Layered film, laminated glass, and production method for laminated glass

Abstract

A layered film according to the present invention includes: a first intermediate layer for laminated glass; and a printed layer that is adjacent to the surface of the first intermediate layer. The first intermediate layer includes a thermoplastic resin and has a shear storage elastic modulus of at least 6×104 Pa at 140°C.

Description

Laminated film, laminated glass, and method for manufacturing laminated glass

[0001] This invention relates to laminated films, laminated glass, and methods for manufacturing laminated glass.

[0002] In recent years, the design demands for laminated glass have become increasingly diverse. For example, in automotive applications, there is a growing need and concept to apply designs to laminated glass to match the body design or body color. Similarly, in architectural applications, there continues to be a demand for decorative elements on laminated glass for exterior or interior use. Furthermore, there is consideration being given to embedding dimming films, sensors, antennas, electronic display media, or solar cells within the laminated glass.

[0003] To enhance the functionality of laminated glass, it is known to form a printed layer in the interlayer. The printed layer may be, for example, an image-supporting layer or a conductive layer. The image-supporting layer may be, for example, a colored layer or an emissive layer. For example, Patent Document 1 discloses an image-supporting interlayer sheet obtained by inkjet printing a colored ink onto at least one surface of an interlayer sheet.

[0004] The printed layer, for example, contains a cured product of a curable ink and is formed on the surface of the intermediate layer. The printed layer and the intermediate layer constitute a laminated film. Glass structures comprising the laminated film are generally manufactured by the following method: A laminate is obtained by sandwiching a laminated film between two glass substrates and pre-bonding them. Next, the laminate is placed in an autoclave and pressed at a temperature of approximately 120°C to 140°C and a pressure of 1.0 MPa to 1.5 MPa.

[0005] Japan Special Table No. 2007-501722

[0006] Traditionally, heat treatments such as autoclaving could cause wrinkles in the printed layer, resulting in appearance defects.

[0007] One embodiment of the present disclosure provides a technology that can suppress defects in the appearance of the printed layer caused by heat treatment.

[0008] As a result of diligent research, the inventors have found that the above-mentioned appearance defects are caused by the fluidity of the first intermediate layer during the lamination process. The inventors have solved the above problem by increasing the shear storage modulus of the first intermediate layer at 140°C. This disclosure provides the following [1] to

[16] : [1] A first intermediate layer for laminated glass comprising a thermoplastic resin, and a printed layer adjacent to the surface of the first intermediate layer, wherein the shear storage modulus of the first intermediate layer at 140°C is 6 × 10 ４ [2] A laminated film having a shear storage modulus of Pa or greater. [2] The laminated film according to claim 1, wherein the printed layer has a first surface adjacent to the first intermediate layer and a second surface facing the opposite direction from the first surface, and the laminated film has a second intermediate layer containing a thermoplastic resin, and the second intermediate layer is adjacent to the second surface of the printed layer. [3] The laminated film according to [2], wherein the shear storage modulus of the second intermediate layer at 140°C is 60,000 Pa or greater. [4] The shear storage modulus of the first intermediate layer at 100°C is G1' １００ Shear storage modulus G1' at 140°C relative to １４０ The ratio (G1') １４０ / G1' １００[1] to [3] A laminated film according to any one of the following items, wherein the ratio of the printed layer is 0.4 or more. [5] A laminated film according to any one of the following items, wherein the average thickness of the printed layer is 1 μm or more and 50 μm or less. [6] A laminated film according to any one of the following items, wherein the printed layer contains a cured product of an ultraviolet-curable ink. [7] A laminated film according to any one of the following items, wherein the first intermediate layer contains a plasticizer. [8] A laminated film according to the following item, wherein the content of the plasticizer in the first intermediate layer is 35 parts by mass or less per 100 parts by mass of thermoplastic resin. [9] A laminated film according to any one of the following items, wherein the thermoplastic resin in the first intermediate layer has intermolecular crosslinking.

[10] A laminated film according to any one of the following items, wherein the thermoplastic resin in the first intermediate layer is at least one of polyvinyl acetal, ethylene vinyl acetate, polyurethane, polyolefin, and ionomer.

[11] The laminated film according to any one of [1] to

[10] , wherein the thermoplastic resin in the first intermediate layer is polyvinyl acetal.

[12] Laminated glass comprising the laminated film according to any one of [1] to

[11] and two glass substrates sandwiching the laminated film.

[13] Printing an ultraviolet-curable ink on the surface of the first intermediate layer; curing the ultraviolet-curable ink on the first intermediate layer to form a printed layer; and sandwiching the laminated film having the first intermediate layer and the printed layer between two glass substrates, wherein the shear storage modulus of the first intermediate layer is 6 × 10 ４ A method for manufacturing laminated glass, comprising heating in a temperature range of Pa or higher.

[14] The method for manufacturing laminated glass according to

[13] , wherein the ultraviolet-curable ink is printed by inkjet printing.

[0009] According to one embodiment of the present disclosure, it is possible to suppress defects in the appearance of the printed layer caused by heat treatment.

[0010] Figure 1 shows an example of a method for manufacturing a laminated film. Figure 2 is a cross-sectional view showing a first example of a laminated film. Figure 3 is a cross-sectional view showing a first example of laminated glass. Figure 4 is a cross-sectional view showing a second example of a laminated film. Figure 5 is a cross-sectional view showing a second example of laminated glass. Figure 6 is a cross-sectional view showing a third example of a laminated film. Figure 7 is a cross-sectional view showing a third example of laminated glass. Figure 8 is a photograph showing the appearance of laminated glass in a modified example of Example 5. Figure 9 is a photograph showing the appearance of laminated glass in a modified example of Example 6.

[0011] The embodiments for implementing this disclosure will be described below with reference to the drawings. In each drawing, identical or similar components will be denoted by the same reference numeral, and their descriptions may be omitted. In the specification, the "~" indicating a numerical range means that the numbers written before and after it are included as the lower and upper limits. The lower and upper limits can be combined in any way. The numerical range includes the rounded range.

[0012] As shown in Figure 1, a printed layer 20 may be formed on the intermediate layer 10 for laminated glass. The printed layer 20 is, for example, an image-supporting layer or a conductive layer. The image-supporting layer is, for example, a colored layer or an emissive layer. The image-supporting layer has a desired design pattern. The design pattern is set according to the application. The conductive layer forms, for example, a dimmable film, a sensor, an antenna, an electronic display medium, or at least part of an electrical circuit such as a solar cell.

