shielding substance. One kind of the heat shielding substance may be used alone, and two or more kinds thereof may be used in combination.
The heat shielding substance may contain at least one kind of Ingredient X among a phthalocyanine compound, a naphthalocyanine compound, and an anthracyanine compound or contain heat shielding particles. In this case, the heat shielding substance may contain both of the Ingredient X and the heat shielding particles.
The interlayer film may contain at least one kind of Ingredient X among a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound. The resin layer may contain the Ingredient X. The layer containing a resin may contain the Ingredient X. Each of the first, second, third, fourth, and fifth layers may contain the Ingredient X. The Ingredient X is a heat shielding substance. One kind of the Ingredient X may be used alone, and two or more kinds thereof may be used in combination.
The Ingredient X is not particularly limited. As the Ingredient X, conventionally known phthalocyanine compound, naphthalocyanine compound and anthracyanine compound can be used.
Examples of the Ingredient X include phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, a derivative of naphthalocyanine, anthracyanine, a derivative of anthracyanine, and the like. It is preferred that each of the phthalocyanine compound and the derivative of phthalocyanine have a phthalocyanine skeleton. It is preferred that each of the naphthalocyanine compound and the derivative of naphthalocyanine have a naphthalocyanine skeleton. It is preferred that each of the anthracyanine compound and the derivative of anthracyanine have an anthracyanine skeleton.
The Ingredient X may contain a vanadium atom or a copper atom. The Ingredient X may contain a vanadium atom, and may contain a copper atom. The Ingredient X may be at least one kind of phthalocyanines containing a vanadium atom or a copper atom, and derivatives of phthalocyanine containing a vanadium atom or a copper atom.
The interlayer film may contain heat shielding particles. The layer containing a cured product may contain heat shielding particles. The layer containing a resin may contain heat shielding particles. The first layer may contain heat shielding particles. The second layer may contain heat shielding particles. The third layer may contain heat shielding particles. The heat shielding particle is of a heat shielding substance. By the use of heat shielding particles, infrared rays (heat rays) can be effectively cut off. One kind of the heat shielding particles may be used alone, and two or more kinds thereof may be used in combination.
As the heat shielding particles, metal oxide particles may be used. As the heat shielding particles, particles formed of an oxide of metal (metal oxide particles) may be used.
The energy amount of an infrared ray with a wavelength of 780 nm or longer which is longer than that of visible light is small as compared with an ultraviolet ray. However, the thermal action of infrared rays is large, and when infrared rays are absorbed into a substance, heat is released from the substance. Accordingly, infrared rays are generally called heat rays. By the use of the heat shielding particles, infrared rays (heat rays) can be effectively cut off. In this connection, the heat shielding particle means a particle capable of absorbing infrared rays.
Specific examples of the heat shielding particles include metal oxide particles such as aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), indium-doped zinc oxide particles (IZO particles), aluminum-doped zinc oxide particles (AZO particles), niobium-doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, rubidium-doped tungsten oxide particles, tin-doped indium oxide particles (ITO particles), tin-doped zinc oxide particles and silicon-doped zinc oxide particles, lanthanum hexaboride (LaB6) particles, and the like. Heat shielding particles other than these may be used.
The interlayer film may contain at least one kind of metal salt (hereinafter, also referred to as Metal salt M) among an alkali metal salt, an alkaline earth metal salt, and a magnesium salt. The layer containing a cured product may contain the Metal salt M. The layer containing a resin may contain the Metal salt M. Each of the first, second, third, fourth, and fifth layers may contain the Metal salt M. By the use of the Metal salt M, controlling the adhesivity between the interlayer film and a lamination glass member such as a glass plate or the adhesivity between respective layers in the interlayer film is facilitated. One kind of the Metal salt M may be used alone, and two or more kinds thereof may be used in combination.
The Metal salt M may contain at least one kind of metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
As the Metal salt M, an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkali earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms can be used.
Examples of the magnesium carboxylate with 2 to 16 carbon atoms and the potassium carboxylate with 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate, and the like.
The interlayer film may contain an ultraviolet ray screening agent. The layer containing a cured product may contain an ultraviolet ray screening agent. The layer containing a resin may contain an ultraviolet ray screening agent. Each of the first, second, third, fourth, and fifth layers may contain an ultraviolet ray screening agent. By the use of an ultraviolet ray screening agent, even when the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance becomes further hard to be lowered. One kind of the ultraviolet ray screening agent may be used alone, and two or more kinds thereof may be used in combination.
Examples of the ultraviolet ray screening agent include an ultraviolet ray absorber. It is preferred that the ultraviolet ray screening agent be an ultraviolet ray absorber.
