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WO2024122517A1 - Corps multicouche fonctionnel et verre feuilleté - Google Patents

Corps multicouche fonctionnel et verre feuilleté Download PDF

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Publication number
WO2024122517A1
WO2024122517A1 PCT/JP2023/043361 JP2023043361W WO2024122517A1 WO 2024122517 A1 WO2024122517 A1 WO 2024122517A1 JP 2023043361 W JP2023043361 W JP 2023043361W WO 2024122517 A1 WO2024122517 A1 WO 2024122517A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
film
resin film
functional
laminated glass
Prior art date
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Ceased
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PCT/JP2023/043361
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English (en)
Japanese (ja)
Inventor
敦 野原
慶介 野村
一樹 清水
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to JP2023578059A priority Critical patent/JPWO2024122517A1/ja
Publication of WO2024122517A1 publication Critical patent/WO2024122517A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor

Definitions

  • the present invention relates to a functional laminate for use in laminated glass, and to laminated glass that includes a functional laminate.
  • laminated glass which is made by inserting an interlayer between two glass sheets to bond them together.
  • Interlayers are often made from plasticized polyvinyl acetal, which is a polyvinyl acetal resin mixed with a plasticizer.
  • Laminated glass is safe because even if it is broken by external impact, few glass fragments are scattered, so it is widely used as window glass for vehicles such as automobiles, aircraft, buildings, etc.
  • Laminated glass is generally produced by placing two glass sheets with an interlayer film, then performing a preliminary degassing process, followed by heating and pressurizing in an autoclave (ACV) process at a temperature of about 130-140°C and a pressure of about 1.3 MPa to pressurize the glass and the interlayer film together.
  • ACV autoclave
  • a functional film such as a photochromic element may be placed between two glass sheets.
  • a functional film such as a photochromic element
  • an interlayer film is placed between the functional film and each glass sheet, and the two glass sheets and the functional film are integrated via the interlayer film (see, for example, Patent Document 2).
  • the present invention aims to provide a functional laminate that, even when a functional film such as a photochromic body is incorporated, does not lose the function of the functional film, prevents poor appearance, and maintains a good appearance even after long-term use in a high-temperature environment.
  • the inventors have found that the above problems can be solved by preparing a thermoplastic resin film in a functional laminate containing a functional film and a thermoplastic resin film so that the thickness change amount when compressed in a specified compression creep test is 80 ⁇ m or more, and have completed the present invention as described below. That is, the present invention provides the following [1] to [22].
  • thermoplastic resin film (A) exhibits a thickness change of 80 ⁇ m or more when compressed in a compression creep test performed under the following conditions: (Compression creep test conditions) A test sample having a diameter of 8 mm and a thickness of 700 to 900 ⁇ m made from the thermoplastic resin film (A) is compressed for 5 minutes under conditions of a load of 410 g and 30° C., and then the thickness (T1) of the test sample is measured. Then, while maintaining the load of 410 g, the temperature is increased from 30° C. to 90° C. at a heating rate of 6° C./min.
  • compression creep test conditions A test sample having a diameter of 8 mm and a thickness of 700 to 900 ⁇ m made from the thermoplastic resin film (A) is compressed for 5 minutes under conditions of a load of 410 g and 30° C., and then the thickness (T1) of the test sample is measured. Then, while maintaining the load of 410 g, the temperature is increased from 30° C. to 90° C. at
  • the thickness (T2) of the test sample A is measured.
  • the absolute value of the difference between the thickness (T1) and the thickness (T2) of the test sample is defined as the thickness change amount.
  • thermoplastic resin film (A) The functional laminate according to any one of the above [1] to [6], wherein the weight average molecular weight of the thermoplastic resin film (A) is 230,000 or more and 310,000 or less.
  • thermoplastic resin film (A) contains a plasticizer.
  • plasticizer is at least one selected from the group consisting of triethylene glycol-di-2-ethylhexanoate (3GO), polyoxyethylene polyoxypropylene glycol, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, or derivatives thereof in which a portion of the hydrogen atoms of the terminal hydroxyl groups are substituted with alkyl groups.
  • thermoplastic resin film (A) The functional laminate described in [10] above, wherein the plasticizer is at least one selected from the group consisting of organic ester plasticizers, polyalkylene glycol plasticizers, polyoxyalkylene ether plasticizers, and alcohol plasticizers.
  • the content of the plasticizer is 10 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the thermoplastic resin (a) contained in the thermoplastic resin film (A).
  • the thickness of the thermoplastic resin film (A) is 100 ⁇ m or more and 2000 ⁇ m or less.
  • the functional laminate according to any one of the above [1] to [16], wherein the functional film is a film having an electronic component.
  • thermoplastic resin film (A) contains a polyvinyl acetal resin
  • the polyvinyl acetal resin is produced by a method including a mixing step of mixing the polyvinyl alcohol and the aldehyde, and an aging step of aging the mixture obtained in the mixing step, and the aging temperature in the aging step is 30°C or higher and 65°C or lower.
  • the present invention provides a functional laminate that incorporates a functional film such as a light control film without losing the functionality of the functional film, prevents poor appearance, and maintains a good appearance even after long-term use in a high-temperature environment.
  • a functional film such as a light control film
  • FIG. 1 shows a laminated glass according to one embodiment of the present invention.
  • the functional laminate of the present invention is a laminate comprising a functional film and a thermoplastic resin film (A), and the thermoplastic resin film (A) exhibits a thickness change of 80 ⁇ m or more when compressed in a compression creep test carried out under the following conditions.
  • a test sample having a diameter of 8 mm and a thickness of 700 to 900 ⁇ m (for example, 800 ⁇ m) is prepared from the thermoplastic resin film (A).
  • the test sample is compressed for 5 minutes under conditions of a load of 410 g and 30° C., and then the thickness (T1) of the test sample is measured.
  • the temperature is increased from 30° C. to 90° C. at a heating rate of 6° C./min.
  • the thickness (T2) of the test sample is measured.
  • the absolute value of the difference between the thickness (T1) and the thickness (T2) of the test sample is taken as the thickness change amount.
  • the test sample may be prepared by stacking two or more thermoplastic resin films, appropriately pressing them together by hot pressing or the like, adjusting the thickness to 700 to 900 ⁇ m by pressing or the like, and then cutting the film into a cylindrical shape with a diameter of 8 mm.
  • the test sample may be prepared by adjusting the thickness to 700 to 900 ⁇ m by hot pressing or the like as necessary, and then cutting the sample into a cylindrical shape with a diameter of 8 mm.
  • the test sample may be appropriately adjusted by hot pressing or the like so that the surface is flat, and then the test sample may be produced by cutting it into a cylindrical shape with a diameter of 8 mm.
  • the thickness change of the thermoplastic resin film (A) is less than 80 ⁇ m, when the thermoplastic resin film (A) is pressed against another component such as a laminated glass component described below by autoclaving at low pressure and low temperature or by other means, residual air or bubbles may form between the thermoplastic resin film (A) and a component such as a glass component or a functional film, resulting in poor appearance. Even if no bubbles form immediately after the laminated glass is produced, when the laminated glass is used for a long period of time in a high-temperature environment, bubbles may form between the glass component or functional film and the thermoplastic resin film (A), resulting in a poor appearance.
  • the thickness change of the thermoplastic resin film (A) is preferably 90 ⁇ m or more, more preferably 120 ⁇ m or more, and even more preferably 140 ⁇ m or more. When the thickness change is large in this manner, the above-mentioned appearance defect or deterioration of the appearance of the laminated glass can be more appropriately prevented.
  • the thickness change of the thermoplastic resin film (A) is, for example, 400 ⁇ m or less, preferably 320 ⁇ m or less, more preferably 220 ⁇ m or less, and even more preferably 180 ⁇ m or less.