[0013] The laminated film 2 is composed of a printed layer 20 and an intermediate layer 10. Laminated glass comprising the laminated film 2 is generally manufactured by the following method: The laminated film 2 is sandwiched between a first glass substrate and a second glass substrate and pre-bonded to obtain a laminate. Next, the laminate is placed in an autoclave and the components are pressed together under high temperature and high pressure. The autoclave treatment is carried out, for example, at a temperature of 120°C to 140°C and a pressure of 1.0 MPa to 1.5 MPa. The intermediate layer 10 preferably contains a thermoplastic resin to improve the bonding properties.

[0014] The inventors identified a problem in which wrinkles form in the printed layer 20 due to heat treatment such as autoclaving, resulting in a poor appearance. They found that this problem arises from insufficient shear storage modulus of the intermediate layer 10 at 140°C. If the shear storage modulus of the intermediate layer 10 at 140°C is too low, the intermediate layer 10, softened by heat treatment, drags the printed layer 20, causing the printed layer 20 to twist and wrinkle. The inventors solved the above problem by increasing the shear storage modulus of the intermediate layer 10 at 140°C. Specifically, the shear storage modulus of the intermediate layer at 140°C is set to 6 × 10⁻⁶. ４ It is Pa or higher.

[0015] The method for manufacturing the laminated film 2 is as follows, as shown in Figure 1: (A) Ink 21 is printed on the surface of a substrate such as an intermediate layer 10. (B) The ink 21 is cured and / or desolvented on the substrate to form a printed layer 20.

[0016] The printing method for ink 21 is not particularly limited, as will be described later, and may be plateless or plateless printing. The printing method for ink 21 is preferably inkjet printing. Inkjet printing is an example of plateless printing.

[0017] The inkjet printer 100 is equipped with a print head 110, which has nozzles 111. The nozzles 111 eject ink 21 using a piezoelectric element or the like. Multiple nozzles 111 may be provided for each color of ink 21. The print head 110 moves relative to the surface of the substrate while ejecting ink 21 from the nozzles 111 onto the surface of the substrate. Either the print head 110 or the substrate may move, or both may move.

[0018] If the ink 21 is an ultraviolet-curing ink, the inkjet printer 100 is equipped with an ultraviolet light source 120. The ultraviolet light source 120 irradiates the ink 21 printed on the surface of the substrate with ultraviolet light. The ultraviolet light source 120 may move together with the print head 110 as shown in Figure 1, or it may remain stationary, although this is not shown.

[0019] [Laminated film] The laminated film 2 of the present embodiment includes an interlayer 10 for laminated glass (first interlayer 10A) containing a thermoplastic resin, and a printed layer adjacent to the surface of the interlayer 10, wherein the shear storage modulus of the interlayer 10 at 140°C is 6×10 ４ Pa or more.

[0020] [Interlayer] The interlayer 10 adjacent to the printed layer 20 is preferably used as a base material layer for holding the printed layer 20. Moreover, the interlayer 10 preferably serves as an adhesive layer for adhering the laminated film to another member such as a glass substrate. Therefore, the first interlayer 10A adjacent to the first surface 20a of the printed layer 20 is preferably disposed on one surface of the laminated film. In addition, when the second interlayer 10B is provided, the second interlayer is preferably disposed on the other surface of the laminated film (the surface opposite to the one surface). By disposing each interlayer on the surface of the laminated film, it can be appropriately used as an adhesive layer for adhering to another member. Furthermore, a third interlayer 10C may be provided between the printed layer 20 and the second interlayer 10B.

[0021] Note that although the base material on which the ink 21 is printed is the interlayer 10 in the present embodiment, it is not limited to the interlayer 10. After forming the printed layer 20 on a base material different from the interlayer 10, the printed layer 20 may be transferred from the base material to the interlayer 10 to form the printed layer 20 on the interlayer 10. The interlayer 10 may be any of the first interlayer 10A, the second interlayer 10B, and the third interlayer 10C described later.

[0022] In the first interlayer adjacent to the surface of the printed layer, the shear storage modulus at 140°C is 6×10 ４ Pa or more. Moreover, in the second interlayer (or the third interlayer) adjacent to the surface of the printed layer, the shear storage modulus at 140°C is 6×10 ４ Pa or more, which is preferable. The shear storage modulus at 140°C is 6×10 ４ Pa or more, preferably 1×10 ５ Pa or more, more preferably 2×10 ５ Pa or more, still more preferably 3×10 ５Pa or higher. The shear storage modulus at 140°C is 6×10 ４ When the Pa or higher is satisfied, the intermediate layer 10 can maintain sufficient rigidity during autoclave treatment when producing laminated glass. Therefore, deformation of the intermediate layer 10 during heating and cooling can be reduced, and the occurrence of wrinkles in the printed layer 20 on the intermediate layer 10 can be suppressed. For example, when the printed layer 20 is an image bearing layer, the occurrence of wrinkles in the image bearing layer can be suppressed, and perspective distortion of the design pattern can be reduced. Further, when the printed layer 20 is a conductive layer, the occurrence of wrinkles in the conductive layer can be suppressed, and short-circuiting of an electric circuit can be suppressed.

[0023] In the intermediate layer, the shear storage modulus G' at 100°C １００ to the shear storage modulus G' at 140°C １４０ ratio (G' １４０ / G' １００ ) is preferably 0.4 or more, more preferably 0.5 or more, and still more preferably 0.6 or more. When the ratio (G' １４０ / G' １００ ) is 0.4 or more, the rate of decrease in shear storage modulus can be suppressed even when heating from 100°C to 140°C in the autoclave treatment for producing laminated glass. Therefore, deformation of the intermediate layer 10 during heating and cooling can be reduced, and the occurrence of wrinkles in the printed layer 20 on the intermediate layer 10 can be suppressed. Here, when the laminated glass further includes a second intermediate layer and the intermediate layers are different from each other, the shear storage modulus of the first intermediate layer is denoted as "G1'", the shear storage modulus of the second intermediate layer is denoted as "G2'", and the numerical value of the measurement temperature [°C] is additionally written as a subscript.

