Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • 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
  • B32B7/027—Thermal properties
  • B32B7/028—Heat-shrinkability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
  • B60K35/00—Instruments specially adapted for vehicles; Arrangement of instruments in or on vehicles
  • B60K35/20—Output arrangements, i.e. from vehicle to user, associated with vehicle functions or specially adapted therefor
  • B60K35/21—Output arrangements, i.e. from vehicle to user, associated with vehicle functions or specially adapted therefor using visual output, e.g. blinking lights or matrix displays
  • B60K35/23—Head-up displays [HUD]
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • 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
  • C09J7/35—Heat-activated
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/01—Head-up displays
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/01—Head-up displays
  • G02B27/0101—Head-up displays characterised by optical features
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/08—Mirrors
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/08—Mirrors
  • G02B5/0808—Mirrors having a single reflecting layer
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/14—Digital output to display device ; Cooperation and interconnection of the display device with other functional units
  • G06F3/147—Digital output to display device ; Cooperation and interconnection of the display device with other functional units using display panels

Definitions

• the present invention relates to a laminate having a hard coat layer, a resin substrate, and a heat seal layer, a bonded body obtained by bonding this laminate to an object to be bonded, an image display system using this laminate, and a method for manufacturing a bonded body in which this laminate is bonded to an object to be bonded.
• a head-up display or head-up display system that projects an image onto the windshield glass of a vehicle, etc., and provides the driver with various information such as a map, driving speed, and the vehicle's condition.
• a virtual image including the above-mentioned various pieces of information is projected onto the windshield glass and is observed by the driver, etc.
• the position at which the virtual image is formed is located outside the vehicle and forward of the windshield glass.
• the position where the virtual image is formed is usually 1000 mm or more forward from the windshield glass, and is located closer to the outside world than the windshield glass. This allows the driver to obtain the above-mentioned various pieces of information while looking at the outside world in front of him/her without moving his/her line of sight significantly. Therefore, when using a head-up display system, it is expected that the driver can drive more safely while obtaining various pieces of information.
• a head-up display system is constructed, for example, by attaching a light-transmitting reflective film, such as a half-mirror film, to the windshield glass to form a projected image display section.
• a light-transmitting reflective film such as a half-mirror film
• Various types of such reflective films have been proposed.
• Patent Document 1 proposes an optical film that can be used as a display medium in a head-up display system, the optical film having an optical functional layer and a blocking layer, the blocking layer having a cured product of a resin composition containing a thermoplastic resin and an ultraviolet-curable resin.
• the optical functional layer include a half-wave plate, a quarter-wave plate, a laminate of a half-wave plate and a circularly polarized light reflective layer, and a laminate of a quarter-wave plate and a circularly polarized light reflective layer, etc.
• an example of the circularly polarized light reflective layer is a light reflective layer using a cholesteric liquid crystal.
• a reflective film used in a head-up display system is attached to glass such as a windshield glass.
• Windshield glass usually has a curved surface.
• a method for laminating a sheet-like material such as a reflective film to an object having such a curved surface a method conceptually shown in Fig. 6 is known which utilizes thermocompression bonding using a heat seal layer.
• a laminate 100 such as a reflective film laminated with a heat seal layer (not shown) is placed between an object 102 to be pasted having a curved surface such as a windshield glass and a mold 104 having a surface corresponding to the curved surface of the object 102 to be pasted, and then, as shown in the second part of FIG. 6, it is placed in a bag 106 such as a rubber bag.
• the pressure inside the bag 106 is reduced while heating, thereby forming a sandwiched body in which the laminate 100 is sandwiched between the object to be affixed 102 and the mold 104, and the laminate 100 (heat seal layer) is vacuum-heat-pressed to the object to be affixed 102.
• the sandwiching body is removed from the bag, and as shown in the third row of FIG. 6, the sandwiching body is heated and pressed using an autoclave, and further, the laminate 100 is heated and pressed to the object 102 to be pasted.
• the laminate is removed from the autoclave as shown in the lower part of Figure 6, and finally the mold 104 is removed from the laminate to obtain a laminate in which the laminate 100 is bonded to the object to be bonded 102.
• this method for producing a laminate the occurrence of wrinkles and the like can be suppressed and a laminate such as a reflective film having a heat seal layer can be laminated along the curved surface of an object to be laminated, such as a curved glass plate.
• this method for producing a laminate requires a mold having a surface that corresponds to the curved surface of the laminated object, and further requires the operation of removing the mold from the clamping body that holds the laminated object and the mold after lamination is completed, which is troublesome. Therefore, it is desired to bond a laminate having a heat seal layer to an object having a curved surface without using a mold.
• the object of the present invention is to solve the problems of the conventional technology and to provide a laminate that, when attached to a curved object, easily conforms to the curved surface of the object and also suppresses the occurrence of wrinkles after attachment, a bonded body using this laminate, an image display system using this laminate, and a method for manufacturing a bonded body in which this laminate is attached to the object.
• the present invention has the following configuration.
• a laminate comprising a windshield glass and the laminate according to any one of [1] to [10] attached to the windshield glass.
• An image display system comprising the laminate according to any one of [1] to [10] and an image display device that projects an image onto the laminate.
• a method for producing a laminate comprising: a step 2 of heat-pressing the laminate obtained in the step 1.
• the method for producing a laminate according to [14] comprising sandwiching a sheet-like member between the laminate and the bag and heating the laminate under reduced pressure.
• the present invention provides a laminate that can be attached to a curved object with good curve-following properties while suppressing the occurrence of wrinkles after bonding.
• FIG. 1 is a diagram conceptually illustrating an example of a laminate of the present invention.
• FIG. 2 is a conceptual diagram for explaining the method for producing a bonded body of the present invention.
• FIG. 2 is a conceptual diagram for explaining the method for producing a bonded body of the present invention.
• FIG. 1 is a diagram conceptually illustrating an example of an image display system of the present invention.
• FIG. 5 is a partially enlarged view of FIG. 4 .
• FIG. 1 is a conceptual diagram for explaining a conventional method for producing a bonded body.
• the laminate, bonded body, image display system, and method for manufacturing the bonded body of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
• the drawings described below are conceptual diagrams for explaining the present invention, and the present invention is not limited to the drawings. Therefore, the size, shape, and positional relationship of each member, as well as the thickness of each layer in the laminate and the thickness relationship between each layer, are different from the actual ones.
• the term "to" indicates a range of values, including the values written on both sides. For example, if ⁇ 1 is a value between ⁇ 1 and ⁇ 1 , the range of ⁇ 1 includes values ⁇ 1 and ⁇ 1 , and expressed in mathematical notation, ⁇ 1 ⁇ ⁇ 1 ⁇ ⁇ 1 .
• the laminate of the present invention has a hard coat layer, a resin substrate and a heat seal layer in this order, with the heat seal layer being positioned on the outermost side.
• FIG. 1 conceptually shows an example of the laminate of the present invention.
• the laminate 10 in the illustrated example has, from the bottom in the figure, a protective film 12, a hard coat layer 14, a resin substrate 16, a retardation layer 18, a reflective layer 20, a polarization conversion layer 24, and a heat seal layer 26.
• the protective film 12, the retardation layer 18, the reflective layer 20, and the polarization conversion layer 24 in the illustrated laminate 10 are provided as preferred embodiments and are not essential components.
• the laminate of the present invention may not have the protective film 12, or may not have one or more of the retardation layer 18, the reflective layer 20, and the polarization conversion layer 24.
• the laminate of the present invention can have various layer configurations as long as it has the hard coat layer 14, the resin substrate 16, and the heat seal layer 26 in this order, with the heat seal layer being positioned on the outermost side.
• various layers such as a linear polarizer and a filter can be used.
• a mold is used to hold the laminate together with the substrate, and vacuum heat pressing using a bag such as a rubber bag and heat pressing by an autoclave are performed to bond the laminate (heat seal layer) to the substrate.
• This method for producing a laminated body can adhere the laminate to the object to be laminated without causing wrinkles in the laminate and by suitably following the curved surface of the object to be laminated.
• this method for producing a laminated body requires a mold that corresponds to the curved surface of the object to be laminated, and further requires the removal of the mold after the laminate is adhered to the object to be laminated, which is time-consuming.
• the laminate of the present invention has a bending stiffness coefficient S of 5 ⁇ 10 6 [GPa ⁇ m 3 ] or more and has good stiffness. Therefore, the laminate of the present invention does not develop locally large wrinkles when it comes into contact with the substrate, and is pressed by a bag in a state of having small uniform wrinkles overall. Furthermore, the laminate of the present invention has an average heat shrinkage rate of 0.3% or more at 140° C. Therefore, wrinkles are eliminated by heat shrinkage during hot pressing in an autoclave. Therefore, the laminate of the present invention can be attached to an object having a curved surface without using a mold, with good conformability to the curved surface, and while suppressing the occurrence of wrinkles after attachment. This will be further explained below with reference to FIGS.
• the bending stiffness coefficient S is preferably 15 ⁇ 10 6 [GPa ⁇ m 3 ] or more, and more preferably 25 ⁇ 10 6 [GPa ⁇ m 3 ] or more.
• there is no upper limit to the bending stiffness coefficient S but it is preferably 3000 ⁇ 10 [GPa ⁇ m 3 ] or less, more preferably 300 ⁇ 10 [GPa ⁇ m 3 ] or less, and even more preferably 100 ⁇ 10 [GPa ⁇ m 3 ] or less.
• the average heat shrinkage rate at 140° C. is preferably 0.4% or more, and more preferably 0.6% or more.
• the upper limit of the average heat shrinkage rate at 140° C. is not limited, but it is preferably 5.0% or less.
• the average tensile elastic modulus and the average heat shrinkage rate for calculating the bending stiffness coefficient S may be measured by the methods described in the examples below. A specific method will be described in detail in the Examples, but when measuring the average tensile modulus, first, a sample piece of a predetermined size is cut out along the length direction in each direction rotated 45° clockwise from one direction based on one in-plane direction of the laminate. Next, the cut-out sample piece is placed in a tensile tester so that the chuck interval in the measurement direction is 100 mm, and stretched at a stretching speed of 300 mm/min under a condition of a measurement temperature of 25° C. so that the chuck interval widens, to obtain a stress-strain curve.
• the tensile modulus is calculated by linear regression of the obtained curve.
• the in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum tensile modulus is defined as the first direction
• the direction perpendicular to the first direction is defined as the second direction
• the average value of the tensile modulus in the first direction and the tensile modulus in the second direction is defined as the average tensile modulus of the laminate.
• a sample piece of a predetermined size is cut out along the length direction in each direction rotated 45° clockwise from one in-plane direction of the laminate as a reference.
• two reference lines are made in advance in the width direction of the cut-out sample piece so that the interval is 100 mm.
• the sample piece is left in a heating oven at 140° C. under no tension for 45 minutes, and then the sample piece is cooled to room temperature, and the interval between the two reference lines is measured.
• the thermal shrinkage of the sample piece is measured from the interval before the treatment and the interval after the treatment.
• the in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum thermal shrinkage of each sample piece is defined as the first direction, and the direction perpendicular to the first direction is defined as the second direction.
• the average value of the thermal shrinkage in the first direction and the thermal shrinkage in the second direction is defined as the average thermal shrinkage of the laminate.
• the lower limit of the average tensile elastic modulus is not particularly limited, but is preferably 0.01 GPa or more, and more preferably 0.1 GPa or more.
• the upper limit of the average tensile elastic modulus is not particularly limited, but is preferably 10.0 GPa or less, and more preferably 8.0 GPa or less.
• the lower limit of the thickness of the laminate is not particularly limited, but is preferably 100 ⁇ m or more, more preferably 150 ⁇ m or more.
• the upper limit of the thickness of the laminate is not particularly limited, but is preferably 1000 ⁇ m or less, more preferably 400 ⁇ m or less.
• the thickness of the laminate may be measured by the method described in the Examples below.