Examples of the ultraviolet ray screening agent include an ultraviolet ray screening agent containing a metal atom, an ultraviolet ray screening agent containing a metal oxide, an ultraviolet ray screening agent having a benzotriazole structure (a benzotriazole compound), an ultraviolet ray screening agent having a benzophenone structure (a benzophenone compound), an ultraviolet ray screening agent having a triazine structure (a triazine compound), an ultraviolet ray screening agent having a malonic acid ester structure (a malonic acid ester compound), an ultraviolet ray screening agent having an oxanilide structure (an oxanilide compound), an ultraviolet ray screening agent having a benzoate structure (a benzoate compound), and the like.
Examples of the ultraviolet ray screening agent containing a metal atom include platinum particles, particles in which the surface of platinum particles is coated with silica, palladium particles, particles in which the surface of palladium particles is coated with silica, and the like. It is preferred that the ultraviolet ray screening agent not be heat shielding particles.
Examples of the ultraviolet ray screening agent containing a metal oxide include zinc oxide, titanium oxide, cerium oxide, and the like. Furthermore, with regard to the ultraviolet ray screening agent containing a metal oxide, the surface thereof may be coated with any material. Examples of the coating material for the surface of the ultraviolet ray screening agent containing a metal oxide include an insulating metal oxide, a hydrolyzable organosilicon compound, a silicone compound, and the like.
Examples of the insulating metal oxide include silica, alumina, zirconia, and the like. For example, the insulating metal oxide has a band-gap energy of 5.0 eV or more.
Examples of the ultraviolet ray screening agent having a benzotriazole structure include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole (“Tinuvin P” available from BASF Japan Ltd.), 2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole (“Tinuvin 320” available from BASF Japan Ltd.), 2-(2′-hydroxy-3′-t-butyl-5-methylphenyl)-5-chlorobenzotriazole (“Tinuvin 326” available from BASF Japan Ltd.), 2-(2′-hydroxy-3′,5′-di-amylphenyl)benzotriazole (“Tinuvin 328” available from BASF Japan Ltd.), and the like.
Examples of the ultraviolet ray screening agent having a benzophenone structure include octabenzone (“Chimassorb 81” available from BASF Japan Ltd.), and the like.
Examples of the ultraviolet ray screening agent having a triazine structure include “LA-F70” available from ADEKA CORPORATION, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (“Tinuvin 1577FF” available from BASF Japan Ltd.), and the like.
Examples of the ultraviolet ray screening agent having a malonic acid ester structure include dimethyl 2-(p-methoxybenzylidene)malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene)bismalonate, 2-(p-methoxybenzylidene)-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)malonate, and the like.
Examples of a commercial product of the ultraviolet ray screening agent having a malonic acid ester structure include Hostavin B-CAP, Hostavin PR-25 and Hostavin PR-31 (any of these is available from Clariant Japan K.K.).
Examples of the ultraviolet ray screening agent having an oxanilide structure include a kind of oxalic acid diamide having a substituted aryl group and the like on the nitrogen atom such as N-(2-ethylphenyl)-N′-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(2-ethylphenyl)-N′-(2-ethoxy-phenyl)oxalic acid diamide and 2-ethyl-2′-ethoxy-oxanilide (“Sanduvor VSU” available from Clariant Japan K.K.).
Examples of the ultraviolet ray screening agent having a benzoate structure include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“Tinuvin 120” available from BASF Japan Ltd.), and the like.
The interlayer film may contain an oxidation inhibitor. The resin layer may contain an oxidation inhibitor. The layer containing a resin may contain an oxidation inhibitor. Each of the first, second, third, fourth, and fifth layers may contain an oxidation inhibitor. One kind of the oxidation inhibitor may be used alone, and two or more kinds thereof may be used in combination.
Examples of the oxidation inhibitor include a phenol-based oxidation inhibitor, a sulfur-based oxidation inhibitor, a phosphorus-based oxidation inhibitor, and the like. The phenol-based oxidation inhibitor is an oxidation inhibitor having a phenol skeleton. The sulfur-based oxidation inhibitor is an oxidation inhibitor containing a sulfur atom. The phosphorus-based oxidation inhibitor is an oxidation inhibitor containing a phosphorus atom.
Examples of the phenol-based oxidation inhibitor include 2,6-di-t-butyl-p-cresol (BHT), butyl hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis-(4-methyl-6-butylphenol), 2,2′-methylenebis-(4-ethyl-6-t-butylphenol), 4,4′-butylidene-bis-(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-hydroxy-5-t-butylphenyl)butane, tetrakis[methylene-3-(3′,5′-butyl-4-hydroxyphenyl)propionate]methane, 1,3,3-tris-(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,3′-t-butylphenol)butyric acid glycol ester, bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene), and the like. One kind or two or more kinds among these oxidation inhibitors are preferably used.