  • the thermoplastic resin film (A) is prevented from becoming too soft, and for example, the gas dissolved in the thermoplastic resin film is prevented from being released to the outside and becoming bubbles. Therefore, the appearance defect or deterioration can be more appropriately prevented.
  • the thermoplastic resin film (A) preferably has a storage modulus of 1.4 ⁇ 10 5 Pa or more at 90° C.
  • the storage modulus of the thermoplastic resin film (A) is equal to or more than the lower limit, the thermoplastic resin film (A) can have a certain mechanical strength while increasing the thickness change amount. Therefore, the performance of the thermoplastic resin film (A) can be improved while preventing poor appearance or deterioration of appearance.
  • the thermoplastic resin film (A) has a certain mechanical strength, it becomes easy to convey the film while applying tension, and therefore the thermoplastic resin film (A) can be easily molded by, for example, extrusion molding, and the film formability is also improved.
  • the storage modulus of the thermoplastic resin film (A) at 90° C. is more preferably 1.8 ⁇ 10 5 Pa or more, further preferably 2.0 ⁇ 10 5 Pa or more, and even more preferably 2.3 ⁇ 10 5 Pa or more.
  • the storage modulus at 90° C. should be a certain value or less in order to ensure a certain degree of flexibility, for example, 1.0 ⁇ 10 7 Pa or less, preferably 1.0 ⁇ 10 6 Pa or less, and more preferably 5.0 ⁇ 10 5 Pa or less.
  • the storage modulus is a shear storage modulus, and can be measured under the measurement conditions described in the examples below.
  • the thickness change and the storage modulus at 90°C can be appropriately adjusted by the thermoplastic resin used in the thermoplastic resin film (A) (hereinafter, the thermoplastic resin contained in the thermoplastic resin film (A) may be referred to as "thermoplastic resin (a)").
  • thermoplastic resin (a) the thermoplastic resin contained in the thermoplastic resin film (A)
  • they can be adjusted by the molecular weight and molecular weight distribution (Mw/Mn) of the thermoplastic resin (a).
  • Mw/Mn molecular weight and molecular weight distribution
  • the thickness change increases while the storage modulus at 90°C tends to decrease.
  • a polyvinyl acetal resin is used, the thickness change amount and the storage modulus at 90° C.
  • the thickness change amount and the storage modulus at 90° C. can be adjusted by the aging conditions in the aging step performed when the polyvinyl acetal resin is produced. It can also be adjusted by the amount and type of plasticizer contained in the thermoplastic resin film (A). For example, when the amount of plasticizer is increased, the thickness change amount increases while the storage modulus at 90 ° C tends to decrease.
  • ether-based plasticizer such as a polyoxyalkylene ether-based plasticizer or a polyoxyalkylene ether-based plasticizer is used as the plasticizer, it is easy to increase the thickness change amount while preventing the storage modulus at 90 ° C from decreasing.
  • the thermoplastic resin film (A) preferably has a weight average molecular weight (Mw) of 230,000 or more and 310,000 or less.
  • Mw weight average molecular weight
  • the Mw of the thermoplastic resin film (A) is equal to or more than the lower limit, bubbles are unlikely to occur and the appearance is unlikely to deteriorate even when used for a long period of time under a high temperature environment.
  • the storage modulus at 90°C is likely to be large, and the strength of the thermoplastic resin film (A) is likely to be improved.
  • the Mw of the thermoplastic resin film (A) is equal to or less than the upper limit, the flexibility of the thermoplastic resin film (A) is likely to be secured.
  • the weight average molecular weight (Mw) of the thermoplastic resin (a) is more preferably equal to or more than 240,000 and 300,000 or less, and more preferably equal to or more than 260,000 and 290,000 or less.
  • the molecular weight distribution of the thermoplastic resin film (A), which is expressed by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 2.5 or less. If the molecular weight distribution (Mw/Mn) is 2.5 or less, the amount of low molecular weight components contained in the thermoplastic resin film (A) can be suppressed, so that the storage modulus can be easily increased while keeping the thickness change within a desired range.
  • the molecular weight distribution (Mw/Mn) of the thermoplastic resin (a) is more preferably 2.3 or less, even more preferably 2.2 or less, and even more preferably 2.0 or less.
  • the molecular weight distribution (Mw/Mn) of the thermoplastic resin (a) is preferably as low as possible, and may be 1.0 or more, but may be 1.1 or more, or may be 1.3 or more in practical use.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the thermoplastic resin film (A) are measured by gel permeation chromatography.
  • the weight average molecular weight and molecular weight distribution of the thermoplastic resin film (A) are values obtained by measuring the molecular weight of the thermoplastic resin film (A). Therefore, the thermoplastic resin film (A) may contain components other than the thermoplastic resin (a), such as plasticizers, and in that case, Mw and Mn are values that take into account the components other than the thermoplastic resin (a).
  • Thermoplastic resin (a) used in the thermoplastic resin film (A) of the present invention includes, for example, (meth)acrylic resins, polyvinyl acetal resins, polyvinyl alcohol resins (PVA), polyurethane resins (PU), ethylene-vinyl acetate copolymer resins (EVA), saponified ethylene-vinyl acetate copolymers (EVOH), ethylene-methacrylic acid copolymer resins, ionomer resins, isobutylene resins, styrene-isoprene copolymer resins, and styrene-butadiene copolymer resins.
  • the thermoplastic resins may be used alone or in combination of two or more.
  • the thermoplastic resin (a) is preferably polyvinyl acetal resin, polyurethane resin (PU), ethylene-vinyl acetate copolymer resin (EVA), saponified ethylene-vinyl acetate copolymer (EVOH), ethylene-methacrylic acid copolymer resin, ionomer resin, isobutylene resin, styrene-isoprene copolymer resin, or styrene-butadiene copolymer resin. Furthermore, among the above, the thermoplastic resin (a) is more preferably polyvinyl acetal resin.
  • thermoplastic resin (a) By using polyvinyl acetal resin, it becomes easier to achieve excellent impact resistance. In addition, it becomes easier to achieve good adhesion to various resin materials and inorganic glass. Below, the polyvinyl acetal resin used in the thermoplastic resin (a) will be described in detail.
  • the polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol (PVA) with an aldehyde.
  • PVA polyvinyl alcohol
  • the aldehyde is not particularly limited, but generally, an aldehyde having 1 to 10 carbon atoms is suitably used.
  • the aldehyde having 1 to 10 carbon atoms is not particularly limited, and examples thereof include n-butyl aldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, formaldehyde, acetaldehyde, benzaldehyde, etc. These aldehydes may be used alone, or two or more of them may be used in combination.
  • the polyvinyl acetal resin is preferably a polyvinyl butyral resin.
  • Polyvinyl alcohol can be obtained, for example, by saponifying a polyvinyl ester such as polyvinyl acetate.
  • the degree of saponification of polyvinyl alcohol is generally 70 to 99.9 mol %.
  • the average polymerization degree of PVA is preferably 200 or more, more preferably 500 or more, even more preferably 1000 or more, and even more preferably 1500 or more.
  • the average polymerization degree is set to be equal to or more than the above lower limit, the penetration resistance of the laminated glass is increased when the PVA is used in the laminated glass.
  • the average polymerization degree 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.
  • the average degree of polymerization of polyvinyl alcohol is determined by a method in accordance with JIS K6726 "Testing method for polyvinyl alcohol".
  • polyvinyl alcohol used as the raw material of the polyvinyl acetal resin two or more kinds of polyvinyl alcohols having different average polymerization degrees may be used. In this case, it is preferable to use a mixture of two or more kinds of polyvinyl alcohols as the raw material to produce the polyvinyl acetal resin by the production method described below.
  • two or more kinds of polyvinyl alcohols for example, it is preferable to use a first polyvinyl alcohol having an average degree of polymerization of 1500 or more and a second polyvinyl alcohol having an average degree of polymerization of 1000 or less.