• the laminate 10 shown in FIG. 1 has, from the bottom in the figure, a protective film 12, a hard coat layer 14, a resin substrate 16, a retardation layer 18, a reflective layer 20, a polarization conversion layer 24, and a heat seal layer 26.
• a protective film 12 can be used from the viewpoints of suppressing transfer of unevenness of a bag when the laminate is placed in a bag such as a rubber bag and subjected to thermocompression bonding, preventing blocking during winding, and stabilizing transport.
• the protective film 12 is not an essential component of the laminate of the present invention.
• the protective film 12 is desirably applied to the surface of the hard coat layer 14 as shown in Fig. 1. More specifically, the protective film 12 is disposed on the side of the hard coat layer 14 opposite to the resin substrate 16 side.
• the protective film 12 may be provided on the hard coat layer 14 after the formation of the hard coat layer 14 and before the curved surface molding, or may be laminated on the hard coat layer 14 during the curved surface molding, for example.
• the protective film 12 may be peeled off at a stage when it is no longer needed during windshield processing, for example.
• Materials for the protective film 12 include resins such as polyethylene resins, polypropylene resins, polystyrene resins, and polyethylene terephthalate resins, nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubbers, acrylic rubbers, thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), and diene elastomers (1,2-polybutadiene, etc.), elastomers such as silicone elastomers, and fluorine elastomers.
• resins such as polyethylene resins, polypropylene resins, polystyrene resins, and polyethylene terephthalate resins
• nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubbers, acrylic rubbers
• the thickness of the protective film 12 is not particularly limited as long as the laminate satisfies the above bending elastic modulus, but is preferably 20 ⁇ m or more, more preferably 100 ⁇ m or more, and even more preferably 200 ⁇ m or more. There is no particular upper limit, but it is often 5000 ⁇ m or less.
• the tensile modulus of the protective film 12 is not particularly limited as long as the laminate satisfies the above bending elastic modulus, but is preferably 0.001 GPa or more, more preferably 0.01 GPa or more, even more preferably 0.1 GPa or more, and particularly preferably 1.0 GPa or more. There is no particular upper limit, but it is often 12.0 GPa or less.
• the tensile modulus of the protective film 12 can be changed, for example, by the material that constitutes the protective film 12, and generally, the tensile modulus tends to increase by increasing the molecular weight and/or crystallinity of the resin or elastomer.
• the tensile modulus of the protective film 12 in the stretching direction can be increased by stretching it. Even if the protective film 12 is made up of multiple layers, the tensile modulus refers to the tensile modulus of the protective film itself.
• the protective film 12 shrinks when exposed to heat.
• the protective film 12 is also produced through a process of stretching, and the stress caused by the stretching exists as residual stress. Therefore, this residual stress can be utilized to cause the protective film 12 to undergo thermal shrinkage by heating when conforming to a curved surface.
• the temperature at which the protective film 12 thermally shrinks varies depending on the material of the protective film 12, but it is preferable for it to shrink in the range of 80 to 200°C, and it is even more preferable for it to shrink in the range of 90 to 140°C, which is the heat treatment temperature in a typical curved surface conforming process. Heating for shrinking the protective film 12 may be applied to the entire curved glass, or may be applied locally to a portion having a high curvature and prone to insufficient conformity.
• the heat shrinkage rate of the protective film 12 is not particularly limited as long as the laminate satisfies the above heat shrinkage rate, but at 140°C, the average heat shrinkage rate in the direction in which the heat shrinkage rate is maximum and in the direction perpendicular to said direction is preferably 0.3 to 10.0%, and more preferably 0.3 to 5.0%.
• the heat shrinkage rate can be adjusted as appropriate by changing the stretching conditions when manufacturing the protective film 12.
• the protective film 12 may have an adhesive layer on at least one side, or may be a self-adhesive protective film with adhesive properties.
• the laminate 10 of the present invention has a hard coat layer (HC layer) 14 .
• the HC layer 14 provides abrasion resistance that makes it difficult to be scratched even when rubbed against a hard substance, scratch resistance that makes it difficult to be scratched even when pressed against a hard substance, and stain resistance that allows dirt to be easily wiped off even if dirt adheres to the surface.
• the HC layer 14 is preferably formed by polymerizing and curing at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in the molecule and fluorine-containing compounds having a polymerizable group in the molecule, and a polymerizable compound having a polymerizable group in the molecule other than these compounds, as described below, and it is more preferable that these polymerizable groups are radically polymerizable groups.
• the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds and the polymerizable compound forming the HC layer 14 exist in a bonded state, and more excellent antifouling properties can be imparted.
• the polymerizable group in the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds described below reacts to form a bond and exists in the HC layer 14.
• the compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds is contained at least in the HC layer farthest from the resin substrate 16, and more preferably, only the HC layer farthest from the resin substrate 16 contains the compound.
• the HC layer 14 farthest from the resin substrate is at least a cured film of the compound, and more preferably, only the HC layer 14 farthest from the resin substrate is a cured film of the compound.
• Specific embodiments of the HC layer 14 will be described below, but the present invention is not limited to the following embodiments.
• the fluorine-containing compound is not particularly limited as long as it can impart abrasion resistance and stain resistance to the HC layer 14, and any compound having a fluorine atom in the molecule can be used.
• a fluorine-containing antifouling agent that exhibits the properties of an antifouling agent is preferably used.
• the fluorine-containing compound may be any of a monomer, an oligomer, and a polymer.
• the fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with other components (e.g., polysiloxane-containing compounds, polymerizable monomers that are components of resins, and resins) in the HC layer 14.
• the substituents may be the same or different, and it is preferable that there are a plurality of them.
• the substituent is preferably a polymerizable group, and may be any polymerizable reactive group exhibiting any one of radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, and addition polymerization, and examples of preferred substituents include acryloyl, methacryloyl, vinyl, allyl, cinnamoyl, epoxy, oxetanyl, hydroxyl, polyoxyalkylene, carboxyl, and amino groups. Among them, radical polymerizable groups are preferred, and acryloyl or methacryloyl groups are more preferred.
• the fluorine-containing compound may be a polymer or oligomer with a compound not containing a fluorine atom.
• the polysiloxane-containing compound in the present invention is not particularly limited, and examples thereof include compounds having a polysiloxane structure in the molecule.
• the polysiloxane structure contained in the polysiloxane-containing compound may be any of linear, branched, and cyclic.
• a polysiloxane antifouling agent exhibiting antifouling properties is preferably used.
• the content of the polysiloxane-containing compound in the curable composition for forming an HC layer is preferably 0.01 to 5 mass%, more preferably 0.1 to 5 mass%, even more preferably 0.5 to 5 mass%, and particularly preferably 0.5 to 2 mass%, based on the total solid content in the curable composition for forming an HC layer.
• the amount of the polysiloxane-containing compound is intended to mean the amount added in the HC layer-forming curable composition that forms the HC layer 14 .
• the HC layer 14 can be obtained by irradiating the HC layer-forming curable composition with active energy rays and curing it.
• active energy rays refers to ionizing radiation, and includes X-rays, ultraviolet rays, visible light, infrared rays, electron beams, alpha rays, beta rays, gamma rays, etc.
• the HC layer-forming curable composition used to form the HC layer 14 contains at least one component having the property of being cured by irradiation with active energy rays (hereinafter, also referred to as "active energy ray curable component").
• active energy ray curable component at least one polymerizable compound selected from the group consisting of radical polymerizable compounds and cationic polymerizable compounds is preferable.
• the "polymerizable compound” refers to a compound having a polymerizable group in the molecule, and one or more polymerizable groups may be present in one molecule.
• the polymerizable group is a group that can participate in a polymerization reaction, and specific examples thereof include groups contained in various polymerizable compounds described below.
• the HC layer 14 is preferably obtained by irradiating with active energy rays a curable composition for forming an HC layer, which contains at least one compound selected from the group consisting of polysiloxane-containing compounds having a polymerizable group in the molecule and fluorine-containing compounds having a polymerizable group in the molecule, and a polymerizable compound having a polymerizable group in the molecule other than these compounds, to polymerize and cure the composition.
• the polymerizable group of the polysiloxane-containing compound, the fluorine-containing compound, and the polymerizable compound is a radical polymerizable group.
• the HC layer 14 may be of a single layer structure or a laminated structure of two or more layers, and an HC layer having a single layer structure or a laminated structure of two or more layers, which will be described in detail below, is preferred.
• a first embodiment is a curable composition for forming an HC layer that contains at least one polymerizable compound having two or more ethylenically unsaturated groups in one molecule.
• An ethylenically unsaturated group refers to a functional group that contains an ethylenically unsaturated double bond.
• a second embodiment is a curable composition for forming an HC layer that contains at least one radically polymerizable compound and at least one cationic polymerizable compound.
• the curable composition for forming the HC layer preferably contains a polymerization initiator, more preferably contains a photopolymerization initiator.
• the curable composition for forming the HC layer containing a radical polymerizable compound preferably contains a radical photopolymerization initiator
• the curable composition for forming the HC layer containing a cationic polymerizable compound preferably contains a cationic photopolymerization initiator. Only one type of radical photopolymerization initiator may be used, or two or more types with different structures may be used in combination. This point is also true for the cationic photopolymerization initiator.
• each photopolymerization initiator will be described in order.
• the radical photopolymerization initiator may be any one capable of generating radicals as active species upon irradiation with light, and any known radical photopolymerization initiator may be used without any limitations.
• the radical photopolymerization initiator and auxiliary can be synthesized by a known method, and are also available as commercial products.
• the content of the radical photopolymerization initiator in the curable composition for forming the HC layer is not particularly limited and may be appropriately adjusted within a range that allows the polymerization reaction (radical polymerization) of the radical polymerizable compound to proceed smoothly.
• the content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound contained in the curable composition for forming the HC layer.
• the cationic photopolymerization initiator may be any that can generate cations as active species upon irradiation with light, and any known cationic photopolymerization initiator may be used without any restrictions.
• cationic photopolymerization initiator in terms of the sensitivity of the photopolymerization initiator to light, the stability of the compound, etc., diazonium salts, iodonium salts, sulfonium salts, or iminium salts are preferred. In terms of weather resistance, iodonium salts are preferred.
• iodonium salt-based cationic photopolymerization initiators include Tokyo Chemical Industry Co., Ltd.'s B2380, Midori Chemical Industry Co., Ltd.'s BBI-102, Wako Pure Chemical Industries Co., Ltd.'s WPI-113, Wako Pure Chemical Industries Co., Ltd.'s WPI-124, Wako Pure Chemical Industries Co., Ltd.'s WPI-169, Wako Pure Chemical Industries Co., Ltd.'s WPI-170, and Toyo Synthetic Chemical Co., Ltd.'s DTBPI-PFBS.
• the content of the cationic photopolymerization initiator in the curable composition for forming the HC layer is not particularly limited and may be appropriately adjusted within a range that allows the polymerization reaction (cationic polymerization) of the cationic polymerizable compound to proceed smoothly. It is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and even more preferably 2 to 100 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound.
• photopolymerization initiators include those described in paragraphs 0052 to 0055 of JP 2009-204725 A, the contents of which are incorporated herein by reference.
• the curable composition for forming the HC layer contains at least one component having a property of being cured by irradiation with active energy rays and a compound selected from the group consisting of polysiloxane-containing compounds and fluorine-containing compounds, and may optionally contain, and preferably contains, at least one polymerization initiator, the details of which are as described above.
• the curable composition for forming the HC layer also preferably contains a solvent.
• the solvent is preferably an organic solvent, and one or more organic solvents may be used in any ratio.
• the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol.
• cyclohexanone methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl acetate and methyl acetate in any desired ratio.
• the amount of the solvent in the curable composition for forming the HC layer can be appropriately adjusted within a range that ensures the coating suitability of the composition.