[0024] [Measurement of Shear Storage Modulus] The shear storage modulus can be measured by a method in accordance with JIS K7244-10:2005. Specifically, a film obtained by cutting an intermediate layer (for example, 10 mm in length and 5 mm in width) is used as a test piece, stored for 12 hours in an environment at a room temperature of 23±2°C and a humidity of 25±5%, and the shear storage modulus can be measured while heating the test piece under the following measurement conditions using a forced oscillation type solid viscoelasticity measuring device (for example, device name: ARES-G2 manufactured by TA INSTRUMENTS). The shear storage modulus G' at 140°C １４０, and the shear storage modulus G' at 100°C １００ Measure the ratio (G' １４０ / G' １００ ) can be calculated. -Measurement conditions- Deformation mode: shear mode, Measurement temperature: -20°C to 100°C, Heating rate: 3°C / min, Measurement frequency: 1 Hz, Strain: 1% Deformation mode: shear mode, Measurement temperature: 100°C to 200°C, Heating rate: 3°C / min, Measurement frequency: 1 Hz, Strain: 5%

[0025] The shear storage modulus of the intermediate layer at 140°C is 6 × 10⁻⁶. ４ Methods to increase the Pa level include adjusting the weight-average molecular weight (Mw) of the polyvinyl acetal, the intermolecular interactions of the polyvinyl acetal, and the plasticizer content in the intermediate layer. Methods to strengthen the intermolecular interactions of the polyvinyl acetal include physically crosslinking the molecules of the polyvinyl acetal or chemically crosslinking them.

[0026] The intermediate layer 10 is a layer containing a thermoplastic resin. The inclusion of a thermoplastic resin in the intermediate layer makes it easier to function as an adhesive layer, resulting in good adhesion to the glass substrate.

[0027] The thermoplastic resin in each intermediate layer 10 is not particularly limited, but examples include polyvinyl acetal, ethylene-vinyl acetate copolymer, polyurethane, polyolefin, ionomer, thermoplastic elastomer, polyacrylate, acrylic-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate, and polystyrene. Using these thermoplastic resins makes it easier to ensure adhesion to the glass substrate. In each intermediate layer, the thermoplastic resin may be used alone or in combination of two or more types.

[0028] Among these, at least one consisting of polyvinyl acetal, ethylene-vinyl acetate copolymer, polyurethane, polyolefin, and ionomer is preferred, at least one selected from polyvinyl acetal resin and ethylene-vinyl acetate copolymer resin is more preferred, and polyvinyl acetal resin is particularly preferred because it exhibits excellent adhesion to glass when used in combination with a plasticizer.

[0029] When there are multiple intermediate layers, the thermoplastic resins constituting each intermediate layer may be different from each other or the same, but it is preferable that they be the same. When a first intermediate layer 10A and a second intermediate layer 10B are provided, the resins used for both the first intermediate layer 10A and the second intermediate layer 10B are preferably at least one selected from polyvinyl acetal resin and ethylene-vinyl acetate copolymer resin, and polyvinyl acetal resin is more preferable.

[0030] (Polyvinyl Acetal) The polyvinyl acetal is not particularly limited as long as it is a polyvinyl acetal obtained by acetalizing polyvinyl alcohol (PVA) with an aldehyde, and can be appropriately selected according to the purpose. The aldehyde is not particularly limited, but generally, aldehydes having 1 to 10 carbon atoms are preferably used. Examples of aldehydes having 1 to 10 carbon atoms include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, and benzaldehyde. These aldehydes may be used individually or in combination of two or more. Among these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferred, with n-butyraldehyde being more preferred. Therefore, polyvinyl butyral (PVB) is preferred as the polyvinyl acetal.

[0031] Polyvinyl alcohol (PVA) is represented, for example, by the following general formula (1), and is obtained by saponifying polyvinyl esters such as polyvinyl acetate. The degree of saponification of polyvinyl alcohol is generally 70 mol% to 99.9 mol%. Polyvinyl acetal may be used alone or in combination of two or more types.

[0032]

[0033] In the general formula (1) above, R represents hydrogen or an alkyl group having 1 to 9 carbon atoms, and l, m, and n each represent an integer independently. R = C ３ H ８ In this case, the polyvinyl acetal represented by the general formula (1) is polyvinyl butyral (PVB), and R = CH ３ In this case, the polyvinyl acetal represented by the general formula (1) is polyvinyl acetal.

[0034] The shear storage modulus of the intermediate layer at 140°C is 6 × 10⁻⁶. ４ From the viewpoint of achieving a Pa or higher, the average degree of polymerization of PVA is preferably 200 or higher, more preferably 500 or higher, even more preferably 1000 or higher, and even more preferably 1500 or higher. Furthermore, setting the average degree of polymerization to 200 or higher increases the penetration resistance of the laminated glass. Also, the average degree of polymerization of PVA is preferably 5000 or less, more preferably 4000 or less, even more preferably 3500 or less, and even more preferably 2500 or less.

[0035] The average degree of polymerization of polyvinyl alcohol is determined by a method in accordance with JIS K6726 "Test Method for Polyvinyl Alcohol".

[0036] The shear storage modulus of the intermediate layer at 140°C is 6 × 10⁻⁶. ４From the viewpoint of achieving a Pa or higher load, the weight-average molecular weight (Mw) of the polyvinyl acetal is preferably 220,000 or higher. Furthermore, an Mw of 220,000 or higher can improve the impact resistance of the polyvinyl acetal. The Mw of the polyvinyl acetal is more preferably 230,000 or higher, even more preferably 240,000 or higher, and even more preferably 260,000 or higher. Furthermore, the Mw of the polyvinyl acetal is preferably 310,000 or lower. When the adherend is glass, the scattering of glass can be suppressed more effectively. The Mw of the polyvinyl acetal is more preferably 305,000 or lower, even more preferably 300,000 or lower, and even more preferably 290,000 or lower.

[0037] The weight-average molecular weight (Mw) of polyvinyl acetal is measured by gel permeation chromatography. The above weight-average molecular weight can be measured by the following method: The sample to be measured is dissolved to a concentration of 0.05% by mass in an N-methyl-2-pyrrolidone solution to which lithium bromide has been added to a concentration of 10 mM, and filtered using a syringe filter (Merck Millex-LH 0.45 μm). After filtration, the measurement is performed using gel permeation chromatography (Waters e2690), and the molecular weight is calculated using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples. In addition, a Shodex GPC KF-806L column (Resonac Holdings Co., Ltd.) is used, and an N-methyl-2-pyrrolidone solution to which lithium bromide has been added to a concentration of 10 mM is used as the eluent.