  • the average degree of polymerization of the first polyvinyl alcohol is preferably 1500 or more and 3500 or less, more preferably 1600 or more and 2500 or less, and even more preferably 1600 or more and 2000 or less.
  • the average degree of polymerization of the second polyvinyl alcohol is preferably 200 or more and 1000 or less, more preferably 300 or more and 900 or less, and even more preferably 400 or more and 700 or less.
  • the blending ratio of the first polyvinyl alcohol to the second polyvinyl alcohol is not particularly limited, but the blending amount of the second polyvinyl alcohol relative to the total amount of the first and second polyvinyl alcohols is, for example, 1 mass% or more and 70 mass% or less, preferably 3 mass% or more and 50 mass% or less, more preferably 5 mass% or more and 40 mass% or less, and even more preferably 10 mass% or more and 30 mass% or less.
  • the polyvinyl alcohol used as the raw material of the polyvinyl acetal resin two or more kinds of polyvinyl alcohols having different average polymerization degrees may be used. In this case, it is preferable to use a mixture of two or more kinds of polyvinyl alcohols as the raw material to produce the polyvinyl acetal resin by the production method described below.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is preferably 15 mol% or more, and preferably 38 mol% or less.
  • the amount of hydroxyl groups 15 mol% or more the adhesiveness is easily improved, and when used in laminated glass, the penetration resistance of the laminated glass is easily improved.
  • the amount of hydroxyl groups 38 mol% or less flexibility is easily ensured, and it is possible to prevent the functional laminate from becoming too hard or the thickness change from decreasing.
  • the amount of hydroxyl groups within the above range the storage modulus is easily adjusted within a desired range.
  • the amount of hydroxyl groups is more preferably 20 mol % or more, and even more preferably 25 mol % or more.
  • the amount of hydroxyl groups is more preferably 35 mol % or less, and even more preferably 33 mol % or less.
  • the amount of hydroxyl groups is 15 mol% or more, and preferably 38 mol% or less, more preferably 20 mol% or more, even more preferably 25 mol% or more, more preferably 35 mol% or less, and even more preferably 33 mol% or less.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is the molar fraction calculated by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which hydroxyl groups are bonded can be measured by the procedure described in the Examples.
  • the acetylation degree of the polyvinyl acetal resin 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 acetylation degree is equal to or less than the upper limit, the moisture resistance of the polymer film is increased.
  • the acetylation degree is not particularly limited, but is preferably 0.01 mol% or more, and more preferably 0.1 mol% or more.
  • the degree of acetylation is a molar fraction calculated by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which acetyl groups are bonded can be measured by the procedure described in the Examples.
  • the degree of acetalization of the polyvinyl acetal resin is preferably 47 mol% or more and preferably 85 mol% or less, more preferably 55 mol% or more, further preferably 60 mol% or more, and more preferably 80 mol% or less, 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 (A) is a polyvinyl butyral resin.
  • the above-mentioned degree of acetalization is a molar fraction calculated by subtracting the amount of ethylene groups bonded to hydroxyl groups and the amount of ethylene groups bonded to acetyl groups from the total amount of ethylene groups in the main chain, and dividing the result by the total amount of ethylene groups in the main chain, expressed as a percentage.
  • the degree of acetalization (degree of butyralization) may be calculated based on the amount of ethylene groups bonded to hydroxyl groups and the amount of ethylene groups bonded to acetyl groups, which are calculated by the procedure described in the Examples.
  • the polyvinyl acetal resin is preferably an unmodified polyvinyl acetal resin, but may also be a modified polyvinyl acetal resin.
  • the modified polyvinyl acetal resin has a structure (modifying group) other than an acetal group, a hydroxyl group, and an acetyl group, and preferably has a modifying group in a side chain.
  • the modifying group include those having a polyalkylene oxide structure in a side chain, and those having an acetal group, an alkyl group other than an acetyl group (e.g., having about 2 to 30 carbon atoms) in a side chain.
  • the modification amount is not particularly limited, but is, for example, about 0.1 mol % to 10 mol %.
  • the modification amount indicates the ratio of functional groups to all vinyl monomer units constituting the polyvinyl acetal resin.
  • the polyvinyl acetal resin may be used alone or in combination of two or more kinds.
  • the thermoplastic resin film (A) may contain a thermoplastic resin other than the polyvinyl acetal resin as long as the effects of the present invention are achieved.
  • the thermoplastic resin other than the polyvinyl acetal resin is as described above.
  • the thermoplastic resin film (A) is mainly composed of polyvinyl acetal resin.
  • the content of polyvinyl acetal resin is, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and most preferably 100 mass% based on the total amount of the thermoplastic resin (a) contained in the thermoplastic resin film (A). Therefore, the thermoplastic resin (a) contained in the thermoplastic resin film (A) of the present invention may be composed only of polyvinyl acetal resin.
  • the polyvinyl acetal resin is preferably produced by a production method including a mixing step of mixing the polyvinyl alcohol and the aldehyde, and an aging step of aging the mixture obtained in the mixing step.
  • polyvinyl alcohol and aldehyde may be mixed according to a conventional method.
  • a catalyst such as an acid catalyst for promoting the acetalization reaction may be further added.
  • aldehyde may be added under low temperature conditions of about 0 to 20°C to a mixture of polyvinyl alcohol and an acid catalyst.
  • a solvent such as water is usually also added.
  • the aging step is not particularly limited, but may be, for example, a catalyst such as an acid catalyst added to the mixture (reaction mixture) obtained by the mixing step, heated to an aging temperature, and maintained at the aging temperature for a certain period of time.
  • a catalyst such as an acid catalyst added to the mixture (reaction mixture) obtained by the mixing step, heated to an aging temperature, and maintained at the aging temperature for a certain period of time.
  • acetalization of polyvinyl alcohol proceeds in the mixing step and the aging step to obtain a polyvinyl acetal resin.
  • the reaction mixture may be maintained at the aging temperature for a certain period of time, and then appropriately cooled and neutralized, and then washed with water and dried, if necessary.
  • Examples of the acid catalyst added in the mixing step and the aging step include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, etc.
  • the concentration of the acid catalyst may be adjusted to, for example, about 0.5% by mass or more and 5% by mass or less, preferably about 1% by mass or more and 2.5% by mass or less.
  • the aging temperature in the aging step may be relatively low, for example, from 30° C. to 65° C., preferably from 35° C. to 60° C., and more preferably from 40° C. to 57° C.
  • the time for which the aging temperature is maintained may be longer than a certain time, for example, from 75 minutes to 180 minutes, preferably from 90 minutes to 150 minutes, and more preferably from 100 minutes to 140° C. It is presumed that when the aging temperature and aging time are within the above desired ranges, the hydroxyl groups in the polyvinyl acetal resin tend to be uniformly distributed in the molecule, and thus the thickness change amount can be increased without significantly decreasing the storage modulus at 90°C. In addition, the amount of low molecular weight components tends to decrease, and the molecular weight distribution (Mw/Mn) tends to decrease. The reason for the decrease in the amount of low molecular weight components is unclear, but it is presumed to be due to the promotion of intermolecular crosslinking.
  • thermoplastic resin film (A) preferably contains a plasticizer.
  • the thermoplastic resin film (A) becomes flexible by containing a plasticizer, and the adhesiveness and penetration resistance of the thermoplastic resin film (A) to various adherends can be improved. In addition, the thickness change amount can be easily increased.
  • plasticizer examples include organic ester plasticizers, organic phosphorus-based plasticizers such as organic phosphate ester plasticizers and organic phosphite ester plasticizers, organic ether-based plasticizers such as polyalkylene glycol-based plasticizers, and alcohol-based plasticizers.