• the content of the solvent is preferably 50 to 500 parts by mass, more preferably 80 to 200 parts by mass, based on 100 parts by mass of the total amount of the polymerizable compound and the photopolymerization initiator.
• the proportion of the solid content of the HC-forming curable composition is preferably 10 to 90 mass %, more preferably 50 to 80 mass %, and even more preferably 65 to 75 mass %, based on the total mass of the HC-forming curable composition.
• the curable composition for forming the HC layer may contain any amount of one or more known additives, such as a surface conditioner, a polymerization inhibitor, and polyrotaxane.
• a surface conditioner such as a silicone dioxide, a silicone dioxide, and alumilicates.
• a polymerization inhibitor such as a polymerization inhibitor, and polyrotaxane.
• the additives are not limited to these, and various additives that can generally be added to the curable composition for forming the HC layer can be used.
• the curable composition for forming the HC layer can be prepared by mixing the various components described above simultaneously or sequentially in any order. There are no particular limitations on the preparation method, and a known mixer or the like can be used for preparation.
• the thickness of the HC layer 14 is preferably 1 ⁇ m or more, more preferably 1 to 100 ⁇ m, even more preferably 1 to 20 ⁇ m, particularly preferably 3 to 20 ⁇ m, and most preferably 5 to 20 ⁇ m.
• the thickness of the HC layer 14 is measured by cutting the HC layer 14 with a microtome to extract a cross section, staining it overnight with an approximately 3% by mass aqueous solution of osmium tetroxide, then cutting out the surface again and observing the cross section using a SEM (Scanning Electron Microscope).
• the HC layer can be formed by applying the curable composition for forming the HC layer and irradiating it with active energy rays.
• the coating can be carried out by a known coating method such as dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, or gravure coating.
• the HC layer can also be formed as a laminated HC layer having two or more layers (eg, about 2 to 5 layers) by simultaneously or successively applying two or more compositions having different compositions.
• the applied HC layer-forming curable composition is irradiated with active energy rays, whereby the HC layer can be formed.
• the HC layer-forming curable composition contains a radical polymerizable compound, a cationic polymerizable compound, a radical photopolymerization initiator, and a cationic photopolymerization initiator
• the polymerization reaction of the radical polymerizable compound and the cationic polymerizable compound can be initiated and progressed by the action of the radical photopolymerization initiator and the cationic photopolymerization initiator, respectively.
• the wavelength of the light to be irradiated may be determined according to the type of the polymerizable compound and the polymerization initiator used.
• Examples of light sources for light irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and LEDs (Light Emitting Diodes) that emit light in the 150 to 450 nm wavelength band.
• the light irradiation amount is preferably 30 to 3000 mJ/ cm2 , more preferably 100 to 1500 mJ/ cm2 .
• Drying treatment may be performed before or after the light irradiation, or both, if necessary. Drying treatment may be performed by blowing hot air, placing in a heating furnace, transporting in the heating furnace, or the like.
• the heating temperature is not particularly limited as long as it is set to a temperature at which the solvent can be dried and removed.
• the heating temperature refers to the temperature of hot air or the atmospheric temperature in a heating furnace.
• the laminate 10 includes a resin base material 16 .
• a resin base material 16 There are no particular limitations on the material of the resin base material 16, so long as the laminate 10 satisfies the above-mentioned requirements for the flexural modulus and thermal shrinkage rate.
• the resin base material 16 is preferably transparent in the visible light region.
• the resin substrate 16 there are no particular limitations on the material of the resin substrate 16.
• the resin substrate 16 include plastic films such as polyesters such as polyethylene terephthalate (PET), polycarbonates, acrylic resins, epoxy resins, polyurethanes, polyamides, polyimides, polyolefins, cellulose derivatives, and silicones.
• the resin substrate 16 is preferably a cellulose acylate film.
• the thickness of the resin substrate 16 is not particularly limited as long as the laminate satisfies the above bending elastic modulus, but is preferably 10 ⁇ m or more, more preferably 25 ⁇ m or more, and even more preferably 40 ⁇ m or more. There is no particular upper limit, but it is often 500 ⁇ m or less.
• the tensile modulus of the resin substrate 16 is not particularly limited as long as the laminate satisfies the above bending modulus of elasticity, but is preferably 1.0 GPa or more, more preferably 2.5 GPa or more, even more preferably 3.0 GPa or more, particularly preferably 3.5 GPa or more, and most preferably 4.0 GPa or more. There is no particular upper limit, but it is often 12.0 GPa or less.
• the tensile modulus of the resin substrate 16 can be changed, for example, depending on the type of resin that constitutes the resin substrate 16, and generally, the tensile modulus tends to increase by increasing the molecular weight and/or crystallinity of the resin.
• the tensile modulus of the resin substrate 16 in the stretching direction can also be increased by stretching the resin substrate 16. Even if the resin substrate 16 is made up of multiple layers, the tensile modulus refers to the tensile modulus of the resin substrate 16 itself.
• the resin substrate 16 may be formed into a film by any method, such as a melt casting method or a solution casting method.
• the melt film-forming method preferably includes a melting step of melting the resin in an extruder, a step of extruding the molten resin from a die into a sheet, and a step of forming the resin into a film.
• a filtering step of the molten resin may be provided after the melting step, or the resin may be cooled when extruded into a sheet.
• the method for producing the resin substrate preferably includes a melting step of melting the resin in an extruder, a filtration step of filtering the molten resin through a filtration device equipped with a filter, a film forming step of extruding the filtered resin into a sheet form from a die and bringing it into close contact with a cooling drum to cool and solidify it into an unstretched resin substrate, and a stretching step of uniaxially or biaxially stretching the unstretched resin substrate.
• a resin substrate can be manufactured. If the pore size of the filter used in the filtration process of the molten resin is 1 ⁇ m or less, foreign matter can be sufficiently removed. As a result, the surface roughness in the film width direction of the obtained resin substrate can be controlled.
• the method for forming the resin substrate may include the following steps.
• the method for producing the resin substrate includes a melting step of melting the resin in an extruder. It is preferable to dry the resin or the mixture of the resin and the additives to a moisture content of 200 ppm or less, and then introduce it into a single-screw (single-screw) or twin-screw extruder and melt it. At this time, it is also preferable to melt it in nitrogen or vacuum in order to suppress decomposition of the resin.
• paragraphs 0051 to 0052 of Japanese Patent No. 4962661 paragraphs 0085 to 0086 of US 2013/0100378) can be used as references, and the method can be carried out according to these publications, and the contents of these publications are incorporated herein.
• the extruder is preferably a single screw kneading extruder. Furthermore, it is also preferable to use a gear pump in order to increase the precision with which the molten resin (melt) is delivered.
• the method for producing the resin substrate includes a filtration step of filtering the molten resin through a filtering device equipped with a filter, and the pore size of the filter used in the filtration step is preferably 1 ⁇ m or less.
• the filtration device having filters with pore sizes in this range may be installed in one set or in two or more sets in the filtration step.
• the method for producing the resin substrate includes a film forming step in which the filtered resin is extruded through a die into a sheet and then brought into close contact with a cooling drum to cool and solidify the sheet into an unstretched resin substrate.
• the resin (melt containing the resin) that has been melted (and kneaded) and filtered is extruded from a die into a sheet shape, it may be extruded as a single layer or as a multilayer.
• a layer containing an ultraviolet absorbing agent and a layer not containing an ultraviolet absorbing agent may be laminated, and more preferably, a three-layer structure in which a layer containing an ultraviolet absorbing agent is an inner layer is preferred in terms of suppressing deterioration of the polarizer due to ultraviolet rays and suppressing bleeding out of the ultraviolet absorbing agent.
• the thickness of the inner layer of the resulting resin substrate is preferably 50 to 99%, more preferably 60 to 99%, and even more preferably 70 to 99% of the total thickness of the layers.
• Such lamination can be carried out by using a feed block die and a multi-manifold die.
• JP 2009-269301 A it is preferable to extrude the resin (melt containing the resin) extruded from a die into a sheet shape onto a cooling drum (casting drum), cool and solidify it, and obtain an unstretched resin substrate (raw material).
• the temperature of the resin extruded from the die is preferably 280 to 320° C., more preferably 285 to 310° C. It is preferable that the temperature of the resin extruded from the die in the melting step is 280° C. or higher, since it is possible to reduce the amount of unmelted raw resin and suppress the generation of foreign matter. It is preferable that the temperature of the resin extruded from the die in the melting step is 320° C. or lower, since it is possible to reduce the decomposition of the resin and suppress the generation of foreign matter.
• the temperature of the resin extruded from the die can be measured without contacting the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, emissivity 0.95).
• the temperature of the resin when it is brought into close contact with the cooling drum is preferably 280° C. or higher. This increases the electrical conductivity of the resin, allowing it to be strongly adhered to the cooling drum by applying static electricity, and suppresses roughness of the film surface.
• the temperature of the resin when it is brought into close contact with the cooling drum can be measured without contacting the surface of the resin using a radiation thermometer (manufactured by Hayashi Denko, model number: RT61-2, emissivity 0.95).
• the method for producing the resin substrate includes a stretching step of uniaxially or biaxially stretching an unstretched resin substrate.
• the longitudinal stretching process a process of stretching in the same direction as the film transport direction
• the resin substrate is preheated and then stretched in the transport direction by a group of rollers having different peripheral speeds (i.e., different transport speeds) while the resin substrate is in a heated state.
• the preheating temperature in the longitudinal stretching process is preferably Tg-40°C or more and Tg+60°C or less, more preferably Tg-20°C or more and Tg+40°C or less, and even more preferably Tg or more and Tg+30°C or less, relative to the glass transition temperature (Tg) of the resin substrate.
• the stretching temperature in the longitudinal stretching process is preferably Tg or more and Tg+60°C or less, more preferably Tg+2°C or more and Tg+40°C or less, and even more preferably Tg+5°C or more and Tg+30°C or less.
• the longitudinal stretching ratio is preferably 1.0 to 2.5 times, and more preferably 1.1 to 2 times.
• the resin substrate is stretched laterally in the width direction by a transverse stretching process (a process in which the substrate is stretched in a direction perpendicular to the film transport direction).
• a transverse stretching process for example, a tenter can be suitably used, which holds both ends of the resin substrate in the width direction with clips and stretches the substrate in the transverse direction. This transverse stretching can increase the tensile modulus of the resin substrate.
• Transverse stretching is preferably performed using a tenter, and the preferred stretching temperature is from Tg to Tg + 60°C, more preferably from Tg + 2°C to Tg + 40°C, and even more preferably from Tg + 4°C to Tg + 30°C, relative to the glass transition temperature (Tg) of the resin substrate.
• the stretching ratio is preferably 1.0 to 5.0 times, and more preferably 1.1 to 4.0 times. It is also preferable to relax the resin substrate in either the longitudinal direction or the transverse direction, or both, after transverse stretching.
• the variation in thickness in both the width direction and the length direction depending on the location be 10% or less, more preferably 8% or less, even more preferably 6% or less, particularly preferably 4% or less, and most preferably 2% or less.
• the thickness variation can be calculated as follows:
• a 10m (meter) sample of the stretched resin substrate is taken, and 20% of each end of the film width direction is removed. 50 samples are taken at equal intervals in both the width direction and length direction from the center of the film, and the thickness is measured.
• Th TD-av The average thickness in the width direction, Th TD-av , the maximum thickness, Th TD-max , and the minimum thickness, Th TD-min , are determined; (Th TD-max - Th TD-min ) ⁇ Th TD-av ⁇ 100 [%] is the thickness variation in the width direction.
• the average thickness value Th MD-av , the maximum value Th MD-max , and the minimum value Th MD-min in the longitudinal direction are determined, (Th MD-max - Th MD-min ) ⁇ Th MD-av ⁇ 100 [%] is the thickness variation in the longitudinal direction.
• the above-mentioned stretching process can improve the thickness accuracy of the resin substrate.
