WO2024005148A1 - 窓材及び透光性屋根材 - Google Patents
窓材及び透光性屋根材 Download PDFInfo
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- WO2024005148A1 WO2024005148A1 PCT/JP2023/024199 JP2023024199W WO2024005148A1 WO 2024005148 A1 WO2024005148 A1 WO 2024005148A1 JP 2023024199 W JP2023024199 W JP 2023024199W WO 2024005148 A1 WO2024005148 A1 WO 2024005148A1
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- adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
- B23Q3/00—Devices holding, supporting, or positioning work or tools, of a kind normally removable from the machine
- B23Q3/02—Devices holding, supporting, or positioning work or tools, of a kind normally removable from the machine for mounting on a work-table, tool-slide, or analogous part
- B23Q3/06—Work-clamping means
- B23Q3/08—Work-clamping means other than mechanically-actuated
- B23Q3/084—Work-clamping means other than mechanically-actuated using adhesive means
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- 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
- B32B7/023—Optical properties
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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
- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- B60J3/00—Antiglare equipment associated with windows or windscreens; Sun visors for vehicles
- B60J3/04—Antiglare equipment associated with windows or windscreens; Sun visors for vehicles adjustable in transparency
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/346—Applications of adhesives in processes or use of adhesives in the form of films or foils for building applications e.g. wrap foil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B2009/2417—Light path control; means to control reflection
Definitions
- the present invention relates to window materials and translucent roofing materials.
- the present invention also relates to buildings, vehicles, ships, or aircrafts equipped with the window materials and/or translucent roof materials.
- Patent Document 1 a temperature-sensitive dimming liquid laminate whose white turbidity changes autonomously in response to temperature stimulation has been proposed as a structure to be provided in a window.
- the present invention was made in view of the above problems, and the present invention is a window material or a translucent roofing material that can autonomously change its white turbidity depending on temperature, has a simple structure, and is easy to manufacture.
- the object of the present invention is to provide a building, a vehicle, a ship, or an aircraft equipped with the window material and/or translucent roof material.
- the first aspect of the present invention is comprising at least one transparent base material layer and at least one adhesive layer
- the adhesive layer is made of an adhesive composition containing 1 to 100 parts by mass of polymer fine particles per 100 parts by mass of a temperature-sensitive adhesive,
- the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and
- the refractive index increase rate of the temperature-sensitive adhesive which is the amount of increase in the refractive index per 1°C, is in a temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive in the vicinity of the melting point of the temperature-sensitive adhesive.
- the adhesive strength of the adhesive composition decreases as the temperature decreases, and
- the rate of decrease in the adhesive strength of the adhesive composition which is the amount of decrease in adhesive strength per 1°C, is higher in the vicinity of the melting point of the temperature-sensitive adhesive than in the temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive. Also big, It is a window material.
- the second aspect of the invention is comprising at least one transparent base material layer and at least one adhesive layer
- the adhesive layer is made of an adhesive composition containing 1 to 100 parts by mass of polymer fine particles per 100 parts by mass of a temperature-sensitive adhesive,
- the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and
- the refractive index increase rate of the temperature-sensitive adhesive which is the amount of increase in the refractive index per 1°C, is in a temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive in the vicinity of the melting point of the temperature-sensitive adhesive.
- the adhesive strength of the adhesive composition decreases as the temperature decreases, and
- the rate of decrease in the adhesive strength of the adhesive composition which is the amount of decrease in adhesive strength per 1°C, is higher in the vicinity of the melting point of the temperature-sensitive adhesive than in the temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive. Also big, It is a translucent roofing material.
- a third aspect of the present invention is a building comprising the window material according to the first aspect and/or the translucent roofing material according to the second aspect.
- a fourth aspect of the present invention is a vehicle, a ship, or an aircraft that includes the window material according to the first aspect and/or the translucent roof material according to the second aspect.
- the fifth aspect of the present invention is An adhesive composition containing 1 to 100 parts by mass of polymer fine particles per 100 parts by mass of a temperature-sensitive adhesive,
- the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and
- the refractive index increase rate of the temperature-sensitive adhesive which is the amount of increase in the refractive index per 1°C, is in a temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive in the vicinity of the melting point of the temperature-sensitive adhesive.
- the adhesive strength of the adhesive composition decreases as the temperature decreases, and
- the rate of decrease in the adhesive strength of the adhesive composition which is the amount of decrease in adhesive strength per 1°C, is higher in the vicinity of the melting point of the temperature-sensitive adhesive than in the temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive. Also big, It is an adhesive composition.
- the sixth aspect of the present invention is This is a pressure-sensitive adhesive sheet including a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to the fifth aspect.
- the seventh aspect of the present invention is Bringing the workpiece into contact with the adhesive layer provided in the adhesive sheet according to the sixth aspect; Confirming that the adhesive layer is exhibiting adhesive force by confirming that the adhesive layer is cloudy or not cloudy; Processing the workpiece fixed on the adhesive layer by the adhesive force developed by the adhesive layer; Confirming that the adhesive layer does not exhibit adhesive force by confirming that the adhesive layer is not cloudy or cloudy; removing the processed workpiece from the adhesive layer that has not developed adhesive strength;
- a method of processing a workpiece including:
- the eighth aspect of the present invention is Bringing the support and the workpiece into contact, or the workpieces together, via the adhesive layer provided in the adhesive sheet according to the sixth aspect; Confirming that the adhesive layer is exhibiting adhesive force by confirming that the adhesive layer is cloudy or not cloudy; The workpiece is fixed on the support via the adhesive layer due to the adhesive force developed by the adhesive layer, or at least one of the plurality of workpieces fixed via the adhesive layer. processing and Confirming that the adhesive layer does not exhibit adhesive force by confirming that the adhesive layer is not cloudy or cloudy; removing the processed workpiece from the adhesive layer that has not developed adhesive strength; A method of processing a workpiece, including:
- a window material and a translucent roofing material that can autonomously change white turbidity depending on temperature, have a simple structure and are easy to manufacture, and a window material and/or a translucent roofing material. Buildings, as well as vehicles, ships, or aircraft, can be provided with flexible roofing materials.
- FIG. 2 is a schematic explanatory diagram showing a heat shielding property evaluation test method in Examples. It is a photograph which shows the evaluation test method of the heat shielding property in an Example. It is a photograph which shows the evaluation test method of the heat shielding property in an Example.
- FIG. 1 shows a cross-sectional view of a first window material 10 as an example of a window material.
- a translucent base layer 11 As shown in FIG. 1, in the first window material 10, a translucent base layer 11, an adhesive layer 12, and a base sheet 13 are laminated in this order.
- the adhesive layer 12 is made of an adhesive composition containing a temperature-sensitive adhesive 12a and fine polymer particles 12b.
- FIG. 2 shows a cross-sectional view of a second window material 20 as another example of the window material.
- an adhesive layer 22 is arranged between two transparent base material layers 21a and 21b.
- the adhesive layer 22 is made of an adhesive composition containing a temperature-sensitive adhesive 22a and fine polymer particles 22b.
- the temperature-sensitive adhesives 12a and 22a have refractive indexes that increase as the temperature decreases, and whose refractive index increase rate, which is the amount of increase in refractive index per 1°C, is near the melting point. is higher than the temperature range other than the vicinity of the melting point. Therefore, when the temperature of the adhesive layers 12 and 22 increases due to solar radiation or air temperature, the difference in refractive index between the temperature-sensitive adhesives 12a and 22a and the polymer particles 12b and 22b increases, and the haze value increases.
- the difference in refractive index between the temperature-sensitive adhesives 12a and 22a and the polymer particles 12b and 22b decreases, and the haze value decreases.
- the window material when the temperature is relatively low and the amount of sunlight is low, such as in the morning or at night, the window material functions as frosted glass, but when the temperature rises during the day as the amount of sunlight increases, the window material functions as frosted glass.
- the material is transparent, allowing efficient lighting into the room.
- the above window materials when installed in a location where they are exposed to the outside air, they become cloudy or transparent as the outside temperature rises, making it difficult for people living in air-conditioned rooms to see. It also has a function to make you aware of the rise in outside temperature.
- the adhesive strength of the adhesive compositions constituting the adhesive layers 12 and 22 decreases as the temperature decreases, and the adhesive strength decrease rate, which is the amount of decrease in adhesive strength per 1°C, is lower than that of the adhesive composition.
- the temperature near the melting point of the temperature-sensitive adhesives 12a and 22a inside is higher than the temperature range other than the melting point. Therefore, even if air bubbles or wrinkles occur when placing the adhesive layers 12 and 22, by lowering the temperature of the adhesive layers 12 and 22, the adhesive layers 12 and 22 can be peeled off and placed again. is possible. Thereby, manufacturing of the window material can be made easier.
- the translucent base material constituting the translucent base material layer is not particularly limited as long as it is a base material that can be used as a window material for buildings, vehicles, ships, and aircraft; for example, a glass plate. or a resin plate can be used.
- the material for the glass plate include soda lime glass, borosilicate glass, high silica glass, and the like.
- the material for the resin plate include polyalkyl methacrylates such as polymethyl methacrylate, polyalkyl acrylates, polycarbonates, polymethylstyrene, acrylonitrile-styrene copolymers, and the like.
- the thickness of the transparent base material layer is not particularly limited, but is, for example, 0.1 mm or more and 10 mm or less.
- Examples of the shape of the light-transmitting base material layer include a planar shape like the first window material 10 and the second window material 20, a curved shape, and the like.
- the translucent base material layer is composed of at least one layer, and may be composed of a single layer like the first window material 10, or two or more layers like the second window material 20. It may be composed of. When composed of two or more layers, each layer may be composed of the same type of base material or may be composed of different types of base materials. Moreover, each layer may have the same thickness or may have different thicknesses.
- the adhesive layer is a layer made of an adhesive composition containing 1 to 100 parts by mass of polymer particles per 100 parts by mass of a temperature-sensitive adhesive, and changes its white turbidity and adhesive strength autonomously depending on the temperature. It has the function of
- the thickness of the adhesive layer is not particularly limited, but is preferably 5 ⁇ m or more and 1 mm or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less. Note that the thicker the adhesive layer is, the more the dimming function tends to be exhibited by adding a small amount of polymer fine particles. The thinner the thickness, the more polymer fine particles tend to need to be added in order to exhibit the light control function.
- the adhesive layer is composed of at least one layer.
- the adhesive layer may be composed of a single layer like the first window material 10 and the second window material 20, or may be composed of two or more layers.
- the arrangement of the adhesive layer with respect to the transparent base material layer is not particularly limited.
- the adhesive layer may be placed on the side where sunlight enters the light-transmitting base material layer, or may be placed on the opposite side.
- an adhesive layer may be disposed between the translucent base material layers like the second window material 20.
- the adhesive layer may cover the entire surface of the surface where the adhesive layer and the transparent base material layer are in contact with each other, or may cover a part of the surface.