  • the plasticizers may be used alone or in combination of two or more. Among the above, organic ester plasticizers and organic ether plasticizers are preferred.
  • Preferred organic ester plasticizers include monobasic organic acid esters and polybasic organic acid esters.
  • monobasic organic acid esters include esters of glycols and monobasic organic acids.
  • 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.
  • glycols may also include monoalkylene glycols having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms (i.e., one repeating unit).
  • glycol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and butylene glycol.
  • monobasic organic acid examples include organic acids having 3 to 10 carbon atoms, and specific examples thereof include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, n-nonyl acid, and decylic acid.
  • 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, dipropylene glycol di-2-ethylbutyrate, and triethylene glycol di-n-octanoate.
  • Examples include diethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, ethylene glycol di-2-ethylbutyrate, 1,2-propylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, and 1,2-butylene glycol di-2-ethylbutyrate.
  • polybasic organic acid esters examples include ester compounds of dibasic organic acids having 4 to 12 carbon atoms, such as adipic acid, sebacic acid, and azelaic acid, with alcohols having 4 to 10 carbon atoms.
  • the alcohols having 4 to 10 carbon atoms may be linear, may have a branched structure, or may have a cyclic structure.
  • adipate examples include dibutyl sebacate, dioctyl azelaate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl carbitol adipate, and mixed adipates.
  • Oil-modified alkyd sebacate may also be used.
  • the mixed adipate include adipates 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.
  • the organic ester plasticizer is not limited to the complete esters of the above-mentioned esters, and may be a partial ester.
  • it may be a partial ester of glycol and a monobasic organic acid, or a partial ester of a dibasic organic acid and an alcohol.
  • a specific example is triethylene glycol-mono-2-ethylhexanoate.
  • it may be a partial ester of a monobasic organic acid with a trihydric or higher alcohol such as glycerin.
  • the monobasic organic acid include monobasic organic acids having 3 to 24 carbon atoms, preferably 6 to 18 carbon atoms.
  • partial ester of a monobasic organic acid with a trihydric or higher alcohol examples include a mono- or diester of glycerin and stearic acid, and a mono- or diester of glycerin and 2-ethylhexyl acid.
  • organic ester plasticizers triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.
  • Organophosphorus plasticizers include phosphate esters such as tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.
  • Polyalkylene glycol plasticizers include polyoxyalkylene compounds having a polyoxyalkylene structure, specifically polyhydric alcohol compounds such as glycol, ester compounds of glycol and monobasic organic acid or polybasic organic acid, ether compounds of monohydric or polyhydric alcohol and polyoxyalkylene, etc.
  • glycols include polyoxyalkylene glycols and derivatives thereof.
  • Polyoxyalkylenes include polyoxyethylene, polyoxypropylene, polyoxybutylene, random copolymers or block copolymers thereof, etc.
  • the polyoxyalkylene compounds may be polyhydric alcohol compounds, ester compounds, ether compounds, or other compounds as described above.
  • Polyoxyalkylene compounds include polyoxyalkylenes and their derivatives. More specifically, they include polyoxyalkylene glycols composed of the above-mentioned polyoxyalkylenes, and ether compounds of polyoxyalkylenes and polyhydric alcohols. All of these may have hydroxyl groups at their terminals, but they may also be derivatives in which some or all of the hydrogen atoms at the terminal hydroxyl groups have been replaced with alkyl groups or acyl groups.
  • the number of carbon atoms in the alkyl and acyl groups is not particularly limited, but may be about 1 to 8, and is preferably 1 to 4.
  • Polyoxyalkylene glycols include polyoxyethylene polyoxypropylene glycols such as polyethylene glycol (polyoxyethylene glycol), polypropylene glycol (polyoxypropylene glycol), poly(ethylene oxide/propylene oxide) block copolymers and poly(ethylene oxide/propylene oxide) random copolymers, and polyoxybutylene glycols such as polytetramethylene glycol.
  • Ether compounds of polyoxyalkylenes and polyhydric alcohols include ether compounds of polyhydric alcohols such as glycerol, diglycerol, trimethylolpropane, erythritol, pentaerythritol, and bisphenol A with polyoxyalkylenes, and specific examples include polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyalkylene pentaerythritol ether, etc.
  • derivatives in which some or all of the hydrogen atoms of the terminal hydroxyl groups are substituted with alkyl groups or acyl groups include the above-mentioned polyoxyalkylene glycols and derivatives in which some or all of the hydrogen atoms of the terminal hydroxyl groups of ether compounds are substituted with alkyl groups or acyl groups.
  • polyoxyethylene glycol monomethyl ether examples include polyoxyethylene glycol monomethyl ether, polyoxyethylene glycol dimethyl ether, polyoxypropylene glycol monomethyl ether, polyoxypropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol monomethyl ether, polyoxyethylene polyoxypropylene glycol dimethyl ether, polyoxyethylene glycol monobutyl ether, polyoxypropylene glycol monobutyl ether, and polyoxyethylene polyoxypropylene monobutyl ether.
  • the polyoxyalkylene compounds are preferably those having a polyoxyethylene, polyoxypropylene, or polyoxyethylene polyoxypropylene structure, and more preferably those having a polyoxypropylene or polyoxyethylene polyoxypropylene structure.
  • polyoxyethylene polyoxypropylene glycol, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, or derivatives in which some of the hydrogen atoms of the terminal hydroxyl groups of these are substituted with alkyl groups are preferred.
  • Alcohol-based plasticizers include various polyhydric alcohols such as butanediol, hexanediol, trimethylolpropane, and pentaerythritol. Of these, trimethylolpropane is preferred.
  • the above plasticizers can be used alone or in combination of two or more.
  • triethylene glycol-di-2-ethylhexanoate (3GO) polyoxyethylene polyoxypropylene glycol, polyoxypropylene glyceryl ether, polyoxypropylene diglyceryl ether, or derivatives in which some of the hydrogen atoms of the terminal hydroxyl groups are substituted with alkyl groups are preferred, with triethylene glycol-di-2-ethylhexanoate (3GO) being more preferred.
  • the content of the plasticizer in the thermoplastic resin film (A) is not particularly limited, but is preferably 10 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the thermoplastic resin (a).
  • the content of the plasticizer is 10 parts by mass or more, the thermoplastic resin film (A) becomes moderately flexible, and the adhesiveness of the thermoplastic resin film (A) and the penetration resistance of the laminated glass become good. Furthermore, the thickness change amount is also easily increased.
  • the content of the plasticizer is 100 parts by mass or less, separation of the plasticizer from the thermoplastic resin film (A) is prevented, and a decrease in the storage modulus and an excessive increase in the thickness change can also be prevented.
  • the above content of the plasticizer is more preferably 15 parts by mass or more, even more preferably 22 parts by mass or more, even more preferably 30 parts by mass or more, and more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less.
  • the thermoplastic resin film (A) may appropriately contain known additives used in combination with the thermoplastic resin (a) in addition to the plasticizer. That is, the thermoplastic resin film (A) may be composed of a thermoplastic resin (a) such as a polyvinyl acetal resin, or a thermoplastic resin (a) and a plasticizer, but may also contain additives other than the plasticizer that are mixed as necessary. Specific examples of additives other than plasticizers include ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesion regulators, colorants (pigments or dyes), fluorescent brighteners, and crystal nucleating agents.
  • additives other than plasticizers include ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesion regulators, colorants (pigments or dyes), fluorescent brighteners, and crystal nucleating agents.
  • the thermoplastic resin film (A) may or may not contain a colorant. By using the colorant, the laminated glass can be well colored to a desired color tone. The colorant may be used alone or in combination of two or more.
  • the thermoplastic resin film (A) may contain only one type of colorant, two or more types, three or more types, 10 or less types, or 5 or less types.
  • the colorants include pigments and dyes.