• the stretched resin substrate can be wound into a roll in a winding process. At that time, the winding tension of the resin substrate is preferably 0.02 kg/mm2 or less .
• the process includes a step of casting a dope solution onto a casting band to form a cast film, a step of drying the cast film, and a step of stretching the cast film.
• it is preferable to employ the following method. For example, a method described in JP-A-11-123732 in which the drying speed of the casting film is set to 300% by mass/min ( 5% by mass/s) or less in terms of the amount of solvent contained on a dry basis, and gentle drying is performed.
• the core layer is preferably formed by casting the core layer.
• the viscosity of the dope to be formed is increased to ensure the strength of the cast film and the viscosity of the dope to form the outer layer is decreased.
• a method in which a film is formed and the surface state is smoothed by a leveling effect of the formed film is also preferred.
• the resin base material 16 it is desirable for the resin base material 16 to shrink when exposed to heat. When the laminate is made to conform to a curved glass surface, excess parts of the flat laminate will be produced in comparison to the curved glass, making it difficult to conform to the curved surface. It is preferable for the resin base material 16 to shrink when exposed to heat, as this causes the excess parts of the laminate to shrink and enable it to conform to the curved surface.
• the manufacturing process of the resin substrate includes a process of stretching, and the stress due to stretching exists as a residual stress. Therefore, this residual stress can be utilized to cause thermal shrinkage by heating during curved surface following. It is presumed that this thermal shrinkage allows the substrate to follow the curved glass.
• the portion where the following is insufficient is likely to occur in the portion of the glass near the outer periphery of the curved glass where the curvature is large, and is unlikely to occur in the portion of the glass where the curvature is small.
• a laminate using a thermally shrinkable resin substrate has the effect of effectively suppressing the occurrence of insufficient following in the portion of the glass where the curvature is large.
• the laminate In the portion of the glass where the curvature is large, the laminate has a degree of freedom to expand in the thickness direction, and shrinks in the surface direction, while in the portion of the glass where the curvature is small, the laminate has a small degree of freedom to expand in the thickness direction, and shrinks almost not in the surface direction. This is considered to be the mechanism of action.
• the temperature at which the resin base material 16 thermally shrinks varies depending on the material from which the resin base material 16 is formed, but it is preferable for the resin base material 16 to shrink in the range of 80 to 200°C, and more preferably in the range of 90 to 140°C, which is the heating treatment temperature in a typical curved surface conforming process. Heating for shrinking the resin base material 16 may be performed on the entire curved glass, or may be performed locally on a portion where the curvature is high and insufficient conformity is likely to occur.
• the amount of shrinkage of the resin substrate 16 required to prevent insufficient conformity varies depending on the curvature and dimensions of the glass.
• the thermal shrinkage rate of the resin substrate 16 there are no particular limitations on the thermal shrinkage rate of the resin substrate 16 as long as it satisfies the above-mentioned thermal shrinkage rate when it is formed into a laminate, but at 140°C, the average thermal shrinkage rate in the direction in which the thermal shrinkage rate is maximum and in the direction perpendicular to said direction is preferably 0.3 to 5.0%, more preferably 0.3 to 3.0%, and even more preferably 0.3 to 2.0%.
• the thermal shrinkage rate can be adjusted as appropriate by adjusting the stretching conditions when manufacturing the resin substrate.
• the laminate 10 has a retardation layer 18.
• the retardation layer 18 is not an essential component of the laminate of the present invention.
• the retardation layer 18 changes the state of the incident polarized light by imparting a phase difference (optical path difference) to two orthogonal polarized light components.
• the front retardation of the retardation layer may be set to a retardation that provides optical compensation.
• the retardation layer 18 preferably has a front retardation of 50 to 160 nm at a wavelength of 550 nm.
• the angle of the slow axis is preferably 10 to 50° or ⁇ 50 to ⁇ 10°.
• the retardation layer 18 converts linearly polarized light into circularly polarized light
• the retardation layer 18 is preferably configured to give a front retardation of ⁇ /4, and may be configured to give a front retardation of 3 ⁇ /4.
• the angle of the slow axis may be arranged so as to be oriented in such a way that the incident linearly polarized light is converted into circularly polarized light.
• the retardation layer 18 preferably has a front retardation at a wavelength of 550 nm in the range of 100 to 450 nm, more preferably in the range of 120 to 200 nm or 300 to 400 nm.
• the direction of the slow axis of the retardation layer 18 is preferably determined according to the incident direction of the projection light for projecting an image when the laminate is used in a head-up display system, and the sense of the helix of the cholesteric liquid crystal layer that constitutes the reflective layer.
• the retardation layer 18 is not particularly limited and can be appropriately selected depending on the purpose.
• Examples of the retardation layer 18 include a stretched polycarbonate film, a stretched norbornene-based polymer film, a transparent film containing and oriented inorganic particles having birefringence such as strontium carbonate, a thin film formed by obliquely depositing an inorganic dielectric on a support, a film in which a polymerizable liquid crystal compound is uniaxially oriented and oriented, and a film in which a liquid crystal compound is uniaxially oriented and oriented.
• a film in which a polymerizable liquid crystal compound is uniaxially aligned and fixed is a suitable example of the retardation layer 18 .
• a retardation layer 18 can be formed by applying a liquid crystal composition containing a polymerizable liquid crystal compound to a transparent substrate, a temporary support, or the surface of an alignment layer, forming the polymerizable liquid crystal compound in the liquid crystal composition into a nematic alignment in a liquid crystal state, and then fixing the alignment by curing.
• the retardation layer 18 may be a layer obtained by applying a composition containing a polymer liquid crystal compound to the surface of a transparent substrate, a temporary support, an alignment layer, or the like, forming a nematic alignment in the liquid crystal state, and then fixing the alignment by cooling.
• the thickness of the retardation layer 18 is not particularly limited, but is preferably 0.2 to 300 ⁇ m, more preferably 0.5 to 150 ⁇ m, and even more preferably 1.0 to 80 ⁇ m.
• the thickness of the retardation layer 18 formed from the liquid crystal composition is not particularly limited, but is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 5.0 ⁇ m, and even more preferably 0.7 to 2.0 ⁇ m.
• the laminate 10 includes a reflective layer 20.
• the reflective layer 20 is not an essential component of the laminate of the present invention.
• the reflective layer 20 is a layer that reflects a part or all of visible light, and is not particularly limited, and examples thereof include a layer containing metal, a layer in which dielectric materials are stacked, and a layer containing liquid crystal.
• the reflective layer 20 preferably includes a cholesteric liquid crystal layer having a selective reflection central wavelength in the red wavelength region, a cholesteric liquid crystal layer having a selective reflection central wavelength in the green wavelength region, and a cholesteric liquid crystal layer having a selective reflection central wavelength in the blue wavelength region.
• the three cholesteric liquid crystal layers have different selective reflection central wavelengths.
• Each cholesteric liquid crystal layer may be in direct contact with any other cholesteric liquid crystal layer.
• a cholesteric liquid crystal layer is a layer in which liquid crystal compounds are fixed in a helical oriented state of the cholesteric liquid crystal phase, and it reflects light with a selective reflection center wavelength that corresponds to the pitch of the helical structure, and transmits light in other wavelength ranges.
• cholesteric liquid crystal layers exhibit selective reflectivity for either left-handed or right-handed circularly polarized light at specific wavelengths.
• the reflective layer 20 satisfy the following requirements (i) to (iii).
• the maximum value of the natural light reflectance is more than 7% (preferably more than 20%)
• the difference between the maximum and minimum values of the natural light reflectance is 3% or more
• the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values of the natural light reflectance is 20 to 80 nm.
• the maximum value of natural light reflectance is more than 7% (preferably more than 20%), the difference between the maximum and minimum values of natural light reflectance is 3% or more, and the total value of the wavelength bandwidth of the region higher than the average value of the maximum and minimum values of natural light reflectance is 20 to 80 nm.
• the maximum natural light reflectance is more than 7% (preferably, 20% or more), and the total wavelength bandwidth of the region higher than the average value of the maximum and minimum natural light reflectance is 120 nm or more.
• the reflected wavelength and reflectance can be adjusted by the selective reflection center wavelength and thickness (helical pitch number) of the cholesteric liquid crystal layer, etc.
• a cholesteric liquid crystal layer that mainly reflects light in the blue wavelength region can realize reflection that satisfies requirement (i)
• a cholesteric liquid crystal layer that reflects light in the green wavelength region can realize reflection that satisfies requirement (ii)
• a cholesteric liquid crystal layer that reflects light in the red wavelength region can realize reflection that satisfies requirement (iii).
• the maximum value of the natural light reflectance at 400 nm or more and less than 500 nm is preferably more than 7%, more preferably 20% or more. There is no particular upper limit, but it is often, for example, 35% or less.
• the maximum natural light reflectance at 500 nm or more and less than 600 nm is preferably more than 7%, more preferably 20% or more. There is no particular upper limit, but it is often, for example, 35% or less.
• the maximum natural light reflectance in the range of 600 to 800 nm is preferably more than 7%, more preferably 20% or more. There is no particular upper limit, but it is often, for example, 35% or less.
• the difference between the maximum and minimum natural light reflectance values at 400 nm or more and less than 500 nm is preferably 4 to 20%, and more preferably 4 to 12%.
• the difference between the maximum and minimum natural light reflectance values at 500 nm or more and less than 600 nm is preferably 4 to 20%, and more preferably 4 to 12%.
• the wavelength band width of the region in which the reflectance is higher than the average value of the maximum and minimum reflectance values of 400 nm or more and less than 500 nm is preferably 30 to 78 nm, and more preferably 35 to 75 nm.
• the wavelength bandwidth of the region in which the reflectance is higher than the average value of the maximum and minimum reflectance values in the range of 500 nm or more and less than 600 nm is preferably 30 to 78 nm, and more preferably 35 to 75 nm.
• the wavelength band width from 400 nm to less than 500 nm and from 500 nm to less than 600 nm the more advantageous it is for the transmittance, but since the wavelength band width from 600 to 800 nm is wide, if the wavelength band width from 400 nm to less than 500 nm and/or the wavelength band width from 500 nm to less than 600 nm is too narrow, the reflected color may deteriorate. From this point of view, it is preferable that the wavelength band width from 400 nm to less than 500 nm and the wavelength band width from 500 nm to less than 600 nm are within the above ranges. Moreover, the wavelength band width of 500 nm or more and less than 600 nm has a larger effect on the transmittance.
• the wavelength band width of the region where the reflectance is higher than the average of the maximum and minimum reflectance values from 600 to 800 nm is preferably 120 to 200 nm.
• the reflective layer 20 preferably has two or more cholesteric liquid crystal layers with different selective reflection center wavelengths.
• each cholesteric liquid crystal layer is preferably in direct contact with any other cholesteric liquid crystal layer.
• the thickness between the layers will be thicker, making it difficult to obtain the effect of interference of the light reflected by each cholesteric liquid crystal layer.
• a configuration in which the cholesteric liquid crystal layers are in contact with each other is preferable because it is possible to narrow the wavelength band width by the effect of interference of the light reflected by each cholesteric liquid crystal layer.
• the thickness of each cholesteric liquid crystal layer is thinner than the wavelength of light (visible light 380 to 780 nm), the effect of interference becomes more pronounced, which is preferable.
• the cholesteric liquid crystal layers are not limited to being in direct contact with each other, but may be stacked via an adhesive layer or the like.
• each cholesteric liquid crystal layer may have at least one selective reflection center wavelength, but at least one of the cholesteric liquid crystal layers may have two or more selective reflection center wavelengths.
• a cholesteric liquid crystal layer having two or more selective reflection center wavelengths is achieved by a helical structure in which the helical pitch changes in the thickness direction.
• the total thickness of the reflective layer 20 is preferably 0.4 to 2.0 ⁇ m, more preferably 0.6 to 1.8 ⁇ m, and even more preferably 0.8 to 1.4 ⁇ m.