[0038] The hydroxyl group content of polyvinyl acetal is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 25 mol% or more, from the viewpoint of adhesion to the glass substrate. Furthermore, the hydroxyl group content is preferably 38 mol% or less, more preferably 35% or less, and even more preferably 33 mol% or less. Setting the hydroxyl group content to 15 mol% or more makes it easier to achieve good adhesion and improve the puncture resistance of the laminated glass. Also, setting the hydroxyl group content to 38 mol% or less prevents the laminated glass from becoming too hard.

[0039] When polyvinyl butyral is used as the polyvinyl acetal, from a similar viewpoint, the amount is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 25 mol% or more. Furthermore, the amount of hydroxyl groups is preferably 38 mol% or less, more preferably 35% or less, and even more preferably 33 mol% or less.

[0040] The amount of hydroxyl groups in polyvinyl acetal is the mole fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are attached by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of hydroxyl groups in polyvinyl acetal is calculated from the degree of acetalization and degree of acetylation using the following formula (1): Amount of hydroxyl groups in polyvinyl acetal [mol%] = 100 - (Degree of acetalization [mol%] + Degree of acetylation [mol%]) (1)

[0041] The degree of acetalization of polyvinyl acetal is preferably 47 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, and also preferably 85 mol% or less, more preferably 80 mol% or less, and even more preferably 75 mol% or less. In the case where the polyvinyl acetal is polyvinyl butyral resin, the acetal group is a butyral group, and the degree of acetalization refers to the degree of butyralization.

[0042] The degree of acetalization is a value expressed as a percentage of the mole fraction obtained by dividing the total amount of ethylene groups in the main chain (total ethylene groups) minus the amount of ethylene groups to which hydroxyl groups and ethylene groups to which acetyl groups are attached, by the total amount of ethylene groups in the main chain. The degree of acetalization (or butyralization) can be measured by NMR (Nuclear Magnetic Resonance). The method for measuring the degree of acetalization will be described later, together with the method for measuring the degree of acetylation.

[0043] The degree of acetylation of the polyvinyl acetal is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and even more preferably 2 mol% or less. When the degree of acetylation is below the above upper limit, the moisture resistance of the laminated film and laminated glass is increased. Furthermore, although the degree of acetylation is not particularly limited, it is preferably 0.01 mol% or more, and more preferably 0.1 mol% or more.

[0044] The degree of acetylation is a value expressed as a percentage of the mole fraction obtained by dividing the amount of ethylene groups to which acetyl groups are attached by the total amount of ethylene groups in the main chain. Like the degree of acetalization, the degree of acetylation can be measured by NMR.

[0045] The measurement conditions for the degree of acetalization and acetylation are as follows: A nuclear magnetic resonance (NMR) spectrometer (Bruker, product name "AVANCE III HD") is used, along with a 400 MHz spectrometer. １ 1H-NMR measurement will be performed. Polyvinyl acetal will be dissolved in deuterated dimethyl sulfoxide (DMSO-d6) to prepare a solution containing 1% by mass of polyvinyl acetal as the measurement sample. １ The chemical shift on the horizontal axis of the 1H-NMR spectrum is expressed in ppm, and the chemical shift of DMSO-d6 is set to 2.49 ppm. １ From the heights of multiple peaks in the 1H-NMR spectrum of polyvinyl acetal, the total amount of ethylene groups in the main chain, the amount of ethylene groups to which hydroxyl groups are attached, and the amount of ethylene groups to which acetyl groups are attached can be determined, respectively. This allows for the determination of the degree of acetylation and the degree of acetalization, respectively.

[0046] (Ethylene-vinyl acetate copolymer) The ethylene-vinyl acetate copolymer may be a non-crosslinked type or a high-temperature crosslinked type. In addition, modified ethylene-vinyl acetate products such as saponified ethylene-vinyl acetate copolymers and hydrolyzed ethylene-vinyl acetate products can also be used as the ethylene-vinyl acetate copolymer. The vinyl acetate content of the ethylene-vinyl acetate copolymer, as measured in accordance with JIS K6730 "Test Method for Ethylene-Vinyl Acetate Resin" or JIS K6924-2:1997, is preferably 10% to 50% by mass, more preferably 20% to 40% by mass. When the vinyl acetate content is 10% by mass or more, the adhesion to glass is increased, and the penetration resistance of the laminated glass tends to improve. When the vinyl acetate content is 50% by mass or less, the breaking strength of the laminated film is increased, and the impact resistance of the laminated glass improves.

[0047] (Plasticizer) It is preferable that each intermediate layer 10 further contains a plasticizer. That is, it is preferable that the first intermediate layer contains a thermoplastic resin and a plasticizer. Also, if a second intermediate layer is provided, it is preferable that the second intermediate layer also contains a thermoplastic resin and a plasticizer.

[0048] The content of the plasticizer in the intermediate layer 10 is preferably 5 by mass or more, and more preferably 10 by mass or more, per 100 parts by mass of thermoplastic resin. The intermediate layer 10 becomes flexible due to the inclusion of the plasticizer, and as a result, the laminated film also becomes flexible. Furthermore, when the laminated film is used as an interlayer for laminated glass, it improves the flexibility of the laminated glass and also improves its puncture resistance. Moreover, it becomes possible to exhibit high adhesion to the glass substrate. On the other hand, as the plasticizer content increases, the shear storage modulus decreases, so the shear storage modulus of the intermediate layer at 140°C should be 6 × 10⁻⁶. ４ From the viewpoint of achieving a Pa or higher, the content of the plasticizer in the intermediate layer is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of thermoplastic resin.

[0049] The plasticizer is particularly effective when included in each intermediate layer 10 when polyvinyl acetal is used as the thermoplastic resin.

[0050] Examples of plasticizers include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphorus-based plasticizers such as organic phosphate ester plasticizers and organic phosphite ester plasticizers. Among these, organic ester plasticizers are preferred.

[0051] Examples of organic ester plasticizers include triethylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di-2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, 1,2-butylene glycol di-2-ethyl butyrate, and diethylene glycol. Examples include di-2-ethyl butyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethyl butyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethyl butyrate, diethylene glycol dicapriate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethyl butyrate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified alkyd sebacate, mixtures of phosphate esters and adipate esters, and mixed adipate esters. Examples of mixed adipate esters include adipate esters made from two or more alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms. Among these plasticizers, triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferred.

[0052] The shear storage modulus of the intermediate layer at 140°C is 6 × 10⁻⁶. ４ From the viewpoint of achieving a Pa or higher, it is preferable that the thermoplastic resin in the intermediate layer 10 has intermolecular crosslinking.