Examples of the phosphorus-based oxidation inhibitor include tridecyl phosphite, tris(tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis(tridecyl)pentaerithritol diphosphite, bis(decyl)pentaerithritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl ester phosphorous acid, 2,2′-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, and the like. One kind or two or more kinds among these oxidation inhibitors are preferably used.
Examples of a commercial product of the oxidation inhibitor include “IRGANOX 245” available from BASF Japan Ltd., “IRGAFOS 168” available from BASF Japan Ltd., “IRGAFOS 38” available from BASF Japan Ltd., “Sumilizer BHT” available from Sumitomo Chemical Co., Ltd., “H-BHT” available from Sakai Chemical Industry Co., Ltd., “IRGANOX 1010” available from BASF Japan Ltd., and the like.
Each of the interlayer film, the resin layer, the layer containing a resin, the first layer, the second layer, the third layer, the fourth layer, and the fifth layer may contain additives such as a coupling agent, a dispersing agent, a surfactant, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force regulator other than metal salt, a moisture-resistance agent, a fluorescent brightening agent, and an infrared ray absorber, as necessary. One kind of these additives may be used alone, and two or more kinds thereof may be used in combination.
The thickness of the interlayer film is not particularly limited. From the viewpoint of the practical aspect and the viewpoint of sufficiently enhancing the penetration resistance and the flexural rigidity of laminated glass, the thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, and is preferably 3 mm or less, more preferably 1.5 mm or less. When the thickness of the interlayer film is the above lower limit or more, the penetration resistance and the flexural rigidity of laminated glass are further enhanced. When the thickness of the interlayer film is the above upper limit or less, the transparency of the interlayer film is further improved.
The thickness of the interlayer film is designated as T. The thickness (thickness per one layer) of the resin layer (layer containing a cured product or a polyolefin resin, and the like) is preferably 0.05T or more, more preferably 0.06T or more, and further preferably 0.07T or more, and is preferably 0.25T or less, more preferably 0.23T or less, and further preferably 0.2T or less. When the thickness is in the range from the aforementioned lower limit to the aforementioned upper limit, the sound insulating property is further enhanced in a wide range of temperature.
The thickness (thickness per one layer) of the layer containing a resin is preferably 0.005T or more, more preferably 0.01T or more, further preferably 0.02T or more, and is preferably 0.17T or less, more preferably 0.15T or less, still more preferably 0.13T or less, yet still more preferably 0.1T or less, and further preferably 0.08T or less. When the thickness is in the range from the aforementioned lower limit to the aforementioned upper limit, the sound insulating property is further enhanced in a wide range of temperature.
The thickness (thickness per one layer) of the resin layer (layer containing a cured product or a polyolefin resin, and the like) is preferably 50 μm or more, more preferably 60 μm or more, and further preferably 70 μm or more, and is preferably 250 μm or less, more preferably 200 μm or less, and further preferably 150 μm or less. When the thickness is in the range from the aforementioned lower limit to the aforementioned upper limit, the sound insulating property is further enhanced in a wide range of temperature.
The thickness (thickness per one layer) of the layer containing a resin is preferably 5 μm or more, more preferably 12 μm or more, and further preferably 25 μm or more, and is preferably 200 μm or less, more preferably 150 pm or less, still more preferably 100 μm or less, yet more preferably 80 μm or less, yet more preferably 60pm or less, and further preferably 45 μm or less. When the thickness is in the range from the aforementioned lower limit to the aforementioned upper limit, the sound insulating property is further enhanced in a wide range of temperature.
The interlayer film may be an interlayer film having a uniform thickness, or may be an interlayer film having varying thickness. The sectional shape of the interlayer film may be a rectangular shape and may be a wedge-like shape.
The production method of the interlayer film according to the present invention is not particularly limited. Examples of the production method of the interlayer film according to the present invention include a method of separately forming resin compositions used for constituting respective layers into respective layers, and then layering the obtained layers, a method of coextruding resin compositions used for constituting respective layers with an extruder and layering the layers, and the like. A production method of extrusion-molding is preferred because the method is suitable for continuous production.
For excellent production efficiency of the interlayer film, when there are two surface layers, it is preferred that the two surface layers contain the same polyvinyl acetal resin, and it is more preferred that the two surface layers contain the same polyvinyl acetal resin and the same plasticizer. For excellent production efficiency of the interlayer film, it is further preferred that the two surface layers be formed of the same resin composition.
It is preferred that the interlayer film have protrusions and recesses on at least one surface of the surfaces of both sides. It is more preferred that the interlayer film have protrusions and recesses on surfaces of both sides. Examples of the method for forming the protrusions and recesses include, but are not particularly limited to, a lip emboss method, an emboss roll method, a calender roll method, a profile extrusion method, and the like. The emboss roll method is preferred because a large number of embosses of the protrusions and recesses, which is a quantitatively constant protrusion and recess pattern, can be formed.