- the adhesive layer When the adhesive layer covers a part of the surface where the adhesive layer and the transparent base layer are in contact with each other, characters, symbols, patterns, figures, designs, etc. may be drawn on the transparent base layer by the adhesive layer. It's okay. In this case, the adhesive layer may form letters or patterns, or the area surrounded by the adhesive layer may form letters or patterns.
- Such window materials have excellent design properties when haze appears or disappears at high temperatures.
- the adhesive layer may have a plurality of types of regions having different haze values at high temperatures or low temperatures.
- the haze value of the adhesive layer can be changed by changing the type of temperature-sensitive adhesive or polymer particles, or by changing the amount of polymer particles used. For example, by continuously forming a plurality of adhesive layers having different haze values at high or low temperatures on a light-transmitting substrate, a gradation of haze can be achieved at high or low temperatures.
- We can provide window materials with excellent design.
- the difference between the haze value at 23°C and the haze value at 60°C of the adhesive layer is preferably 10% or more.
- the haze value of the adhesive layer at 60°C is 10% or more higher than the haze value at 23°C. This tends to make it easier to visually recognize changes in white turbidity depending on temperature.
- the haze value of the adhesive layer is a value measured by the method described in Examples below.
- the haze value of the adhesive layer at 23°C is preferably 20% or less, more preferably 10% or less.
- the lower limit of the haze value at 23°C is not particularly limited.
- the haze value of the adhesive layer at 60° C. is preferably 12% or more, more preferably 20% or more.
- the upper limit of the haze value at 60° C. is not particularly limited, but is, for example, 70% or less and 50% or less.
- the difference between the solar transmittance at 23°C and the solar transmittance at 60°C of the adhesive layer is preferably 10% or more.
- the solar transmittance of the adhesive layer at 60°C is preferably 10% or more lower than the solar transmittance at 23°C.
- the solar radiation transmittance of an adhesive layer is the value measured by the method described in the below-mentioned Example.
- the solar transmittance of the adhesive layer at 23° C. is preferably 30% or more, more preferably 40% or more.
- the upper limit of the solar transmittance at 23° C. is not particularly limited, but is, for example, 95% or less, or 85% or less.
- the solar transmittance of the adhesive layer at 60° C. is preferably 60% or less, more preferably 40% or less, and still more preferably 30% or less.
- the lower limit of the solar transmittance at 60° C. is not particularly limited, but is, for example, 5% or more, or 15% or more.
- the average particle diameter of the polymer fine particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. Further, the average particle diameter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 10 ⁇ m or less. In particular, from the viewpoint of easily increasing haze, the average particle diameter is more preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and most preferably 1 ⁇ m or more and 6 ⁇ m or less. From the viewpoint of easily suppressing the transmission of solar radiation, the average particle diameter is more preferably 6 ⁇ m or more and 25 ⁇ m or less, and most preferably 6 ⁇ m or more and 10 ⁇ m or less.
- the average particle diameter is more preferably 6 ⁇ m or more and 25 ⁇ m or less, and most preferably 6 ⁇ m or more and 10 ⁇ m or less.
- the D90 particle diameter of the polymer fine particles is preferably equal to or less than the thickness of the adhesive layer, and is, for example, 1 ⁇ m or more and 1000 ⁇ m or less, 3 ⁇ m or more and 100 ⁇ m or less.
- the average particle diameter of polymer fine particles is a value measured by the method described in Examples below.
- the polymer constituting the polymer fine particles preferably contains a structural unit derived from a monomer containing one ethylenically unsaturated group.
- the ethylenically unsaturated group include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, and a (meth)allyl group, with a (meth)acryloyl group and a vinyl group being preferred.
- Monomers containing one ethylenically unsaturated group include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, hydroxy
- (meth)acrylates such as ethyl (meth)acrylate; vinyl monomers such as styrene, vinyl acetate, and acrylonitrile; and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the monomer containing one ethylenically unsaturated group to the mass of the polymer constituting the polymer fine particles is preferably 70% by mass or more, more preferably 80% by mass or more, More preferably, it is 90% by mass or more.
- the above ratio may be 100% by mass, but is preferably 98% by mass or less.
- the polymer constituting the polymer fine particles may contain a structural unit derived from another monomer copolymerizable with a monomer containing one ethylenically unsaturated group.
- examples of other monomers include polyfunctional monomers, refractive index adjusting monomers, and the like. That is, the polymer constituting the polymer fine particles may include a structural unit derived from a polyfunctional monomer or a refractive index adjusting monomer.
- the polyfunctional monomer can crosslink multiple molecular chains contained in the polymer constituting the polymer fine particles. From the viewpoint of maintaining the dispersed state of the polymer fine particles during use, suppressing deformation, and maintaining repeatability of functions, it is preferable that the polymer constituting the polymer fine particles contains a structural unit derived from a polyfunctional monomer. That is, it is preferable that the polymer fine particles and the polymer constituting them are crosslinked.
- the polyfunctional monomer has two or more, preferably 2 to 4, radically polymerizable double bonds in the molecule. Examples of the polyfunctional monomer include bifunctional (meth)acrylate, trifunctional (meth)acrylate, and tetrafunctional (meth)acrylate.
- Specific examples include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polyethylene glycol 200 di(meth)acrylate.
- the polyfunctional monomer may be at least one selected from bifunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional (meth)acrylates.
- the ratio of the mass of the structural unit derived from the polyfunctional monomer to the mass of the polymer constituting the polymer fine particles is preferably 0.1% by mass or more, more preferably 1% by mass or more. Moreover, the said ratio becomes like this. Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less.
- the refractive index adjusting monomer may be a monomer having a refractive index of 1.300 to 1.600.
- the refractive index adjusting monomer include 2-(O-phenylphenoxy)ethyl acrylate (refractive index: 1.577), 2-propenoic acid (3-phenoxyphenyl) methyl ester (refractive index: 1.566), 1 - Naphthyl acrylate (refractive index: 1.595), acrylamide (refractive index: 1.515), hydroxyacrylamide (refractive index: 1.515), EO-modified bisphenol A diacrylate (refractive index: 1.537), acrylamide ( Refractive index: 1.515), 2,2,2-trifluoroethyl acrylate (refractive index: 1.348), methacryl-modified polydimethylsiloxane (refractive index: 1.408), and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the refractive index adjusting monomer to the mass of the polymer constituting the polymer fine particles is preferably 0.1% by mass or more, more preferably 1% by mass or more. Further, the above ratio is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
- the polymer fine particles do not contain a structural unit derived from a reactive emulsifier, since they tend to have good dispersibility in a temperature-sensitive adhesive.
- a reactive emulsifier is an emulsifier having a polymerizable unsaturated bond such as a vinyl group in its molecule.
- the reactive emulsifier is a polymerizable monomer that has an emulsifying function and has a polymerizable group having an unsaturated bond such as a vinyl group in its molecule, and a hydrophilic group.
- the content of the polymer particles is 1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the temperature-sensitive adhesive.
- the content is preferably 5 parts by mass or more, more preferably 20 parts by mass or more. Further, the content is preferably 70 parts by mass or less, more preferably 40 parts by mass or less.
- the method for producing polymer fine particles is not particularly limited, and they can be obtained by conventionally known polymerization methods such as miniemulsion polymerization and suspension polymerization.
- a temperature-sensitive adhesive has a melting point.
- a temperature-sensitive adhesive crystallizes at a temperature below the melting point, and undergoes a phase transition and exhibits fluidity at a temperature above the melting point.
- the adhesive strength of an adhesive composition containing a temperature-sensitive adhesive decreases as the temperature decreases, and the adhesive strength reduction rate, which is the amount of decrease in adhesive strength per 1°C, is lower than that of the adhesive composition.
- the temperature near the melting point of the temperature-sensitive adhesive inside is higher than the temperature range other than the melting point.
- the adhesive force of an adhesive composition means the peel strength with respect to polyethylene terephthalate (PET), and is a value measured by the method described in the below-mentioned example.
- the peel strength of the adhesive composition against polyethylene terephthalate (PET) at 23° C. is preferably 0.1 N/25 mm or less.
- the lower limit of the above peel strength is not particularly limited.
- the peel strength of the adhesive composition against polyethylene terephthalate (PET) at 60° C. is preferably 1.0 N/25 mm or more.
- the upper limit of the peel strength is not particularly limited.
- the melting point of the temperature-sensitive adhesive is preferably 25°C or higher, more preferably 40°C or higher. Further, the melting point is preferably 70°C or lower, more preferably 60°C or lower. In addition, in this specification, the melting point of a temperature-sensitive adhesive is a value measured by the method described in the below-mentioned Examples.
- the melting point of the temperature-sensitive adhesive can be adjusted, for example, by changing the composition of the monomer components constituting the side chain crystalline polymer contained in the temperature-sensitive adhesive. For example, by changing the length of the side chain in a side chain crystalline polymer, the melting point can be adjusted. When the length of the side chain is long, the temperature-sensitive adhesive tends to have a high melting point.
- FIG. 4 is a graph showing changes in refractive index with respect to temperature changes in a temperature-sensitive adhesive (melting point: 55° C.) manufactured in an example described below.
- the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and the refractive index increase rate, which is the amount of increase in the refractive index per 1°C, is near the melting point. It is larger than the temperature range other than the vicinity of the melting point.
- the refractive index is a value measured by the method described in Examples below.
- the refractive index of the temperature-sensitive adhesive at 23°C is preferably 0.02 or more higher than the refractive index of the temperature-sensitive adhesive at 60°C. This tends to make it easier to visually recognize changes in white turbidity depending on temperature.
- the temperature-sensitive adhesive contains a side chain crystalline polymer.
- the side chain crystalline polymer preferably contains a structural unit derived from a (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms.
- the linear alkyl group having 14 or more carbon atoms acts as a side chain crystalline moiety in a side chain crystalline polymer. Function. That is, the side chain crystalline polymer is, for example, a comb-shaped polymer having a linear alkyl group having 14 or more carbon atoms in the side chain.
- the side chain crystalline polymer is crystallized.
- the above-mentioned (meth)acrylic monomer is an acrylic monomer or a methacrylic monomer.
- the upper limit of the number of carbon atoms in the linear alkyl group is preferably 50 or less, more preferably 30 or less.
- Examples of the (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms include cetyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, and behenyl (meth)acrylate. . These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms to the mass of the side chain crystalline polymer is preferably 30% by mass or more, more preferably 40% by mass. % or more.
- the above ratio is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.
- the side chain crystalline polymer may contain a structural unit derived from a (meth)acrylic monomer having a linear alkyl group having 1 to 12 carbon atoms, and a structural unit derived from a functional group monomer for crosslinking. preferable. Further, the side chain crystalline polymer may contain structural units derived from other monomers copolymerizable with these monomers. Examples of other monomers include refractive index adjusting monomers. That is, the side chain crystalline polymer may include a structural unit derived from a refractive index adjusting monomer.
- Examples of (meth)acrylic monomers having a linear alkyl group having 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. ) acrylate, hexyl (meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, methyl (meth)acrylate is preferred in that it has a high cohesive force and can easily suppress a decrease in adhesive strength when the temperature rises.