  • the colorants may be pigments, dyes, or both pigments and dyes. There are also colorants that are classified as both pigments and dyes.
  • the colorant may contain a pigment or may be a pigment.
  • the thermoplastic resin film (A) may contain a pigment or may not contain a pigment.
  • the pigment may be used alone or in combination of two or more.
  • the thermoplastic resin film (A) may contain only one type of pigment, two or more types, three or more types, 10 or less types, or 5 or less types.
  • the above pigments include perylene compounds, threne compounds, quinacridone compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, perinone compounds, phthalocyanine compounds, indanthrene compounds, indigo compounds, isoindolinone compounds, nickel complex compounds, methine compounds, azomethine compounds, dioxazines, azo compounds, and carbon black.
  • the content of the pigment in 100% by mass of the thermoplastic resin film (A) is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, preferably 0.15% by mass or less, and more preferably 0.12% by mass or less.
  • the content of the pigment is equal to or more than the lower limit and equal to or less than the upper limit, the effects of the present invention can be exhibited even more effectively.
  • the colorant may contain a dye or may be a dye.
  • the thermoplastic resin film (A) may contain a dye or may not contain a dye. The dye may be used alone or in combination of two or more.
  • the thermoplastic resin film (A) may contain only one dye, two or more dyes, three or more dyes, 10 or less dyes, or 5 or less dyes.
  • the above dyes include perylene compounds, threne compounds, quinacridone compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, perinone compounds, phthalocyanine compounds, indanthrene compounds, indigo compounds, isoindolinone compounds, nickel complex compounds, methine compounds, azomethine compounds, dioxazines, and azo compounds.
  • the content of the dye in 100% by mass of the thermoplastic resin film (A) is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, even more preferably 0.001% by mass or more, preferably less than 0.015% by mass, and more preferably 0.01% by mass or less.
  • the content of the dye is equal to or more than the lower limit and equal to or less than the upper limit (or less than the upper limit), the effects of the present invention can be exhibited even more effectively.
  • the content of the colorant in 100% by mass of the thermoplastic resin film (A) is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, even more preferably 0.001% by mass or more, preferably 0.15% by mass or less, and more preferably 0.12% by mass or less.
  • the content of the colorant is equal to or more than the lower limit and equal to or less than the upper limit (or less than the upper limit), the effects of the present invention can be exhibited even more effectively.
  • the thickness of the thermoplastic resin film (A) is not particularly limited, but is, for example, 100 ⁇ m to 2000 ⁇ m, preferably 200 ⁇ m to 1300 ⁇ m, and more preferably 300 ⁇ m to 1000 ⁇ m.
  • the thickness of the thermoplastic resin film (A) is equal to or greater than the lower limit, impact resistance can be increased and adhesion to laminated glass members and the like can be easily ensured.
  • the thickness is equal to or less than the upper limit, the thickness of the functional laminate and the laminated glass can be prevented from becoming unnecessarily thick.
  • the thermoplastic resin film (A) may be a single-layer film having a single layer structure.
  • the single-layer thermoplastic resin film (A) may have the composition as described for the thermoplastic resin film (A) above. That is, the layer constituting the single-layer thermoplastic resin film (A) contains the thermoplastic resin (a) described above, and may contain a plasticizer as necessary, and may contain additives other than the plasticizer as appropriate.
  • the thermoplastic resin film (A) may be a multilayer film of two or more layers.
  • the multilayer film may have the composition of the entire film as described in the above thermoplastic resin film (A), but each layer (hereinafter also referred to as the "first layer") may have the composition as described in the above thermoplastic resin film (A). That is, each first layer contains the thermoplastic resin (a) as described in the above thermoplastic resin film (A), and may contain a plasticizer as necessary, and may be appropriately blended with additives other than the plasticizer, and each first layer preferably contains the above polyvinyl acetal resin as the thermoplastic resin (a).
  • thermoplastic resin (a), plasticizer, and additives in each first layer of the multilayer film, and the details of the content of each component are as described in the above thermoplastic resin film (A).
  • the thermoplastic resin (a) that is the basis of the content is the thermoplastic resin (a) contained in each first layer.
  • each first layer may satisfy the above-mentioned physical properties (thickness change amount, storage modulus, weight average molecular weight, molecular weight distribution).
  • each of the first layers may be of the same composition or of different composition.
  • the multilayer film may also be a laminate of the above-mentioned first layer and a layer other than the first layer (hereinafter also referred to as the "second layer").
  • the second layer may be provided in a plurality of layers.
  • the second layer may be a thermoplastic resin layer.
  • the first layer occupies a certain proportion or more of the total thickness of the thermoplastic resin film (A).
  • the total thickness of the first layer is preferably 0.3 to 1, more preferably 0.5 to 1, and even more preferably 0.75 to 1 with respect to the total thickness of the thermoplastic resin film (A).
  • the method for producing the thermoplastic resin film (A) is not particularly limited, and it may be produced by a conventionally known method such as extrusion molding or press molding, but production by extrusion molding is preferred.
  • the thermoplastic resin film (A) may have an uneven shape on one or both surfaces.
  • the method for forming the uneven shape is not particularly limited, and examples thereof include a lip embossing method, an embossing roll method, and a calendar roll method.
  • the functional film used in the present invention may be a light control film, a display element film, or an optical film such as a polarizing film, a retardation film, or an anti-reflection film.
  • the functional film is preferably a film having electronic components such as a light control film and a display element film.
  • Films having electronic components are likely to deteriorate or lose their functions when pressed in an autoclave under high temperature and high pressure conditions, but the functional laminate of the present invention can be pressed to other members such as glass members under low temperature and low pressure conditions without causing appearance defects, by having the above-mentioned thermoplastic resin film (A). Therefore, even if the film has electronic components, it can be incorporated into laminated glass or the like for practical use.
  • window glass with high added value can be provided. Therefore, in the present invention, it is desirable to use either of these as a functional film.
  • the light control film is a film-like member having a light control element.
  • the light control element is preferably a light control film having two resin films and a light control layer disposed between the two resin films. Therefore, the adhesive surface of the light control film with the thermoplastic resin film (A) becomes a resin material, and the adhesive strength to the thermoplastic resin film (A) tends to be high.
  • the resin film used in the light control element is not particularly limited, but examples include polyester resin films such as PET film and PEN film, (meth)acrylic resin film, TAC film, PES resin film, polyimide resin film, etc. Among these, polyester resin film is preferred from the viewpoint of handling, and PET film is more preferred.
  • a conductive layer constituting an electrode is provided on the surface of each of the two resin films facing the light control layer.
  • the light control layer changes the visible light transmittance by switching between application and non-application of a voltage between the conductive layers of two resin films.
  • the light control layer is composed of a liquid crystal layer such as a polymer dispersed liquid crystal (PDLC), and the light control film may be a PDLC film.
  • the light control film may be an SPD (Suspended Particle Device) film, an electrochromic film, an electrophoretic film device, a GHLC (Guest-Host Liquid Crystal) film, or the like.
  • the light control layer may be an SPD layer containing a resin matrix and a light control suspension dispersed in the resin matrix, an electrochromic material layer, or an electrophoretic layer containing electrophoretic particles and a dispersant for dispersing the electrophoretic particles. It may also be a layer composed of host molecules and guest molecules.
  • the display element film is a film-like member having a display element.
  • An example of the display element film is one having a resin film and a display element mounted on the resin film.
  • the display element film may be one having a pair of resin films with a display element provided therebetween. With such a configuration, the display element film can be easily bonded to the thermoplastic resin film with high adhesiveness.
  • the resin film used for the display element film can be appropriately selected from the resin films listed in the light control film.
  • the resin film may be provided with a conductive layer forming an electrode on the surface on the display element side.
