JP2020083688A - Interlayer film for laminated glass, and laminated glass - Google Patents

Abstract

To provide an interlayer film for laminated glass having followability and extensibility so that it can fit a curved surface of automobile window glass and the like.SOLUTION: An interlayer film for laminated glass 10 has a first resin layer 11, and a transparent conductive layer 14, the transparent conductive layer 14 formed on one face 11A of the first resin layer 11 by printing.SELECTED DRAWING: Figure 1

Description

The present invention relates to an interlayer film for laminated glass and a laminated glass including the interlayer film for laminated glass.

Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, and therefore it is safe to use on the windshield, side glass, rear glass, roof glass of vehicles such as automobiles, windows of aircraft, buildings, etc. Widely used as glass, etc. As a laminated glass, there is widely known one in which an interlayer film for laminated glass containing a resin component such as a polyvinyl acetal resin is interposed between a pair of glasses to be integrated.

In recent years, the performance required for glass has been diversified, and laminated glass has various functions. For example, it is known that a so-called defroster function, which is capable of heating a frozen laminated glass by heating by applying a voltage and melting frost and ice, is provided. In the laminated glass having a defroster function, for example, as disclosed in Patent Document 1, a base material containing a thermoplastic resin, a conductive layer made of a conductive material formed on the base material, and a conductive layer of the base material. It is known to use an interlayer film having a polyvinyl acetal-containing resin layer laminated on the side. In Patent Document 1, the conductive layer is formed by sputtering.

International publication 2017/090712

By the way, it has been studied to give various applications to the laminated glass in addition to the defroster function. For example, in the application of window glass for automobiles, it has been considered to make the laminated glass into a touch panel. In order to make a laminated glass into a touch panel, as disclosed in Patent Document 1, it is necessary to provide a conductive layer on the interlayer film for laminated glass.
On the other hand, as for window glass of automobiles, those having curved surfaces are increasing as a recent design trend. In particular, a full glass top design in which most of the roof is covered with glass, and a seamless design in which the joint between the glass and the body is removed are being considered, and the curvature tends to increase.

However, when the conductive layer is formed by sputtering or the like, the stretchability becomes low, and the interlayer film for laminated glass also has poor followability and stretchability, and it may be difficult to bend it according to the curved surface of an automobile window glass.

Therefore, it is an object of the present invention to provide an interlayer film for laminated glass having followability and extensibility so that it can be adapted to a curved surface such as an automobile window glass even when a transparent conductive layer is provided. ..

As a result of intensive studies, the present inventors have found that the above problems can be solved by forming a transparent conductive layer by printing, and have completed the following present invention. The present invention provides the following [1] to [14].
[1] An interlayer film for laminated glass, comprising a first resin layer and a transparent conductive layer, wherein the transparent conductive layer is formed on at least one surface of the first resin layer by printing.
[2] The interlayer film for laminated glass according to the above [1], which has the first resin layer, the transparent conductive layer, and the second resin layer in this order along the thickness direction.
[3] The laminated glass according to the above [1], which has a third resin layer, the first resin layer, a transparent conductive layer, and a second resin layer in this order along the thickness direction. Intermediate film.
[4] Any of the above [1] to [3], wherein the transparent conductive layer contains at least one selected from the group consisting of conductive metal oxides, conductive polymer compounds, metal nanowires and carbon materials. The interlayer film for laminated glass according to Item 1.
[5] The intermediate for laminated glass according to any one of the above [1] to [4], wherein the first resin layer contains at least one selected from the group consisting of a thermoplastic resin and a thermoplastic elastomer. film.
[6] The interlayer film for laminated glass according to the above [5], wherein the thermoplastic resin is at least one selected from the group consisting of polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, and polyolefin resin.
[7] The interlayer film for laminated glass according to the above [5] or [6], wherein the second resin layer contains the same kind of thermoplastic resin or thermoplastic elastomer as the first resin layer.
[8] The interlayer film for laminated glass according to any one of the above [1] to [7], wherein one surface of the first resin layer has an arithmetic average height roughness (Ra) of 10 μm or less. ..
[9] The interlayer film for laminated glass according to any one of the above [1] to [8], which comprises a functional layer selected from any of a light control body, a light emitting element, and a light emitting layer.
[10] The intermediate film for laminated glass according to any one of the above [1] to [9], wherein the transparent conductive layer is a conductive layer for a touch panel or a touch switch.
[11] The interlayer film for laminated glass according to any one of the above [1] to [10], and first and second glass plates, wherein the interlayer film for laminated glass is the first and the second. A laminated glass arranged between two glass plates.
[12] The transparent conductive layer is a conductive layer for a touch panel or a touch switch,
The laminated glass according to the above [11], wherein the interlayer film for laminated glass includes a functional layer that is operated by touch input on the transparent conductive layer.
[13] The functional layer includes a dimmer that changes optical characteristics by the touch input, a light emitting element that switches light emission and non-light emission by the touch input, and a light emitting layer that switches display and non-display of an image by the touch input. The laminated glass according to the above [12], which is either one.
[14] The laminated glass according to any one of [11] to [13], which is either an automobile roof glass or an automobile side glass.

According to the present invention, it is possible to provide an interlayer film for laminated glass having followability and extensibility so that it can be adapted to curved surfaces such as automobile window glass.

The laminated glass provided with the interlayer film for laminated glasses of 1st Embodiment is shown. It is a top view which shows an example of the pattern shape of a transparent conductive layer. It is a top view which shows another example of the pattern shape of a transparent conductive layer. The laminated glass provided with the interlayer film for laminated glasses of 2nd Embodiment is shown. The laminated glass provided with the interlayer film for laminated glasses of 3rd Embodiment is shown. The laminated glass provided with the interlayer film for laminated glasses of 4th Embodiment is shown. The laminated glass provided with the interlayer film for laminated glasses of 5th Embodiment is shown.

Hereinafter, the present invention will be described in detail with reference to embodiments.
[First Embodiment]
FIG. 1 shows a laminated glass 15 having an interlayer film 10 for laminated glass according to the first embodiment of the present invention. The laminated glass 15 includes first and second glass plates 16A and 16B, and the interlayer film 10 for laminated glass arranged between the first and second glass plates 16A and 16B.

The interlayer film 10 for laminated glass of the first embodiment includes first, second, and third resin layers 11, 12, and 13. In the interlayer film 10 for laminated glass, the transparent conductive layer 14 is provided on one surface 11A of the first resin layer 11. The transparent conductive layer 14 is formed on the one surface 11A of the first resin layer 11 by printing. In the present invention, since the transparent conductive layer 14 is formed by printing, the conductive layer itself has a certain degree of stretchability, and the stretchability of the interlayer film 10 for laminated glass is adjusted so that the transparent conductive layer 14 can be adapted to the curved surface of an automobile window glass. And followability is imparted. Further, by providing the transparent conductive layer 14, for example, a touch panel function, a touch switch function, etc. can be imparted to the laminated glass intermediate film 10.

The transparent conductive layer 14 is a layer formed on at least one surface 11A of the first resin layer 11, but it may be partially provided on one surface 11A by printing or may be provided entirely. Although it may be provided, it is preferably provided partially. By providing the transparent conductive layer 14 partially, the stretchability and the followability of the interlayer film 10 for laminated glass become better. Further, since the transparent conductive layer 14 is partially provided, the first resin layer 11 can be easily bonded to the second resin layer 12 via the one surface 11A.

In the interlayer film 10 for laminated glass, the third resin layer 13, the first resin layer 11, the transparent conductive layer 14, and the second resin layer 12 are provided in this order along the thickness direction. In the interlayer film 10 for laminated glass, one surface 11A of the first resin layer 11 is bonded to one surface 12A of the second resin layer 12 via the transparent conductive layer 14. Here, when the transparent conductive layer 14 is partially provided on the one surface 11</b>A, the one surface 11</b>A of the first resin layer 11 is provided on the second resin layer 12 in a portion where the transparent conductive layer 14 is not provided. Will be glued directly to.
The other surface 11B of the first resin layer 11 is bonded to the one surface 13A of the third resin layer 13. The other surfaces 12B and 13B of the second and third resin layers 12 and 13 are adhered to the first and second glass plates 16A and 16B, respectively.

The interlayer film 10 for laminated glass has three resin layers, and the first resin layer 11 on which the transparent conductive layer 14 is printed and the resin layer for bonding the interlayer film 10 for laminated glass to the glass plates 16A and 16B. (That is, the second and third resin layers 12 and 13) are different layers. Therefore, for example, it is possible to increase the mechanical strength of the first resin layer 11 and to make the second and third resin layers 12 and 13 into layers having high adhesiveness and flexibility, thereby improving printability. While being good, the adhesion to the glass plates 16A and 16B can be good. Further, the interlayer film 10 for laminated glass is likely to have excellent followability to curved surfaces and excellent stretchability.

Next, the configuration of each layer used in the interlayer film 10 for laminated glass will be described in detail.
[Transparent conductive layer]
The transparent conductive layer 14 preferably contains at least one selected from conductive metal oxides, conductive polymer compounds, metal nanowires, and carbon materials. These are materials that give conductivity to the transparent conductive layer 14 (hereinafter, also referred to as “conductive material”).

Examples of the conductive metal oxide include tin oxide, indium tin oxide (ITO), antimony tin oxide (ATO), indium gallium oxide (IGO), indium zinc oxide (IZO), and zinc oxide (Zinc Oxide). Among these, ITO is preferable. The conductive metal oxide is preferably in the form of particles, needles or scales.
Examples of the conductive polymer compound include thiophene-based compounds, and specifically, polyethylenedioxythiophene (PEDOT), a mixture of polyethylenedioxythiophene and polystyrene sulfonate (PEDOT:PSS), poly(3-thiophene-). β-ethanesulfonic acid) and the like. Among these, PEDOT and PEDOT:PSS are preferable.