- the ratio of the mass of the structural unit derived from the (meth)acrylic monomer having a linear alkyl group having 1 to 12 carbon atoms to the mass of the side chain crystalline polymer is preferably 1% by mass or more, more preferably The content is 20% by mass or more, more preferably 40% by mass or more. The above ratio is preferably 69% by mass or less, more preferably 60% by mass or less.
- Examples of functional group monomers include (meth)acrylates having a hydroxyalkyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxyhexyl (meth)acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Examples include ethylenically unsaturated monomers having a carboxyl group such as maleic acid and fumaric acid. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the functional monomer to the mass of the side chain crystalline polymer is preferably 1% by mass or more, more preferably 3% by mass or more. Moreover, the said ratio becomes like this. Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less. When the content is 1% by mass or more, shape retention tends to be good. When the amount is 20% by mass or less, the viscosity is not excessively high and coating properties tend to be good.
- the refractive index adjusting monomer may be a monomer having a refractive index of 1.300 to 1.600.
- the refractive index adjusting monomer include 2-(O-phenylphenoxy)ethyl acrylate (refractive index: 1.577), 2-propenoic acid (3-phenoxyphenyl) methyl ester (refractive index: 1.566), 1 - Naphthyl acrylate (refractive index: 1.595), acrylamide (refractive index: 1.515), hydroxyacrylamide (refractive index: 1.515), EO-modified bisphenol A diacrylate (refractive index: 1.537), acrylamide ( Refractive index: 1.515), 2,2,2-trifluoroethyl acrylate (refractive index: 1.348), methacryl-modified polydimethylsiloxane (refractive index: 1.408), and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the refractive index adjusting monomer to the mass of the side chain crystalline polymer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. . Moreover, the said ratio becomes like this. Preferably it is 30 mass % or less.
- the weight average molecular weight of the temperature-sensitive adhesive is preferably 200,000 or more, more preferably 400,000 or more.
- the weight average molecular weight is preferably 2 million or less, more preferably 1 million or less. When it is 200,000 or more, the adhesive strength tends to be sufficient. When it is 2 million or less, coating properties tend to be sufficient due to the decrease in viscosity.
- the weight average molecular weight of the temperature-sensitive adhesive is a value measured by the method described in the below-mentioned Examples.
- the weight average molecular weight of the temperature-sensitive adhesive can be adjusted, for example, by using a chain transfer agent during polymerization.
- chain transfer agent include thiol compounds such as dodecylmercaptan, mercaptopropionic acid, mercaptosuccinic acid, ethylhexylmercaptoacetate, mercaptoethanol, and cyclohexanethiol. These may be used alone or in combination of two or more.
- the difference in refractive index at 23° C. between the temperature-sensitive adhesive and the polymer particles is preferably less than 0.015, more preferably less than 0.010. Further, the refractive index difference at 60° C. is preferably 0.015 or more.
- the upper limit of the refractive index difference at 60° C. is not particularly limited, but is, for example, 0.1.
- the adhesive layer exhibits high translucency in a warm atmosphere where humans and pets can spend time comfortably, and in high-temperature atmospheres such as summer, the adhesive layer exhibits haze. Translucency decreases.
- the refractive index difference between the temperature-sensitive adhesive and the polymer particles at 23°C is 0.015 or more, and the refractive index difference at 60°C is It can also be designed to be less than 0.015.
- the window glass will function as frosted glass under conditions of relatively low temperature and low sunlight, such as in the morning or at night, but during the day, as the amount of sunlight increases, the window glass will function as frosted glass.
- the window glass becomes transparent, allowing more light to enter the room. In this way, it is possible to easily let light into the room only during the daytime without opening or closing the curtains.
- the ratio of the mass of the temperature-sensitive adhesive to the mass of the solid content of the adhesive composition is not particularly limited, but is, for example, 50% by mass or more and 95% by mass or less.
- the solid content of an adhesive composition means all the components except a solvent, such as an aqueous solvent and an organic solvent, from the adhesive composition.
- the method for producing the temperature-sensitive adhesive is not particularly limited, and it can be obtained by conventionally known polymerization methods such as solution polymerization and UV polymerization.
- the adhesive composition may contain a crosslinking agent for crosslinking the temperature-sensitive adhesive. That is, the temperature-sensitive adhesive may be crosslinked.
- crosslinking agents used include aziridine crosslinking agents, metal chelate crosslinking agents, epoxy crosslinking agents, and isocyanate crosslinking agents.
- the content of the crosslinking agent is not particularly limited, but is, for example, 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the temperature-sensitive adhesive.
- the amount is 0.1 parts by mass or more, shape retention tends to be less likely to decrease. Further, when the amount is 10 parts by mass or less, high adhesive strength tends to be easily exhibited.
- the adhesive composition includes a solvent such as an organic solvent, an inhibitor that suppresses the progress of crosslinking, a tackifying resin (tackifier), an ultraviolet (UV) absorber, a light stabilizer (HALS), an antioxidant, an infrared absorber, Other additives such as dyes and pigments may also be included.
- a solvent such as an organic solvent, an inhibitor that suppresses the progress of crosslinking, a tackifying resin (tackifier), an ultraviolet (UV) absorber, a light stabilizer (HALS), an antioxidant, an infrared absorber, Other additives such as dyes and pigments may also be included.
- the above-mentioned adhesive composition is not limited in the manner in which it is used.
- the mode of use of the above-mentioned adhesive composition can be appropriately selected depending on the purpose.
- the above adhesive composition can autonomously change its white turbidity depending on the temperature. If the adhesive composition is designed to produce haze at high temperatures, it can soften direct sunlight during high temperatures in summer and allow sunlight to enter during low temperatures in winter. It can be suitably used for. On the other hand, if the adhesive composition is designed to produce haze at low temperatures, for example, when the adhesive composition is applied to window glass, the temperature is relatively low and the amount of sunlight is low, such as in the morning or at night.
- the window glass functions as frosted glass, but when the amount of sunlight increases and the temperature rises during the day, the window glass becomes transparent, allowing efficient daylight to enter the room.
- the above-mentioned adhesive composition develops or disappears haze due to heat sources such as lighting, sunlight, or high temperatures, designs such as letters, symbols, patterns, figures, and pictures appear or disappear. It becomes possible to impart excellent display properties (designs such as letters, symbols, etc.) and decorative properties (designs such as patterns, figures, pictures, etc.) to the object provided with the adhesive layer. Therefore, it can be used, for example, to decorate light covers, to decorate transparent substrates such as window materials and transparent roofing materials, and to display transparent substrates such as window materials and transparent roofing materials. It can be used suitably.
- the above window material may or may not be provided with a base sheet.
- the base sheet has a function as a support when laminating the adhesive layer on the transparent base layer, and a function as a protective layer for the adhesive layer.
- the base material constituting the base sheet is not particularly limited as long as it is a translucent base material.
- a base material for example, PET such as corona treated PET, untreated PET, highly transparent PET, annealed PET, UV cut PET, heat shielding PET, anti-fog PET, hard coat PET, blasted PET; transparent PI etc. are used. can.
- the method for manufacturing the above window material is not particularly limited, and examples include a method in which an adhesive composition is applied to a base sheet to produce an adhesive sheet, and then the adhesive sheet is laminated to a translucent base material. It will be done.
- the adhesive layer may be formed by applying the adhesive composition directly to the transparent substrate. In this case, it is preferable to cover the exposed surface of the adhesive layer formed on the translucent base material with a base sheet so that the tacky surface of the adhesive layer is not exposed indoors or outdoors.
- the light-transmitting base material layer is comprised of two or more layers like the 2nd window material 20, the method of arranging an adhesive layer between the light-transmitting base material layers, etc. are also mentioned.
- another base material layer may be bonded to the exposed surface of the adhesive layer.
- two laminates are prepared in which one translucent base material layer and one adhesive layer are laminated so that they are in contact with each other, and the two laminates are bonded together with the exposed surface of the adhesive layer.
- the second window material 20 having an adhesive layer between the light-transmitting substrates can also be manufactured by this method.
- window material described above can be appropriately selected depending on the purpose.
- the window material described above can be suitably used, for example, in buildings such as houses, buildings, warehouses, and arcades, as well as in vehicles, ships, and aircraft.
- FIG. 3 is a sectional view showing an example of a translucent roofing material.
- a translucent base material layer 31 As shown in FIG. 3, in the translucent roof material 30, a translucent base material layer 31, an adhesive layer 32, and a base material sheet 33 are laminated in this order.
- the adhesive layer 32 is composed of an adhesive composition containing a temperature-sensitive adhesive 32a and fine polymer particles 32b.
- the temperature-sensitive adhesive 32a has a refractive index that increases as the temperature decreases, and a refractive index increase rate, which is the amount of increase in the refractive index per 1°C, in the vicinity of the melting point. It is larger than other temperature ranges. Therefore, when the temperature of the adhesive layer 32 increases due to sunlight or air temperature, the difference in refractive index between the polymer particles 32b and the temperature-sensitive adhesive 32a increases, and the haze value increases. On the other hand, when the temperature of the adhesive layer 32 decreases, the haze value decreases due to a decrease in the refractive index difference between the polymer particles 32b and the temperature-sensitive adhesive 32a.
- the adhesive strength of the adhesive composition constituting the adhesive layer 32 decreases as the temperature decreases, and the adhesive strength reduction rate, which is the amount of decrease in adhesive strength per 1°C, is lower than that of the adhesive composition.
- the temperature near the melting point of the temperature-sensitive adhesive 32a is higher than the temperature range other than the melting point. Therefore, even if bubbles are trapped or wrinkles occur when the adhesive layer 32 is placed, the adhesive layer 32 can be peeled off and placed again by lowering the temperature of the adhesive layer 32. Thereby, manufacturing of the window material can be made easier.
- the translucent base material layer, adhesive layer, base sheet, manufacturing method, and usage are the same as each layer, manufacturing method, and usage of the window material.
- the adhesive composition contains 1 to 100 parts by mass of polymer fine particles per 100 parts by mass of the temperature-sensitive adhesive.
- the refractive index of a temperature-sensitive adhesive increases as the temperature decreases, and the refractive index increase rate, which is the amount of increase in refractive index per 1°C, is higher in the vicinity of the melting point than in the temperature range other than the vicinity of the melting point. It's also big. If each refractive index is adjusted so that the difference in refractive index between the polymer fine particles and the temperature-sensitive adhesive at low temperatures is small, when the temperature of the adhesive layer formed from the adhesive composition increases due to sunlight, air temperature, or heating, The difference in refractive index between the polymer particles and the temperature-sensitive adhesive increases, resulting in a high haze value.
- an adhesive layer is formed using an adhesive composition so that designs such as letters, symbols, patterns, figures, pictures, etc. are drawn, haze appears or disappears due to heat sources such as lighting, sunlight, and high temperatures Accordingly, the design can appear or disappear.