  • Examples of the display element include an organic EL element, an LED display, and a segment display, and among these, an organic EL element is preferable. Therefore, the organic EL film is preferable as the display element film.
  • the functional film having electronic components is not limited to the above-mentioned display element film and light control film, but may be other functional films.
  • the electronic components may be mounted on the resin film in the same manner as the display element film and light control film, but a preferred embodiment is one in which the electronic components are arranged between a pair of resin films.
  • the thickness of the functional film is not particularly limited, but is, for example, 0.01 mm or more and 0.50 mm or less, preferably 0.01 mm or more and 0.20 mm or less, and more preferably 0.02 mm or more and 0.10 mm or less.
  • thermoplastic resin films (A) In the functional laminate, one or more thermoplastic resin films (A) may be provided, but two or more are preferably provided. At least one outermost layer of the functional laminate may be composed of the thermoplastic resin film (A).
  • the functional laminate By disposing the thermoplastic resin film (A) as the outermost layer in the functional laminate, the functional laminate can be pressure-bonded to other members such as laminated glass members at low temperatures and low pressures while preventing poor appearance and deterioration of appearance due to air bubbles, etc.
  • the outermost layer in the functional laminate constitutes the adhesive surface that is bonded to members such as laminated glass members.
  • the thermoplastic resin film (A) In the case where one thermoplastic resin film (A) is provided in the functional laminate, the thermoplastic resin film (A) may be provided on one side of the functional film, and the thermoplastic resin film (A) may be disposed as the outermost layer of the functional laminate.
  • the functional laminate preferably comprises a pair of thermoplastic resin films (A) and a functional film disposed between them.
  • at least one outermost layer of the functional laminate may be composed of a thermoplastic resin film (A), but it is preferable that both outermost layers of the functional laminate are composed of a thermoplastic resin film (A) so that both surfaces of the functional laminate can be easily pressure-bonded to other members.
  • the thermoplastic resin film (A) may be disposed on both sides of the functional film, and the functional laminate may have a layer structure of thermoplastic resin film (A)/functional film/thermoplastic resin film (A).
  • thermoplastic resin films (A) may be provided in the functional laminate.
  • two or more functional films may be provided, and the thermoplastic resin film (A) and the functional film may be provided alternately, and the thermoplastic resin film (A) may be provided on both outermost layers.
  • the thermoplastic resin film (A) is three, it is preferable to have a layer structure of thermoplastic resin film (A)/functional film/thermoplastic resin film (A)/functional film/thermoplastic resin film (A).
  • the functional laminate may have layers other than the thermoplastic resin film (A) and the functional film, and may have a thermoplastic resin film other than the thermoplastic resin film (A). Specifically, when the functional laminate has a plurality of thermoplastic resin films, it is preferable that all the thermoplastic resin films are composed of the thermoplastic resin film (A) as described above, but some of the thermoplastic resin films may be thermoplastic resin films other than the thermoplastic resin film (A).
  • the functional laminate has two or more thermoplastic resin films (A)
  • the functional laminate has a pair of thermoplastic resin films and a functional film disposed between them, but one of the pair of thermoplastic resin films may be the thermoplastic resin film (A), and the other may be a thermoplastic resin film other than the thermoplastic resin film (A).
  • the layer structure may be thermoplastic resin film (A)/functional film/thermoplastic resin film other than thermoplastic resin film (A).
  • the layer structure may be thermoplastic resin film (A)/functional film/thermoplastic resin film other than thermoplastic resin film (A)/functional film/thermoplastic resin film (A).
  • an adhesive layer or the like may be appropriately provided between the thermoplastic resin film (A) and the functional film.
  • the functional laminate of the present invention may be used by being pressed onto another member, and is preferably pressed onto a laminated glass member described below to form a laminated glass.
  • the laminated glass of the present invention has the above-mentioned functional laminate, and more specifically, has first and second laminated glass members and a functional laminate disposed between the first and second laminated glass members.
  • the first and second laminated glass members used in the laminated glass include glass plates.
  • the glass plates 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 glass plate, tempered glass, colored glass, polished glass plate, figured glass, wired glass plate, lined glass plate, ultraviolet absorbing glass plate, infrared reflecting glass plate, infrared absorbing glass plate, green glass, etc.
  • organic glass what is generally called resin glass is used, and examples thereof include various organic glass plates such as polycarbonate plate, (meth)acrylic plate such as polymethyl methacrylate plate, polyester plate such as acrylonitrile styrene copolymer plate, acrylonitrile butadiene styrene copolymer plate, polyethylene terephthalate plate, fluorine-based resin plate, polyvinyl chloride plate, chlorinated polyvinyl chloride plate, polypropylene plate, polystyrene plate, polysulfone plate, epoxy resin plate, phenol resin plate, unsaturated polyester resin plate, polyimide resin plate, etc.
  • the organic resin plate may be appropriately subjected to a surface treatment or the like.
  • the first and second laminated glass members may be made of the same material or different materials, for example, one may be inorganic glass and the other organic glass, but it is preferred that both the first and second laminated glass members are inorganic glass or organic glass.
  • the thickness of each of the glass plates used in the first and second laminated glass members is not particularly limited, but is, for example, about 0.1 to 15 mm, and preferably 0.5 to 5 mm.
  • the thicknesses of the glass plates may be the same or different from each other.
  • the laminated glass member may be composed of a single glass plate, or may be composed of glass plates to which other members are attached.
  • the laminated glass member may have various functions imparted thereto by attaching a functional member to the glass plates.
  • the lamination is performed at low temperature and low pressure, so that even if a laminated glass is produced using a laminated glass member to which a functional member is attached, the functional member can be prevented from deteriorating or becoming inactive.
  • the other member may be, for example, a member constituting an electronic device, an optical member, or the like, and may be, for example, a member constituting a display device.
  • the display device may be a liquid crystal display device, an organic EL display device, an LED display device, a segment display device, or the like. Of these, the display device is preferably a liquid crystal display device.
  • the display device may be, for example, a display panel having a glass plate as a substrate on which a display layer such as a liquid crystal layer or an organic EL layer, light-emitting elements, etc. are provided, and the glass plate that serves as the substrate of the display panel may be used as a laminated glass member.
  • functional layers such as a conductive layer constituting a functional film, electrode, sensor, etc., described below, an antireflection layer, a hard coat layer, etc., may be laminated on the glass plate, and the laminated glass member may be a glass plate on which such a functional film or functional layer is laminated. Therefore, the bonding surface with the thermoplastic resin film (A), on which the thermoplastic resin film (A) is directly laminated, may be the glass plate itself, or it may be the surface of a functional film or a functional layer.
  • the laminated glass preferably includes a functional laminate having multiple thermoplastic resin films between the first and second laminated glass members.
  • each thermoplastic resin film may be the thermoplastic resin film (A) described above.
  • the thermoplastic resin film (A) described above it is possible to further suppress poor appearance or deterioration of appearance due to residual air or bubbles, even when the functional laminate is integrated with the first and second laminated glass members under low pressure and low temperature conditions.
  • thermoplastic resin films 13A, 13B provided between first and second laminated glass members 11, 12, and further has a functional film 14 provided between the thermoplastic resin films 13A, 13B.
  • Both of the thermoplastic resin films 13A, 13B are the above-mentioned thermoplastic resin films (A).
  • the thermoplastic resin film 13A is adhered to both the first laminated glass member 11 and the functional film 14, joining them together, and the thermoplastic resin film 13B is adhered to both the second laminated glass member 12 and the functional film 14, joining them together.
  • the first and second laminated glass members 11 and 12 are integrated together by the functional laminate 15 consisting of the thermoplastic resin films 13A and 13B and the functional film 14.
  • the functional laminate may have three or more thermoplastic resin films (A) and two or more functional films.