• the laminate 10 has a polarization conversion layer 24.
• the polarization conversion layer 24 is not an essential component of the laminate of the present invention.
• the polarization conversion layer 24 is a layer in which the helical orientation structure of a liquid crystal compound is fixed, and it is preferable that the pitch number x of the helical orientation structure and the film thickness y (unit: ⁇ m) of the polarization conversion layer satisfy all of the following relational expressions (a) to (c): 0.1 ⁇ x ⁇ 1.0... Formula (a) 0.5 ⁇ y ⁇ 3.0... Formula (b) 3000 ⁇ (1560 ⁇ y)/x ⁇ 50000...
• One pitch of the helical structure of a liquid crystal compound is one turn of the helix of the liquid crystal compound. That is, one pitch is defined as a state in which the director of the helically aligned liquid crystal compound (the long axis direction in the case of rod-shaped liquid crystal) rotates 360°.
• the polarization conversion layer 24 When the polarization conversion layer 24 has a helical structure of a liquid crystal compound, it exhibits optical rotation and birefringence for visible light, which has a shorter wavelength than the reflection peak wavelength in the infrared range. This allows for control of polarization in the visible range.
• the pitch number x of the helical orientation structure of the polarization conversion layer 24 and the film thickness y of the polarization conversion layer within the above ranges, it is possible to impart the polarization conversion layer with the function of optically compensating for visible light, or the function of converting linearly polarized light (p-polarized light) incident on the laminate into circularly polarized light.
• the polarization conversion layer 24 exhibits optical rotation and birefringence for visible light because the liquid crystal compound has a helical structure that satisfies the relational expressions (a) to (c).
• the pitch P of the helical structure of the polarization conversion layer 24 is set to a length that corresponds to the pitch P of the cholesteric liquid crystal layer, whose selective reflection center wavelength is in the long infrared wavelength range, the polarization conversion layer 24 exhibits high optical rotation and birefringence for short wavelength visible light.
• the relational expression (a) is "0.1 ⁇ x ⁇ 1.0".
• the pitch number x of the helical structure is 0.1 or more, sufficient optical rotation and birefringence are obtained, which is preferable.
• the pitch number x of the helical structure is 1.0 or less, the optical rotation and birefringence are sufficient, and the desired elliptically polarized light is easily obtained.
• the relationship (b) is "0.5 ⁇ y ⁇ 3.0".
• the thickness y of the polarization conversion layer is 0.5 ⁇ m or more, sufficient optical rotation and birefringence can be obtained.
• the thickness y of the polarization conversion layer is 3.0 ⁇ m or less, the optical rotation and birefringence are sufficient, and the desired circularly polarized light is easily obtained.
• the relationship (c) is "3000 ⁇ (1560 ⁇ y)/x ⁇ 50000".
• (1560 x y)/x" is 3000 or more, the desired polarization is easily obtained.
• (1560 x y)/x" is 50,000 or less, a desired polarization is easily obtained.
• the pitch number x of the helical structure of the polarization conversion layer 24 is more preferably 0.1 to 0.8, and the film thickness y is more preferably 0.6 to 2.6 ⁇ m.
• "(1560 ⁇ y)/x" is more preferably 5000 to 13000.
• the pitch P of the helical structure of the polarization conversion layer 24 is long and the pitch number x is small.
• the polarization conversion layer 24 has a helical pitch P equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection central wavelength in the long infrared wavelength range, and a small pitch number x.
• the polarization conversion layer 24 has a helical pitch P equivalent to the pitch P of a cholesteric liquid crystal layer having a selective reflection central wavelength of 3000 to 10000 nm, and a small pitch number x.
• the selective reflection central wavelength corresponding to the pitch P is much longer than the wavelength of visible light, and therefore the polarization conversion layer 24 more suitably exhibits the optical rotation property and birefringence for visible light described above.
• Such a polarization conversion layer 24 can basically be formed in the same way as a known cholesteric liquid crystal layer. However, when forming the polarization conversion layer 24, it is preferable to adjust the liquid crystal compound used, the chiral agent used, the amount of chiral agent added, the film thickness, etc. so that the pitch number x and film thickness y [ ⁇ m] of the helical structure in the polarization conversion layer 24 satisfy all of the relational expressions (a) to (c).
• the laminate 10 has a heat seal layer 26 .
• the heat seal layer 26 is a layer for physically bonding the laminate to an object to be pasted.
• the heat seal layer 26 preferably comprises a thermoplastic resin or an elastomer.
• the thermoplastic resin is preferably one having good affinity and adhesion with the substrate (e.g., glass substrate), and examples thereof include 1,2-polybutadiene resin, ethylene-vinyl acetate copolymer (abbreviated as "EVA", which usually contains 3% by mass or more of vinyl acetate constituent units), polyolefin resin such as polyethylene, polyvinyl chloride resin, polystyrene resin, vinyl ester resin (excluding EVA), saturated polyester resin, polyamide resin, fluororesin (polyvinylidene fluoride, etc.), polycarbonate resin, polyacetal resin, urethane resin, epoxy resin, (meth)acrylate resin (also called (meth)acrylic resin, meaning (meth)acrylic acid ester resin, etc.), unsaturated polyester resin, silicon resin, and modified resins of these resins.
• urethane resin include urethane-modified polyester resin
• Polyvinyl butyral can be obtained by acetalizing polyvinyl alcohol with butyraldehyde.
• the degree of acetalization of polyvinyl butyral is not particularly limited, but is preferably 40% or more, more preferably 60% or more.
• the upper limit is not particularly limited, but is preferably 85% or less, more preferably 75% or less.
• Polyvinyl alcohol used in the synthesis of polyvinyl butyral is usually obtained by saponifying polyvinyl acetate, and polyvinyl alcohol having a saponification degree of 80 to 99.8 mol % is generally used.
• the degree of polymerization of the polyvinyl alcohol is preferably 200 to 3,000.
• Elastomers include block (co)polymers of conjugated dienes, acrylic block (co)polymers, styrene block (co)polymers, block copolymers of aromatic vinyl compounds and conjugated dienes, hydrogenated block (co)polymers of conjugated dienes, hydrogenated block copolymers of aromatic vinyl compounds and conjugated dienes, ethylene- ⁇ -olefin copolymers, polar group-modified olefin copolymers, elastomers consisting of polar group-modified olefin copolymers and metal ions and/or metal compounds, nitrile rubbers such as acrylonitrile-butadiene rubbers, butyl rubber, acrylic rubbers, thermoplastic elastomers such as thermoplastic polyolefin elastomers (TPO), thermoplastic polyurethane elastomers (TPU), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPAE), diene elastomers
• thermoplastic resin or elastomer may be synthesized by a known method, or a commercially available product may be used.
• Commercially available elastomers include, for example, Clarity LA1114, Clarity LA2140, Clarity LA2250, Clarity LA2330, Clarity LA4285, Hybrar 5127, Hybrar 7311F, Septon 2104, and Septon 2063 (trade names, manufactured by Kuraray Co., Ltd.).
• Clarity LA1114, Clarity LA2140, Clarity LA2250, Clarity LA2330, Clarity LA4285, Hybrar 5127, Hybrar 7311F, Septon 2104, and Septon 2063 (trade names, manufactured by Kuraray Co., Ltd.).
• an acrylic block (co)polymer or a styrene block (co)polymer is preferred.
• the weight average molecular weight of the thermoplastic resin and elastomer is preferably 10,000 to 1,000,000, and more preferably 50,000 to 500,000, from the viewpoint of the balance between solubility in the solvent and storage modulus.
• the heat seal layer 26 may contain a plasticizer.
• the storage modulus of the heat seal layer changes, improving the slipperiness against glass and the adhesion to glass.
• the plasticizer is not particularly limited, but examples of the plasticizer that can be used include phosphate esters, carboxylate esters, carbohydrate derivatives, barbituric acid derivatives, rosin ester resins, rosin resins, hydrogenated rosin ester resins, petrochemical resins, hydrogenated petrochemical resins, terpene resins, terpene phenol resins, aromatic modified terpene resins, hydrogenated terpene resins, and alkylphenol resins, and these can be used alone or in combination of two or more.
• Examples of the phosphoric acid esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP).
• Phthalic acid esters and citrate esters are typical of carboxylic acid esters.
• Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP).
• Examples of citrate esters include triethyl O-acetyl citrate (OACTE) and tributyl O-acetyl citrate (OACTB).
• carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate and various trimellitic acid esters.
• Phthalic acid ester plasticizers DMP, DEP, DBP, DOP, DPP, DEHP are used.
• the above carboxylic acid esters include triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di- 2-ethyl butyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol
• the carbohydrate derivative is preferably a monosaccharide or a carbohydrate derivative containing 2 to 10 monosaccharide units (hereinafter also referred to as a carbohydrate derivative-based plasticizer).
• the carbohydrate derivative plasticizer include maltose octaacetate, cellobiose octaacetate, sucrose octaacetate, sucrose acetate isobutyrate, xylose tetrapropionate, glucose pentapropionate, fructose pentapropionate, mannose pentapropionate, galactose pentapropionate, maltose octapropionate, cellobiose octapropionate, sucrose octapropionate, xylose tetrabenzoate, glucose pentabenzoate, fructose pentabenzoate, mannose pentabenzoate, galactose pentabenzoate, maltos
• the above barbituric acid derivatives can be synthesized, for example, using a method for synthesizing barbituric acid in which a urea derivative and a malonic acid derivative are condensed.
• Barbituric acid having two substituents on the nitrogen atom can be obtained by heating N,N'-disubstituted urea and malonic acid chloride, or by mixing malonic acid with an activator such as acetic anhydride and heating the mixture.
• an activator such as acetic anhydride
• a synthesis method for example, the methods described in Journal of the American Chemical Society, Vol. 61, p. 1015 (1939), Journal of Medicinal Chemistry, Vol. 54, p. 2409 (2011), Tetrahedron Letters, Vol. 40, p. 8029 (1999), and the pamphlet of International Publication No. 2007/150011 can be preferably used.
• the plasticizer may be synthesized by known methods or a commercially available product may be used.
• commercially available plasticizers include Super Ester A75, A115, and A125 (all manufactured by Arakawa Chemical Industry Co., Ltd., rosin ester resins), Pine Crystal KR-85, KE-311, and PE-590 (all manufactured by Arakawa Chemical Industry Co., Ltd., rosin resins), Petrotack 60, 70, 90, 100, 100V, and 90HM (all manufactured by Tosoh Corporation, petrochemical resins), YS Polystar T30, T80, T100, T115, T130, T145, and T160 (all manufactured by Yasuhara Chemical Co., Ltd., terpene phenol resins), and YS Resin PX800, PX1000, PX1150, and PX1250 (all manufactured by Yasuhara Chemical Co., Ltd., terpene resins).
• Examples include MORESCO White P-40, P-55, P-60, P-70, P-80, P-100, P-120, P-150, P-200, P-260, and P-350P (all manufactured by MORESCO, paraffin-based oils), DIANA Process Oil NS-24, NS-100, NM-26, NM-68, NM-150, NM-280, NP-24, NU-80, and NF-90 (all manufactured by Idemitsu Kosan, naphthenic oils), and DIANA Process Oil AC-12, AC-460, AE-24, AE-50, AE-200, AH-16, and AH-58 (all manufactured by Idemitsu Kosan, aromatic oils).
• the content of the plasticizer is preferably 1 to 80% by mass, and more preferably 5 to 70% by mass, of the solid content of the heat seal layer, taking into consideration the balance of the storage modulus of the heat seal layer at 25°C and 95°C.
• the heat seal layer 26 is preferably formed using a composition (composition for forming a heat seal layer) containing a polymerizable compound for chemically bonding with the reflective layer or the polarization conversion layer.