- This makes it possible to impart excellent display properties (designs such as letters, symbols, etc.) and decorative properties (designs such as patterns, figures, pictures, etc.) to the object provided with the adhesive layer.
- the haze value of the adhesive layer becomes lower or higher, so the following changes in adhesive strength can be visually recognized even in situations where a contact thermometer is not available. can do.
- the adhesive strength of the adhesive composition decreases as the temperature decreases, and the adhesive strength reduction rate, which is the amount of decrease in adhesive strength per 1°C, is lower than the melting point of the temperature-sensitive adhesive in the adhesive composition. In the vicinity, the temperature is higher than in the temperature range other than the vicinity of the melting point. Therefore, even if air bubbles or wrinkles occur when the adhesive layer is placed, the adhesive layer can be peeled off and placed again by increasing the temperature of the adhesive layer. In addition, it is possible to firmly temporarily fix the workpieces and the like in the manufacturing process and to peel them off without destroying the workpieces.
- the average particle diameter of the polymer fine particles is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. Further, the average particle diameter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 10 ⁇ m or less. In particular, from the viewpoint of easily increasing haze, the average particle diameter is more preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and most preferably 1 ⁇ m or more and 6 ⁇ m or less. From the viewpoint of easily suppressing the transmission of solar radiation, the average particle diameter is more preferably 6 ⁇ m or more and 25 ⁇ m or less, and most preferably 6 ⁇ m or more and 10 ⁇ m or less.
- the average particle diameter is more preferably 6 ⁇ m or more and 25 ⁇ m or less, and most preferably 6 ⁇ m or more and 10 ⁇ m or less.
- the D90 particle diameter of the polymer fine particles is preferably equal to or less than the thickness of the adhesive layer, and is, for example, 1 ⁇ m or more and 1000 ⁇ m or less, 3 ⁇ m or more and 100 ⁇ m or less. When the D90 particle size is less than or equal to the thickness of the adhesive layer, the surface of the adhesive layer becomes uniform and the adhesive strength tends to be less likely to be impaired.
- the polymer constituting the polymer fine particles preferably contains a structural unit derived from a monomer containing one ethylenically unsaturated group.
- the ethylenically unsaturated group include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, and a (meth)allyl group, with a (meth)acryloyl group and a vinyl group being preferred.
- Monomers containing one ethylenically unsaturated group include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, hydroxy
- (meth)acrylates such as ethyl (meth)acrylate; vinyl monomers such as styrene, vinyl acetate, and acrylonitrile; and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the monomer containing one ethylenically unsaturated group to the mass of the polymer constituting the polymer fine particles is preferably 70% by mass or more, more preferably 80% by mass or more, More preferably, it is 90% by mass or more.
- the above ratio may be 100% by mass, but is preferably 98% by mass or less.
- the polymer constituting the polymer fine particles may contain a structural unit derived from another monomer copolymerizable with a monomer containing one ethylenically unsaturated group.
- examples of other monomers include polyfunctional monomers, refractive index adjusting monomers, and the like. That is, the polymer constituting the polymer fine particles may include a structural unit derived from a polyfunctional monomer or a refractive index adjusting monomer.
- the polyfunctional monomer can crosslink multiple molecular chains contained in the polymer constituting the polymer fine particles. From the viewpoint of maintaining the dispersed state of the polymer fine particles during use, suppressing deformation, and maintaining repeatability of functions, it is preferable that the polymer constituting the polymer fine particles contains a structural unit derived from a polyfunctional monomer. That is, it is preferable that the polymer fine particles and the polymer constituting them are crosslinked.
- the polyfunctional monomer has two or more, preferably 2 to 4, radically polymerizable double bonds in the molecule. Examples of the polyfunctional monomer include bifunctional (meth)acrylate, trifunctional (meth)acrylate, and tetrafunctional (meth)acrylate.
- Specific examples include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polyethylene glycol 200 di(meth)acrylate.
- the polyfunctional monomer may be at least one selected from bifunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional (meth)acrylates.
- the ratio of the mass of the structural unit derived from the polyfunctional monomer to the mass of the polymer constituting the polymer fine particles is preferably 0.1% by mass or more, more preferably 1% by mass or more. Moreover, the said ratio becomes like this. Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less.
- the refractive index adjusting monomer may be a monomer having a refractive index of 1.300 to 1.600.
- the refractive index adjusting monomer include 2-(O-phenylphenoxy)ethyl acrylate (refractive index: 1.577), 2-propenoic acid (3-phenoxyphenyl) methyl ester (refractive index: 1.566), 1 - Naphthyl acrylate (refractive index: 1.595), acrylamide (refractive index: 1.515), hydroxyacrylamide (refractive index: 1.515), EO-modified bisphenol A diacrylate (refractive index: 1.537), acrylamide ( Refractive index: 1.515), 2,2,2-trifluoroethyl acrylate (refractive index: 1.348), methacryl-modified polydimethylsiloxane (refractive index: 1.408), and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the refractive index adjusting monomer to the mass of the polymer constituting the polymer fine particles is preferably 0.1% by mass or more, more preferably 1% by mass or more. Further, the above ratio is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
- the polymer fine particles do not contain a structural unit derived from a reactive emulsifier, since they tend to have good dispersibility in a temperature-sensitive adhesive.
- a reactive emulsifier is an emulsifier having a polymerizable unsaturated bond such as a vinyl group in its molecule.
- the reactive emulsifier is a polymerizable monomer that has an emulsifying function and has a polymerizable group having an unsaturated bond such as a vinyl group in its molecule, and a hydrophilic group.
- the content of the polymer particles is 1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the temperature-sensitive adhesive.
- the content is preferably 5 parts by mass or more, more preferably 20 parts by mass or more. Further, the content is preferably 70 parts by mass or less, more preferably 40 parts by mass or less.
- the method for producing polymer fine particles is not particularly limited, and they can be obtained by conventionally known polymerization methods such as miniemulsion polymerization and suspension polymerization.
- a temperature-sensitive adhesive has a melting point.
- a temperature-sensitive adhesive crystallizes at a temperature below the melting point, and undergoes a phase transition and exhibits fluidity at a temperature above the melting point.
- the adhesive strength of an adhesive composition containing a temperature-sensitive adhesive decreases as the temperature decreases, and the adhesive strength reduction rate, which is the amount of decrease in adhesive strength per 1°C, is lower than that of the adhesive composition.
- the temperature near the melting point of the temperature-sensitive adhesive inside is higher than the temperature range other than the melting point.
- the peel strength of the adhesive composition against polyethylene terephthalate (PET) at 23° C. is preferably 0.1 N/25 mm or less.
- the lower limit of the above peel strength is not particularly limited.
- the peel strength of the adhesive composition against polyethylene terephthalate (PET) at 60° C. is preferably 1.0 N/25 mm or more.
- the upper limit of the peel strength is not particularly limited.
- the melting point of the temperature-sensitive adhesive is preferably 25°C or higher, more preferably 40°C or higher. Further, the melting point is preferably 70°C or lower, more preferably 60°C or lower.
- the melting point of the temperature-sensitive adhesive can be adjusted, for example, by changing the composition of the monomer components constituting the side chain crystalline polymer contained in the temperature-sensitive adhesive. For example, by changing the length of the side chain in a side chain crystalline polymer, the melting point can be adjusted. When the length of the side chain is long, the temperature-sensitive adhesive tends to have a high melting point.
- FIG. 4 is a graph showing changes in refractive index with respect to temperature changes in a temperature-sensitive adhesive (melting point: 55° C.) manufactured in an example described below.
- the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and the refractive index increase rate, which is the amount of increase in the refractive index per 1°C, is near the melting point. It is larger than the temperature range other than the vicinity of the melting point.
- the refractive index of the temperature-sensitive adhesive at 23°C is preferably 0.02 or more higher than the refractive index of the temperature-sensitive adhesive at 60°C. This tends to make it easier to visually recognize changes in white turbidity depending on temperature.
- the temperature-sensitive adhesive contains a side chain crystalline polymer.
- the side chain crystalline polymer preferably contains a structural unit derived from a (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms.
- the linear alkyl group having 14 or more carbon atoms acts as a side chain crystalline moiety in a side chain crystalline polymer. Function. That is, the side chain crystalline polymer is, for example, a comb-shaped polymer having a linear alkyl group having 14 or more carbon atoms in the side chain.
- the side chain crystalline polymer is crystallized.
- the above-mentioned (meth)acrylic monomer is an acrylic monomer or a methacrylic monomer.
- the upper limit of the number of carbon atoms in the linear alkyl group is preferably 50 or less, more preferably 30 or less.
- Examples of the (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms include cetyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, and behenyl (meth)acrylate. . These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the (meth)acrylic monomer having a linear alkyl group having 14 or more carbon atoms to the mass of the side chain crystalline polymer is preferably 30% by mass or more, more preferably 40% by mass. % or more.
- the above ratio is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less.
- the side chain crystalline polymer may contain a structural unit derived from a (meth)acrylic monomer having a linear alkyl group having 1 to 12 carbon atoms, and a structural unit derived from a functional group monomer for crosslinking. preferable. Further, the side chain crystalline polymer may contain structural units derived from other monomers copolymerizable with these monomers. Examples of other monomers include refractive index adjusting monomers. That is, the side chain crystalline polymer may include a structural unit derived from a refractive index adjusting monomer.
- Examples of (meth)acrylic monomers having a linear alkyl group having 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and pentyl (meth)acrylate. ) acrylate, hexyl (meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, methyl (meth)acrylate is preferred in that it has a high cohesive force and can easily suppress a decrease in adhesive strength when the temperature rises.
- the ratio of the mass of the structural unit derived from the (meth)acrylic monomer having a linear alkyl group having 1 to 12 carbon atoms to the mass of the side chain crystalline polymer is preferably 1% by mass or more, more preferably The content is 20% by mass or more, more preferably 40% by mass or more. The above ratio is preferably 69% by mass or less, more preferably 60% by mass or less.
- Examples of functional group monomers include (meth)acrylates having a hydroxyalkyl group such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxyhexyl (meth)acrylate; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Examples include ethylenically unsaturated monomers having a carboxyl group such as maleic acid and fumaric acid. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the functional monomer to the mass of the side chain crystalline polymer is preferably 1% by mass or more, more preferably 3% by mass or more. Moreover, the said ratio becomes like this. Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less. When the content is 1% by mass or more, shape retention tends to be good. When the amount is 20% by mass or less, the viscosity is not excessively high and coating properties tend to be good.
- the refractive index adjusting monomer may be a monomer having a refractive index of 1.300 to 1.600.
- the refractive index adjusting monomer include 2-(O-phenylphenoxy)ethyl acrylate (refractive index: 1.577), 2-propenoic acid (3-phenoxyphenyl) methyl ester (refractive index: 1.566), 1 - Naphthyl acrylate (refractive index: 1.595), acrylamide (refractive index: 1.515), hydroxyacrylamide (refractive index: 1.515), EO-modified bisphenol A diacrylate (refractive index: 1.537), acrylamide ( Refractive index: 1.515), 2,2,2-trifluoroethyl acrylate (refractive index: 1.348), methacryl-modified polydimethylsiloxane (refractive index: 1.408), and the like. These may be used alone or in combination of two or more.