[0053] The crosslinking agent can be appropriately selected depending on the type of thermoplastic resin used. When the thermoplastic resin is a resin having hydroxyl groups, such as polyvinyl acetal, there are no particular restrictions on the crosslinking agent as long as it can crosslink the hydroxyl groups of the thermoplastic resin by chelate coordination, but a crosslinking agent containing a metal is preferred. Preferably, the metal contains at least one of zirconium and titanium. Examples of crosslinking agents include metal alkoxides, organic sulfonic acids, and crosslinking agents obtained by reacting or mixing β-ketoesters. Examples of metal alkoxides include zirconium tripoxymonoacetylacetonate. By including a crosslinking agent, it is possible to suppress defects in the appearance of the printed layer due to heat treatment.

[0054] The amount of crosslinking agent can be appropriately set according to the desired effect, but is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 0.3 parts by mass, per 100 parts by mass of thermoplastic resin.

[0055] The presence of intermolecular crosslinking in thermoplastic resins can be determined by methods such as analyzing the metallic component of the crosslinking agent using an inductively-coupled plasma mass spectrometer (ICP-MS), or by analyzing the higher-order structure of the resin using Fourier transform infrared spectroscopy (FT-IR).

[0056] The intermediate layer 10 may appropriately contain various additives such as heat shielding agents, ultraviolet absorbers, antioxidants, and light stabilizers.

[0057] The thickness of the intermediate layer 10 is not particularly limited, but for example, it is 0.05 mm or more and 1 mm or less, preferably 0.1 mm or more and 0.8 mm or less, and more preferably 0.2 mm or more and 0.5 mm or less. By setting the thickness of each intermediate layer 10 to 0.05 mm or more and 1 mm or less, the printed layer can be properly supported by the intermediate layer 10 without making the thickness of the laminated film unnecessarily large, and the laminated film can be easily bonded to other members such as laminated glass members.

[0058] [Printed layer] The printed layer 20 is preferably formed from an ink containing a colorant, a light-emitting material, a conductive material, etc. Examples of inks include curable inks, inks containing a binder resin, aqueous inks containing an aqueous solvent, and solvent inks containing an organic solvent. Examples of resins used in curable inks include curable resins such as active energy ray curable resins and thermosetting resins. Among these, active energy ray curable resins, and especially ultraviolet curable resins, are preferred. It is preferable that the ink is an ultraviolet curable ink containing an ultraviolet curable resin, and it is preferable that the printed layer 20 is a cured product of a curable ink, and more preferably a cured product of an ultraviolet curable ink.

[0059] The thickness of the printed layer 20 is preferably 5 μm or more. In conventional laminated films, wrinkles occur in the printed layer 20 due to the softening of the intermediate layer 10 by heat treatment, and the effect of wrinkles is particularly noticeable when the thickness of the printed layer 20 is 5 μm or more. According to this embodiment, the shear storage modulus of the intermediate layer 10 at 140°C is 6 × 10⁻⁶. ４ Since it has a Pa or higher and possesses a sufficient shear storage modulus even under heat treatment conditions, the intermediate layer 10 can restrain the printed layer 20 and limit the occurrence of wrinkles in the printed layer 20, even if the thickness of the printed layer 20 is 5 μm or more. The thickness of the printed layer 20 is more preferably 10 μm or more, and even more preferably 20 μm or more. When the printed layer 20 is an image-supporting layer, the thicker the image-supporting layer, the darker the color that can be produced. From the viewpoint of thinning the laminated film 2, the thickness of the printed layer 20 may be 50 μm or less.

[0060] The printing method for ink 21 may be either plateless printing or plated printing, and is not particularly limited, but examples include screen printing, inkjet printing, flexographic printing, and offset printing. Among these, screen printing and inkjet printing are preferred.

[0061] The printed layer 20 may be formed on the entire surface of the substrate such as the intermediate layer 10 by so-called solid printing, but it is preferable that the printed layer 20 is printed in a predetermined pattern such as a picture, design, icon, character, or a combination thereof, and formed on a part of the substrate surface.

[0062] In a plan view, the area of ​​the printed layer 20 is preferably 1 mm². ２ That concludes the explanation. Here, a plan view means viewing from a direction perpendicular to the second surface 20b. When an opening pattern is formed in the printed layer 20, the area of ​​the printed layer 20 does not include the area of ​​the opening. The larger the area of ​​the printed layer 20, the greater the stress acting on the printed layer 20 due to the thermal deformation of the intermediate layer 10. Since the printed layer 20 in this embodiment is sufficiently hard, the area of ​​the printed layer 20 in a plan view is 1 mm². ２ Even with the above, the occurrence of wrinkles in the printed layer 20 can be limited. Preferably, the area of ​​the printed layer 20 in plan view is 100 mm². ２ The above, and more preferably 300 mm ２ That concludes the explanation. In plan view, the area of ​​the printed layer 20 should be less than or equal to the area of ​​the laminated glass, but preferably 90,000 mm². ２ The following applies:

[0063] In a plan view, the ratio of the area of ​​the printed layer 20 to the area of ​​the intermediate layer 10 is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more. Furthermore, in a plan view, the ratio of the area of ​​the printed layer 20 to the area of ​​the intermediate layer 10 is preferably 95% or less, and more preferably 90% or less.

[0064] When at least a portion of the printed layer 20 has a linear shape in plan view, the minimum line width of the printed layer 20 is preferably 100 mm or less. The smaller the minimum line width of the printed layer 20, the lower the rigidity of the printed layer 20. Since the printed layer 20 of this embodiment is sufficiently rigid, even if the minimum line width of the printed layer 20 is 100 mm or less, the occurrence of wrinkles in the printed layer 20 can be limited. The minimum line width of the printed layer 20 is more preferably 50 mm or less. The minimum line width of the printed layer 20 is preferably 1 mm or more.

[0065] As shown in Figure 2, the laminated film 2A has a first intermediate layer 10A and a printed layer 20. The printed layer 20 is adjacent to the surface of the first intermediate layer 10A. As shown in Figure 3, the laminated glass 3A comprises a first glass substrate 5, a laminated film 2A, and a second glass substrate 6. The first glass substrate 5 and the second glass substrate 6 may be either inorganic glass or organic glass, but inorganic glass is preferable from the viewpoint of scratch resistance. The inorganic glass is preferably tempered glass. The tempered glass may be either air-cooled tempered glass or chemically tempered glass.