The metal nanowire is a metal having a diameter in the order of nanometer, and has a wire shape or a hollow tube shape. Examples of the type of metal include gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium and iridium. Of these, silver is preferable because it has excellent conductivity.
Examples of carbon materials include carbon nanotubes, graphene, and conductive carbon black. Graphene, conductive carbon black and the like are preferably in the form of particles, needles or flakes. Carbon nanotubes are preferable as the carbon material.
Among the above, conductive metal oxides, conductive polymer compounds, and carbon materials are preferable from the viewpoints of conformability and extensibility, and conductive metal oxides and conductive metals are preferable from the viewpoint of improving transparency. Polymer compounds are preferred.
The above conductive materials may be used alone or in combination of two or more.

The transparent conductive layer 14 may further include a binder. The binder makes it possible to bind the conductive materials to each other and coat the transparent conductive layer 14 on the first resin layer 11 with high adhesive force. The binder can be preferably used when a conductive metal oxide, a metal nanowire and a carbon material are used. On the other hand, since the conductive polymer compound can often be coated on the first resin layer 11 without using a binder, when the conductive polymer compound is used as the conductive material, the transparent conductive compound can be used. The layer 14 may not contain a binder.

As the binder, a conventionally known binder resin used for conductive ink is used. Specifically, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polymethylmethacrylate, nitrocellulose, chlorinated polyethylene, chlorinated polypropylene, vinylidene fluoride, ethyl cellulose, hydroxypropylmethyl cellulose, polyester, polyolefin, polycarbonate, poly Thermoplastic resin such as acrylate, polyurethane, polyvinyl acetal resin, alkyd resin, epoxy resin, phenoxy resin, melamine resin, phenol resin, acrylic melamine resin, polyisocyanate resin, polyurethane resin, curable resin such as silicone resin and the like. ..
Further, the transparent conductive layer may further contain additives such as a surfactant, a viscosity modifier, a dispersant, a curing accelerating catalyst, a plasticizer, and an antioxidant.

The transparent conductive layer 14 may be formed by printing a conductive ink on the first resin layer 11. The conductive ink contains the above-mentioned conductive material and may optionally contain the above-mentioned binder and additive, and these components are preferably diluted with an organic solvent or water. A known organic solvent used for conductive ink is used as the organic solvent, and is not particularly limited.

The transparent conductive layer 14 may be printed by a known method of printing a conductive ink, for example, gravure printing, screen printing, offset printing, inkjet printing, electrostatic printing, flexographic printing, gravure offset printing, letterpress reverse offset. Examples include printing. Of these, screen printing, inkjet printing and gravure printing are preferable, and screen printing is particularly preferable.

The transparent conductive layer 14 of the interlayer film 10 for laminated glass is preferably used as a conductive layer for a touch panel or a touch switch. That is, when a finger, a touch pen, or another object approaches or contacts the glass plate of the laminated glass 15, the transparent conductive layer causes an electrical change such as capacitance, current, or voltage, and touch input is performed. Is done. In the present specification, the touch input does not require that a finger, a touch pen, or any other object strictly contacts the laminated glass, and a finger or the like may approach the transparent conductive layer 14 to cause an electrical change. Wide touch input. The method of the touch panel is not particularly limited, but an electrostatic capacity method can be mentioned, and a surface type electrostatic capacity method is preferable.

The transparent conductive layer 14 may be partially printed on the one surface 11A of the first resin layer 11 as described above, but may be formed in a pattern, for example. By being formed in a pattern, it becomes easy to detect the presence/absence of a touch input and the position at which the touch input is made, and it can be suitably used as a conductive layer for a touch panel.
As shown in FIG. 2, the pattern formed by the transparent conductive layer 14 may be a lattice pattern. The lattice pattern may be formed by a plurality of lines 91 arranged in parallel with each other and a plurality of lines 92 intersecting with the lines 91 and arranged in parallel with each other. In such a lattice pattern, a large number of openings 93 are defined by the lines 91 and 92, and a portion corresponding to the openings 93 is a portion where the transparent conductive layer 14 is not printed. As shown in FIG. 2, the lattice pattern does not have to be formed by the plurality of lines 91 and the plurality of lines 92, and may have any shape as long as the opening 93 is defined.
Further, the pattern of the transparent conductive layer 14 is not limited to a lattice pattern, and may be formed into a pattern in which a plurality of diamond-shaped quadrangles are continuous, a pattern in which a large number of lines are arranged side by side, a pattern having disordered intersecting contact portions, or the like. Patterns are preferred.

Further, the transparent conductive layer 14 is provided with a region (also referred to as a “print region”) 95 to be printed and a region 96 not to be printed on the one surface 11A of the first resin layer 11 as shown in FIG. 3, for example. Therefore, the transparent conductive layer 14 may be partially provided. In this case, in the printed region 95, the transparent conductive layer 14 may be formed in a pattern, but may be so-called solid coating without being formed in a pattern.
When the print area 95 is partially provided as shown in FIG. 3, the print area 95 can be used as a touch switch, for example. That is, when there is a touch input in the print area 95 and an electrical change occurs, it is preferable to detect that there is a switch input.

The thickness of the transparent conductive layer 14 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 μm or more and 500 μm or less, more preferably 1 μm or more and 100 μm or less. When the thickness of the transparent conductive layer 14 is not less than these lower limit values, the conductive layer 14 can be provided with sufficient electric conductivity. Further, when the content is not more than the upper limit value, it becomes possible to sufficiently impart the followability and the stretchability to the interlayer film 10 for laminated glass. In addition, it becomes easy to ensure the transparency of the transparent conductive layer 14.
The transparent conductive layer 14 is not particularly limited as long as it has transparency, but, for example, the total light transmittance measured according to JIS K 7105 is preferably 50% or more.

[First resin layer]
The first resin layer 11 preferably contains a resin component, and at least one selected from a thermoplastic resin and a thermoplastic elastomer is used as the resin component. By using either a thermoplastic resin or a thermoplastic elastomer, the first resin layer 11 can be easily bonded to another resin layer or a glass plate by thermocompression bonding or the like.

As described above, the first resin layer is a resin layer on which the transparent conductive layer is printed and preferably has a certain mechanical strength. In addition, it is preferable to use a resin having a certain degree of flexibility in order to provide the interlayer film 10 for laminated glass with conformability and extensibility. From such a viewpoint, as the thermoplastic resin used for the first resin layer, a polyolefin resin, a polyester resin, a polycarbonate resin, polystyrene, a styrene resin such as acrylonitrile/styrene copolymer, or a polyamide resin is used. , Polyurethane resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ionomer resin, polylactic acid, polybutyl succinate and other biodegradable polymers.

Here, as the resin used for the first resin layer, among the above, a polyolefin resin, a polyester resin, a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, a thermoplastic elastomer and the like are preferable. By using these resins, the printability is improved, and it is easy to provide the intermediate film for laminated glass with the followability and the stretchability.
Further, among the above, from the viewpoint of further improving the followability and the extensibility, a polyolefin resin, a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, and a thermoplastic elastomer are more preferable. Among these, a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, and a thermoplastic elastomer are more preferable from the viewpoint of enhancing adhesiveness, and a polyvinyl acetal resin is still more preferable from the viewpoint of improving impact absorption and the like.
Further, from the viewpoint of improving the mechanical strength while imparting followability and extensibility, a polyolefin resin, a polyester resin or the like may be used.

(Polyester resin)
Examples of the polyester-based resin used for the first resin layer 11 include polypropylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and the like. Polyethylene terephthalate (PET) is preferable from the viewpoint of imparting the following properties and extensibility to the interlayer film 10 for laminated glass while imparting a certain mechanical strength to the first resin layer 11.

(Polyolefin resin)
Examples of the polyolefin resin include polyethylene resin, polypropylene resin, polybutene resin, and poly(4-methylpentene-1) resin.

(Polyvinyl acetal resin)
The polyvinyl acetal resin is obtained by acetalizing polyvinyl alcohol with an aldehyde. Further, polyvinyl alcohol is obtained by saponifying polyvinyl ester such as polyvinyl acetate. The polyvinyl acetal resin may be used alone or in combination of two or more.

The aldehyde used for acetalization is not particularly limited, but an aldehyde having 1 to 10 carbon atoms is preferably used, more preferably an aldehyde having 2 to 6 carbon atoms, and further preferably an aldehyde having 4 carbon atoms.
The aldehyde having 1 to 10 carbon atoms is not particularly limited, and examples thereof include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among them, n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable. These aldehydes may be used alone or in combination of two or more.

As the polyvinyl alcohol, polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is generally used. The average degree of polymerization of polyvinyl alcohol is preferably 500 or more and preferably 4000 or less in order to adjust the average degree of polymerization of the polyvinyl acetal resin within a desired range. The average degree of polymerization of polyvinyl alcohol is more preferably 1000 or more, and further preferably 3600 or less. The average degree of polymerization of polyvinyl alcohol is determined by a method according to JIS K6726 "Testing method for polyvinyl alcohol".

The number of carbon atoms of the acetal group contained in the polyvinyl acetal resin is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and even more preferably 4. As the acetal group, a butyral group is particularly preferable, and therefore, as the polyvinyl acetal resin, a polyvinyl butyral resin is preferable.
The degree of acetalization of the polyvinyl acetal resin is preferably 40 mol% or more, and preferably 85 mol% or less. The degree of acetalization is more preferably 60 mol% or more, and further preferably 75 mol% or less. The degree of acetalization means the degree of butyralization when the acetal group is a butyral group and the polyvinyl acetal resin is a polyvinyl butyral resin.