The laminated glass according to the present invention includes a first lamination glass member, a second lamination glass member and the aforementioned interlayer film for laminated glass. In the laminated glass according to the present invention, the above-mentioned interlayer film for laminated glass is arranged between the first lamination glass member and the second lamination glass member.
The laminated glass 31 shown in
The first lamination glass member 21 is layered on a first surface 11a of the interlayer film 11. The second lamination glass member 22 is layered on a second surface 11b opposite to the first surface 11a of the interlayer film 11. The first lamination glass member 21 is layered on an outer surface 2a of the second layer 2. The second lamination glass member 22 is layered on an outer surface 3a of a third layer 3.
The laminated glass 31A shown in
The first lamination glass member 21 is layered on a first surface 11a of the interlayer film 11A. The second lamination glass member 22 is layered on a second surface 11b opposite to the first surface 11a of the interlayer film 11A. The first lamination glass member 21 is layered on an outer surface 4a of the fourth layer 4. The second lamination glass member 22 is layered on an outer surface 5a of the fifth layer 5A.
As described above, the laminated glass according to the present invention includes a first lamination glass member, a second lamination glass member, and an interlayer film, and the interlayer film is the interlayer film for laminated glass according to the present invention. In the laminated glass according to the present invention, the above-mentioned interlayer film is arranged between the first lamination glass member and the second lamination glass member.
It is preferred that the first lamination glass member be the first glass plate. It is preferred that the second lamination glass member be the second glass plate.
Examples of the first and second lamination glass members include a glass plate, a PET (polyethylene terephthalate) film, and the like. As the laminated glass, laminated glass in which an interlayer film is sandwiched between a glass plate and a PET film or the like, as well as laminated glass in which an interlayer film is sandwiched between two glass plates, is included. The laminated glass is a laminate provided with a glass plate, and it is preferred that at least one glass plate be used. It is preferred that each of the first lamination glass member and the second lamination glass member be a glass plate or a PET film, and the laminated glass be provided with a glass plate as at least one among the first lamination glass member and the second lamination glass member. It is especially preferred that both of the first and second lamination glass members be glass plates.
Examples of the glass plate include a sheet of inorganic glass and a sheet of organic glass. Examples of the inorganic glass include float plate glass, heat ray-absorbing plate glass, heat ray-reflecting plate glass, polished plate glass, figured glass, wired plate glass, and the like. The organic glass is synthetic resin glass substituted for inorganic glass. Examples of the organic glass include a polycarbonate plate, a poly(meth)acrylic resin plate, and the like. Examples of the poly(meth)acrylic resin plate include a polymethyl (meth)acrylate plate, and the like.
The thicknesses of each of the first lamination glass member and the second lamination glass member is preferably 1 mm or more, and is preferably 5 mm or less, and more preferably 3 mm or less. Moreover, when the lamination glass member is a glass plate, the thickness of the glass plate is preferably 0.5 mm or more, more preferably 0.7 mm or more, preferably 5 mm or less and more preferably 3 mm or less. When the lamination glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more and is preferably 0.5 mm or less.
The method for producing the laminated glass is not particularly limited. First, the interlayer film is sandwiched between the first lamination glass member and the second lamination glass member to obtain a laminate. Then, for example, by passing the obtained laminate through pressure rolls or subjecting the obtained laminate to decompression suction in a rubber bag, the air remaining between the first and the second lamination glass members and the interlayer film is removed. Then, the laminate is preliminarily bonded together at about 70 to 110° C. to obtain a preliminarily press-bonded laminate. Next, by putting the preliminarily press-bonded laminate into an autoclave or by pressing the laminate, the laminate is press-bonded at about 120 to 150° C. and under a pressure of 1 to 1.5 MPa. In this way, laminated glass can be obtained. At the time of producing the laminated glass, a first layer, a second layer and a third layer may be layered.
Each of the interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings and the like. Each of the interlayer film and the laminated glass can also be used for applications other than these applications. It is preferred that the interlayer film and the laminated glass be an interlayer film and laminated glass for vehicles or for buildings respectively, and it is more preferred that the interlayer film and the laminated glass be an interlayer film and laminated glass for vehicles respectively. Each of the interlayer film and the laminated glass can be used for a windshield, side glass, rear glass or roof glass of an automobile, and the like. The interlayer film and the laminated glass are suitably used for automobiles. The interlayer film is used for obtaining laminated glass of an automobile.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited only to these examples.
The following materials were prepared.