[0066] Laminated glass 3A is obtained by sandwiching a laminated film 2A between a first glass substrate 5 and a second glass substrate 6 to create a laminate, then placing the laminate in an autoclave and pressing the components together under high temperature and pressure. During the autoclave process, the first intermediate layer 10A softens and adheres to both the first glass substrate 5 and the second glass substrate 6. The printed layer 20 is adjacent to the second glass substrate 6 as shown in Figure 5. The second glass substrate 6 may be placed on the outdoor side or the indoor side of the first glass substrate 5.

[0067] As shown in Figure 4, the laminated film 2B has a second intermediate layer 10B in addition to the first intermediate layer 10A and the printed layer 20. The printed layer 20 is adjacent to the surface of the first intermediate layer 10A. The printed layer 20 has a first surface 20a adjacent to the first intermediate layer 10A and a second surface 20b facing the opposite direction from the first surface 20a. The second intermediate layer 10B, like the first intermediate layer 10A, contains a thermoplastic resin. The second intermediate layer 10B is positioned on the opposite side of the printed layer 20 from the first intermediate layer 10A and is adjacent to the second surface 20b of the printed layer 20.

[0068] The method for laminating the second intermediate layer 10B is not particularly limited, and any known method may be used, for example, a lamination method may be used. For example, the second intermediate layer 10B can be laminated by extruding a thermoplastic resin onto the laminated film 2A shown in Figure 2. Alternatively, the second intermediate layer 10B can be laminated by press molding a film-like thermoplastic resin onto the laminated film 2A shown in Figure 2.

[0069] The printed layer 20 may be formed on either the first intermediate layer 10A or the second intermediate layer 10B. The first intermediate layer 10A may be laminated onto a laminated film composed of the second intermediate layer 10B and the printed layer 20. Furthermore, the first intermediate layer 10A and the second intermediate layer 10B may not be integrated until immediately before being sandwiched between the first glass substrate 5 and the second glass substrate 6, and may be integrated during autoclave processing.

[0070] As shown in Figure 5, the laminated glass 3B comprises a first glass substrate 5 and a second glass substrate 6 in addition to the laminated film 2B. The laminated glass 3B is obtained by sandwiching the laminated film 2B between the first glass substrate 5 and the second glass substrate 6 to form a laminate, and then placing the laminate in an autoclave and pressing the components together under high temperature and high pressure. During the autoclave process, the first intermediate layer 10A softens and adheres to the first glass substrate 5, and the second intermediate layer 10B softens and adheres to the second glass substrate 6.

[0071] As shown in Figure 5, the second intermediate layer 10B is placed between the printed layer 20 and the second glass substrate 6. Compared to the case without the second intermediate layer 10B, the adhesive strength between the printed layer 20 and the second glass substrate 6 can be improved. The second glass substrate 6 may be placed on the outdoor side or the indoor side of the first glass substrate 5.

[0072] As shown in Figure 6, the laminated film 2C has a third intermediate layer 10C in addition to the first intermediate layer 10A and the printed layer 20. The printed layer 20 is adjacent to the surface of the first intermediate layer 10A. The printed layer 20 has a first surface 20a adjacent to the first intermediate layer 10A and a second surface 20b facing the opposite direction from the first surface 20a. The third intermediate layer 10C is adjacent to the second surface 20b of the printed layer 20 and has a shear storage modulus at 140°C that is higher than that of the first intermediate layer 10A.

[0073] The method for laminating the third intermediate layer 10C is not particularly limited, and any known method may be used, for example, a lamination method may be used. For example, the third intermediate layer 10C can be laminated by extruding a thermoplastic resin onto the laminated film 2A shown in Figure 2. Alternatively, the third intermediate layer 10C can be laminated by press molding a film-like thermoplastic resin onto the laminated film 2A shown in Figure 2.

[0074] The printed layer 20 may be formed on either the first intermediate layer 10A or the third intermediate layer 10C. The first intermediate layer 10A may be laminated onto a laminated film composed of the third intermediate layer 10C and the printed layer 20. Furthermore, the first intermediate layer 10A and the third intermediate layer 10C may not be integrated until immediately before being sandwiched between the first glass substrate 5 and the second glass substrate 6, and may be integrated during autoclave processing.

[0075] As shown in Figure 6, the laminated film 2C may further have a second intermediate layer 10B. The second intermediate layer 10B is positioned on the opposite side of the printed layer 20 with respect to the third intermediate layer 10C. The second intermediate layer 10B contains a thermoplastic resin, similar to the first intermediate layer 10A. The third intermediate layer 10C has a higher shear storage modulus at 140°C than the second intermediate layer 10B.

[0076] The method for laminating the second intermediate layer 10B is not particularly limited, and any known method may be used, for example, a lamination method may be used. For example, the second intermediate layer 10B can be laminated by laminating a thermoplastic resin on the third intermediate layer 10C by extrusion molding. Alternatively, the second intermediate layer 10B can be laminated by laminating a film-like thermoplastic resin on the third intermediate layer 10C by press molding.

[0077] Furthermore, the second intermediate layer 10B and the third intermediate layer 10C may not be integrated until immediately before being sandwiched between the first glass substrate 5 and the second glass substrate 6, and may be integrated during the autoclave process.

[0078] As shown in Figure 7, the laminated glass 3C comprises a first glass substrate 5 and a second glass substrate 6 in addition to the laminated film 2C. The laminated glass 3C is obtained by sandwiching the laminated film 2C between the first glass substrate 5 and the second glass substrate 6 to form a laminate, and then placing the laminate in an autoclave and pressing the components together under high temperature and high pressure.

[0079] During autoclave treatment, the first intermediate layer 10A softens and adheres to the first glass substrate 5, and the second intermediate layer 10B softens and adheres to the second glass substrate 6. Although not shown in the figures, if the second intermediate layer 10B is absent, the third intermediate layer 10C is adjacent to the second glass substrate 6. However, if the second intermediate layer 10B is present, the shear storage modulus of the second intermediate layer 10B at 140°C is lower than that of the third intermediate layer 10C, making it more easily deformable and thus more likely to adhere to the second glass substrate 6.

[0080] As described above, the third intermediate layer 10C is adjacent to the second surface 20b of the printed layer 20 and has a shear storage modulus at 140°C that is higher than that of the first intermediate layer 10A. Therefore, the third intermediate layer 10C can restrain the printed layer 20 and limit the occurrence of wrinkles in the printed layer 20. This effect is particularly noticeable when the third intermediate layer 10C is used as a substrate for printing curable ink.