The amount of hydroxyl groups of the polyvinyl acetal resin is preferably 15 mol% or more, and preferably 35 mol% or less. By setting the amount of hydroxyl groups to 15 mol% or more, the adhesiveness to a glass plate or the like tends to be good, and the penetration resistance of the laminated glass or the like tends to be good. Further, by setting the amount of hydroxyl groups to 35 mol% or less, it is possible to prevent the laminated glass from becoming too hard. The amount of hydroxyl groups of the polyvinyl acetal resin is more preferably 20 mol% or more, and further preferably 33 mol% or less.

The acetylation degree (the amount of acetyl groups) of the polyvinyl acetal resin is preferably 0.1 mol% or more, and preferably 20 mol% or less. When the degree of acetylation is at least the above lower limit, the compatibility with the plasticizer and the like tends to be good. Further, when the content is not more than the above upper limit, the moisture resistance of the interlayer film becomes high. From these viewpoints, the acetylation degree is more preferably 0.3 mol% or more, further preferably 0.5 mol% or more, more preferably 10 mol% or less, and further preferably 5 mol% or less. is there.
The amount of hydroxyl group, the degree of acetalization (degree of butyralization), and the degree of acetylation can be calculated from the results measured by the method according to JIS K6728 “Polyvinyl butyral test method”.

The average degree of polymerization of the polyvinyl acetal resin is preferably 500 or more, and preferably 4000 or less. When the average degree of polymerization is 500 or more, the laminated glass has good penetration resistance. Further, when the average degree of polymerization is 4000 or less, the laminated glass can be easily molded. The degree of polymerization is more preferably 1000 or more, and further preferably 3600 or less. The average degree of polymerization of the polyvinyl acetal resin is the same as the average degree of polymerization of polyvinyl alcohol as a raw material, and can be determined by the average degree of polymerization of polyvinyl alcohol.

(Ethylene-vinyl acetate copolymer resin)
The ethylene-vinyl acetate copolymer resin may be a non-crosslinking type ethylene-vinyl acetate copolymer resin or a high temperature crosslinking type ethylene-vinyl acetate copolymer resin. As the ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate modified resin such as saponified product of ethylene-vinyl acetate copolymer and hydrolyzate of ethylene-vinyl acetate can also be used.

The ethylene-vinyl acetate copolymer resin preferably has a vinyl acetate content of 10% by mass or more and 50% by mass or less, which is measured according to JIS K 6730 “Ethylene/vinyl acetate resin test method” or JIS K 6924-2:1997. , And more preferably 20 mass% or more and 40 mass% or less. When the vinyl acetate content is at least these lower limits, the adhesion to glass will be high and the penetration resistance of the laminated glass will tend to be good. Further, by setting the vinyl acetate content to be not more than these upper limits, the breaking strength of the interlayer film for laminated glass becomes high and the impact resistance of the laminated glass becomes good.

(Thermoplastic elastomer)
Examples of the thermoplastic elastomer include styrene-based thermoplastic elastomer and aliphatic polyolefin. The styrene-based thermoplastic elastomer is not particularly limited, and known ones can be used. The styrene-based thermoplastic elastomer generally has a styrene monomer polymer block that becomes a hard segment and a conjugated diene compound polymer block that becomes a soft segment or a hydrogenated block thereof. Specific examples of the styrene-based thermoplastic elastomer include styrene-isoprene diblock copolymer, styrene-butadiene diblock copolymer, styrene-isoprene-styrene triblock copolymer, and styrene-butadiene/isoprene-styrene triblock copolymer. Examples thereof include polymers, styrene-butadiene-styrene triblock copolymers, and hydrogenated products thereof.
The aliphatic polyolefin may be a saturated aliphatic polyolefin or an unsaturated aliphatic polyolefin. The aliphatic polyolefin may be a polyolefin having a chain olefin as a monomer, or may be a polyolefin having a cyclic olefin as a monomer. From the viewpoint of effectively improving the storage stability and sound insulation of the interlayer film, the aliphatic polyolefin is preferably a saturated aliphatic polyolefin.
Examples of the material of the aliphatic polyolefin include ethylene, propylene, 1-butene, trans-2-butene, cis-2-butene, 1-pentene, trans-2-pentene, cis-2-pentene, 1-hexene, trans. 2-hexene, cis-2-hexene, trans-3-hexene, cis-3-hexene, 1-heptene, trans-2-heptene, cis-2-heptene, trans-3-heptene, cis-3-heptene , 1-octene, trans-2-octene, cis-2-octene, trans-3-octene, cis-3-octene, trans-4-octene, cis-4-octene, 1-nonene, trans-2-nonene , Cis-2-nonene, trans-3-nonene, cis-3-nonene, trans-4-nonene, cis-4-nonene, 1-decene, trans-2-decene, cis-2-decene, trans-3 -Decene, cis-3-decene, trans-4-decene, cis-4-decene, trans-5-decene, cis-5-decene, 4-methyl-1-pentene, vinylcyclohexane and the like.

[Plasticizer]
The first resin layer 11 may further contain a plasticizer in addition to the resin component. The first resin layer 11 becomes soft by containing the plasticizer, and the followability to the curved surface of the interlayer film for laminated glass and the stretchability are further improved. Furthermore, it becomes possible to exhibit high adhesiveness. When the polyvinyl acetal resin is used as the thermoplastic resin, the plasticizer makes the first resin layer 11 flexible and easily exhibits high adhesiveness.
Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. .. Of these, organic ester plasticizers are preferable.

Examples of the monobasic organic acid ester include esters of glycol and monobasic organic acid. Examples of glycols include polyalkylene glycols in which each alkylene unit has 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and the number of repeating alkylene units is 2 to 10, preferably 2 to 4. Further, the glycol may be a monoalkylene glycol having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and 1 repeating unit.
Specific examples of the glycol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and butylene glycol.
Examples of the monobasic organic acid include organic acids having 3 to 10 carbon atoms, and specifically, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, 2-ethylpentanoic acid, heptyl acid, n-octyl acid. Acid, 2-ethylhexyl acid, n-nonyl acid, decyl acid and the like can be mentioned.

Specific monobasic organic acids include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, Triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, di Propylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethyl pentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol Di-n-heptanoate, triethylene glycol di-2-ethyl butyrate, ethylene glycol di-2-ethyl butyrate, 1,2-propylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di-2 -Ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, 1,2-butylene glycol di-2-ethyl butyrate and the like can be mentioned.

Examples of the polybasic organic acid ester include ester compounds of a dibasic organic acid having 4 to 12 carbon atoms such as adipic acid, sebacic acid, and azelaic acid, and an alcohol having 4 to 10 carbon atoms. .. The alcohol having 4 to 10 carbon atoms may have a straight chain, may have a branched structure, or may have a cyclic structure.
Specific examples include dibutyl sebacate, dioctyl azelate, dihexyl adipate, dioctyl adipate, hexyl adipate cyclohexyl, diisononyl adipate, heptylnonyl adipate, dibutylcarbitol adipate, and mixed adipate. Further, oil-modified sebacic acid alkyd or the like may be used. Examples of the mixed adipic acid ester include adipic acid esters prepared from two or more kinds of alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms.
Examples of the organic phosphoric acid plasticizer include phosphoric acid esters such as tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.
The plasticizers may be used alone or in combination of two or more.
Among the above, the plasticizer is preferably an ester of glycol and a monobasic organic acid, and triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.

The content of the plasticizer in the first resin layer 11 is not particularly limited, but is a certain amount from the viewpoint of imparting flexibility, excellent followability to a curved surface and extensibility, and excellent adhesiveness. It is better to contain the above. From such a viewpoint, the content of the plasticizer in the first resin layer 11 is preferably 20 parts by mass or more with respect to 100 parts by mass of the resin component. The content of the plasticizer is preferably 80 parts by mass or less. When the content is 80 parts by mass or less, the plasticizer is prevented from separating from the first resin layer. The content of the plasticizer is more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, more preferably 70 parts by mass or less, and further preferably 63 parts by mass or less.

On the other hand, by reducing the amount of the plasticizer in the first resin layer 11, the bleed-out plasticizer is prevented from deteriorating the conductivity of the transparent conductive layer 14. Therefore, in order to make the conductivity of the transparent conductive layer 14 excellent, the content of the plasticizer is preferably 40 parts by mass or less, 10 parts by mass or less, more preferably 5 parts by mass or less, and 0 parts by mass. More preferably, the plasticizer may not be contained in the first resin layer 11.
In the first resin layer 11, a resin component or a resin component and a plasticizer are the main components, and the total amount of the resin component and the plasticizer is usually 70% by mass or more on the basis of the total amount of the first resin layer, It is preferably 80% by mass or more, more preferably 90% by mass or more and 100% by mass or less.

[Other additives]
The first resin layer 11 may contain, if necessary, an infrared absorber, an ultraviolet absorber, an antioxidant, a light stabilizer, a fluorescent whitening agent, a crystal nucleating agent, a dispersant, a dye, a plasticizer such as a pigment. You may contain an additive.

The thickness of the first resin layer is not particularly limited, but is, for example, 0.01 mm or more and 1.0 mm or less, more preferably 0.03 mm or more and 0.6 mm or less, and further preferably 0.05 mm or more and 0.4 mm or less. is there.