- the ratio of the mass of the structural unit derived from the refractive index adjusting monomer to the mass of the side chain crystalline polymer is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. . Moreover, the said ratio becomes like this. Preferably it is 30 mass % or less.
- the weight average molecular weight of the temperature-sensitive adhesive is preferably 200,000 or more, more preferably 400,000 or more.
- the weight average molecular weight is preferably 2 million or less, more preferably 1 million or less. When it is 200,000 or more, the adhesive strength tends to be sufficient. When it is 2 million or less, coating properties tend to be sufficient due to the decrease in viscosity.
- the weight average molecular weight of the temperature-sensitive adhesive can be adjusted, for example, by using a chain transfer agent during polymerization.
- chain transfer agent include thiol compounds such as dodecylmercaptan, mercaptopropionic acid, mercaptosuccinic acid, ethylhexylmercaptoacetate, mercaptoethanol, and cyclohexanethiol. These may be used alone or in combination of two or more.
- the difference in refractive index at 23°C between the temperature-sensitive adhesive and the polymer particles is preferably less than 0.015, more preferably less than 0.010. Further, the refractive index difference at 60° C. is preferably 0.015 or more.
- the upper limit of the refractive index difference at 60° C. is not particularly limited, but is, for example, 0.1.
- the ratio of the mass of the temperature-sensitive adhesive to the mass of the solid content of the adhesive composition is not particularly limited, but is, for example, 50% by mass or more and 95% by mass or less.
- the method for producing the temperature-sensitive adhesive is not particularly limited, and it can be obtained by conventionally known polymerization methods such as solution polymerization and UV polymerization.
- the adhesive composition may contain a crosslinking agent for crosslinking the temperature-sensitive adhesive. That is, the temperature-sensitive adhesive may be crosslinked.
- crosslinking agents used include aziridine crosslinking agents, metal chelate crosslinking agents, epoxy crosslinking agents, and isocyanate crosslinking agents.
- the content of the crosslinking agent is not particularly limited, but is, for example, 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the temperature-sensitive adhesive.
- the amount is 0.1 parts by mass or more, shape retention tends to be less likely to decrease. Further, when the amount is 10 parts by mass or less, high adhesive strength tends to be easily exhibited.
- the adhesive composition includes a solvent such as an organic solvent, an inhibitor that suppresses the progress of crosslinking, a tackifying resin (tackifier), an ultraviolet (UV) absorber, a light stabilizer (HALS), an antioxidant, an infrared absorber, Other additives such as dyes and pigments may also be included.
- a solvent such as an organic solvent, an inhibitor that suppresses the progress of crosslinking, a tackifying resin (tackifier), an ultraviolet (UV) absorber, a light stabilizer (HALS), an antioxidant, an infrared absorber, Other additives such as dyes and pigments may also be included.
- the adhesive sheet includes an adhesive layer made of an adhesive composition.
- the temperature-sensitive light control liquid laminate of Patent Document 1 requires a dedicated structure for maintaining the shape of the temperature-sensitive light control liquid. Therefore, when installing it later on existing windows or roofs, large-scale construction work such as replacing the entire window is required, which poses a problem that it is difficult to introduce.
- Adhesive sheets do not require a special structure to maintain their shape, and can be easily installed by simply pasting them onto existing windows or roofs, and can autonomously change their white turbidity depending on the temperature. It has the advantage that it can be easily provided with the function of
- the thickness of the adhesive layer is not particularly limited, but is preferably 5 ⁇ m or more and 1 mm or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less. Note that the thicker the adhesive layer is, the more the dimming function tends to be exhibited by adding a small amount of polymer fine particles. The thinner the thickness, the more polymer fine particles tend to need to be added in order to exhibit the light control function.
- the difference between the haze value at 23°C and the haze value at 60°C of the adhesive layer is preferably 10% or more.
- the haze value of the adhesive layer at 60°C is 10% or more higher than the haze value at 23°C. This tends to make it easier to visually recognize changes in white turbidity depending on temperature.
- the haze value of the adhesive layer at 23°C is preferably 20% or less, more preferably 10% or less.
- the lower limit of the haze value at 23°C is not particularly limited.
- the haze value of the adhesive layer at 60° C. is preferably 12% or more, more preferably 20% or more.
- the upper limit of the haze value at 60° C. is not particularly limited, but is, for example, 70% or less and 50% or less.
- the difference between the solar transmittance at 23°C and the solar transmittance at 60°C of the adhesive layer is preferably 10% or more.
- the solar transmittance of the adhesive layer at 60°C is preferably 10% or more lower than the solar transmittance at 23°C.
- the solar radiation transmittance of an adhesive layer is the value measured by the method described in the below-mentioned Example.
- the solar transmittance of the adhesive layer at 23° C. is preferably 30% or more, more preferably 40% or more.
- the upper limit of the solar transmittance at 23° C. is not particularly limited, but is, for example, 95% or less, or 85% or less.
- the solar transmittance of the adhesive layer at 60° C. is preferably 60% or less, more preferably 40% or less, and still more preferably 30% or less.
- the lower limit of the solar transmittance at 60° C. is not particularly limited, but is, for example, 5% or more, or 15% or more.
- the adhesive sheet may include a base sheet.
- the base material constituting the base sheet is not particularly limited as long as it is a translucent base material.
- PET such as corona treated PET, untreated PET, highly transparent PET, annealed PET, UV cut PET, heat shielding PET, anti-fog PET, hard coat PET, blasted PET; transparent PI etc. are used. can.
- the adhesive layer may be formed only on one side of the base sheet, or may be formed on both sides. Alternatively, an adhesive layer may be formed on one side of the base sheet, and an adhesive layer other than the adhesive layer described above may be formed on the other side.
- a release sheet may be laminated on the surface of the adhesive layer in the same way as the base sheet.
- a pressure-sensitive adhesive sheet can be produced by a conventional method using the pressure-sensitive adhesive composition described above.
- a method may be used in which a coating solution prepared by adding a solvent and a crosslinking agent to an adhesive composition as necessary is applied to a base sheet using a coater or the like, and then dried by heating or the like to form an adhesive layer.
- coater examples include a knife coater, roll coater, calendar coater, comma coater, and the like. Further, depending on the coating thickness and the viscosity of the coating liquid, gravure coaters, rod coaters, etc. may also be used.
- ⁇ Processing method of workpiece>> The adhesive strength of the adhesive sheet described above decreases as the temperature decreases, and the rate of decrease in adhesive strength is greater in the vicinity of the melting point of the temperature-sensitive adhesive than in the temperature range other than the vicinity of the melting point. By adjusting, it is possible to firmly temporarily fix the workpiece in the manufacturing process and to peel it off without destroying the workpiece. Furthermore, the refractive index of the temperature-sensitive adhesive increases as the temperature decreases, and the rate of increase in the refractive index is larger near the melting point than in the temperature range other than the melting point, so the haze value of the adhesive layer increases.
- the above pressure-sensitive adhesive sheet can be suitably used in the following method (1) or (2) for processing a workpiece.
- an adhesive sheet comprising an adhesive layer and a base sheet laminated on one side of the adhesive sheet is used, and the adhesive layer is attached to the workpiece at a temperature equal to or higher than the melting point of the temperature-sensitive adhesive.
- the adhesive layer is attached to a support (such as a pedestal) or a workpiece using an adhesive sheet having a release sheet and a temperature that is higher than the melting point of the temperature-sensitive adhesive. Thereafter, the release sheet is peeled off, and the other adhesive layer is attached to the other support or workpiece.
- a heating means such as a heater may be used, for example.
- the haze value of the adhesive layer decreases or increases depending on the temperature, so changes in adhesive strength can be visually recognized even in situations where a contact thermometer is not available. Therefore, in (b) and (b'), by confirming that the adhesive layer is cloudy or not cloudy, it can be confirmed that the adhesive layer has developed adhesive strength, and the workpiece can be You can confirm that it is temporarily fixed.
- the processing method is not particularly limited, and examples include grinding, dicing, die bonding, wire bonding, etching, vapor deposition, molding, circuit formation, inspection, inspection, cleaning, transfer, Examples include alignment, repair, and protection of device surfaces.
- the temperature of the adhesive sheet is lower than the melting point of the temperature-sensitive adhesive.
- a cooling means such as a fan may be used.
- the workpiece is not particularly limited as long as it requires temporary fixation during processing, but examples include electronic components such as ceramic capacitors, semiconductor chips, and LED chips, and film components such as film touch sensors. .
- VA Blenmar VA (behenyl acrylate) manufactured by NOF Corporation
- MMA Methyl methacrylate St manufactured by Tokyo Chemical Industry Co., Ltd.: Styrene A-HD-N manufactured by Tokyo Chemical Industry Co., Ltd.: A-HD-N (1,6-hexane manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) diol diacrylate)
- C1A Methyl acrylate AA manufactured by Nippon Shokubai Co., Ltd.: Acrylic acid NF-13 manufactured by Nippon Shokubai Co., Ltd.: Hitenol NF-13 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Perloyl L Perloil L (dilauroyl peroxide) manufactured by NOF Corporation Perbutyl ND: Perbutyl ND (t-butyl peroxyneodecanoate) manufactured by NOF Corporation Perhexyl PV: Perhexyl PV (t-hexyl peroxypivalate) manufactured by NOF Corporation PZ33: Chemitite PZ33 (aziridine-based crosslinking agent) manufactured by Nippon Shokubai Co., Ltd.
- a monofunctional monomer, a polyfunctional monomer, and an initiator were added to the reaction vessel in the proportions shown in Table 1.
- the mixture in the reaction vessel was stirred with a spatula to ensure uniform mixing.
- an aqueous medium and an emulsifier in the proportions shown in Table 1 were added to the reaction vessel to obtain a mixed solution.
- Water was used as the aqueous medium.
- the aqueous medium was added so that the ratio of the mass of the monofunctional monomer to the sum of the mass of the monofunctional monomer in the mixed liquid and the mass of the aqueous medium was 40% by mass.
- the mixed solution was stirred for 5 minutes at 7500 rpm using a homogenizer manufactured by IKA (main unit: T 25 digital ULTRA-TURRAX, shaft generator: S25N-25F) to form monomer components into particles.
- a homogenizer manufactured by IKA main unit: T 25 digital ULTRA-TURRAX, shaft generator: S25N-25F
- nitrogen was introduced and bubbled into the mixed liquid to remove air (oxygen) from the mixed liquid, and the monomer components were polymerized by heating and stirring at 67°C for 2 hours and at 80°C for 2 hours, respectively.
- the aqueous medium was removed from the generated fine particles by suction filtration and vacuum drying to obtain polymer fine particles 1 to 3.