[0081] The third intermediate layer 10C may contain a different thermoplastic resin than the first intermediate layer 10A and the second intermediate layer 10B. On the other hand, the first intermediate layer 10A and the second intermediate layer 10B may contain the same thermoplastic resin. The combination of thermoplastic resins is not particularly limited, but for example, the first intermediate layer 10A and the second intermediate layer 10B may contain at least one selected from polyvinyl acetal, ethylene vinyl acetate, polyurethane, and polyolefin, and the third intermediate layer 10C may contain polyethylene terephthalate.

[0082] [Laminated Glass] Laminated glass has a laminated film 2, a first glass substrate 5, and a second glass substrate 6. The first glass substrate 5 and the second glass substrate 6 are arranged with the laminated film 2 in between. Glass plates can be used as the first glass substrate 5 and the second glass substrate 6. The glass plates can be either inorganic glass or organic glass, but inorganic glass is preferred. Inorganic glass is not particularly limited, but examples include clear glass, float glass, polished glass, patterned glass, wired glass, reinforcing glass, green glass, etc.

[0083] Furthermore, organic glass generally refers to what is called resin glass, and while not particularly limited, examples of organic glass composed of resins such as polycarbonate, acrylic resin, acrylic copolymer resin, and polyester can be found.

[0084] The two glass plates may be made of the same material or of different materials. For example, one may be inorganic glass and the other organic glass, but it is preferable that both glass plates be either inorganic glass or organic glass.

[0085] Furthermore, the thickness of each glass plate is not particularly limited, but is, for example, about 0.1 mm to 15 mm, preferably 0.5 mm to 5 mm. The thicknesses of each glass plate may be the same or different, but it is preferable that they be the same.

[0086] The method for manufacturing laminated glass is not particularly limited, but it involves sandwiching a laminated film 2 having a first intermediate layer 10A and a printed layer 20 between two glass substrates (a first glass substrate 5 and a second glass substrate 6), and maintaining a temperature of 120°C or higher and the shear storage modulus of the first intermediate layer being 6 × 10⁻⁶ ４ It is preferable that the process involves heating in a temperature range of Pa or higher. The method for manufacturing the laminated film 2 preferably involves printing an ultraviolet-curable ink onto the surface of a first intermediate layer 10A for laminated glass, which contains a thermoplastic resin, and curing the ultraviolet-curable ink on the first intermediate layer to form a printed layer.

[0087] For example, a laminated film 2 is placed between a first glass substrate 5 and a second glass substrate 6, and the air remaining between the glass substrate and the laminated film 2 is removed by passing it through a pressure roll or by placing it in a rubber bag and applying reduced pressure and suction. Then, a laminate is obtained by pre-bonding at approximately 70 to 110°C. Next, the laminate is placed in an autoclave or pressed to bond it at a temperature of approximately 120 to 140°C and a pressure of 1.0 MPa to 1.5 MPa. In this way, laminated glass can be obtained.

[0088] Laminated glass can be used as a glass structure, such as window glass, in various fields. For example, it can be used in vehicles such as automobiles, railway cars, aircraft, and ships, as well as in architectural applications. Among these, its use in various vehicle applications, such as automobiles, is particularly preferable. When used in automobiles, it can be used for the windshield, side windows, rear windows, and roof windows. When used in automobiles, it is preferable that the laminated glass has a curved surface that follows the body lines of the automobile.

[0089] Laminated glass is preferable for applications requiring high design quality because it can support images within the glass structure. For example, when used in automotive windows, it allows for decoration to match the body design and color. It is also preferable for use in architectural applications as decorative glass for exterior or interior finishes. Furthermore, electrical circuits can be embedded within the glass structure instead of images.

[0090] Furthermore, as described above, when the printed layer 20 contains a light-emitting material, the laminated glass is preferably used together with a light source device that emits excitation light. The light source device is not particularly limited, but when the laminated glass is used in vehicle applications, it is preferably placed inside the vehicle, for example. When used in building applications, the light source device may be placed inside the building or outside the building.

[0091] The present invention will be described in more detail by reference to examples, but the present invention is not limited in any way by these examples. Examples 1 to 4 below are examples, and Examples 5 to 6 below are comparative examples.

[0092] [Example 1] (Formation of Laminated Film) First, a 0.4 mm thick resin film was prepared as the first and second intermediate layers, consisting of 100 parts by mass of PVB (polyvinyl butyral resin, average degree of polymerization 1700, hydroxyl group content 30.5 mol%, degree of acetylation 1 mol%, degree of acetalization 68.5 mol%) and 30 parts by mass of a plasticizer (3GO: triethylene glycol-di-2-ethylhexanoate). An ultraviolet-curable ink (Mimaki LUS120, manufactured by Mimaki Engineering Co., Ltd.) was applied to one side of the prepared resin film for the first intermediate layer by inkjet printing to create a predetermined image shape, and ultraviolet light was applied at 3 W / cm². ２ The ink was cured by irradiation under these conditions to form a printed layer. The image shape consisted of five lines, each 130 mm long, spaced 10 mm apart. Each line had a thickness of 25 μm, and its widths were 0.1 mm, 1 mm, 3 mm, 5 mm, and 10 mm. Subsequently, a second intermediate layer resin film was laminated onto the printed layer using a lamination method to obtain a laminated film with the structure shown in Figure 4, measuring 15 cm in length, 15 cm in width, and 0.8 mm in thickness.

[0093] (Formation of Laminated Glass) The obtained laminated film (interlayer for laminated glass) was sandwiched between two sheets of clear glass (15 cm long x 15 cm wide x 2.5 mm thick) to obtain a laminate. This laminate was placed in a rubber bag and degassed at a vacuum of 2.6 kPa for 20 minutes. Then, while still degassed, it was transferred to an oven and held at 90°C for 30 minutes to vacuum press and temporarily bond the laminate. The temporarily bonded laminate was then pressed in an autoclave at 135°C and a pressure of 1.2 MPa for 20 minutes to obtain laminated glass.

[0094] [Example 2] The procedure was carried out in the same manner as in Example 1, except that the amount of plasticizer per 100 parts by mass of thermoplastic resin was changed to 20 parts by mass in the first and second intermediate layers.

[0095] [Example 3] The procedure was carried out in the same manner as in Example 1, except that the amount of plasticizer per 100 parts by mass of thermoplastic resin was changed to 0 parts by mass in the first and second intermediate layers.