One surface 11A of the first resin layer 11 on which the transparent conductive layer 14 is printed preferably has an arithmetic average height roughness (Ra) of 10 μm or less. By setting the arithmetic average height roughness (Ra) to 10 μm or less, the printability of the transparent conductive layer 14 can be improved. From the viewpoint of further improving printability, the arithmetic average height roughness (Ra) is more preferably 7 μm or less. From the viewpoint of printability, the lower the arithmetic average height roughness (Ra), the better, but it may be 10 nm or more, for example.
The first resin layer 11 may be subjected to a surface smoothing treatment or the like before the transparent conductive layer 14 is printed so that the arithmetic average height roughness (Ra) becomes low.
The arithmetic average height roughness (Ra) is an arithmetic average roughness measured by a contact type profiler according to ISO 4287 and a measurement length of 2000 μm.

[Second and third resin layers]
Each of the second and third resin layers 12 and 13 contains a resin component, and as the resin component, it is preferable to use at least one selected from a thermoplastic resin and a thermoplastic elastomer, respectively.
Here, the thermoplastic resin and the thermoplastic elastomer may be appropriately selected and used from the resins listed as the resin used for the first resin 11 above, but a resin having adhesiveness to a glass plate is preferably used. it can. In addition, the second and third resin layers 12 and 13 are preferably layers having higher extensibility and flexibility than the first resin layer 11, respectively.
From such a viewpoint, as the resin used for the second and third resin layers, a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, and a thermoplastic elastomer are preferable. In each of the second and third resin layers, these may be used alone or in combination of two or more.
Further, as the resin used for each of the second and third resin layers 12 and 13, among the above-mentioned resins, polyvinyl acetal resin is more preferable.

A detailed description of the polyvinyl acetal resin, the ethylene-vinyl acetate copolymer resin, and the thermoplastic elastomer used for the second resin layer 12 and the third resin layer 13 is given in the first resin layer 11. The description is omitted because it is as described above.

The resins contained in the second resin layer 12 and the third resin layer 13 may be of the same type or of different types. Similarly, the resin contained in the first resin layer 11 may be the same type as the second resin layer 12 and the third resin layer 13, or may be different types. May be used.

However, the second resin layer 12 preferably contains the same type of thermoplastic resin or thermoplastic elastomer as the first resin layer 11. When the same kind of thermoplastic resin or thermoplastic elastomer is used for the first and second resin layers 11 and 12, the first and second resin layers 11 and 12 are easily adhered to each other. That is, the first and second resin layers 11 and 12 are bonded to each other with a small bonding area, for example, via the transparent conductive layer 14 partially provided on the one surface 11A of the first resin layer 11. However, even in such a case, the use of the same type of resin facilitates the adhesion with high adhesive strength. Furthermore, by using the same type of resin, the difference in refractive index between layers can be reduced or eliminated, so that the optical quality is improved.

Similarly, the third resin layer 13 preferably contains the same type of thermoplastic resin or thermoplastic elastomer as the first resin layer 11. That is, it is preferable that all of the first to third resin layers 11, 12, and 13 contain the same kind of thermoplastic resin or thermoplastic elastomer. By using the same type of resin as the first resin layer 11 for the third resin layer 13, the first resin layer 11 and the third resin layer 13 can be easily bonded with high adhesive force.

The same type means that the type of resin (thermoplastic resin or thermoplastic elastomer) contained in the first resin layer 11 is the same as that of the resin contained in the second resin layer 12 (thermoplastic resin or thermoplastic resin or thermoplastic elastomer). It means that the resins are the same as the type of the thermoplastic elastomer, but the resins having the same types do not have to have the same molecular weight, monomer composition, and content.
That is, if the resin contained in the first resin layer 11 is a polyvinyl acetal resin, the polyvinyl acetal resin must also be contained in the second resin layer 12, but these first and second resin layers 11 It is not necessary that the polyvinyl acetal resin contained in each of No. 12 and No. 12 has the same monomer composition, molecular weight, and content in each layer.
Therefore, for example, while the same kind of resin is used for the first and second resin layers, the monomer composition, the molecular weight, the content, etc. are changed as appropriate to make the second resin layer more than the first resin layer. The extensibility and flexibility may be increased.
When each resin layer contains two or more kinds of resins, for example, two or more kinds of resins contained in one resin layer are such that at least one of them is the same as the kind of resin contained in the other resin layer. It may be the same, but it is more preferable that the types of resins contained in both resin layers are the same.

Further, each of the second resin layer 12 and the third resin layer 13 may further contain a plasticizer in addition to the resin component. Each of the second and third resin layers 12 and 13 becomes soft by containing the plasticizer, and the followability to the curved surface of the interlayer film for laminated glass 10 and the extensibility are improved. Furthermore, it becomes possible to exhibit high adhesiveness to the glass plates 16A and 16B. The plasticizer is used particularly effectively when it is contained when a polyvinyl acetal resin is used as the resin component. The details of the plasticizer are as described above, and the detailed description thereof is the same as the above, and thus will be omitted.

The content of the plasticizer in each of the second and third resin layers 12 and 13 is not particularly limited, but from the viewpoint of excellent followability to curved surfaces, stretchability, and adhesiveness, The content of the plasticizer in the third resin layers 12 and 13 is preferably 20 parts by mass or more with respect to 100 parts by mass of the resin component. When the content of the plasticizer is 20 parts by mass or more, the interlayer film for laminated glass becomes moderately flexible, and the followability to curved surfaces and the extensibility become good. When the content of the plasticizer is 80 parts by mass or less, the plasticizer is prevented from separating from the second and third resin layers. The content of the plasticizer is more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, more preferably 70 parts by mass or less, and further preferably 63 parts by mass or less.

Further, in order to make the transparent conductive layer 14 excellent in conductivity, the content of the plasticizer in the second resin layer 12 may be reduced as in the case of the first resin layer 11. From such a viewpoint, the content of the plasticizer in the second resin layer 12 may be 40 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even 0 parts by mass. Even more preferably, the plasticizer may not be contained in the second resin layer 12.
As described above, when the content of the plasticizer in the second resin layer 12 is reduced, the content of the plasticizer in the third resin layer 13 may be further reduced. From such a viewpoint, the content of the plasticizer in the third resin layer 13 may be 40 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even 0 parts by mass. Even more preferably, the plasticizer may not be contained in the third resin layer 13.

In each of the second and third resin layers 12 and 13, the resin component or the resin component and the plasticizer is the main component, and the total amount of the resin component and the plasticizer is the second resin layer or The total amount of the third resin layer is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more and 100% by mass or less.
Further, in the second and third resin layers 12 and 13, respectively, if necessary, an infrared absorber, an ultraviolet absorber, an antioxidant, a light stabilizer, a fluorescent whitening agent, a crystal nucleating agent, a dispersant, You may contain additives other than a plasticizer, such as a dye and a pigment.
The thickness of each of the second and third resin layers is not particularly limited, but is, for example, 0.05 mm or more and 1.5 mm or less, more preferably 0.1 mm or more and 1 mm or less, and further preferably 0.2 mm or more and 0.6 mm. It is below.

The interlayer film for laminated glass has a visible light transmittance of, for example, 10% or more, and is 30% or more, when a laminated glass sample is produced using two predetermined clear glass plates. It is preferably 50% or more, more preferably 70% or more. In the present invention, since the transparent conductive layer has transparency, the interlayer film for laminated glass can secure a visible light transmittance of a certain level or more and can be suitably used in automobiles and the like. Further, when it is 70% or more, it can be used for, for example, a windshield of a car or a windshield. Even if it is less than 70%, it can be used for roof glass and side glass, for example.
The visible light transmittance is measured with a spectrophotometer (“U-4100” manufactured by Hitachi High-Technologies Corporation) in accordance with JIS R 3106 (1998) at a wavelength of 380 to 780 nm. To do.
Further, the clear glass used in the measurement of visible light transmittance is a clear glass having a visible light transmittance of 90.4% according to JIS R 3202:2011. In the measurement of visible light transmittance, a laminated glass sample may be prepared by using the above-mentioned clear glass as an intermediate film for laminated glass in the same manner as in the laminated glass described later.

[Glass plate]
The first and second glass plates 16A and 16B used in the laminated glass 15 may be either inorganic glass or organic glass, but inorganic glass is preferred. The inorganic glass is not particularly limited, but includes clear glass, float plate glass, tempered glass, colored glass, polished plate glass, template glass, netted plate glass, lined plate glass, ultraviolet absorbing plate glass, infrared reflecting plate glass, infrared absorbing plate glass, green glass. Etc.
Moreover, what is generally called a resin glass is used as the organic glass, and it is not particularly limited, and examples thereof include an organic glass composed of a polycarbonate plate, a polymethylmethacrylate plate, a polyester plate and the like.
The two glass plates may be made of the same material as each other, or may be made of different materials. For example, one may be inorganic glass and the other may be organic glass, but it is preferable that both of the two glass plates are inorganic glass or organic glass.
The thickness of the first and second glass plates 16A and 16B is not particularly limited, but is, for example, 0.1 mm or more and 10 mm or less, preferably 0.3 mm or more and 5 mm or less, more preferably 0.5 mm or more and 3 mm or less. Is. The thicknesses of the first and second glass plates 16A and 16B may be the same or different from each other.

When the touch panel function and the touch switch function are given to the laminated glass interlayer film 10, touch input may be performed from the first glass plate 16A side or touch input may be performed from the second glass plate 16B. It is preferable that the touch input is performed from the side of the first glass plate 16A. Since only one resin layer (second resin layer 12) is provided between the first glass plate 16A and the transparent conductive layer 14, touch input from the first glass 16A plate side results in high sensitivity. Touch input is detected by.

Further, when the first and second glass plates 16A and 16B have different thicknesses, it is preferable that the touch input is performed from the thinner glass plate. When touch input is performed on a thin glass plate, the transparent conductive layer 14 detects the touch input with high sensitivity. Therefore, in the present embodiment, it is preferable that the first glass plate 16A be thinner than the second glass plate 16B. When the thickness of the first glass plate 16A is reduced, the fact that only one resin layer is provided between the first glass plate 16A and the transparent conductive layer 14 is combined with the touch input from the first glass plate 16A side. The touch input is detected with higher sensitivity.