With regard to the polyvinyl acetal resin, the acetalization degree (the butyralization degree), the acetylation degree and the content of the hydroxyl group were measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. In this connection, even in the cases of being measured according to ASTM D1396-92, numerical values similar to those obtained by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral” were exhibited. When the acetal is acetoacetal or the like, the acetalization degree is calculated by measuring the acetylation degree and the content of the hydroxyl group, and calculating a mole fraction from the obtained measurement results, and then subtracting the acetylation degree and the content of hydroxyl groups from 100% by mole.
Polyvinyl acetal resin (1) (n-butyraldehyde is used, polymerization degree: 1700, content of hydroxyl group: 30.4% by mole, acetylation degree: 0.9% by mole, acetalization degree: 68.7% by mole)
Polyvinyl acetal resin (A) (n-butyraldehyde is used, polymerization degree: 3000, content of hydroxyl group: 24.3% by mole, acetylation degree: 12.5% by mole, acetalization degree: 63.2% by mole)
PET film (1) (“TOYOBO ester film E5100” available from TOYOBO CO., LTD., 50 μm thick)
PET film (2) (“Lumilar T60” available from TORAY INDUSTRIES, INC., 50 μm thick)
Aliphatic polyolefin (“ABSORTOMER EP-1001” available from Mitsui Chemicals, Inc.; thermoplastic elastomer)
(Meth)acrylic Polymers (1) to (5):
A polymerizable composition having the blending composition shown in the following Table 1 was sandwiched between two PET sheets having subjected to a mold release treatment on one side (available from Nippa Corporation, having a thickness of 50 μm) to form a polymerizable composition layer having a thickness of 100 μm. A spacer was arranged around the two PET sheets. The polymerizable composition layer was irradiated with ultraviolet rays at a dose of 3000 mJ/cm2 with a chemical lamp (FL2OSBL, available from TOSHIBA CORPORATION) to cure the polymerizable composition by reaction, and thus meth(acryl) polymers (1) to (5) were obtained.
Triethylene Glycol di-2-ethylhexanoate (3GO)
Paraffin oil (“Diana process oil PW-32” available from Idemitsu Kosan Co., Ltd.)
Mg mixture (50:50 (weight ratio) mixture of magnesium 2-ethylbutyrate and magnesium acetate)
Tinuvin 326 (2-(2′-hydroxy-3′-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, “Tinuvin 326” available from BASF Japan Ltd.)
BHT (2,6-di-t-butyl-p-cresol)
Preparation of First Layer:
A first layer (layer containing a cured product, 100 μm thick) containing 100 parts by weight of the (meth)acrylic polymer (1) obtained in the above, and 25 parts by weight of a plasticizer (3GO) was prepared.
Preparation of Second Layer and Third Layer:
PET films (1) were prepared as the second layer and the third layer.
Preparation of Fourth Layer and Fifth Layer:
The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a fourth layer and a fifth layer.
100 parts by weight of Polyvinyl acetal resin (1)
Plasticizer (3GO) 35 parts by weight
Metal salt M (Mg mixture) in such an amount that is 70 ppm in the obtained fourth layer and fifth layer
Ultraviolet ray screening agent (Tinuvin 326) in an amount of 0.2% by weight in the obtained fourth layer and fifth layer
Oxidation inhibitor (BHT) in an amount of 0.2% by weight in the obtained fourth layer and fifth layer
The composition for forming a fourth layer and a fifth layer was extruded with an extruder to obtain a fourth layer and the fifth layer (each having a thickness of 380 μm).
Preparation of Interlayer Film for Evaluation of Sound Insulating Property:
The first layer was sandwiched between the second layer and the third layer to obtain a three-layer laminate. By arranging the fourth layer and the fifth layer on the outer sides of the laminate, and laminating with a roll laminator (“GDRB316 A3” available from ACCO BRANDS JAPAN K.K.) at 100° C. and a speed setting 3, an interlayer film having a structure of the fourth layer/the second layer/the first layer/the third layer/the fifth layer was obtained.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
The obtained interlayer film was cut into a size of 25 mm wide and 300 mm long. As the first lamination glass member, and the second lamination glass member, two glass plates (clear float glass, 25 mm wide, 300 mm long and 2 mm thick) were prepared. The interlayer film was sandwiched between the two glass plates to obtain a laminate. The laminate was put into a rubber bag and the inside thereof was degassed for 20 minutes with a degree of vacuum of 2.6 kPa, after which the laminate in the degassed condition was transferred into an oven, and vacuum-pressed by retention at 90° C. for 30 minutes, and thus the laminate was preliminarily press-bonded. The preliminarily press-bonded laminate was subjected to press-bonding for 20 minutes under conditions of 135° C. and a pressure of 1.2 MPa in an autoclave to obtain a sheet of laminated glass.