[0096] [Example 4] The procedure was carried out in the same manner as in Example 1, except that the amount of plasticizer per 100 parts by mass of thermoplastic resin was changed to 40 parts by mass in the first and second intermediate layers.

[0097] [Example 5] The procedure was carried out in the same manner as in Example 1, except that the amount of plasticizer per 100 parts by mass of thermoplastic resin was changed to 60 parts by mass in the first and second intermediate layers.

[0098] [Example 6] The procedure was carried out in the same manner as in Example 3, except that a resin film consisting of 100 parts by mass of EVA (ethylene vinyl alcohol resin, Tosoh Corporation, Mersen G) was used as the first and second intermediate layers.

[0099] (Evaluation) [Measurement of Shear Storage Modulus] The shear storage modulus was measured according to the method in accordance with JIS K7244-10:2005. Specifically, an intermediate layer (hereinafter referred to as the test specimen) measuring 10 mm in length and 5 mm in width was cut from a region in the laminated film where no printed layer was formed. The shear storage modulus was measured while heating the test specimen under the following measurement conditions using a forced vibration type solid viscoelasticity measuring device (ARES-G2 manufactured by TAINSTRUMENTS). Shear storage modulus G' at 140°C １４０ , and the shear storage modulus G' at 100°C １００ Measure the ratio (G' １４０ / G' １００ The following values ​​were calculated: -Measurement conditions- Deformation mode: shear mode, Measurement temperature: -20°C to 100°C, Heating rate: 3°C / min, Measurement frequency: 1 Hz, Strain: 1% Deformation mode: shear mode, Measurement temperature: 100°C to 200°C, Heating rate: 3°C / min, Measurement frequency: 1 Hz, Strain: 5%

[0100] [Observation of Appearance Defects] After autoclaving, each of the obtained laminated glass samples was allowed to cool naturally to room temperature (23°C). The printed layer of the laminated glass was then visually inspected, and appearance defects were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 and 2. -Evaluation Criteria- A: No wrinkles are formed in the printed layer. B: Wrinkles are formed in the printed layer.

[0101]

[0102]

[0103] In Examples 1 to 4 above, the shear storage modulus of each intermediate layer at 140°C is 6 × 10⁻⁶. ４ By having a Pa or higher pressure, the fluidity of each intermediate layer during the bonding process was reduced, thereby reducing the occurrence of appearance defects such as wrinkles in the printed layer due to heat treatment.

[0104] In contrast, in each of Examples 5 and 6, the shear storage modulus of each intermediate layer at 140°C is 6 × 10⁻⁶. ４ Because the pressure was not above Pa, it was not possible to reduce the occurrence of appearance defects such as wrinkles in the printed layer due to heat treatment.

[0105] Specifically, Figures 8-9 show a modified example in which laminated glass was formed in the same manner as in Examples 5 and 6, except that the printed layer was formed over the entire surface of the first intermediate layer. The length of the scale bar in Figures 8-9 is 5 cm. As shown in Figures 8-9, after autoclaving, the printed layer had appearance defects such as cracks and / or periodic interference wrinkles (worm-like appearance, wrinkle-like).

[0106] The laminated film, laminated glass, and method for manufacturing laminated glass described above have been explained, but this disclosure is not limited to the embodiments described above. Various changes, modifications, substitutions, additions, deletions, and combinations are possible within the scope of the claims. These also naturally fall within the technical scope of this disclosure.

[0107] This application claims priority based on Japanese Patent Application No. 2025-055357, filed with the Japan Patent Office on March 28, 2025, and the entire contents of Japanese Patent Application No. 2025-055357 are incorporated herein by reference.

[0108] 2. Laminated film 10. Intermediate layer 10A. First intermediate layer 10B. Second intermediate layer 10C. Third intermediate layer 20. Printing layer 21. Ink

Claims

1. A first intermediate layer for laminated glass containing a thermoplastic resin, and a printed layer adjacent to the surface of the first intermediate layer, wherein the shear storage modulus of the first intermediate layer at 140°C is 6 × 10⁻⁶. ４ Laminated film with a hardness of Pa or higher.

2. The laminated film according to claim 1, wherein the printed layer has a first surface adjacent to the first intermediate layer and a second surface facing the opposite direction from the first surface, and the laminated film has a second intermediate layer containing a thermoplastic resin, the second intermediate layer being adjacent to the second surface of the printed layer.

3. The shear storage modulus of the second intermediate layer at 140°C is 6 × 10⁻⁶. ４ The laminated film according to claim 2, wherein the hardness is Pa or greater.

4. In the first intermediate layer, the shear storage modulus G1' at 100°C. １００ Shear storage modulus G1' at 140°C relative to １４０ The ratio (G1') １４０ / G1' １００ A laminated film according to any one of claims 1 to 3, wherein the ratio is 0.4 or more.

5. The laminated film according to any one of claims 1 to 4, wherein the average thickness of the printed layer is 1 μm or more and 50 μm or less.

6. The laminated film according to any one of claims 1 to 5, wherein the printed layer contains a cured product of an ultraviolet-curable ink.

7. The laminated film according to any one of claims 1 to 6, wherein the first intermediate layer contains a plasticizer.

8. The laminated film according to claim 7, wherein the content of the plasticizer in the first intermediate layer is 35 parts by mass or less per 100 parts by mass of thermoplastic resin.

9. The laminated film according to any one of claims 1 to 8, wherein the thermoplastic resin in the first intermediate layer has intermolecular crosslinking.

10. The laminated film according to any one of claims 1 to 9, wherein the thermoplastic resin in the first intermediate layer is at least one of polyvinyl acetal, ethylene-vinyl acetate copolymer, polyurethane, polyolefin, and ionomer.

11. The laminated film according to any one of claims 1 to 10, wherein the thermoplastic resin in the first intermediate layer is polyvinyl acetal.

12. Laminated glass comprising a laminated film according to any one of claims 1 to 11, and two glass substrates sandwiching the laminated film.

13. Printing an ultraviolet-curable ink onto the surface of a first intermediate layer for laminated glass containing a thermoplastic resin; curing the ultraviolet-curable ink on the first intermediate layer to form a printed layer; sandwiching the laminated film having the first intermediate layer and the printed layer between two glass substrates, with a temperature of 120°C or higher and a shear storage modulus of the first intermediate layer of 6 × 10⁻⁶ ４ A method for manufacturing laminated glass, comprising heating in a temperature range of Pa or higher.

14. The method for manufacturing laminated glass according to claim 13, wherein the ultraviolet-curable ink is printed by inkjet printing.

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