Therefore, the first glass plate 16A is preferably arranged on the side where touch input is expected. For example, when used as an automobile window glass described later, when a touch input from the outside is expected, the first glass plate 16A is arranged on the outside of the vehicle and the second glass plate 16B is arranged on the inside of the vehicle. Good. When touch input from the inside of the vehicle is assumed, the first glass plate 16A may be placed inside the vehicle and the second glass plate 16B may be placed outside the vehicle.

As described above, since the transparent conductive layer 14 is provided in the interlayer film 10 for laminated glass of the first embodiment, the laminated glass 15 can be used as a touch panel, a touch switch, or the like. Here, since the transparent conductive layer 14 is formed by printing, it is possible to impart stretchability and flexibility to the interlayer film 10 for laminated glass. Therefore, for example, even when the laminated glass 15 has a curved surface, the interlayer film 10 for laminated glass can sufficiently follow the laminated glass 15.

The laminated glass may be manufactured by arranging the first to third resin layers between two glass plates and integrating them by pressure bonding or the like. At this time, a transparent conductive layer may be formed on one surface of the first resin layer by printing in advance, and then the first resin layer may be disposed between the two glass plates.
Each of the first to third resin layers may be formed, for example, by mixing a resin, a plasticizer that is blended as necessary, and other additives, and by extrusion molding.
In addition, each of the first to third resin layers is, for example, a resin, a resin composition obtained by mixing a resin, a plasticizer to be blended if necessary, and other additives You may form by apply|coating to a film etc. and heating and drying as needed. At this time, the resin composition may be diluted with a solvent or the like. Further, the resin layer formed on the resin film or the like may be peeled from the resin film, a release film, or the like, or the resin film may form another resin layer, in which case it is peeled from the resin film. You don't have to.

In the first embodiment described above, the interlayer film for laminated glass having three resin layers has been described, but any number of resin layers may be used as long as it is one or more. Hereinafter, configurations in which the resin layer is two layers or one layer will be described as second and third embodiments.

[Second Embodiment]
FIG. 4 shows a laminated glass 25 including the interlayer film 20 for laminated glass of the second embodiment. The interlayer film 20 for laminated glass of the second embodiment has two resin layers, and the third resin layer 13 is omitted from the first embodiment. Hereinafter, differences between the second embodiment and the first embodiment will be described, and description of configurations that are similar to those of the first embodiment will be omitted.

In the interlayer film 20 for laminated glass of the second embodiment, the first resin layer 11, the transparent conductive layer 14, and the second resin layer 12 are provided in this order along the thickness direction. The transparent conductive layer 14 is printed on one surface of the first resin layer 11A as described above.
In the interlayer film 20 for laminated glass, one surface 11A of the first resin layer 11 is bonded to one surface 12A of the second resin layer 12 via the transparent conductive layer 14. Here, when the transparent conductive layer 14 is partially provided on the one surface 11A, the one surface 11A of the first resin layer 11 is partially bonded directly to the second resin layer 12.

The other surfaces 11B and 12B of the first and second resin layers 11 and 12 are adhered to the glass plates 16B and 16A, respectively. In the interlayer film 20 for laminated glass, the transparent conductive layer 14 is provided between the two resin layers 11 and 12, so that it is necessary to provide the transparent conductive layer between the glass plates 16B and 16A and the resin layers 11 and 12. Since it is not present, the adhesiveness between the interlayer film for laminated glass 20 and the glass plates 16A and 16B becomes good.
In the second embodiment, the thickness of each of the first and second resin layers is not particularly limited, but is, for example, 0.05 mm or more and 2.0 mm or less, more preferably 0.1 mm or more and 1.5 mm or less, and It is preferably 0.2 mm or more and 0.9 mm or less.

In the present embodiment, the details of the first and second resin layers 11 and 12 are as described in the first embodiment above, and the resin component contained in the first resin layer 11 includes It is preferable to use a thermoplastic resin or a thermoplastic elastomer, and as the thermoplastic resin or the thermoplastic elastomer, the resins as described above are used. Further, a plasticizer, other additives, etc. may be contained, and the details thereof are the same as those in the first embodiment.
However, as the resin used for the first resin layer 11 in the second embodiment, it is preferable to use a resin having a high adhesive force to the glass plate. Therefore, in the second embodiment, it is preferable to use polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, or thermoplastic elastomer for the first resin layer 11 from the viewpoint of enhancing the adhesiveness with the glass plate. Among them, polyvinyl acetal resin is particularly preferable.
On the other hand, the resin used for the second resin layer 12 is the same as the second resin layer of the first embodiment, and the resin preferably used is the same as the second resin layer of the first embodiment. It is the same. Also in the second embodiment, the second resin layer 12 preferably contains the same type of thermoplastic resin or thermoplastic elastomer as the first resin layer 11.

[Third Embodiment]
FIG. 5: shows the laminated glass 35 provided with the intermediate film 30 for laminated glasses of 3rd Embodiment. The interlayer film 30 for laminated glass of the third embodiment is provided with one resin layer, and specifically, the second resin layer 12 is further omitted from the second embodiment. is there. Hereinafter, the difference between the interlayer film 30 for laminated glass of the third embodiment and that of the second embodiment will be described.

Also in the present embodiment, the interlayer film 30 for laminated glass is one in which the transparent conductive layer 14 is provided by printing on one surface 11A of the first resin layer 11. One surface 11A of the first resin layer 11 is bonded to one glass plate 16A constituting the laminated glass 15 via the transparent conductive layer 14. The other surface 11B of the first resin layer 11 is adhered to the other glass plate 16B forming the laminated glass 35.
In the interlayer film 30 for laminated glass, the transparent conductive layer 14 is partially provided. Since the transparent conductive layer 14 is partially provided, the one surface 11A of the first resin layer 11 is bonded to the glass plate 16A even if the transparent conductive layer 14 is provided between the surface 11A and the glass plate 16A.
In the present embodiment, the configurations of the first resin layer 11 and the transparent conductive layer 14 are the same as those of the above-described second embodiment, and thus the description thereof will be omitted.
However, in the third embodiment, the thickness of the first resin layer 11 is not particularly limited, but is, for example, 0.1 mm or more and 3.0 mm or less, preferably 0.2 mm or more and 2.0 mm or less, It is preferably 0.3 mm or more and 1.5 mm or less.

Although the interlayer film for laminated glass of the above first to third embodiments has a configuration in which 1 to 3 resin layers are provided, four or more resin layers may be provided. For example, in the interlayer film 10 for laminated glass, a resin layer is additionally provided between the first resin layer 11 and the third resin layer 13 or between the second resin layer 12 and the transparent conductive layer 14. May be.

Further, in each of the above embodiments, only one layer of the transparent conductive layer 14 is provided, but two or more layers may be provided. When two layers are provided, for example, transparent conductive layers may be provided on both surfaces of the first resin layer 11 by printing. When a resin layer is additionally provided as described above, the resin layer may be provided with a transparent conductive layer by printing.
When two layers of the transparent conductive layer 14 are provided, for example, the touch panel can be a projection type electrostatic capacitance type.

[Fourth Embodiment]
The interlayer film for laminated glass of the present invention may be used as a functional layer by imparting a function to any of the resin layers. As the functional layer, preferably, one of the resin layers contains a light emitting material to form a light emitting layer. Hereinafter, a specific example in which a resin layer is used as a light emitting layer will be described as a fourth embodiment.
FIG. 6 shows a laminated glass 45 having an interlayer film 40 for laminated glass according to the fourth embodiment of the present invention. The fourth embodiment is different from the first embodiment only in the configuration of the third resin layer. The differences between the fourth embodiment and the first embodiment will be described below.

In the fourth embodiment, a light emitting material is contained in the third resin layer 13 to form a light emitting layer 13X. Since the third resin layer 13 adheres to the other surface 11B of the first resin layer 11 where the transparent conductive layer 14 is not provided, the third resin layer 13 has a high adhesive force to the first resin layer 11 even if it contains a light emitting material. Is secured. Further, since the light emitting material does not contact the transparent conductive layer 14, the light emitting material does not adversely affect the transparent conductive layer 14.
The light emitting material is a material that is excited by absorbing light such as ultraviolet rays and emits light having a wavelength different from the absorbed wavelength such as visible light. The light emitting layer 13X causes the light emitting material to emit light and causes the interlayer film 40 for laminated glass to display an image.

Specific examples of the light emitting material include a lanthanoid complex having a ligand containing a halogen atom because it can exhibit a high light emitting property. Among the lanthanoid complexes, the lanthanoid complex having a ligand containing a halogen atom emits light with high emission intensity when irradiated with light. Examples of the lanthanoid complex having a ligand containing a halogen atom include a lanthanoid complex having a monodentate ligand containing a halogen atom, a lanthanoid complex having a bidentate ligand containing a halogen atom, and a tridentate ligand containing a halogen atom. Halogen such as lanthanoid complex having a ligand, lanthanoid complex having a tetradentate ligand containing a halogen atom, lanthanoid complex having a pentadentate ligand containing a halogen atom, and lanthanoid complex having a hexadentate ligand containing a halogen atom The lanthanoid complex which has a multidentate ligand containing an atom is mentioned.