Preparation of Interlayer Film for Foaming Test:
A three-layer laminate was obtained in the same manner as that for the interlayer film for evaluation of sound insulating property. Next, the three-layer laminate, the fourth layer, and the fifth layer were cut into a size of 30 cm long×15 cm wide. In the cut fourth layer and fifth layer, through-holes having a diameter of 6 mm were made at four intersections of the positions at 8 cm from the ends of the fourth layer and the fifth layer inwardly in the longitudinal direction, and the positions at 5 cm from the ends of the fourth layer and the fifth layer inwardly in the traverse direction. Both faces of the fourth layer and the fifth layer are embossed, and the 10-point average roughness of the embossing was 30 μm. The obtained interlayer film was stored in an environment at a temperature of 23° C. for 10 hours.
Preparation of Laminated Glass for Foaming Test:
A three-layer laminate was obtained in the same manner as that for the interlayer film for evaluation of sound insulating property. The fourth layer and the fifth layer were layered on the outer sides of the obtained three-layer laminate to obtain an interlayer film having a structure of the fourth layer/the second layer/the first layer/the third layer/the fifth layer. This interlayer film was sandwiched between two sheets of transparent float glass (30 cm in length×15 cm in width×2.5 mm in thickness) to obtain a laminate. By sealing the periphery of the laminate by sealing the width of 2 cm from the end part by heat seal with a sealing agent, the air remaining in the embossing and the air remaining in through-holes was contained. By press-bonding the laminate in an autoclave at 135° C. and under a pressure of 1.2 MPa for 20 minutes, the remaining air was melted in the interlayer film, and thus a laminated glass for use in a foaming test was obtained.
An interlayer film was prepared in the same manner as that in Example 1 except that the kinds and the amounts of the ingredients were set to that shown in the following Table 2, and the thickness was set as shown in the following Table 2. In the fourth layer and the fifth layer, Metal salt M, an ultraviolet ray screening agent, and an oxidation inhibitor were blended in the same kinds and amounts as those in Example 1 (omitted in Table 2).
Laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
Preparation of First Layer:
The (meth)acrylic polymer (2) obtained in the above (layer containing a cured product, having a thickness of 100 μm) was prepared.
Preparation of Second Layer and Third Layer:
The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a second layer and a third layer.
100 parts by weight of Polyvinyl acetal resin (1)
Plasticizer (3GO) 35 parts by weight
Metal salt M (Mg mixture) in such an amount that is 70 ppm in the obtained second layer and third layer
Ultraviolet ray screening agent (Tinuvin 326) in an amount of 0.2% by weight in the obtained second layer and third layer
Oxidation inhibitor (BHT) in an amount of 0.2% by weight in the obtained second layer and third layer
Preparation of Interlayer Film for Evaluation of Sound Insulating Property:
By arranging the second layer and the third layer on the outer sides of the first layer, and laminating with a roll laminator (“GDRB316 A3” available from ACCO BRANDS JAPAN K.K.) at 100° C. and a speed setting 3, an interlayer film having a structure of the second layer/the first layer/the third layer was obtained.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
Laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
Preparation of Interlayer Film for Foaming Test:
An interlayer film was obtained in the same manner as that in Example 1 except that the obtained first layer was used in place of the three-layer laminate in Example 1, and the obtained second layer and the third layer were used in place of the fourth layer and the fifth layer.
Preparation of Laminated Glass for Foaming Test:
A laminated glass was obtained in the same manner as that in Example 1 except that the obtained first layer was used in place of the three-layer laminate in Example 1, and the obtained second layer and the third layer were used in place of the fourth layer and the fifth layer.
Preparation of Three-Layer Laminate of Second Layer/First Layer/Third Layer:
PET films (2) were prepared as the second layer and the third layer.
Aliphatic polyolefin (“ABSORTOMER EP-1001” available from Mitsui Chemicals, Inc.; thermoplastic elastomer) was dissolved in toluene to obtain a 25% by weight aliphatic polyolefin solution in toluene. To the toluene solution, paraffin oil (“Diana process oil PW-32” available from Idemitsu Kosan Co., Ltd.) was added in an amount of 35 parts by weight per 100 parts by weight of aliphatic polyolefin, and stirred so that the solution was homogenous. Next, the solution was applied on a PET film (2) (second layer) so that the thickness after drying was 100 μm by using a coater, and dried at 120° C. for 1 hour, to obtain a first layer. A PET film (third layer) was layered on the first layer to obtain an interlayer film having a structure of the second layer/the first layer/the third layer.
Preparation of Fourth Layer and Fifth Layer:
A composition for forming a fourth layer and a fifth layer the same as those in Example 1 was prepared.