- Polymer fine particles 4 were obtained in the same manner as in the manufacturing method of polymer fine particles 3, except that the mixed liquid was stirred for 5 minutes at 2800 rpm using a homogenizer.
- Polymer fine particles 5 were obtained in the same manner as in the manufacturing method of polymer fine particles 3, except that the mixed liquid was stirred for 2 minutes at 2800 rpm using a homogenizer.
- the particle size distribution of the polymer fine particles was measured using a laser diffraction particle size distribution meter "Mastersizer 3000" manufactured by Malvern. In the particle size distribution, the particle size corresponding to 50% of the cumulative volume frequency calculated from the smaller particle size of the polymer fine particles was defined as the "average particle size.” The results are shown in Table 1.
- the 180° peel strength against polyethylene terephthalate (PET) at 23° C. and 60° C. was measured in accordance with JIS Z0237. Specifically, the adhesive sheet was bonded to PET, left to stand for 20 minutes, and then peeled off at 180° at a speed of 300 mm/min using a load cell. The PET used was in the form of a film with a thickness of 25 ⁇ m and was untreated. The adhesive sheet was laminated to PET by moving a 2 kg roller back and forth 5 times on the adhesive sheet. The results are shown in Tables 3 and 4.
- the peel strength of the pressure-sensitive adhesive sheets was also measured at temperatures between 23°C and 60°C, and changes in the rate of decrease in adhesive strength, which is the amount of decrease in adhesive strength per 1°C of the pressure-sensitive adhesive sheets, were confirmed. As a result, it was confirmed that the rate of decrease in adhesive strength near 55° C., which is the melting point of the temperature-sensitive adhesive, was greater than in the temperature range other than the vicinity of the melting point of the temperature-sensitive adhesive.
- the solar transmittance of the obtained pressure-sensitive adhesive sheet at 23° C. and 60° C. was measured in accordance with JIS A5759:2016 6.5 using a spectrophotometer “V770DS” manufactured by JASCO Corporation. However, since the measurement was performed after heating to 60° C., ITO glass (GMT-100-12, manufactured by Geomatec) with a thickness of 1.1 mm was used as the object to which the adhesive sheet was attached. Specifically, a test piece was prepared by pasting an adhesive sheet on one side of ITO glass. At 23° C. and 60° C.
- the spectral transmittance of each wavelength from 300 to 2500 nm was measured using a spectrophotometer with the glass surface of the test piece facing the light source.
- the solar transmittance was calculated based on the relative spectral distribution of solar radiation as specified in JIS A5759:2016. The results are shown in Tables 3 and 4.
- thermometer (thermocouple) 3 was installed at a position 10 mm below the glass surface.
- the sides and bottom of the wooden frame 4 were covered with polyethylene sheets as a windbreak.
- the wooden frame 4 on which the test piece was placed was placed on a metal rack 5 so that the height from the ground 6 was 1000 mm.
- thermocouple 3 The temperature rise value of thermocouple 3 was recorded during solar radiation (solar radiation time: about 360 minutes, average temperature: 32°C). A glass plate to which no adhesive sheet was attached was used as a blank test piece, and the temperature rise value was recorded in the same manner. The difference from the temperature rise value of the blank was calculated. The results are shown in Tables 3 and 4.
- the adhesive layers of Examples 1 and 2 having the above-described predetermined configuration autonomously change the white turbidity depending on the temperature. I know that I can do it. It can also be seen that the adhesive strength decreases as the temperature decreases. Therefore, from Examples 1 and 2, window materials and translucent roofing materials equipped with the adhesive layer can autonomously change their white turbidity depending on the temperature, and the adhesive layer can be peeled off and repositioned. It can be seen that manufacturing is easy because it is possible to
- First window material 11 Transparent base material layer 12 Adhesive layer 12a Temperature-sensitive adhesive 12b Polymer fine particles 13 Base sheet 20 Second window material 21a, 21b Transparent base material layer 22 Adhesive layer 22a Temperature-sensitive Temperature-sensitive adhesive 22b Polymer fine particles 30 Transparent roofing material 31 Transparent base material layer 32 Adhesive layer 32a Temperature-sensitive adhesive 32b Polymer fine particles 33 Base sheet
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Abstract
Description
少なくとも1層の透光性基材層と、少なくとも1層の粘着層とを備え、
前記粘着層が、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物からなり、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
窓材である。
少なくとも1層の透光性基材層と、少なくとも1層の粘着層とを備え、
前記粘着層が、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物からなり、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
透光性屋根材である。
感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物であって、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
粘着性組成物である。
第5の態様に係る粘着性組成物からなる粘着層を備える粘着シートである。
被加工物を、第6の態様に係る粘着シートが備える前記粘着層に接触させることと、
前記粘着層が白濁していること又は白濁していないことを確認することにより、前記粘着層が粘着力を発現していることを確認することと、
前記粘着層が発現した粘着力により前記粘着層上に固定された前記被加工物を加工することと、
前記粘着層が白濁していないこと又は白濁していることを確認することにより、前記粘着層が粘着力を発現していないことを確認することと、
加工された前記被加工物を、粘着力を発現していない前記粘着層上から取り除くことと、
を含む、被加工物の加工方法である。
支持体と被加工物と、又は被加工物同士を、第6の態様に係る粘着シートが備える前記粘着層を介して接触させることと、
前記粘着層が白濁していること又は白濁していないことを確認することにより、前記粘着層が粘着力を発現していることを確認することと、
前記粘着層が発現した粘着力により、前記粘着層を介して前記支持体上に固定されている前記被加工物、又は前記粘着層を介して固定された複数の前記被加工物の少なくとも一つを加工することと、
前記粘着層が白濁していないこと又は白濁していることを確認することにより、前記粘着層が粘着力を発現していないことを確認することと、
加工された前記被加工物を、粘着力を発現していない前記粘着層上から取り除くことと、
を含む、被加工物の加工方法である。
図1に、窓材の一例として第1の窓材10の断面図を示す。図1に示すように、第1の窓材10では、透光性基材層11と、粘着層12と、基材シート13とがこの順に積層されている。粘着層12は、感温性粘着剤12aと、ポリマー微粒子12bとを含む粘着性組成物から構成されている。
なお、温度の上昇により、感温性粘着剤12a及び22aとポリマー微粒子12b及び22bの屈折率差が小さくなるように設計することもできる。