Among them, the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom emits high visible light by irradiating light with a wavelength of 300 to 410 nm. It is possible to emit light with high intensity.
Moreover, the lanthanoid complex having a bidentate ligand containing a halogen atom or the lanthanoid complex having a tridentate ligand containing a halogen atom has excellent heat resistance. Since window glass for vehicles is often used in a high temperature environment by being irradiated with infrared rays of sunlight, the lanthanoid complex having a bidentate ligand containing a halogen atom or the tridentate compound containing a halogen atom is used. By using the lanthanoid complex having a ligand, deterioration of the light emitting material can be prevented.

In the present specification, the lanthanoid includes lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. The lanthanoid is preferably neodymium, europium, or terbium, more preferably europium or terbium, and even more preferably europium, because even higher emission intensity can be obtained.

Examples of the bidentate ligand containing a halogen atom include a ligand having a structure represented by the following general formula (1) and a ligand having a structure represented by the following general formula (2). Can be mentioned.

In the general formula (1), R ¹ and R ³ represents an organic group, at least one of R ¹ and R ³ is an organic group containing a halogen atom, R ² is the number 1 or more linear carbon Represents an organic group. R ¹ and R ³ are preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 1 to 5 carbon atoms, A hydrocarbon group having 1 to 3 carbon atoms is particularly preferable. In the above hydrocarbon group, a part of hydrogen atoms may be replaced with atoms other than hydrogen atoms and functional groups. As the hydrocarbon group having 1 to 3 carbon atoms, a methyl group in which a hydrogen atom is not substituted, an ethyl group, a propyl group, a methyl group in which a part of a hydrogen atom is substituted with a halogen atom, an ethyl group, a propyl group Groups and the like. A fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be used as the halogen atom of the methyl group, ethyl group, or propyl group in which a part of the hydrogen atoms are substituted with a halogen atom. As the hydrocarbon group having 1 to 3 carbon atoms, since it emits light with high emission intensity, a methyl group, an ethyl group, or a propyl group in which a part of hydrogen atoms are substituted with a halogen atom is preferable. It is more preferably a fluoromethyl group.
R ² is preferably an alkylene group having 1 or more carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group having 1 carbon atom. In the alkylene group having 1 or more carbon atoms, some hydrogen atoms may be replaced with atoms other than hydrogen atoms and functional groups.

The lanthanoid complex having a halogen atom-containing ligand may have at least one halogen atom-containing ligand, and may have a halogen atom-free ligand. As the ligand containing no halogen atom, a ligand having the same structure as the above general formula (1) except that it does not contain a halogen atom, and a structure represented by the following general formulas (2) to (8) are used. Examples thereof include a ligand. In the ligand having a structure represented by the following general formulas (2) to (8), some or all of the hydrogen atoms are —COOR, —SO ₃ , —NO ₂ , —OH, alkyl group, —NH. ₂ may be substituted.

In the above formula (2), the two Ns may be anywhere in the bipyridine skeleton. For example, there are two Ns at the 2,2′ position, 3,3′ position, 4,4′ position, 2,3′ position, 2,4′ position, and 3,4′ position of the bipyridine skeleton. .. Above all, it is preferable that there are two N at the 2,2′ position.

In the above formula (3), the two N may be anywhere in the bipyridine skeleton. Above all, it is preferable that there are two Ns at the 1st and 10th positions.

In the above formula (4), the two N may be anywhere in the bipyridine skeleton. Above all, it is preferable that there are two Ns at the 1st and 10th positions.

In the above formula (5), the three Ns may be anywhere in the terpyridine skeleton.

In the above formula (6), R ^{4 at} the center represents a linear organic group having 1 or more carbon atoms.

In the above formula (7), two R ^{5 s} represent a linear organic group having 1 or more carbon atoms.

In the above formula (8), n represents an integer of 1 or 2.

Examples of the lanthanoid complex having a bidentate ligand containing a halogen atom include tris(trifluoroacetylacetone)phenanthroline europium (Eu(TFA) ₃ phen) and tris(trifluoroacetylacetone)diphenylphenanthroline europium (Eu(TFA) ₃ dpphen), tris(hexafluoroacetylacetone)diphenylphenanthroline europium, tris(hexafluoroacetylacetone)bis(triphenylphosphine) europium, tris(trifluoroacetylacetone)2,2′-bipyridine europium, tris(hexafluoroacetylacetone)2,2 '-Bipyridine europium, tris(5,5,6,6,7,7,7-heptafluoro-2,4-pentanedionate)2,2'-bipyridine europium ([Eu(FPD) ₃ ]bpy), Tris(trifluoroacetylacetone)3,4,7,8-tetramethyl-1,10 phenanthroline europium ([Eu(TFA) ₃ ]tmphen), tris(5,5,6,6,7,7,7-hepta) Examples thereof include fluoro-2,4-pentanedionate)phenanthroline europium ([Eu(FPD) ₃ ]phen), terpyridine trifluoroacetylacetone europium, and terpyridine hexafluoroacetylacetone europium.

Other examples of the lanthanoid complex having a bidentate ligand containing a halogen atom include tris(trifluoroacetylacetone)phenanthroline terbium (Tb(TFA) ₃ phen) and tris(trifluoroacetylacetone)diphenylphenanthroline terbium (Tb( TFA) ₃ dpphen), tris(hexafluoroacetylacetone)diphenylphenanthroline terbium, tris(hexafluoroacetylacetone)bis(triphenylphosphine)terbium, tris(trifluoroacetylacetone)2,2′-bipyridineterbium, tris(hexafluoroacetylacetone) 2,2'-bipyridine terbium, tris (5,5,6,6,7,7,7-heptafluoro-2,4-pentanedionate) 2,2'-bipyridine terbium ([Tb(FPD) ₃ ] bpy), tris(trifluoroacetylacetone) 3,4,7,8-tetramethyl-1,10 phenanthroline terbium ([Tb(TFA) ₃ ]tmphen), tris (5,5,6,6,7,7, 7-heptafluoro-2,4-pentanedionate)phenanthroline terbium ([Tb(FPD) ₃ ]phen), terpyridine trifluoroacetylacetone terbium, terpyridine hexafluoroacetylacetone terbium, and the like.

As the halogen atom of the lanthanoid complex having a ligand containing a halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be used. Of these, a fluorine atom is preferable because it stabilizes the structure of the ligand.

Among the lanthanoid complexes having a bidentate ligand containing a halogen atom or the lanthanoid complexes having a tridentate ligand containing a halogen atom, those having an acetylacetone skeleton containing a halogen atom are particularly preferable because they are excellent in initial light emission. Lanthanoid complexes with bidentate ligands are preferred.
Examples of the lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing a halogen atom include Eu(TFA) ₃ phen, Eu(TFA) ₃ dpphen, Eu(HFA) ₃ phen, and [Eu(FPD) ₃ ]. bpy, [Eu(TFA) ₃ ]tmphen, [Eu(FPD) ₃ ]phen and the like. A structure of a lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing these halogen atoms is shown.

Other examples of the lanthanoid complex having a bidentate ligand having an acetylacetone skeleton containing a halogen atom include Tb(TFA) ₃ phen, Tb(TFA) ₃ dpphen, Tb(HFA) ₃ phen, and [Tb(FPD ) ₃ ]bpy, [Tb(TFA) ₃ ]tmphen, [Tb(FPD) ₃ ]phen and the like.

The lanthanoid complex having a ligand containing a halogen atom is preferably in the form of particles. The particulate form makes it easier to finely disperse the lanthanoid complex having the ligand containing a halogen atom in the light emitting layer.
When the lanthanoid complex having a ligand containing a halogen atom is particulate, a preferable lower limit of the average particle diameter of the lanthanoid complex is 0.01 μm, a preferable upper limit thereof is 10 μm, and a more preferable lower limit thereof is 0.03 μm, and more preferable. The upper limit is 1 μm.

As the light emitting material, a light emitting material having a terephthalic acid ester structure can also be used. The light emitting material having the terephthalic acid ester structure emits light when irradiated with light.
Examples of the light emitting material having a terephthalic acid ester structure include compounds having a structure represented by the following general formula (9) and compounds having a structure represented by the following general formula (10). These may be used alone or in combination of two or more.

In the general formula (9), R ⁶ represents an organic group, and x is 1, 2, 3 or 4.
Since the visible light transmittance of the vehicle window glass is further increased, x is preferably 1 or 2, more preferably a hydroxyl group at the 2-position or 5-position of the benzene ring, and the 2-position of the benzene ring. And having a hydroxyl group at the 5-position is more preferable.
The organic group for R ⁶ is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 1 to 5 carbon atoms, A hydrocarbon group having 1 to 3 carbon atoms is particularly preferable. When the number of carbon atoms in the hydrocarbon group is 10 or less, the light emitting material having the terephthalic acid ester structure can be easily dispersed in the light emitting layer. The hydrocarbon group is preferably an alkyl group.

Examples of the compound having the structure represented by the general formula (9) include diethyl-2,5-dihydroxyterephthalate and dimethyl-2,5-dihydroxyterephthalate. Among them, the compound having the structure represented by the general formula (9) is preferably diethyl-2,5-dihydroxyterephthalate (“diethyl 2,5-dihydroxyterephthalate” manufactured by Aldrich).

In the general formula (10), R ⁷ represents an organic group, R ⁸ and R ⁹ represent a hydrogen atom or an organic group, and y is 1, 2, 3 or 4.
The organic group for R ⁷ is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and further preferably a hydrocarbon group having 1 to 5 carbon atoms, A hydrocarbon group having 1 to 3 carbon atoms is particularly preferable. When the number of carbon atoms in the hydrocarbon group is not more than the upper limit, the light emitting material having the terephthalic acid ester structure can be easily dispersed in the light emitting layer. The hydrocarbon group is preferably an alkyl group.
In the general formula (10), NR ⁸ R ⁹ is an amino group. R ⁸ and R ⁹ are preferably hydrogen atoms. Among the hydrogen atoms of the benzene ring of the compound having the structure represented by the general formula (10), one hydrogen atom may be the above amino group or two hydrogen atoms may be the above amino group. , Three hydrogen atoms may be the above amino groups, and four hydrogen atoms may be the above amino groups.
As the compound having the structure represented by the general formula (10), diethyl-2,5-diaminoterephthalate (for example, manufactured by Aldrich) is preferable.