  • the functional laminate may have the thermoplastic resin films (A) and the functional films alternately arranged, and the thermoplastic resin films (A) may be arranged in positions closest to the first and second laminated glass members (i.e., the outermost layers of the functional laminate). In the laminated glass, it is not necessary that all of the thermoplastic resin films in the functional laminate are the thermoplastic resin films (A). As described above, some of the thermoplastic resin films may be thermoplastic resin films other than the thermoplastic resin film (A).
  • the laminated glass is preferably integrated at low temperature and low pressure as described below, but even if it is integrated at low temperature and low pressure, the use of thermoplastic resin film (A) can prevent the occurrence of poor or deteriorated appearance due to remaining air or bubbles. Furthermore, by integrating the laminated glass at low temperature and low pressure, deterioration or deactivation of the functional film can be prevented.
  • the laminated glass of the present invention may be produced by a production method in which a member constituting a functional laminate is placed between a first laminated glass member and a second laminated glass member, and these are bonded together by pressure to obtain a laminated glass.
  • the first and second laminated glass members and the members constituting the functional laminate are prepared, and the members constituting the functional laminate are disposed between the first laminated glass member and the second laminated glass member, and these are bonded together to form an integrated laminated glass.
  • the members to be placed between the first and second laminated glass members may be appropriately selected depending on the structure of the laminated glass (i.e., functional laminate) to be obtained, and the members constituting the laminate may be placed between the first and second laminated glass members in the same stacking order as the laminate. For example, in the configuration of the embodiment shown in Fig.
  • thermoplastic resin film (A), the functional film, and the thermoplastic resin film (A) may be placed in this order between the first and second laminated glass members.
  • the members constituting the functional laminate may be disposed between the first and second laminated glass members as separate members, or may be integrated in advance by pressure bonding or the like to form a functional laminate and disposed between the first and second laminated glass members. Also, only some of the members constituting the functional laminate may be integrated.
  • the lamination may be performed in a vacuum bag, an autoclave, or by a press machine other than these, but among these, it is preferable to perform it in a vacuum bag. Also, before performing the lamination, temporary pressure bonding may be performed using a rubber roll or the like.
  • the lamination In this manufacturing method, the lamination must be carried out under low temperature and low pressure conditions; specifically, it is preferable to perform compression bonding at a temperature of 110°C or less and a pressure of 1.2 MPa or less. By carrying out the lamination under low temperature and low pressure conditions in this way, it is possible to prevent the functional film from deteriorating or becoming inactive.
  • the temperature during lamination is preferably 100° C. or lower from the viewpoint of more reliably preventing deterioration or inactivation of the functional component, and is preferably 60° C. or higher, more preferably 70° C. or higher, from the viewpoint of preventing the generation of residual air or foaming.
  • the pressure during lamination is preferably 1.0 MPa or less from the viewpoint of more reliably preventing deterioration or deactivation of the functional member.
  • the pressure may be, for example, 0.095 MPa or less, preferably 0.08 MPa or less, and more preferably 0.06 MPa or less.
  • the pressure during lamination is not particularly limited with respect to the lower limit, but when lamination is performed under pressure such as in an autoclave, the pressure is preferably 0.5 MPa or more, more preferably 0.7 MPa or more. When lamination is performed under negative pressure such as in a vacuum bag, the pressure is preferably 0.001 MPa or more, more preferably 0.005 MPa or more.
  • the time for lamination under the above temperature and pressure is not particularly limited, but is, for example, 5 to 120 minutes, and preferably 10 to 60 minutes.
  • the functional laminate of the present invention may also be applied to things other than laminated glass. Therefore, it is not necessary to use it to integrate two members by placing it between them, but it may be used, for example, to simply bond a functional film onto a member such as a glass plate.
  • a member constituting the functional laminate, or a functional laminate prepared in advance may be superimposed on one side of a glass plate, and the laminate may be bonded to a member such as a glass plate under the same conditions as above.
  • the details of the glass plate are as described above, and other members besides the glass plate may be attached as appropriate.
  • the laminate and laminated glass of the present invention can be used for a variety of applications, including, but not limited to, various vehicles such as automobiles and trains, ships and airplanes, various buildings such as buildings, condominiums, detached houses, halls and gymnasiums, machine tools for cutting and polishing, construction machines such as shovels and cranes, and partitions inside various vehicles and buildings.
  • various vehicles such as automobiles and trains, ships and airplanes
  • various buildings such as buildings, condominiums, detached houses, halls and gymnasiums
  • machine tools for cutting and polishing construction machines such as shovels and cranes
  • partitions inside various vehicles and buildings including, but not limited to, various vehicles such as automobiles and trains, ships and airplanes, various buildings such as buildings, condominiums, detached houses, halls and gymnasiums, machine tools for cutting and polishing, construction machines such as shovels and cranes, and partitions inside various vehicles and buildings.
  • applications to vehicles such as automobiles are preferred, and it is even more preferred to use it as window glass for vehicles.
  • the cooling tube was washed using 25 mL of pyridine, and the sample solution after the reaction was cooled to room temperature. After cooling, 20 mL of 1,2-dichloroethane was added to the sample solution, and the solution was shaken, and then 50 mL of water was added, shaken, and left at room temperature for 30 minutes. Then, the sample solution was subjected to potentiometric titration with 0.5 mol/L (0.5N) sodium hydroxide solution. A blank test was performed in the same manner, except that no sample was used, and the content (mass%) of ethylene groups bonded to hydroxyl groups in the sample was calculated based on the following formula.
  • W OH is the content (mass%) of ethylene groups bonded to hydroxyl groups
  • V BL is the amount (mL) of sodium hydroxide solution used in the blank test
  • V sp is the amount (mL) of sodium hydroxide solution used in the sample titration
  • f NaOH is the factor of the 0.5 mol/L sodium hydroxide solution actually used in the potentiometric titration
  • m is the sample mass (g).
  • ethylene group content (mass%) to which an acetyl group is bonded 0.4 g of sample was precisely weighed into a 200 mL Erlenmeyer flask with a stopper. After adding 100.0 mL of ethanol to the sample, the sample was dissolved in ethanol by heating and ultrasonic irradiation on a water bath at a bath temperature of 90 ° C. While shaking the Erlenmeyer flask, 10.0 mL of 0.2 mol/L (0.2N) sodium hydroxide was added. A reflux condenser was attached to the Erlenmeyer flask, and the mixture was heated and refluxed in a water bath for 60 minutes.
  • the cooling tube was washed using 25 mL of ethanol, and the sample solution after the reaction was cooled to room temperature.
  • 10.0 mL of 0.2 mol/L (0.2N) hydrochloric acid was added, shaken well, and left at room temperature for 30 minutes.
  • the sample solution was then subjected to potentiometric titration with 0.1 mol/L (0.1N) sodium hydroxide solution.
  • a blank test was carried out in the same manner, except that no sample was used, and the content (mass%) of ethylene groups bonded to acetyl groups in the sample was calculated based on the following formula.
  • W Ac is the content (mass%) of ethylene groups bonded to acetyl groups
  • V BL is the amount (mL) of sodium hydroxide solution used in the blank test
  • V sp is the amount (mL) of sodium hydroxide solution used in the sample titration
  • f NaOH is the factor of the 0.1 mol/L sodium hydroxide solution actually used in the potentiometric titration
  • m is the sample mass (g).
  • the hydroxyl group amount (mol %), the acetylation degree (mol %) and the acetalization degree (mol %) were calculated based on the following formulas using the content of ethylene groups bonded to hydroxyl groups, the content of ethylene groups bonded to acetyl groups and the content of ethylene groups bonded to butyral groups calculated by the above-mentioned methods.
  • thermoplastic resin film of each Example and Comparative Example was cut out to prepare a test sample having a diameter of 8 mm.
  • the thickness change of the prepared test sample was determined according to the method described in the specification.