• the polymerizable compound is preferably one that can chemically bond with the polymerizable liquid crystal compound used to form the reflective layer or the polarization conversion layer.
• the polymerizable liquid crystal compound has an ethylenically unsaturated polymerizable group
• the polymerizable compound also preferably has an ethylenically unsaturated polymerizable group.
• Examples of the ethylenically unsaturated polymerizable group-containing compound include the following: However, the present invention is not limited to the following example compounds.
• NK Ester A-BPE-20 manufactured by Shin-Nakamura Chemical Co., Ltd.
• hydrogenated bisphenol A EO-added di(meth)acrylate NK Ester A-HPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.
• bisphenol A PO-added di(meth)acrylate commercially available products include, for example, Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.
• bisphenol A epichlorohydrin-added di(meth)acrylate commercially available products include, for example, Ebecryl 150 manufactured by Daicel UCB Co., Ltd.
• bisphenol A EO/PO-added di(meth)acrylate commercially available products include, for example, BP-023-PE manufactured by Toho Chemical Co., Ltd.
• bisphenol F examples of bifunctional (meth)acrylate compounds include EO-added di(meth)acrylate (commercially available products include ARONIX M-208 manufactured by Toagose
• trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (commercially available products include, for example, TPMTA manufactured by Nippon Kayaku Co., Ltd.) and its EO, PO, and epichlorohydrin modified products, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate and its EO, PO, and epichlorohydrin modified products, isocyanuric acid EO modified tri(meth)acrylate (commercially available products include, for example, Aronix M-315 manufactured by Toagosei Co., Ltd.), tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate and its EO, PO, and epichlorohydrin modified products; Examples of such tetrafunctional (meth)acrylate compounds include
• Two or more of the ethylenically unsaturated polymerizable group-containing compounds may be used in combination.
• a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, "DPHA” (manufactured by Nippon Kayaku Co., Ltd.), or the like, can be preferably used.
• polyester (meth)acrylates and epoxy (meth)acrylates having a weight average molecular weight of 200 or more and less than 1000 are also preferred.
• Commercially available polyester (meth)acrylates include the Beamset 700 series manufactured by Arakawa Chemical Industries Co., Ltd., such as Beamset 700 (6-functional), Beamset 710 (4-functional), and Beamset 720 (3-functional).
• Epoxy (meth)acrylates include the SP series manufactured by Showa Polymer Co., Ltd., such as SP-1506, 500, SP-1507, and 480, and the VR series, such as VR-77, and Shin-Nakamura Chemical Co., Ltd., such as EA-1010/ECA, EA-11020, EA-1025, and EA-6310/ECA.
• the I/O ratio (ratio of inorganic value (I value) to organic value (O value)) of the polymerizable compound (particularly an ethylenically unsaturated polymerizable group-containing compound) is preferably 0.40 or more, more preferably 0.60 or more, and even more preferably 1.2 or more, in terms of adhesion to the glass substrate.
• the I/O ratio is calculated using the calculation method in the organic conceptual diagram.
• the organic conceptual diagram was proposed by Fujita et al., and is an effective method for predicting various physicochemical properties from the chemical structure of an organic compound (see Organic Conceptual Diagram - Basics and Applications, by Koda Yoshio, Sankyo Publishing (1984)). Since the polarity of an organic compound depends on the number of carbon atoms and the substituents, the inorganic value and organic value of other substituents are determined based on the organic value of the methylene group being set at 20 and the inorganic value of the hydroxyl group being set at 100, and the inorganic value and organic value of the organic compound are calculated from these. Organic compounds with a high inorganic value have high polarity, and organic compounds with a high organic value have low polarity.
• the content of the polymerizable compound is preferably 5 to 80 mass %, more preferably 10 to 60 mass %, and even more preferably 15 to 50 mass %, relative to the solid content in the composition.
• the solid content of a composition means the other components in the composition excluding the solvent. Even if the other components are in a liquid state, they are counted as solids.
• the composition used to form the heat seal layer 26 (composition for forming a heat seal layer) preferably contains a polymerization initiator from the viewpoint of adhesion to glass.
• the polymerization initiator may, for example, be a photopolymerization initiator.
• the photopolymerization initiator may be any one capable of generating radicals as active species by irradiation with light, and known photopolymerization initiators may be used without any restrictions.
• Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, and 2-hydroxy-1- ⁇ 4- Acetophenones such as ⁇ 4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], and ethan
• triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like may be used in combination.
• the above polymerization initiators and auxiliary agents can be synthesized by known methods, and are also available as commercial products.
• the content of the polymerization initiator contained in the composition used to form the heat seal layer 26 is not particularly limited and may be appropriately adjusted within a range that allows the polymerization reaction of the polymerizable compound to proceed smoothly.
• the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable compound contained in the composition.
• the heat seal layer 26 may contain inorganic particles.
• the heat seal layer 26 contains inorganic particles, unevenness is formed on the surface of the heat seal layer 26, and when the heat seal layer 26 is rolled in a state where the heat seal layer 26 and the HC layer 14 are in direct contact with each other, friction between the heat seal layer 26 and the HC layer 14 can be reduced, which is preferable because the heat seal layer 26 can be rolled without wrinkles.
• the inorganic particles contained in the heat seal layer 26 are preferably inorganic oxide particles, more preferably silica (silicon dioxide) particles, aluminum oxide particles, titanium dioxide particles, or zirconium oxide particles, and even more preferably silica particles.
• the inorganic particles are preferably made up of primary particles, with secondary particles being formed by agglomeration of the primary particles.
• the average primary particle size of the inorganic particles is not particularly limited, but is preferably 5 to 50 nm, and more preferably 5 to 15 nm.
• the average secondary particle size of the inorganic particles is not particularly limited, but is preferably 100 to 500 nm.
• the content of inorganic particles in the heat seal layer 26 is not particularly limited, but is preferably 1% by mass or more, and more preferably 9% by mass or more, relative to the total mass of the heat seal layer 26. There is no particular upper limit, but is preferably 40% by mass or less, and more preferably 30% by mass or less.
• the average primary particle size of inorganic particles is measured by observation with a transmission electron microscope. Specifically, the diameters of circles circumscribing the primary particles are determined for 50 randomly selected primary particles, and the arithmetic average is taken as the average primary particle size.
• the magnification of the transmission electron microscope is set to any magnification between 500,000 and 5,000,000 that allows the primary particle size to be determined.
• the average secondary particle diameter is a value measured by performing spherical fitting (refractive index 1.46) using a laser diffraction scattering type particle size distribution measuring device.
• the measuring device for example, MicroTrac MT3000 manufactured by Microtrac Bell can be used.
• the heat seal layer 26 may include a leveling agent.
• a leveling agent a known leveling agent can be used, for example, a surfactant can be mentioned, and among them, a fluorine-based surfactant or a silicone-based surfactant is preferable.
• the fluorine content in the fluorosurfactant is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 7 to 25 mass%.
• a fluorosurfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and liquid saving properties.
• the amount of the leveling agent contained in the heat seal layer 26 is not particularly limited, but is preferably 0.005 to 0.5% by mass, and more preferably 0.01 to 0.1% by mass, relative to the total mass of the heat seal layer 26.
• the heat seal layer 26 is preferably formed by applying a composition for forming a heat seal layer.
• the composition for forming a heat seal layer is a composition that contains the above-mentioned components and is used to form the heat seal layer 26 .
• the composition for forming a heat seal layer preferably contains a solvent.
• the type of the solvent is not particularly limited, and examples thereof include water and organic solvents, with organic solvents being preferred. Examples of the organic solvent include ketones, alkyl halides, amides, sulfoxides, heterocyclic compounds, hydrocarbons, esters, and ethers.
• the method of applying the composition for forming the heat seal layer is not particularly limited, and examples include wire bar coating, curtain coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spin coating, dip coating, spray coating, and slide coating.
• the coating film obtained by coating may be subjected to a drying treatment, if necessary.
• the drying treatment may be a heat treatment.
• the heating temperature in the heat treatment is not particularly limited, but is preferably 50 to 150° C., and more preferably 60 to 140° C.
• the heating time is not particularly limited, but is preferably 0.5 to 20 minutes, and more preferably 0.5 to 10 minutes.
• the surface of the formed heat seal layer 26 (the surface opposite to the reflective layer or the polarization conversion layer) may be subjected to a surface treatment as required.
• a hydrophilization treatment may be performed on the surface of the heat seal layer 26.
• the hydrophilization treatment include plasma treatment, ultraviolet irradiation treatment, corona treatment, and electron beam irradiation treatment, and corona treatment is preferred.
• the conditions for the hydrophilic treatment are appropriately selected depending on the type of treatment to be carried out, and are preferably adjusted so that the water contact angle of the surface of the heat seal layer 26 falls within the above-mentioned range.
• the average thickness of the heat seal layer 26 is preferably 0.2 ⁇ m or more, more preferably 0.4 ⁇ m or more, and even more preferably 0.8 ⁇ m or more, from the viewpoint of adhesion to the glass substrate, the reflective layer, or the polarization conversion layer.
• the method for measuring the average thickness is as follows: the heat seal layer 26 is cut with a microtome to cut out a cross section, the cross section is observed using a SEM (Scanning Electron Microscope), the thickness is measured at three different positions on the heat seal layer 26, and the average value (arithmetic mean value) of the measured values is calculated to obtain the average thickness.
• SEM Sccanning Electron Microscope
• the heat seal layer 26 may have a single layer structure or a multi-layer structure having two or more layers. When the heat seal layer 26 has a multi-layer structure, the average total thickness of the heat seal layer 26 may be within the above range.
• the storage modulus of the heat seal layer at 25°C and 90°C is determined as follows.
• the heat seal layer is dissolved in a solvent or melted, and the coating liquid obtained is applied to the release-treated surface of a release-treated release PET (polyethylene terephthalate) sheet so that the thickness after drying is 40 ⁇ m. After drying, the heat seal layer is peeled off from the release PET sheet to prepare a test piece of the heat seal layer.
• the storage modulus of the above test pieces which had been previously conditioned for 2 hours or more in an atmosphere at a temperature of 25°C and a relative humidity of 60%, was measured at 25°C and 90°C under the following conditions using a dynamic viscoelasticity measuring device (DVA-225 manufactured by ITS Japan Co., Ltd.). Sample: 5 mm x 20 mm Grip distance: 20 mm Set distortion: 0.10% Measurement temperature: -40 to 140°C Temperature rise condition: 5° C./min
• the storage modulus of the heat seal layer at 25°C is preferably 50 MPa or more, more preferably 100 MPa or more, and even more preferably 200 MPa or more, from the viewpoint of slipperiness with glass. There is no particular upper limit to the storage modulus of the heat seal layer at 25°C, but it is often 6 GPa or less.
• the storage modulus of the heat seal layer at 90°C is preferably 300 MPa or less, more preferably 150 MPa or less, even more preferably 100 MPa or less, and even more preferably 50 MPa or less, from the viewpoint of adhesion to glass during heat-pressing at 90°C. There is no particular lower limit for the storage modulus of the heat seal layer at 90°C, but it is often 0.01 MPa or more.
• the laminate of the present invention comprises glass having a curved surface and the laminate of the present invention bonded to the glass having the curved surface.
• the glass having a curved surface There is no limitation on the glass having a curved surface, and various known glass can be used. Examples include window glass having a curved surface, glass having a curved surface used for the interior and exterior of buildings, and glass having a curved surface used for lenses.
• the laminate of the present invention has a windshield glass and the laminate of the present invention laminated to the windshield glass.
• the windshield glass there are no limitations on the windshield glass, and various types of windshield glass (wind guard glass) used in vehicles such as automobiles, ships, aircraft, trains, and motorcycles can be used. Therefore, the windshield glass may be a single sheet of glass or a laminated glass in which a plurality of sheets of glass are laminated together.
• the laminated glass may have an intermediate film such as polyvinyl butyral between the sheets of glass or may not have an intermediate film.