The content of the light emitting material in the light emitting layer 13X is preferably 10% by mass or less, more preferably 5% by mass or less, in order to improve the transparency of the obtained interlayer film for laminated glass. It is more preferable that the content is not more than mass %.
The content of the light emitting material in the light emitting layer 13X is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and 0 because the emission of the light emitting layer becomes clearer. More preferably, it is at least 1% by mass.

The light emitting layer 13X is the same as the third resin layer 13 in the first embodiment except that it contains a light emitting material. Therefore, it is preferable that the light emitting layer 13X contains a resin component and at least one selected from a thermoplastic resin and a thermoplastic elastomer is used as the resin component. The light emitting layer 13X may contain a plasticizer, and may contain other additives as necessary.
The detailed description and content of the thermoplastic resin, thermoplastic elastomer, plasticizer, and other additives used in the light emitting layer 13X are the same as those of the third resin layer 13 in the first embodiment. Therefore, the description thereof will be omitted.

The light source for irradiating the light emitting layer 13X with light rays such as ultraviolet rays is not particularly limited as long as it is a light source capable of emitting excitation light for exciting the light emitting material, and examples thereof include a laser light source, an LED light source, and a xenon lamp. The excitation light is generally ultraviolet light, and the light-emitting material usually emits visible light when irradiated with the excitation light. The excitation light need not be ultraviolet light as long as it can excite the light emitting material.
The light from the light source may be directly applied to the laminated glass 45 (light emitting layer 13X), or may be applied to the laminated glass 45 via various lenses, a diffusion plate, a ride guide, or the like. Further, the laminated glass 45 (light emitting layer 13X) may be irradiated with light via a MEMS (Micro Electro Mechanical Systems) mirror. By irradiating through the MEMS mirror, the light emitting layer 13X can be irradiated with the scanning light, so that a complicated image can be displayed.
Further, a light source unit using a DMD (Digital Micromirror Device) method using DLP (Digital Light Processing) or LCOS (Liquid crystal on silicon) may be used.

In the fourth embodiment, by providing the transparent conductive layer 14 and the light emitting layer 13X, the laminated glass 45 can be used as a touch panel or a touch switch, and an image can be displayed on the laminated glass intermediate film 40. .. Further, the light emission of the light emitting layer 13X may be operated by a touch input of a touch panel or a touch switch.
Specifically, the display and non-display of the image by the light emitting layer 13X may be switched according to the touch input on the transparent conductive layer 14. Further, the image displayed on the light emitting layer 13X may be appropriately switched according to the touch input. That is, when there is a touch input, on/off of the light source, the amount of light, the type of image to be displayed, and the like may be appropriately changed based on the input signal.

Further, in the fourth embodiment, an image may be displayed by the light emitting layer 13X so that the transparent conductive layer 14 is superimposed on the printed region (for example, the printed region 95 in FIG. 3). When the image is superimposed on the print area, the position of the touch switch or the touch panel is recognized by the user by the image display, and the laminated glass having high usability can be provided.
For example, when the touch switch is used to open and close the door lock when used on the side glass of an automobile, a key icon image or the like is printed on the print area to indicate that the switch is the lock open/close switch. It is good to superimpose on.

In the fourth embodiment described above, the third resin layer is the light emitting layer in the interlayer film for laminated glass including the first to third resin layers, but any one of the first to third resin layers is used. It may be a light emitting layer. For example, instead of the third resin layer 13, either the first resin layer 11 or the second resin layer 12 may be used as the light emitting layer.
Further, for example, in the interlayer film for laminated glass 20 having two resin layers as in the second embodiment, either the first resin layer 11 or the second resin layer 12 may be used as the light emitting layer. .. Further, for example, in the interlayer film 30 for laminated glass having one resin layer as in the third embodiment, the first resin layer 11 may be used as the light emitting layer.

[Fifth Embodiment]
The interlayer film for laminated glass of the present invention may have a functional layer in addition to the resin layer. Examples of the functional layer include a light emitting element and a dimmer. When the interlayer film for laminated glass has a light emitting element, a light control body, and the like, functions such as a light emitting function and a light control function are imparted.
Hereinafter, the interlayer film for laminated glass provided with a functional layer will be described as a fifth embodiment. FIG. 7: shows the laminated glass 55 which has the intermediate film 50 for laminated glasses of 5th Embodiment. Hereinafter, the differences between the laminated glass intermediate film 50 of the fifth embodiment and the first embodiment will be described.

The fifth embodiment differs from the first embodiment in that the functional layer 36 is provided. The functional layer 36 is provided between the third resin layer 13 and the first resin layer 11 in the laminated glass intermediate film 50 having three resin layers. Examples of the functional layer 36 include a light control body and a light emitting element as described above.
In the interlayer film 50 for laminated glass, when the functional layer 36 is provided between the third resin layer 13 and the first resin layer 11, the functional layer 36 forms the transparent electrode layer 14 of the first resin layer 11. It is adhered to the other surface 11B of the first resin layer 11 which is not formed and the one surface 13A of the third resin layer 13. Therefore, it is properly held by the first and third resin layers 11 and 13.
The thickness of the functional layer 36 is not particularly limited, but is preferably 0.1 to 4 mm, more preferably 0.2 to 1.5 mm.

(Light emitting element)
A surface emitting element is preferable as the light emitting element. By using the surface emitting element as the light emitting element, the light emitting element can be easily arranged between the third resin layer 13 and the first resin layer 11. Examples of the surface emitting element include an inorganic EL element and an organic EL element.

(Dimmer)
The dimmer is a sheet-like or layer-like member that dimmers by changing the optical characteristics such as transmittance at a predetermined wavelength by applying various energies such as light energy, electric energy, and heat energy, and is preferable. Is a material whose optical characteristics are changed by applying electric energy. Specifically, the dimmer preferably includes either a liquid crystal layer or an electrochromic layer.

The light control body has, for example, a pair of transparent electrodes, and a liquid crystal layer is disposed between the transparent electrodes to form a liquid crystal cell. Further, an alignment film or the like may be provided between the electrode and the liquid crystal layer depending on the type of liquid crystal. In the liquid crystal layer, when a voltage is applied between the transparent electrodes, the liquid crystal is oriented in one direction and light is transmitted in the thickness direction of the light control body. Therefore, when the light control body has a liquid crystal layer, the light control body becomes transparent with high light transmittance when a voltage is applied. On the other hand, when no voltage is applied, the light control device has a low light transmittance and becomes opaque, for example.

The electrochromic layer is a layer composed of an electrochromic material. The electrochromic material is not limited as long as it is a compound having electrochromic properties, and may be an inorganic compound, an organic compound, or a mixed-valence complex.
Even when the dimmer has an electrochromic layer, it may have a pair of transparent electrodes, and the electrochromic layer may be disposed between the transparent electrodes. By applying a voltage between the transparent electrodes, the electrochromic layer changes, for example, the transmittance in a specific wavelength range, which causes the light control body to change from transparent to opaque or when irradiated with visible light. The color tone changes. Therefore, for example, it is possible to make the material colorless and transparent when no voltage is applied, and to have a color tone such as blue, yellow, green, or red when a voltage is applied.
The dimmer generally has a pair of base materials made of a resin film or the like, and a pair of transparent electrodes and an electrochromic layer or a liquid crystal layer are arranged between the pair of base materials. is there.

In the fifth embodiment, the laminated glass 55 can be used as a touch panel or a touch switch by providing the transparent conductive layer 14 as in the above embodiments. When the functional layer 36 is a dimmer, the dimmer may be operated by touch input on the transparent conductive layer 14. Specifically, it is advisable to change the optical characteristics of the light control body by touching the transparent conductive layer 14 to switch whether or not a voltage is applied to the light control body.
Also, when a light emitting element is used as the functional layer 36, similarly, the light emitting element may be operated by touch input on the transparent conductive layer 14. Specifically, touch input on the transparent conductive layer 14 may switch between light emission and non-light emission. Further, the amount of light emission and the like may be adjusted by touch input.
The functional layer 36 is not limited to the dimmer and the light emitting element, and may be, for example, an infrared shielding material, a holographic layer, a light scattering layer, or the like. The light scattering layer is a layer containing scattering fine particles, and a projected image can be displayed on the interlayer film by projecting an image.

The laminated glass of each of the above-described embodiments can be used for various purposes, such as window glass of vehicles such as automobiles and trains, ships and airplanes, and various types of buildings, condominiums, detached houses, halls, gymnasiums, etc. It is preferably used for window glass of buildings and the like. Among these, automobile window glass is preferable.
Further, the automobile window glass may be any of a windshield, a rear glass, a side glass and a roof glass, but it is preferably any one of the side glass and the roof glass. The side glass may be either a front side glass or a rear side glass. Since side glass and roof glass often have curved surfaces, it is possible to impart stretchability and flexibility to the interlayer film for laminated glass by imparting stretchability to the transparent conductive layer as in the present invention, thereby making these glasses It can be used preferably. At least a part of the roof glass may be arranged on the roof, and for example, the glass arranged over the roof and the rear is also the roof glass.