この場合、例えば、朝や夜のような比較的気温が低く日照量が少ない条件下では、窓材がすりガラスとして機能する一方で、昼間に日照量の増加とともに気温が上昇した場合には、窓材が透明になり、室内に効率よく採光できる。
また、上記の窓材が、外気に触れるような位置に施工される場合、上記の窓材は、外気温の上昇にともない白濁、又は透明化するため、空調された室内で過ごす人に、視覚的に外気温の上昇を認識させる機能も有する。
透光性基材層を構成する透光性基材としては、建築物用や車両用、船舶用、航空機用の窓材として適用可能な基材であれば特に限定されず、例えば、ガラス板や樹脂板を用いることができる。ガラス板の材料としては、ソーダライムガラス、ホウケイ酸ガラス、高シリカガラス等が挙げられる。また、樹脂板の材料としては、ポリメチルメタアクリレート等のポリアルキルメタアクリレート、ポリアルキルアクリレート、ポリカーボネート、ポリメチルスチレン、アクリロニトリル-スチレン共重合体等が挙げられる。
粘着層は、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物からなる層であり、温度に応じて自律的に白濁度と粘着力を変化させる機能を有する。
なお、粘着層は、粘着層と透光性基材層とが接する面の全面を覆ってもよく、一部を覆ってもよい。
粘着層が、粘着層と透光性基材層とが接する面の一部を覆う場合、透光性基材層上に、粘着層によって、文字、記号、柄、図形、絵柄等が描かれてもよい。この場合、粘着層が文字や柄を形成してもよく、粘着層に囲われた領域が文字や柄を形成してもよい。このような窓材は、高温でヘイズが発現、又は消失した際の意匠性に優れる。
さらに、粘着層は、高温時、又は低温時のヘイズ値が異なる複数の種類の領域を有してもよい。粘着層のヘイズ値は、感温性粘着剤やポリマー微粒子の種類を変えたり、ポリマー微粒子の使用量を変えることにより変えることができる。
例えば、透光性基材上に、高温時、又は低温時のヘイズ値が異なる複数の粘着層を、帯状に連続して形成することにより、高温時、又は低温時にグラデーションのかかったヘイズを示す意匠性に優れる窓材を提供できる。
ポリマー微粒子の平均粒子径は、好ましくは0.1μm以上、より好ましくは1μm以上である。また、上記平均粒子径は、好ましくは100μm以下、より好ましくは30μm以下、さらに好ましくは10μm以下である。特に、ヘイズを高めやすい点からは、上記平均粒子径が0.1μm以上10μm以下であることが更に好ましく、1μm以上6μm以下であることが最も好ましい。日射の透過を抑制しやすい点からは、上記平均粒子径が6μm以上25μm以下であることが更に好ましく、6μm以上10μm以下であることが最も好ましい。熱を遮断しやすい点からは、上記平均粒子径が6μm以上25μm以下であることが更に好ましく、6μm以上10μm以下であることが最も好ましい。
また、ポリマー微粒子のD90粒子径は、粘着層の厚み以下であることが好ましく、例えば、1μm以上1000μm以下、3μm以上100μm以下である。D90粒子径が粘着層の厚み以下であると粘着層の表面が均一となり、粘着力を阻害しにくい傾向がある。なお、本明細書において、ポリマー微粒子の平均粒子径は、後述の実施例に記載の方法により測定される値である。
感温性粘着剤は、融点を有する。感温性粘着剤は、融点未満の温度で結晶化し、かつ融点以上の温度では相転移して流動性を示す。これにより、感温性粘着剤を含む粘着性組成物は、粘着力が温度の低下にともない低下し、且つ、1℃当たりの粘着力の低下量である粘着力低下率が、粘着性組成物中の感温性粘着剤の融点の近傍において、融点の近傍以外の温度域よりも大きい。なお、本明細書において、粘着性組成物の粘着力とは、ポリエチレンテレフタレート(PET)に対する剥離強度を意味し、後述の実施例に記載の方法により測定される値である。
また、粘着性組成物の60℃におけるポリエチレンテレフタレート(PET)に対する剥離強度は、1.0N/25mm以上であることが好ましい。上記剥離強度の上限は特に限定されない。
そうすると、一般的にヒトやペットが快適に過ごすことができる温暖な雰囲気下では、粘着層が高い透光性を示し、夏季のような高温雰囲気下では、粘着層におけるヘイズの発現により粘着層の透光性が低下する。
また、感温性粘着剤、及びポリマー微粒子の屈折率を調整することで、感温性粘着剤とポリマー微粒子の23℃における屈折率差が0.015以上であり、60℃における屈折率差が0.015未満であるように設計することもできる。
この場合、例えば、粘着層を窓ガラスに適用すると、朝や夜のような比較的気温が低く日照量が少ない条件下では、窓ガラスがすりガラスとして機能する一方で、昼間に日照量の増加とともに気温が上昇した場合には、窓ガラスが透明になり、室内に効率よく採光できる。そうすると、カーテンの開閉を行わなくても、昼間のみの室内への採光を容易に行うことができる。
上記の粘着性組成物は、使用される態様に制限はない。上記の粘着性組成物の使用の態様は、目的に応じて適宜選択することができる。
上記の粘着性組成物は、温度に応じて自律的に白濁度を変化させることができる。
粘着性組成物を、高温でヘイズが発現するように設計した場合、夏の高温時には直射日光を和らげ、冬の低温時には日射を採り入れることができるため、例えば、窓材や透光性屋根材等に好適に使用できる。
他方、粘着性組成物を低温でヘイズが発現するように設計した場合、例えば、当該粘着性組成物を窓ガラスに適用した場合に、朝や夜のような比較的気温が低く日照量が少ない条件下では、窓ガラスがすりガラスとして機能する一方で、昼間に日照量の増加とともに気温が上昇した場合には、窓ガラスが透明になり、室内に効率よく採光できる。
また、上記の粘着性組成物は、照明等の熱源や日射、気温による高温でヘイズが発現したり消失したりした際に、文字、記号、柄、図形、絵柄等の意匠を出現、又は消失させることができ、粘着層を備える対象に優れた表示性(文字、記号等の意匠)や装飾性(柄、図形、絵柄等の意匠)を付与することが可能となる。そのため、例えば、照明カバーの装飾用、窓材や透光性屋根材等の透光性基材の装飾用、窓材や透光性屋根材等の透光性基材の表示用、等に好適に使用できる。
上記の窓材は基材シートを備えていてもよいし備えていなくてもよい。基材シートは、粘着層を透光性基材層に積層する際の支持体としての機能や、粘着層の保護層としての機能を有する。
上記の窓材の製造方法は特に限定されず、例えば、基材シートに粘着性組成物を塗布して粘着シートを作製した後、透光性基材に粘着シートを貼合する方法等が挙げられる。透光性基材に、直接粘着性組成物を塗布して粘着層を形成してもよい。この場合、粘着層のタックを示す面が室内や屋外に露出しないように、透光性基材に形成された粘着層の露出している面を基材シートで被覆するのが好ましい。また、第2の窓材20のように透光性基材層が二層以上から構成されている場合は、粘着層を透光性基材層の間に配置する方法等も挙げられる。この場合、1つの基材層上に、粘着性組成物を塗布して粘着層を形成した後、粘着層の露出している面に、他の基材層を貼合わせればよい。
また、1つの透光性基材層と、1つの粘着層とが両者が接するように積層した積層体を2つ用意し、2つの積層体を、粘着層の露出している面で貼合わせることによっても、透光性基材間に粘着層を備える第2の窓材20を製造できる。
上記の窓材は、使用される態様に制限はない。上記の窓材の使用の態様は、目的に応じて適宜選択することができる。上記の窓材は、例えば、住宅、ビル、倉庫、アーケード等の建築物や、車両、船舶、又は航空機等に好適に使用できる。
図3は、透光性屋根材の一例を示す断面図である。図3に示すように、透光性屋根材30では、透光性基材層31と、粘着層32と、基材シート33とがこの順に積層されている。粘着層32は、感温性粘着剤32aと、ポリマー微粒子32bとを含む粘着性組成物から構成されている。
なお、温度の上昇により、ポリマー微粒子32bと感温性粘着剤32aの屈折率差が小さくなるように設計することもできる。
粘着性組成物は、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する。
低温時におけるポリマー微粒子と感温性粘着剤の屈折率差が小さくなるように各屈折率を調整した場合、粘着性組成物から形成した粘着層の温度が日射や気温、加温によって上昇すると、ポリマー微粒子と感温性粘着剤の屈折率差が大きくなってヘイズ値が高くなる。他方、粘着層の温度が低下すると、ポリマー微粒子と感温性粘着剤の屈折率差が小さくなってヘイズ値が低くなる。逆に、高温時におけるポリマー微粒子と感温性粘着剤の屈折率差が小さくなるように各屈折率を調整した場合、粘着層の温度が上昇するとヘイズ値が低くなり、粘着層の温度が低下するとヘイズ値が高くなる。
このため、前者の場合に、窓材や透光性屋根材等に粘着層を配置すると、温度に応じて自律的に白濁度を変化させることができ、夏の高温時には直射日光を和らげ、冬の低温時には日射を採り入れることができる。
また、粘着性組成物を用いて、文字、記号、柄、図形、絵柄等の意匠が描かれるように粘着層を形成した場合、照明等の熱源や日射、気温による高温によるヘイズの発現又は消失にともない、当該意匠を出現させたり消失させたりすることができる。これにより、粘着層を備える対象に優れた表示性(文字、記号等の意匠)や装飾性(柄、図形、絵柄等の意匠)を付与することが可能となる。
さらに、いずれの場合でも、粘着層を備える粘着シートとして使用すると、粘着層のヘイズ値が低くなったり高くなったりすることで、接触温度計がないような場面でも以下の粘着力の変化を視認することができる。
このため、粘着層を配置する際に気泡の巻き込みやシワ等が入った場合でも、粘着層の温度を上昇させることで、粘着層を剥離して再度配置することが可能である。また、製造工程における加工部材等を強固に仮止めしつつ、加工部材等を破壊せずに剥離することができる。
ポリマー微粒子の平均粒子径は、好ましくは0.1μm以上、より好ましくは1μm以上である。また、上記平均粒子径は、好ましくは100μm以下、より好ましくは30μm以下、さらに好ましくは10μm以下である。特に、ヘイズを高めやすい点からは、上記平均粒子径が0.1μm以上10μm以下であることが更に好ましく、1μm以上6μm以下であることが最も好ましい。日射の透過を抑制しやすい点からは、上記平均粒子径が6μm以上25μm以下であることが更に好ましく、6μm以上10μm以下であることが最も好ましい。熱を遮断しやすい点からは、上記平均粒子径が6μm以上25μm以下であることが更に好ましく、6μm以上10μm以下であることが最も好ましい。
また、ポリマー微粒子のD90粒子径は、粘着層の厚み以下であることが好ましく、例えば、1μm以上1000μm以下、3μm以上100μm以下である。D90粒子径が粘着層の厚み以下であると粘着層の表面が均一となり、粘着力を阻害しにくい傾向がある。
感温性粘着剤は、融点を有する。感温性粘着剤は、融点未満の温度で結晶化し、かつ融点以上の温度では相転移して流動性を示す。これにより、感温性粘着剤を含む粘着性組成物は、粘着力が温度の低下にともない低下し、且つ、1℃当たりの粘着力の低下量である粘着力低下率が、粘着性組成物中の感温性粘着剤の融点の近傍において、融点の近傍以外の温度域よりも大きい。
また、粘着性組成物の60℃におけるポリエチレンテレフタレート(PET)に対する剥離強度は、1.0N/25mm以上であることが好ましい。上記剥離強度の上限は特に限定されない。
粘着シートは、粘着性組成物からなる粘着層を備える。
上記の粘着シートは、粘着力が温度の低下にともない低下し、且つ、粘着力低下率が、感温性粘着剤の融点の近傍において、融点の近傍以外の温度域よりも大きいので、温度を調整することで、製造工程における被加工物を強固に仮止めしつつ、被加工物を破壊せずに剥離することができる。さらに、感温性粘着剤の屈折率が温度の低下にともない上昇し、且つ、屈折率上昇率が、融点の近傍において、融点の近傍以外の温度域よりも大きいので、粘着層のヘイズ値が低くなったり高くなったりすることで、接触温度計がないような場面でも粘着力の変化を視認することができる(例えば、高温時におけるポリマー微粒子と感温性粘着剤の屈折率差が大きくなるように各屈折率を調整すると、粘着層が白濁していることにより粘着力の発現を視認することができ、屈折率差が小さくなるように各屈折率を調整すると、粘着層が白濁していないことにより粘着力の発現を視認することができる)。そのため、上記の粘着シートは、以下の(1)又は(2)の被加工物の加工方法に好適に使用できる。
VA:日油(株)製のブレンマーVA(ベヘニルアクリレート)
MMA:東京化成工業(株)製のメタクリル酸メチル
St:東京化成工業(株)製のスチレン
A-HD-N:新中村化学工業(株)製のA-HD-N(1,6-ヘキサンジオールジアクリレート)
C1A:(株)日本触媒製のメチルアクリレート
AA:(株)日本触媒製のアクリル酸
NF-13:第一工業製薬(株)製のハイテノールNF-13
パーロイルL:日油(株)製のパーロイルL(ジラウロイルパーオキサイド)
パーブチルND:日油(株)製のパーブチルND(t-ブチルパーオキシネオデカノエート)
パーヘキシルPV:日油(株)製のパーヘキシルPV(t-ヘキシルパーオキシピバレート)
PZ33:(株)日本触媒製のケミタイトPZ33(アジリジン系架橋剤)