• Such a laminate of the present invention is preferably produced by the production method of the laminate of the present invention described below.
• 2 and 3 conceptually show an example of a method for producing a laminate of the present invention.
• the laminate of the present invention is attached to a windshield glass.
• the present invention is not limited to this, and various known objects can be used as long as they have a curved surface.
• the substrate to which the adhesive film may be applied other than the windshield glass include glass having various curved surfaces as described above.
• a windshield glass 28 and the laminate 10 of the present invention are laminated together as shown in the upper part of Fig. 2.
• the laminate is laminated so that the heat seal layer 26 of the laminate 10 faces the windshield glass 28.
• the laminate 10 is caused to conform to the curved shape of the windshield glass 28, causing wrinkles to form in the laminate 10 as shown in the upper part of FIG.
• the material is placed in a bag 106 such as a rubber bag similar to the example shown in FIG.
• the mold 104 used in the conventional production method shown in FIG. 6 is not used.
• the laminate 10 of the present invention has a bending stiffness coefficient S of 5 ⁇ 10 6 [GPa ⁇ m 3 ] or more and has sufficient stiffness. Therefore, the laminate 10 is not locally wrinkled by the pressure of the bag 106, and is pressed by the bag 106 with small wrinkles generated all over, as shown in the middle part of FIG.
• a sheet (sheet-like member) such as a film, rubber, or cloth may be sandwiched between the laminate 10 and the bag 106 and vacuum-heated and pressed.
• sandwiching a sheet and vacuum-heating and pressing it is possible to suppress indentations caused by dust mixed between the laminate 10 and the bag 106 being pressed against the laminate 10.
• slipperiness between the laminate 10 and the bag 106 is poor, uneven deaeration can be reduced by sandwiching a sheet with good slipperiness between both the laminate 10 and the bag 106.
• the material of the above-mentioned film is not particularly limited, but examples include acrylic resin film, polycarbonate (PC) resin film, cellulose ester resin film such as triacetyl cellulose (TAC) resin film, polyethylene terephthalate (PET) resin film, polyolefin resin film, polyester resin film, and acrylonitrile-butadiene-styrene copolymer film, and from the viewpoint of heat resistance, polycarbonate resin film, cellulose ester resin film, or polyethylene terephthalate resin film are preferred.
• acrylic resin film polycarbonate (PC) resin film
• cellulose ester resin film such as triacetyl cellulose (TAC) resin film
• PET polyethylene terephthalate
• PET polyolefin resin film
• polyester resin film polyolefin resin film
• acrylonitrile-butadiene-styrene copolymer film and from the viewpoint of heat resistance, polycarbonate resin film, cellulose ester resin film, or polyethylene ter
• the above film may have an uneven surface in order to improve the slipperiness.
• the uneven surface can be imparted by a known method such as adding a matting agent to the film or embossing the film.
• the above-mentioned film is preferably antistatically treated on its surface in order to reduce adhesion of foreign matter during vacuum heat bonding.
• Antistatic treatment can be performed by a known method such as adding an antistatic agent.
• the above rubber is not particularly limited in terms of its material, but examples include butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), silicone rubber, fluororubber, etc., with EPDM rubber, silicone rubber, and fluororubber being preferred from the standpoint of heat resistance. These may be used alone or in combination of two or more types.
• the above rubber may have an uneven surface in order to improve slipperiness.
• the uneven surface can be imparted by known methods such as adding a matting agent to the rubber or embossing.
• the rubber is preferably antistatically treated on its surface to reduce adhesion of foreign matter during vacuum heat bonding.
• Antistatic treatment can be performed by known methods such as adding an antistatic agent.
• the rubber may be formed into a film by a known method, or a commercially available product may be used.
• Commercially available rubbers include EB240N, EB250N, EB260N, EB270N, EB280W, EB265N, EB565N, EB360E2 (all EPDM rubbers, manufactured by Maxell Kureha Co., Ltd.), SW940D, SW950D, SW960D, SW970D, SR950D, SR930T, SR940T, SH950T, SW955T (all silicone rubbers, manufactured by Maxell Kureha Co., Ltd.), FB750N, FB760N, FB770N, FB780N, FB880N, FB970N (all fluororubbers, manufactured by Maxell Kureha Co., Ltd.).
• the above-mentioned cloth is preferably made of a dust-free material in order to reduce the generation and adhesion of foreign matter during vacuum heat bonding, and is preferably sewn with conductive carbon threads in order to prevent static electricity.
• the cloth may be made by a known method, or a commercially available product may be used.
• Examples of commercially available cloth include HM-CLC (manufactured by Tanimura Co., Ltd.).
• the above-mentioned film, rubber, cloth, or other sheet-like member is preferably the same size as or larger than the laminate 10, so that the pressure from the bag 106 can be uniformly transmitted to the laminate 10.
• the above-mentioned film, sheet-like member such as rubber or cloth may be the same size as the windshield glass 28 or may be larger in size.
• the conditions for vacuum heat pressing such as the degree of vacuum and the heating temperature, may be set appropriately depending on the material forming the heat seal layer 26, the heat resistance of the other materials forming the laminate 10, and the thickness of the laminate 10, etc.
• the laminate 10 and the windshield glass 28 are removed from the bag, and the laminate 10 and the windshield glass 28 are further heat-pressed in an autoclave in the same manner as above, as shown in the third row of FIG. 2.
• the laminated body is taken out of the autoclave and cooled, as shown in the lower part of FIG.
• the laminate 10 of the present invention has an average heat shrinkage rate of 0.3% or more at 140° C. Therefore, as shown in the lower part of FIG. 3, fine wrinkles are eliminated by the heat shrinkage of the laminate 10 due to heating in an autoclave. That is, the laminate 10 of the present invention can be attached to a curved windshield glass with good conformability and sufficient suppression of wrinkles after lamination, even without using a mold 104 as shown in FIG. 6 .
• the conditions of the autoclave such as the pressure and heating temperature, may be set appropriately depending on the material forming the heat seal layer 26, the heat resistance of the other materials forming the laminate 10, and the thickness of the laminate 10, etc.
• the image display system of the present invention comprises the laminate of the present invention and an image display device that projects an image onto the laminate of the present invention.
• 4 conceptually shows an example in which the image display system of the present invention is used in a head-up display system.
• the head-up display system is also referred to as HUD.
• the HUD 30 shown in FIG. 4 includes a laminate 10A of the present invention and a projector 32.
• the laminate 10A is attached to a windshield glass 28 with the heat seal layer 26 facing the windshield glass 28 side.
• the laminate 10A is obtained by attaching the laminate 10 shown in FIG. 1 to a windshield glass 28 and then peeling off the protective film 12.
• the projector 32 shown in FIG. 4 is composed of an image forming section 34, an intermediate image screen 36, a mirror 38, and a concave mirror 40.
• the projection light projected by the projector 32 passes through a transparent window 46 provided on the dashboard 42 of the vehicle in which the HUD 30 is mounted, as shown by the dotted line, enters the laminate 10A attached to the windshield glass 28, is reflected by the reflective layer 20, and is observed by the driver D (dotted line).
• the driver D observes a virtual image of the image projected onto the windshield glass 28 .
• the image forming unit 34 includes an LCD (Liquid Crystal Display) 50 and a projection lens 52 .
• the LCD 50 and the projection lens 52 are both known components used in a projector for a HUD.
• the image forming unit 34 projects the image displayed by the LCD 50 onto the intermediate image screen 36 by the projection lens 52.
• the projected image is converted into a real image by the intermediate image screen 36, and this real image is reflected along a predetermined optical path by the mirror 38 and the concave mirror 40. As described above, this reflected light passes through the transparent window 46 provided in the dashboard 42, enters the laminated body 10A, and is reflected, so that the projected image is observed by the driver D.
• the LCD 50 displays an image (projected image) of p-polarized light. That is, in a preferred embodiment, the projector 32 of the HUD 30 of the present invention irradiates p-polarized projection light. Therefore, if the LCD 50 does not display p-polarized projection light, it is preferable to provide a polarizer that converts the projection light from the LCD 50 to p-polarized light, for example, in the optical path of the projection light from the LCD 50 to the concave mirror 40. Any known polarizer can be used. Alternatively, a polarizer that converts the projected light from the LCD 50 to p-polarized light may be provided outside the projector 32, that is, along the optical path of the projected light from the concave mirror 40 to the windshield glass 28.
• the illustrated laminate 10A uses a cholesteric liquid crystal layer as the reflective layer 20, for example.
• the retardation layer 18 is, for example, a quarter-wave plate. This quarter-wave plate converts the incident p-polarized light into circularly polarized light in the rotation direction that is selectively reflected by the reflective layer 20, i.e., the cholesteric liquid crystal layer. Therefore, the laminate 10A converts p-polarized light into circularly polarized light by the retardation layer 18, reflects this circularly polarized light by the reflective layer 20, and converts the circularly polarized light back to p-polarized light by the retardation layer 18. In this way, the laminate 10A selectively reflects p-polarized light.
• polarized sunglasses selectively block S-polarized light. Therefore, by emitting p-polarized projection light from the projector 32, a p-polarized projection image can be projected, and even if the driver D is wearing polarized sunglasses, the driver D can observe the image projected by the HUD 30.
• the image forming unit 34 is not limited to using the LCD 50, and various known image forming means used in HUD projectors can be used.
• various known image forming means used in HUD projectors can be used, such as a fluorescent display tube, a liquid crystal on silicon (LCOS), an organic electroluminescence (organic EL) display, and a digital light processing (DLP) using a digital micromirror device (DMD).
• LCOS liquid crystal on silicon
• organic EL organic electroluminescence
• DLP digital light processing
• a projection image is projected onto the intermediate image screen 36 by a projection lens, similar to the LCD 50.
• an image forming means using light beam scanning can also be used.
• the projection light emitted from the image forming section 34 is then turned into a real image (visible image) by the intermediate image screen 36 .
• the intermediate image screen 36 there are no limitations on the intermediate image screen 36, and various known intermediate image screens that convert a projected image into a real image in a HUD projector can be used.
• the intermediate image screen 36 include a scattering film, a microlens array, and a screen for rear projection.
• the projected light that is imaged on the intermediate image screen 36 is reflected along a predetermined optical path by the mirror 38 and the concave mirror 40 as described above, passes through a transparent window 46 provided in the dashboard 42, and is projected onto the laminate 10A attached to the windshield glass 28, and is observed by the driver D (see dashed line).
• the mirror 38 is a known mirror used to adjust the optical path of the projection light in a projector, or may be a so-called cold mirror that reflects visible light and transmits infrared light to prevent heating of components of the projector 32 due to sunlight entering through the windshield glass.
• the concave mirror 40 is a known concave mirror that enlarges and projects the projection light and is used in a HUD projector.
• the projector 32 in the illustrated example uses the mirror 38 and the concave mirror 40 as members for changing the optical path of the projection light
• the present invention is not limited to this.
• projector 32 may have only one of mirror 38 and concave mirror 40, or it may have one or more other light reflecting elements, such as freeform mirrors, in addition to or instead of mirror 38 and/or concave mirror 40.
• the projector constituting the HUD of the present invention can be configured using various types of light reflecting elements.
• the projector 32 emits p-polarized projection light.
• the p-polarized projection light projected by the projector 32 and transmitted through the transmission window 46 is transmitted through the hard coat layer 14 and the resin substrate 16, and enters the retardation layer 18.
• the retardation layer 18 is a quarter-wave plate, and converts the incident p-polarized projection light into circularly polarized light in the rotation direction that is selectively reflected by the reflective layer 20 (cholesteric liquid crystal layer).
• the circularly polarized projection light converted by the retardation layer 18 is reflected by the reflective layer 20 and enters the retardation layer 18 again, where it is converted by the retardation layer 18 back to the original p-polarized light.
• the projection light converted into p-polarized light by the polarization conversion layer 24 is irradiated to the observation position of the driver D.