For example, when the laminated glass of the present invention is used as a roof glass, the laminated glass intermediate film is provided with a functional layer made of a light-emitting element as in the fifth embodiment to form an laminated glass intermediate film. The provided light emitting element can be used as an interior light. According to such a configuration, the interior light can be turned on or off by touching the roof glass or the like for touch input.
When the laminated glass of the present invention is used for a windshield, a side glass, and a roof glass, a laminated glass intermediate film is provided with a functional layer made of a dimmer as in the fifth embodiment. By touch-inputting on these glasses, it is possible to switch the glasses from transparent to opaque, or from opaque to transparent, and to add a color tone to the glasses.

Furthermore, when the laminated glass of the present invention is used for a side glass, for example, as in the fourth embodiment, a light emitting layer is provided to display an image on the side glass, and a touch panel and a touch switch are used as an in-vehicle audio device. It may be an input means for operating the air conditioning, the interior light, the opening and closing of the door lock, and the like. At this time, the image displayed on the side glass is displayed by superimposing images such as switch buttons, key buttons, arrow buttons, and other icons on the print area, and the positions of the touch switches and the touch panel are displayed by the image display. It is good to let the user recognize.
It should be noted that opening and closing the door lock is an example in which touch input is assumed from outside the vehicle, and the image may be displayed outside the vehicle. On the other hand, the operation of the audio, air conditioning, and interior lights is an example in which touch input is assumed from the inside of the vehicle, and the image may be displayed toward the inside of the vehicle.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The polyvinyl butyral resins and plasticizers used in Examples and Comparative Examples are as follows.
PVB (1): degree of acetalization 68 mol %, amount of hydroxyl group 31 mol %, degree of acetylation 1 mol %, degree of polymerization 1700
PVB (2): degree of acetalization 68 mol%, amount of hydroxyl group 31 mol%, degree of acetylation 1 mol%, degree of polymerization 1700
PVB (3): degree of acetalization 68 mol%, amount of hydroxyl group 31 mol%, degree of acetylation 1 mol%, degree of polymerization 1700
Plasticizer: Triethylene glycol di-2-ethylhexanoate (3GO)

(Example 1)
First, as a first resin layer, a polyethylene terephthalate (PET) film having a thickness of 100 μm was prepared. One side of the PET film had an arithmetic average height roughness (Ra) of 50 nm. In addition, a conductive ink containing carbon nanotubes was prepared. A transparent conductive layer was formed on one side of the PET film by screen printing using a conductive ink. As shown in FIG. 3, the transparent conductive layer formed a touch switch from a circular printing area having a diameter of 40 mm.

(Example 2)
The same procedure as in Example 1 was performed except that a silver nanowire-containing conductive ink (trade name: manufactured by Henkel, trade name “Loctite ECI-5005”) was used as the conductive ink.

(Example 3)
The same procedure as in Example 1 was carried out except that a PEDOT-containing conductive ink (trade name. DuPont, trade name “ME801”) was used as the conductive ink.

(Example 4)
The same procedure as in Example 1 was carried out except that ITO particle-containing conductive ink was used as the conductive ink.

(Examples 5 and 6)
First, a polyvinyl butyral resin (PVB(1)) having a solid content of 12.5 mass% dissolved in toluene was applied to a PET film and dried by heating to a thickness of 90 μm as a first resin layer. A PVB resin sheet was formed. A transparent conductive layer was formed on one surface of the PVB resin sheet in the same manner as in Examples 2 and 3. The arithmetic average height roughness (Ra) of one surface of the first resin layer (PVB resin sheet) on which the transparent conductive layer was formed was 250 nm. The laminated film composed of the first resin layer and the transparent conductive layer was peeled from the PET film and subjected to various evaluations.

(Comparative Example 1)
ITO was sputtered to form a 50 nm-thick transparent conductive layer on one surface of the PET film similar to that of Example 1. The shape and size of the pattern were the same as those in each example.

(Comparative example 2)
A transparent conductive layer formed of silver in a mesh shape having a line width of 10 μm was formed on one surface of the PET film similar to that of Example 1 by photolithography.

The laminated films composed of the first resin layer and the transparent conductive layer obtained in each of Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated as follows.
(Flexibility)
Based on JIS K 5600-5-1:1999, a cylindrical mandrel test is performed under the conditions of test type 1, mandrel diameter 8 mm, temperature 23° C., and humidity 50% RH, and evaluated by the presence or absence of cracks in the laminated film. did. The sample in which no crack was generated was evaluated as "A", and the sample in which crack was generated was evaluated as "B".
(Stretchability)
Using a universal testing machine with a constant temperature bath (Instron) at a bath temperature of 80° C. and a pulling speed of 100 mm/min, the laminated film was stretched 10% from its original length and then cracked when restored. The presence or absence was evaluated. The sample in which no crack was generated was evaluated as "A", and the sample in which crack was generated was evaluated as "B".

(Example 7)
A resin composition obtained by kneading 100 parts by mass of polyvinyl butyral resin (PVB(2)) and 40 parts by mass of a plasticizer was extruded as a second resin layer in a sheet shape with a thickness of 380 μm. Further, a resin composition obtained by kneading 100 parts by mass of polyvinyl butyral resin (PVB(3)) and 40 parts by mass of a plasticizer was extruded as a third resin layer in a sheet shape with a thickness of 380 μm.
Clear glass (second glass plate) having a size of 300 mm×300 mm and a thickness of 2.1 mm, a third resin layer, the laminated film obtained in Example 3, a second resin layer, and 300 mm×300 mm Clear glass (first glass plate) having a size of 1.6 mm and a thickness of 1.6 mm was stacked in this order to obtain a laminate. In the laminated body, the laminated film was arranged so that the transparent conductive layer was in contact with the second resin layer. The obtained laminate was placed in a rubber bag, vacuumed for 10 minutes, placed in an oven set to 130° C. in a vacuumed state, taken out when the glass surface temperature reached 80° C., and temporarily press-bonded. .. The temporarily bonded laminate was pressure bonded using an autoclave under the conditions of 140° C. and a pressure of 14 MPa for 20 minutes to produce a laminated glass.

(Example 8)
It carried out like Example 7 except having used the laminated film obtained in Example 6 instead of the laminated film obtained in Example 3.

[Operation check test]
In the laminated glass obtained in Examples 7 and 8, a touch switch was connected to an external LED. A touch input was performed from the first glass plate side of the laminated glass, and an operation confirmation test was performed depending on whether or not the external LED was turned on. The case where the external LED was turned on was evaluated as "A" and the case where the external LED was not turned on was evaluated as "B".

As shown in Examples 1 to 6 above, when the transparent conductive layer was formed by printing, the stretchability of the transparent conductive layer was good, and the evaluation results of the followability and the stretchability were good. Moreover, when the laminated glass was assembled and the operation was confirmed, it could be used as a touch switch without any problem. On the other hand, in Comparative Examples 1 and 2, when the transparent conductive layer was formed by a method other than printing, the stretchability of the transparent conductive layer was insufficient, and the evaluation results of followability and stretchability were not good results. ..

10, 20, 30, 40, 50 Intermediate film body for laminated glass 11 First resin layer 11A, 12A, 13A One surface 11B, 12B, 13B Other surface 12 Second resin layer 13 Third resin layer 13X Light-emitting layer 14 Transparent conductive layer 15, 25, 35, 45, 55 Laminated glass 16A First glass plate 16B Second glass plate 36 Functional layer 91, 92 Line 93 Opening
95 print area 96 non-print area

Claims (14)

An intermediate film for laminated glass, comprising a first resin layer and a transparent conductive layer, wherein the transparent conductive layer is formed on at least one surface of the first resin layer by printing. The interlayer film for laminated glass according to claim 1, which has the first resin layer, the transparent conductive layer, and the second resin layer in this order along the thickness direction. The interlayer film for laminated glass according to claim 1, which has a third resin layer, the first resin layer, a transparent conductive layer, and a second resin layer in this order along the thickness direction. 4. The transparent conductive layer according to claim 1, wherein the transparent conductive layer contains at least one selected from the group consisting of a conductive metal oxide, a conductive polymer compound, a metal nanowire and a carbon material. Intermediate film for laminated glass. The interlayer film for laminated glass according to any one of claims 1 to 4, wherein the first resin layer contains at least one selected from the group consisting of a thermoplastic resin and a thermoplastic elastomer. The interlayer film for laminated glass according to claim 5, wherein the thermoplastic resin is at least one selected from the group consisting of a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer resin, and a polyolefin resin. The interlayer film for laminated glass according to claim 5 or 6, wherein the second resin layer contains the same type of thermoplastic resin or thermoplastic elastomer as the first resin layer. The interlayer average film for laminated glass according to any one of claims 1 to 7, wherein one surface of the first resin layer has an arithmetic average height roughness (Ra) of 10 µm or less. The interlayer film for laminated glass according to claim 1, comprising a functional layer selected from any one of a light control body, a light emitting element, and a light emitting layer. The interlayer film for laminated glass according to any one of claims 1 to 9, wherein the transparent conductive layer is a conductive layer for a touch panel or a touch switch. An interlayer film for laminated glass according to any one of claims 1 to 10, and first and second glass plates, wherein the interlayer film for laminated glass is disposed between the first and second glass plates. Laminated glass. The transparent conductive layer is for a touch panel, or a conductive layer for a touch switch,
The laminated glass according to claim 11, wherein the interlayer film for laminated glass includes a functional layer operated by a touch input on the transparent conductive layer. The functional layer is any one of a dimmer that changes optical characteristics by the touch input, a light emitting element that switches between light emission and non-light emission by the touch input, and a light emitting layer that switches between display and non-display of an image by the touch input. The laminated glass according to claim 12, which is present. The laminated glass according to any one of claims 11 to 13, which is either an automobile roof glass or an automobile side glass.