Preparation of Interlayer Film for Evaluation of Sound Insulating Property:
An interlayer film having a structure of the fourth layer/the second layer/the first layer/the third layer/the fifth layer was obtained in the same manner as that in Example 1.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
Laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
Preparation of Interlayer Film for Foaming Test and Laminated Glass for Foaming Test:
An interlayer film was prepared in the same manner as that in Example 1 except that the obtained three-layer laminate, and the prepared fourth layer and fifth layer were used, and a laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
Preparation of First Layer:
The (meth)acrylic polymer (4) obtained in the above (layer containing a cured product, having a thickness of 100 μm) was prepared. After dissolving and mixing the following ingredients in ethyl acetate, the resultant mixture was applied so that the thickness after drying was 100 μm, and ethyl acetate was dried out in an oven at 100° C. for 30 minutes to obtain a composition for forming a first layer.
(Meth)acrylic polymer (4) 100 parts by weight
Plasticizer (3GO) 50 parts by weight
Preparation of Second Layer and Third Layer:
The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a second layer and a third layer.
100 parts by weight of Polyvinyl acetal resin (1)
Plasticizer (3GO) 30 parts by weight
Metal salt M (Mg mixture) in such an amount that is 70 ppm in the obtained second layer and third layer
Ultraviolet ray screening agent (Tinuvin 326) in an amount of 0.2% by weight in the obtained second layer and third layer
Oxidation inhibitor (BHT) in an amount of 0.2% by weight in the obtained second layer and third layer
Preparation of Interlayer Film for Evaluation of Sound Insulating Property:
An interlayer film having a structure of the second layer/the first layer/the third layer was obtained in the same manner as that in Example 4.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
A laminated glass was obtained in the same manner as that in Example 4 except that the obtained interlayer film was used.
Preparation of Interlayer Film for Foaming Test:
An interlayer film was obtained in the same manner as that in Example 4.
Preparation of Laminated Glass for Foaming Test:
A laminated glass was obtained in the same manner as that in Example 4.
Preparation of First Layer:
The (meth)acrylic polymer (5) obtained in the above (layer containing a cured product, having a thickness of 100 μm) was prepared. The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a first layer.
(Meth)acrylic polymer (5) 100 parts by weight
Plasticizer (3GO) 45 parts by weight
Preparation of Second Layer and Third Layer:
The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a second layer and a third layer.
100 parts by weight of Polyvinyl acetal resin (1)
Plasticizer (3GO) 32 parts by weight
Metal salt M (Mg mixture) in such an amount that is 70 ppm in the obtained second layer and third layer
Ultraviolet ray screening agent (Tinuvin 326) in an amount of 0.2% by weight in the obtained second layer and third layer
Oxidation inhibitor (BHT) in an amount of 0.2% by weight in the obtained second layer and third layer
Preparation of Interlayer Film for Evaluation of Sound Insulating Property:
An interlayer film having a structure of the second layer/the first layer/the third layer was obtained in the same manner as that in Example 4.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
A laminated glass was obtained in the same manner as that in Example 4 except that the obtained interlayer film was used.
Preparation of Interlayer Film for Foaming Test:
An interlayer film was obtained in the same manner as that in Example 4.
Preparation of Laminated Glass for Foaming Test:
A laminated glass was obtained in the same manner as that in Example 4.
An interlayer film was prepared in the same manner as that in Example 1 except that the kinds and the amounts of the ingredients were set to that shown in the following Table 3, and the thickness was set as shown in the following Table 3. In the fourth layer and the fifth layer, Metal salt M, an ultraviolet ray screening agent, and an oxidation inhibitor were blended in the same kinds and amounts as those in Example 1 (omitted in Table 3).
Laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
Preparation of First Layer:
One hundred parts by weight of a polyvinyl acetal resin (A), 75 parts by weight of a plasticizer (3GO), an ultraviolet ray screening agent (Tinuvin 326) in such an amount that is to be 0.2% by weight in the obtained first layer, and an oxidation inhibitor (BHT) in such an amount that is to be 0.2% by weight in the obtained first layer were mixed sufficiently with a mixing roll to obtain a composition for forming a first layer.
Preparation of Second Layer and Third Layer:
The following ingredients were mixed, and kneaded sufficiently with a mixing roll to obtain a composition for forming a second layer and a third layer.
Polyvinyl acetal resin (A) 100 parts by weight
Plasticizer (3GO) 37.5 parts by weight
Metal salt M (Mg mixture) in such an amount that is 70 ppm in the obtained second layer and third layer
Ultraviolet ray screening agent (Tinuvin 326) in an amount of 0.2% by weight in the obtained second layer and third layer
Oxidation inhibitor (BHT) in an amount of 0.2% by weight in the obtained second layer and third layer
Preparation of Interlayer Film:
By coextruding the obtained composition for forming a first layer and the obtained composition for forming a second layer and a third layer using a coextruder, an interlayer film having a structure of the second layer/the first layer/the third layer was obtained.