単官能モノマー、多官能モノマー、及び開始剤を表1に示す割合で反応容器に加えた。反応容器内の混合物を、均一に混ざるようヘラで撹拌した。次に、水性媒体と、表1に示す割合の乳化剤を反応容器に加え、混合液を得た。水性媒体としては、水を使用した。水性媒体は、混合液中の単官能モノマーの質量と水性媒体の質量との合計に対する単官能モノマーの質量の比率が40質量%であるように添加した。更に、IKA社製のホモジナイザー(本体:T 25 digital ULTRA-TURRAX、シャフトジェネレーター:S25N-25F)によって7500rpmで5分間混合液を攪拌し、モノマー成分を粒子状にした。最後に、混合液に窒素を導入してバブリングし、混合液中の空気(酸素)を除いた後、67℃で2時間、80℃で2時間、それぞれ加熱撹拌してモノマー成分を重合させた。そして、吸引ろ過、及び真空乾燥により、生成した微粒子から水性媒体を除去し、ポリマー微粒子1~3を得た。
ホモジナイザーによって2800rpmで5分間混合液を攪拌したこと以外は、ポリマー微粒子3の製造方法と同様にして、ポリマー微粒子4を得た。
ホモジナイザーによって2800rpmで2分間混合液を攪拌したこと以外は、ポリマー微粒子3の製造方法と同様にして、ポリマー微粒子5を得た。
マルバーン社製のレーザー回折式粒度分布計「マスターサイザー3000」を用いて、ポリマー微粒子の粒度分布を測定した。当該粒度分布において、ポリマー微粒子の粒子径の小さい方から計算した累積体積頻度が50%に相当する粒子径を「平均粒子径」とした。結果を表1に示した。
反応容器に表2に示す割合でモノマーを投入した。反応容器に、溶媒(酢酸エチル/ヘプタン=70/30(質量比))を加えて、モノマーの濃度が30質量%であるようにモノマーを希釈した。次に、モノマーの希釈液に窒素を導入してバブリングしながら、モノマーの希釈液を撹拌加熱した。液温が55℃になった時点で表2に示す割合で、モノマーの希釈液に開始剤を加えた。更に、55℃で4時間、反応容器内の液を加熱撹拌した後、オイルバスの温度を80℃に上げた。液温が70℃を超えた時点で表2に示す割合で、反応溶液内に促進剤を加えた。最後に、80℃で2時間加熱撹拌し、感温性粘着剤を得た。
ゲルパーミエーションクロマトグラフィー(GPC)で測定し、得られた測定値をポリスチレン換算した。結果を表2に示す。
セイコーインスツル(株)製のDSC(示差走査熱量計)を用いて10℃/分の掃引速度で-30~100℃の範囲を測定した際の吸熱ピークトップの温度から、感温性粘着剤の融点を測定した。結果を表2に示す。
得られたポリマー微粒子を溶剤(ヘプタン)に添加し、スパチュラで撹拌して分散液を得た。得られた感温性粘着剤に分散液を添加した。ポリマー微粒子及び感温性粘着剤は表3及び4に示す割合で添加し、溶剤は固形分濃度が25質量%になる割合で添加した。
この粘着性組成物に表3及び4に示す割合で禁止剤を添加してスパチュラで均一に撹拌した後、表3及び4に示す割合で架橋剤を添加した。粘着性組成物を、PETフィルム(厚み100μm)のコロナ処理した面にバーコーターにて塗布した。その後、PETフィルムを、熱風循環オーブンにて110℃3分間加熱乾燥することで、架橋した粘着性組成物からなる粘着層(厚み40μm)を備える粘着シート(実施例1~5)を得た。
得られたポリマー微粒子及び感温性粘着剤について、Anton Paar社製の自動屈折計「Abbemat 350」を用い、23℃及び60℃における屈折率を測定した。結果を表3及び4に示す。
得られた粘着シートの粘着層について、ASTM D1003に準拠し、コニカミノルタ(株)製の分光測色計「CM3600」(C光源)を用いて、23℃及び60℃におけるヘイズ値を測定した。ITOガラスをリファレンスとし、ITOガラス面に粘着シートを貼合して測定した。結果を表3及び4に示す。
得られた粘着シートについて、JIS Z0237に準拠し、23℃及び60℃におけるポリエチレンテレフタレート(PET)に対する180°剥離強度を測定した。具体的には、粘着シートをPETに貼合して20分間静置した後、ロードセルを用いて300mm/分の速度で180°剥離した。PETは、厚み25μmのフィルム状であって、未処理のものを使用した。PETに対する粘着シートの貼合は、粘着シートの上で2kgのローラーを5往復させることによって行った。結果を表3及び4に示す。
なお、粘着シートについて、23℃と60℃の間の温度でも剥離強度を測定し、粘着シートの1℃当たりの粘着力の低下量である粘着力低下率の変化を確認した。その結果、感温性粘着剤の融点である55℃近傍での粘着力低下率が、感温性粘着剤の融点の近傍以外の温度域よりも大きいことが確認された。
得られた粘着シートについて、JIS A5759:2016の6.5に準拠し、日本分光(株)製の分光光度計「V770DS」を用いて、23℃及び60℃における日射透過率を測定した。ただし、60℃に加温して測定するため、粘着シートを貼り付ける対象として、厚み1.1mmのITOガラス(ジオマテック社製の「GMT-100-12」)を用いた。具体的には、粘着シートをITOガラスの片面に貼り付けて試験片を作製した。23℃及び60℃(接触温度計によって測定されたITOガラスの表面温度)において、試験片のガラス面を光源に向けて、分光光度計により300~2500nmの各波長の分光透過率を測定した。JIS A5759:2016に規定されているように、日射の相対分光分布によって日射透過率を算出した。結果を表3及び4に示す。
得られた粘着シートについて、図5~7に示すようにして遮熱性を評価した。具体的には、粘着シート1をガラス板2に貼り付けて試験片を作製した。粘着シート面が上向きになるように、幅120mm×奥行200mm×高さ100mmの木枠4上に天面として試験片を置いた。ガラス面から10mm下の位置に温度計(熱電対)3を設置した。風除けとして木枠4の側面と底面をポリエチレンシートで覆った。試験片が置かれた木枠4を、地面6からの高さが1000mmとなるようにメタルラック5上に設置した。日射時(日射時間:約360分、平均気温:32℃)の熱電対3の温度上昇値を記録した。粘着シートを貼り付けていないガラス板をブランクの試験片とし、同様にして温度上昇値を記録した。ブランクの温度上昇値との差を算出した。結果を表3及び4に示す。
11 透光性基材層
12 粘着層
12a 感温性粘着剤
12b ポリマー微粒子
13 基材シート
20 第2の窓材
21a、21b 透光性基材層
22 粘着層
22a 感温性粘着剤
22b ポリマー微粒子
30 透光性屋根材
31 透光性基材層
32 粘着層
32a 感温性粘着剤
32b ポリマー微粒子
33 基材シート
Claims (15)
- 少なくとも1層の透光性基材層と、少なくとも1層の粘着層とを備え、
前記粘着層が、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物からなり、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
窓材。 - 前記感温性粘着剤が側鎖結晶性ポリマーを含み、
前記側鎖結晶性ポリマーは、炭素原子数14以上の直鎖状アルキル基を有する(メタ)アクリルモノマーに由来する構成単位を30~90質量%含む、請求項1に記載の窓材。 - 前記粘着層の60℃におけるヘイズ値と前記粘着層の23℃におけるヘイズ値の差が、10%以上である、請求項1に記載の窓材。
- 少なくとも1層の透光性基材層と、少なくとも1層の粘着層とを備え、
前記粘着層が、感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物からなり、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
透光性屋根材。 - 前記感温性粘着剤が側鎖結晶性ポリマーを含み、
前記側鎖結晶性ポリマーは、炭素原子数14以上の直鎖状アルキル基を有する(メタ)アクリルモノマーに由来する構成単位を30~90質量%含む、請求項4に記載の透光性屋根材。 - 前記粘着層の60℃におけるヘイズ値と前記粘着層の23℃におけるヘイズ値の差が、10%以上である、請求項4に記載の透光性屋根材。
- 請求項1~3のいずれか一項に記載の窓材、及び/又は請求項4~6のいずれか一項に記載の透光性屋根材を備える建築物。
- 請求項1~3のいずれか一項に記載の窓材、及び/又は請求項4~6のいずれか一項に記載の透光性屋根材を備える車両、船舶、又は航空機。
- 感温性粘着剤100質量部に対して、ポリマー微粒子1~100質量部を含有する粘着性組成物であって、
前記感温性粘着剤の屈折率が、温度の低下にともない上昇し、且つ、
1℃当たりの屈折率の上昇量である前記感温性粘着剤の屈折率上昇率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きく、
前記粘着性組成物の粘着力が、温度の低下にともない低下し、且つ、
1℃当たりの粘着力の低下量である前記粘着性組成物の粘着力低下率が、前記感温性粘着剤の融点の近傍において、前記感温性粘着剤の融点の近傍以外の温度域よりも大きい、
粘着性組成物。 - 粘着力が、60℃において1N/25mm以上であり、23℃において0.1N/mm以下である、請求項9に記載の粘着性組成物。
- 前記感温性粘着剤が側鎖結晶性ポリマーを含み、
前記側鎖結晶性ポリマーは、炭素原子数14以上の直鎖状アルキル基を有する(メタ)アクリルモノマーに由来する構成単位を30~90質量%含む、請求項9に記載の粘着性組成物。 - 請求項9~11のいずれか一項に記載の粘着性組成物からなる粘着層を備える粘着シート。
- 前記粘着層の60℃におけるヘイズ値と前記粘着層の23℃におけるヘイズ値の差が、10%以上である、請求項12に記載の粘着シート。
- 被加工物を、請求項12に記載の粘着シートが備える前記粘着層に接触させることと、
前記粘着層が白濁していること又は白濁していないことを確認することにより、前記粘着層が粘着力を発現していることを確認することと、
前記粘着層が発現した粘着力により前記粘着層上に固定された前記被加工物を加工することと、
前記粘着層が白濁していないこと又は白濁していることを確認することにより、前記粘着層が粘着力を発現していないことを確認することと、
加工された前記被加工物を、粘着力を発現していない前記粘着層上から取り除くことと、
を含む、被加工物の加工方法。 - 支持体と被加工物と、又は被加工物同士を、請求項12に記載の粘着シートが備える前記粘着層を介して接触させることと、
前記粘着層が白濁していること又は白濁していないことを確認することにより、前記粘着層が粘着力を発現していることを確認することと、
前記粘着層が発現した粘着力により、前記粘着層を介して前記支持体上に固定されている前記被加工物、又は前記粘着層を介して固定された複数の前記被加工物の少なくとも一つを加工することと、
前記粘着層が白濁していないこと又は白濁していることを確認することにより、前記粘着層が粘着力を発現していないことを確認することと、
加工された前記被加工物を、粘着力を発現していない前記粘着層上から取り除くことと、
を含む、被加工物の加工方法。
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| JP3337810B2 (ja) | 1993-03-01 | 2002-10-28 | アフィニティー株式会社 | 自律応答積層体、その製法およびそれを使用した窓 |
| JP2018178060A (ja) * | 2017-04-21 | 2018-11-15 | ニッタ株式会社 | 感温性粘着剤 |
| JP2019055580A (ja) * | 2017-09-21 | 2019-04-11 | ダイニック株式会社 | ドットインパクトプリンタ用インクリボンカセット |
| JP2021055089A (ja) * | 2019-09-30 | 2021-04-08 | ニッタ株式会社 | 調光フィルム用添加剤および感温性調光フィルム |
| JP2021125516A (ja) * | 2020-02-04 | 2021-08-30 | 株式会社巴川製紙所 | 半導体装置製造用粘着シート |
| JP2022013326A (ja) * | 2020-07-03 | 2022-01-18 | 住友化学株式会社 | 粘着剤層付き偏光板 |
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| WO2023182500A1 (ja) * | 2022-03-24 | 2023-09-28 | ニッタ株式会社 | 窓材及び透光性屋根材 |
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| JP3337810B2 (ja) | 1993-03-01 | 2002-10-28 | アフィニティー株式会社 | 自律応答積層体、その製法およびそれを使用した窓 |
| JP2018178060A (ja) * | 2017-04-21 | 2018-11-15 | ニッタ株式会社 | 感温性粘着剤 |
| JP2019055580A (ja) * | 2017-09-21 | 2019-04-11 | ダイニック株式会社 | ドットインパクトプリンタ用インクリボンカセット |
| JP2021055089A (ja) * | 2019-09-30 | 2021-04-08 | ニッタ株式会社 | 調光フィルム用添加剤および感温性調光フィルム |
| JP2021125516A (ja) * | 2020-02-04 | 2021-08-30 | 株式会社巴川製紙所 | 半導体装置製造用粘着シート |
| JP2022013326A (ja) * | 2020-07-03 | 2022-01-18 | 住友化学株式会社 | 粘着剤層付き偏光板 |
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