  • thermoplastic resin films obtained in the Examples and Comparative Examples were stored for 12 hours in an environment of room temperature 23 ⁇ 2°C and humidity 25 ⁇ 5%, and the viscoelasticity was measured under the following measurement conditions using a dynamic viscoelasticity device (manufactured by TA Instruments, product name "ARES-G2", jig "diameter 8 mm parallel plate") to detect the shear storage modulus (G') at 90°C.
  • a dynamic viscoelasticity device manufactured by TA Instruments, product name "ARES-G2", jig "diameter 8 mm parallel plate
  • Deformation mode shear mode
  • measurement temperature -10°C to 100°C
  • heating rate 3°C/min
  • measurement frequency 1Hz
  • strain 1%
  • ⁇ Appearance after boil test> The laminated glass obtained in the examples and comparative examples was subjected to a boiling test.
  • the boiling test was performed by boiling the laminated glass in boiling water at 100° C. for 2 hours.
  • the appearance of the laminated glass after the boiling test was evaluated according to the following evaluation criteria.
  • thermoplastic resins used in the examples and comparative examples were prepared as follows.
  • (Resin 1) In a reactor equipped with a stirrer, 1800 ml of ion-exchanged water and 200 g of polyvinyl alcohol A (average polymerization degree 1700, saponification degree 99 mol%) were placed, and the mixture was heated and dissolved while stirring to obtain a polyvinyl alcohol solution.
  • 30% hydrochloric acid was added as a catalyst to this solution so that the hydrochloric acid concentration was 0.2 mass%, and the temperature was adjusted to 15 ° C., and n-butyl aldehyde was added to 10 mol % while stirring.
  • plasticizers used in the examples and comparative examples are as follows.
  • 3GO Triethylene glycol-di-2-ethylhexanoate
  • DGP Polyoxypropylene diglyceryl ether, "Unilube DGP-700", NOF Corporation, number average molecular weight 700
  • PPG Polypropylene Grigol, "PPG1000”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as "PPG1000”, number average molecular weight is 1000
  • the light control films and display devices used in the examples and comparative examples were as follows.
  • Light control 1 SPD film, "LCF-1103DHA30", manufactured by Showa Denko
  • Light control 2 SPD film, "LCF-1103DHA90”, manufactured by Showa Denko
  • Light control 3 PDLC film, "MIYO film”, manufactured by Kyushu Nanotec Optical Co., Ltd.
  • Light control 4 PDLC film, "LCMSGIC”, manufactured by Toppan Printing Co., Ltd.
  • the lamination conditions A and B in each of the examples and comparative examples were as follows.
  • (Lamination Condition A) The laminates obtained in each of the Examples and Comparative Examples were placed in a rubber bag, which was a vacuum bag, and degassed for 5 minutes at a vacuum pressure of 0.09 MPa. Next, while still degassed, the laminates were heated to 90° C. at a heating rate of 1° C./min, and held at 90° C. for 30 minutes, and then cooled to 30° C. Next, the pressure was returned to normal to obtain laminated glass.
  • Example 1 A resin composition was obtained by mixing 40 parts by mass of a plasticizer (triethylene glycol-di-2-ethylhexanoate: 3GO) with 100 parts by mass of resin 1.
  • the obtained resin composition was used in a hydraulic press and a spacer having a thickness of 800 ⁇ m to produce a thermoplastic resin film having a thickness of 800 ⁇ m.
  • two pieces of 2.5 mm clear glass and the light control film shown in Table 1 were prepared.
  • a thermoplastic resin film first thermoplastic resin film
  • a light control film and a thermoplastic resin film (second thermoplastic resin film) were laminated in this order on one of the clear glasses, and the other clear glass was further laminated on the thermoplastic resin film to obtain a laminate.
  • the laminate was pressed under lamination condition A to obtain a laminated glass.
  • Example 2 The same procedure as in Example 1 was carried out except that the light-control film was changed as shown in Table 1.
  • Examples 5 to 7 The same procedure as in Example 1 was carried out except that the amount and type of plasticizer used were changed as shown in Table 1.
  • Example 8 to 11 The same procedures as in Examples 1 to 4 were carried out except that the thermoplastic resin used was changed to Resin 2.
  • thermoplastic resin used was changed to Resin 3 and the laminate was pressed under lamination condition B.
  • Example 4 The same procedure as in Example 1 was carried out, except that the thermoplastic resin used was changed to Resin 3.
  • Example 12 Phthalocyanine pigment (P.B.15-1): Amount that results in 0.0142% by mass in the resulting resin film Perylene pigment (P.R.149): Amount that results in 0.0030% by mass in the resulting resin film Phthalocyanine pigment (P.G.7): Amount that results in 0.0015% by mass in the resulting resin film Carbon black pigment (P.Bk.7): Amount that results in 0.0300% by mass in the resulting resin film
  • Example 13 Phthalocyanine pigment (P.B.15-1): Amount that results in 0.0148% by mass in the resulting resin film Perylene pigment (P.R.149): Amount that results in 0.0054% by mass in the resulting resin film Phthalocyanine pigment (P.G.7): Amount that results in 0.00
  • the laminated glass of Examples 1 to 14 described above the laminated glass was produced using a thermoplastic resin film (A) that exhibited a large change in thickness when compressed in a compression creep test. Therefore, even though the lamination conditions were low temperature and low pressure, no residual air or bubbles were generated, and the laminated glass produced had a good appearance. In addition, the laminated glass also had a good appearance after a boil test, and was able to maintain a good appearance even when used in a high-temperature environment for a long period of time. Furthermore, because lamination was performed at low temperature and low pressure, the light control film was not damaged. In contrast, in Comparative Examples 1 to 3, the lamination conditions when producing the laminated glass were high temperature and high pressure, so the light control film was damaged during lamination.
  • A thermoplastic resin film

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un corps multicouche fonctionnel qui comprend un film fonctionnel et un film de résine thermoplastique (A), si le film de résine thermoplastique (A) est comprimé dans un test de fluage par compression qui est effectué dans des conditions spécifiques, la quantité de changement d'épaisseur étant égal ou supérieur à 80 µm.
PCT/JP2023/043361 2022-12-05 2023-12-04 Corps multicouche fonctionnel et verre feuilleté Ceased WO2024122517A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7709577B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体、膜及び積層膜
JP7709579B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体、膜及び積層膜
JP7709576B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス用中間膜、積層膜及び合わせガラス構成体
JP7709575B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体及び積層膜
JP7709578B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス用中間膜、積層膜及び合わせガラス構成体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255827A (ja) * 1998-03-12 1999-09-21 Sekisui Chem Co Ltd ポリビニルアセタール樹脂及びこれを用いた合わせガラス用中間膜
JP2003146710A (ja) * 2001-11-13 2003-05-21 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス並びに合わせガラスの製造方法
WO2021117596A1 (fr) * 2019-12-09 2021-06-17 積水化学工業株式会社 Film de couche intermédiaire de verre feuilleté et verre feuilleté

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11255827A (ja) * 1998-03-12 1999-09-21 Sekisui Chem Co Ltd ポリビニルアセタール樹脂及びこれを用いた合わせガラス用中間膜
JP2003146710A (ja) * 2001-11-13 2003-05-21 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス並びに合わせガラスの製造方法
WO2021117596A1 (fr) * 2019-12-09 2021-06-17 積水化学工業株式会社 Film de couche intermédiaire de verre feuilleté et verre feuilleté

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7709577B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体、膜及び積層膜
JP7709579B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体、膜及び積層膜
JP7709576B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス用中間膜、積層膜及び合わせガラス構成体
JP7709575B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス構成体及び積層膜
JP7709578B1 (ja) * 2024-07-12 2025-07-16 積水化学工業株式会社 合わせガラス用中間膜、積層膜及び合わせガラス構成体

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