Preparation of Laminated Glass for Evaluation of Sound Insulating Property:
Laminated glass was obtained in the same manner as that in Example 1 except that the obtained interlayer film was used.
A first layer was prepared in the same manner as that in preparation of the interlayer film for evaluation of sound insulating property. By appropriately cutting and stacking the first layer, a test piece having a thickness of 0.5 mm was prepared. Viscoelasticity measurement was conducted using this test piece. When the first layer is a thermoplastic resin, the obtained composition may be press-molded by a press molder to form a test piece having a thickness of 0.5 mm. The obtained test piece was left to stand at 25° C. and a relative humidity of 30% for 12 hours. After leaving to stand for 12 hours, viscoelasticity was measured using “ARES-G2” available from TA Instruments. As a jig, a parallel plate of 8 mm in diameter was used. The measurement was performed under the condition in which the temperature is decreased from 100° C. to −20° C. at a temperature decreasing rate of 3° C./minute and under the condition of a frequency of 1 Hz and a strain of 1%. In the measurement results obtained, the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). From the obtained measurement result, a value of loss tangent tan δ at Tg, and a value of storage modulus G′ at −5° C. were read.
The obtained laminated glass was stored in an environment at room temperature of 23±2° C. and a humidity of 25±5%. After 1 month after completion of the autoclave, the obtained laminated glass was excited with a vibration generator for damping test (“Vibrator G21-005D” available from Shinken. Co., Ltd.) in a thermostatic oven at 20° C. The resultant vibration characteristic obtained therefrom was amplified with a mechanical impedance measuring device (“XG-81” available from RION Co., Ltd.). The vibration spectrum was analyzed by a FFT spectrum analyzer (“FFT analyzer SA-01A2” available from RION Co., Ltd.), to determine resonance frequency and loss factor.
From the primary loss factor, sound insulating property was judged according to the following criteria.
◯◯: temperature range in which primary loss factor is 0.25 or more has a width of temperature range of 20° C. in temperature region of 10° C. to 30° C.
◯: temperature range in which primary loss factor is 0.25 or more has a width of temperature range of 15° C. or more and less than 20° C. in temperature region of 10° C. to 30° C.
×: temperature range in which primary loss factor is 0.25 or more has a width of temperature range of less than 15° C. in temperature region of 10° C. to 30° C.
Ten sheets of laminated glass used in the foaming test were left to stand in an oven at 50° C. for 100 hours. In the laminated glass after standing, whether foaming occurs was determined according to the following criteria for judgment.
Foaming was judged according to the following criteria.
◯: the number of sheets in which foaming was visually observed was zero in ten sheets of laminated glass
Δ: the number of sheets in which foaming was visually observed was one or more and nine or less in ten sheets of laminated glass
×: the number of sheets in which foaming was visually observed was ten in ten sheets of laminated glass
The details and the results are shown in the following Tables 2 and 3. In the following Tables 2 and 3, description of Metal salt M, the ultraviolet ray screening agent, and the oxidation inhibitor was omitted. In Tables 2 and 3, “E+04” means “×104”, “E+05” means “×105”, and “E+06” means “×106”.
The details and the results are shown in the following Tables 1 to 3.
The details of the ingredients shown in Table 1 used in synthesis of (meth)acrylic polymers (1) to (5) are as follows.
EA: ethyl acrylate (available from NIPPON SHOKUBAI CO., LTD.)
BzA: benzyl acrylate (available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD., VISCOAT #160)
THF-A: tetrahydrofurfuryl acrylate (available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD., VISCOAT #150)
HPA: hydroxypropyl acrylate (available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)
CTFA (#200): cyclic trimethylolpropane formal acrylate (available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD., VISCOAT #200)
IBOA: isobornyl acrylate (available from NIPPON SHOKUBAI CO., LTD.)
4HBA: 4-hydroxybutyl acrylate (available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)
IRGACURE 184: 2,2-dimethoxy-1,2-diphenylethan-1-one (available from BASF)
1, 1A: First layer
1
a: First surface
1
b: Second surface
2, 2A: Second layer
2
a: Outer surface
3, 3A: Third layer
3
a: Outer surface
4A: Fourth layer
4
a: Outer surface
5A: Fifth layer
5
a: Outer surface
11, 11A: Interlayer film
11
a: First surface
11
b: Second surface
21: First lamination glass member
22: Second lamination glass member
31, 31A: Laminated glass
| Number | Date | Country | Kind |
|---|---|---|---|
| 2018-017725 | Feb 2018 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2019/003182 | 1/30/2019 | WO | 00 |