• the driver D since the projected image is p-polarized, as described above, the driver D can properly observe the projected image even if he or she is wearing polarized sunglasses.
• the laminate of the present invention can be attached to a curved substrate such as the windshield glass 28 without wrinkles. Therefore, the HUD 30, which reflects the projection light from the projector 32 by the laminate 10A of the present invention, can project a high-quality image without image distortion caused by wrinkles in the laminate 10A, regardless of whether polarized sunglasses are worn or not.
• this s-polarized light passes through the windshield glass 28 and enters the laminate 10A, and then passes through the heat seal layer 26 and enters the polarization conversion layer 24.
• the s-polarized light incident on the polarization conversion layer 24 is converted into elliptically polarized light with a rotation direction corresponding to the s-polarized light, for example, by the helical structure of the liquid crystal compound in the polarization conversion layer 24 .
• the elliptically polarized light that has passed through the polarization conversion layer 24 then enters the reflective layer 20 .
• the reflective layer 20 is a cholesteric liquid crystal layer that selectively reflects circularly polarized light converted from p-polarized light by the retardation layer 18. Therefore, elliptically polarized light with a rotation direction corresponding to s-polarized light is transmitted through the reflective layer 20. Furthermore, by transmitting through the reflective layer 20 (cholesteric liquid crystal layer), the elliptically polarized light with a rotation direction corresponding to s-polarized light is converted into circularly polarized light with a rotation direction corresponding to s-polarized light.
• the circularly polarized light that has passed through the reflective layer 20 is incident on the retardation layer 18 .
• the retardation layer 18 is a quarter-wave plate that converts p-polarized light into circularly polarized light that is selectively reflected by the cholesteric liquid crystal layer that constitutes the reflective layer 20. Therefore, the circularly polarized light having a rotation direction corresponding to the s-polarized light that is incident on the retardation layer 18 is transmitted through the retardation layer 18 and converted into s-polarized light. In this way, the s-polarized light that becomes glare and enters from outside the vehicle passes through the laminate 10A as s-polarized light.
• the laminate of the present invention has a polarization conversion layer, it is possible to compensate for the change in polarization of external light caused by the retardation layer and the reflective layer when used in a HUD, and to transmit the s-polarized light that becomes glare and enters from outside the vehicle as s-polarized light, making it possible to block the light with polarized sunglasses.
• the image display system of the present invention is not limited to the HUD shown in the figure. That is, the image display system of the present invention can be used in various known image display systems, so long as it has the laminate of the present invention and an image display device that projects an image onto the laminate of the present invention.
• HC Layer ⁇ Preparation of Curable Composition for Forming Hard Coat Layer (HC Layer)> The components were mixed according to the composition shown in Table 1 below, and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare a curable composition for forming an HC layer, HC-1. The amount of each component shown in Table 1 is expressed in parts by mass.
• PAG-1 is the following compound:
• composition for forming reflective layer, composition for forming retardation layer, and composition for forming polarization conversion layer The components were mixed according to the ratios shown in Table 3 below, and filtered through a polypropylene filter having a pore size of 10 ⁇ m to prepare compositions BG1, R1, and IR1 for forming a reflective layer, composition A1 for forming a retardation layer, and composition TW-1 for forming a polarization conversion layer.
• the amount of each component shown in Table 3 is expressed in parts by mass.
• the mixture 1, alignment control agent 1 and alignment control agent 2 are the following compounds.
• a cellulose acylate film having a thickness of 100 ⁇ m was produced by the same production method as in Example 20 of International Publication No. 2014/112575.
• UV-531 manufactured by Teisei Kako Co., Ltd. was added to this cellulose acylate film as an ultraviolet absorbent. The amount added was 3 phr (per hundred resin).
• the prepared cellulose acylate film was passed through a dielectric heating roll at 60°C to raise the surface temperature of the film to 40°C, and then an alkaline solution having the composition shown below was applied to one side of the film at a coating amount of 14 mL/ m2 using a bar coater, and the film was allowed to remain under a steam type far-infrared heater (manufactured by Noritake Co., Limited) heated to 110°C for 10 seconds. Next, 3 mL/m 2 of pure water was applied using the same bar coater. Next, after washing with water using a fountain coater and draining with an air knife were repeated three times, the film was allowed to stay in a drying zone at 70° C.
• Cellulose acylate films 2 and 3 were prepared in the same manner as in the preparation of cellulose acylate film 1, except that the film thickness was adjusted to 140 ⁇ m and 180 ⁇ m.
• Cellulose acylate film 4 was prepared in the same manner as in the preparation of cellulose acylate film 1, except that the film thickness was adjusted to 180 ⁇ m and the stretching conditions were adjusted so that the residual stress was increased.
• Cellulose acylate film 5 was prepared in the same manner as in the preparation of cellulose acylate film 1, except that the film thickness was adjusted to 180 ⁇ m and the stretching conditions were adjusted so that the residual stress would be greater.
• Cellulose acylate film 6 was prepared in the same manner as in the preparation of cellulose acylate film 5, except that the film thickness was adjusted to 40 ⁇ m.
• Cellulose acylate film 7 was prepared in the same manner as in the preparation of cellulose acylate film 1, except that the film thickness was adjusted to 80 ⁇ m.
• Cellulose acylate film 8 was prepared in the same manner as in the preparation of cellulose acylate film 1, except that the stretching conditions were adjusted so as to reduce the residual stress.
• a curable composition for forming an HC layer, HC-1 was applied to the surface opposite to the saponification treatment surface of the cellulose acylate film 1 prepared above and cured to form an HC1 layer having a thickness of 6 ⁇ m.
• the coating and curing methods were as follows.
• the HC layer-forming curable composition HC-1 was coated at a conveying speed of 30 m/min by a die coating method using a slot die described in Example 1 of JP-A-2006-122889, and dried for 60 seconds at an atmospheric temperature of 60° C. to obtain a coating film.
• the coating film was irradiated with ultraviolet light at an illuminance of 150 mW/cm 2 and an exposure dose of 600 mJ/cm 2 using an air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.) with an oxygen concentration of about 0.1% by volume and an oxygen concentration of 160 W/cm 2 to cure the coating film to form an HC layer, thereby obtaining a film HC1 having a resin substrate and an HC layer.
• an air-cooled metal halide lamp manufactured by iGraphics Co., Ltd.
• the heat seal layer forming composition HS-1 was applied to the surface of the film HC1 opposite to the hard coat layer using a wire bar so that the film thickness after drying would be 0.8 ⁇ m, and then the film was dried at 120° C. for 1 minute to form a coating film. Thereafter, under a nitrogen purge, the coating was irradiated with ultraviolet light at an illuminance of 150 mW/ cm2 and an exposure dose of 300 mJ/ cm2 using an air-cooled metal halide lamp (manufactured by Eye Graphics) at an oxygen concentration of approximately 0.1 volume % to harden the coating, thereby producing a laminate of Example 1 having a structure of HC layer/resin substrate/heat seal layer.
• Examples 2 to 5 Comparative Examples 1 to 3> Laminates of Examples 2 to 5 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1, except that cellulose acylate films 2 to 5 and 7 to 8 were used as the resin substrates. In addition, a laminate of Comparative Example 3 was prepared in the same manner as in Comparative Example 2, except that a hard coat layer was not formed.
• Example 6 ⁇ Formation of alignment film> On the saponified surface of the saponified cellulose acylate film 5 (resin substrate) obtained above, a coating solution for forming an alignment film having the composition shown below was applied at 24 mL/ m2 using a wire bar coater, and then dried with hot air at 100° C. for 120 seconds to obtain an alignment film having a thickness of 0.5 ⁇ m.
• the alignment film prepared above was subjected to a rubbing treatment (rayon cloth, pressure: 0.1 kgf (0.98 N), rotation speed: 1000 rpm (revolutions per minute), conveying speed: 10 m/min, number of reciprocations: 1) in a direction rotated 45° clockwise with respect to the long side direction of the resin substrate.
• composition IR1 for forming a reflective layer was applied to the surface of the alignment film rubbed as described above using a wire bar at room temperature so that the thickness of the dried film after drying would be 0.4 ⁇ m, thereby obtaining a coating film.
• the coating film was dried at room temperature for 30 seconds, and then heated for 2 minutes in an atmosphere at 85° C. Thereafter, in an environment with an oxygen concentration of 1000 ppm or less, the coating film was irradiated with ultraviolet light at an output of 60% for 6 to 12 seconds using a D bulb (90 mW/cm lamp) manufactured by Fusion Co., Ltd. at 60° C.
• a film A1 having a reflective layer composed of three cholesteric liquid crystal layers was obtained.
• the transmission spectrum of the film A1 was measured with a spectrophotometer (V-670, manufactured by JASCO Corporation), and the transmission spectrum had selective reflection central wavelengths of 515 nm, 685 nm, and 775 nm.
• the heat seal layer forming composition HS-1 was applied to the reflective layer side of the cellulose acylate film 1 in the film A1 prepared above using a wire bar so that the film thickness after drying would be 0.8 ⁇ m, and then the film was dried at 120° C. for 1 minute to form a coating film. Thereafter, under a nitrogen purge, the coating was irradiated with ultraviolet light at an illuminance of 150 mW/ cm2 and an exposure dose of 300 mJ/ cm2 using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an oxygen concentration of approximately 0.1 volume % to harden the coating, thereby obtaining a film HS1 having a structure of resin substrate/reflective layer/heat seal layer.
• a curable composition for forming an HC layer, HC-1 was applied to the surface of the film HS1 prepared above opposite to the HS layer, and cured to form an HC1 layer with a thickness of 6 ⁇ m.
• the coating and curing methods were as follows.
• the HC layer-forming curable composition was coated at a conveying speed of 30 m/min by the die coating method using a slot die described in Example 1 of JP-A-2006-122889, and dried for 60 seconds at an atmospheric temperature of 60° C. to obtain a coating film.
• the coating film was irradiated with ultraviolet light at an illuminance of 150 mW/cm 2 and an exposure dose of 600 mJ/cm 2 using an air-cooled metal halide lamp (manufactured by iGraphics Co., Ltd.) with an oxygen concentration of about 0.1% by volume and an oxygen concentration of 160 W/cm 2 to cure the coating film to form an HC layer, and a laminate of Example 6 having a configuration of HC layer/resin substrate/reflective layer/heat seal layer was obtained.
• an air-cooled metal halide lamp manufactured by iGraphics Co., Ltd.
• Example 7 A composition A1 for forming a retardation layer was applied to the rubbed alignment film surface using a wire bar, and then dried and cured under the following conditions.
• a laminate of Example 7 having a structure of HC layer/resin substrate/retardation layer/reflective layer/heat seal layer was produced in the same manner as in Example 6, except that a composition IR1 for forming a reflective layer was applied onto the cured retardation layer A1.
• ⁇ Curing conditions of the composition A1 for forming a retardation layer> After applying and drying the composition A1 for forming a retardation layer to obtain a coating film, the film was placed on a hot plate at 50° C. and irradiated with ultraviolet light for 6 seconds by an electrodeless lamp "D bulb" (60 mW/ cm2 ) manufactured by Fusion UV Systems in an environment with an oxygen concentration of 1000 ppm or less to form a retardation layer. This resulted in a retardation layer with a thickness adjusted to obtain the desired front retardation, i.e., the desired retardation.
• the retardation of the produced retardation layer at 550 nm was measured using an AxoScan manufactured by Axometrics, and was found to be 126 nm.
• Example 8 A laminate of Example 8 having a structure of HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 7, except that a polarization conversion layer TW1 was provided on top of the cholesteric liquid crystal layer R1 to a thickness of 1.5 ⁇ m.
• the polarization conversion layer TW1 was prepared by applying the polarization conversion layer-forming composition TW1 onto the cholesteric liquid crystal layer R1 at room temperature using a wire bar, drying the coating film at room temperature for 30 seconds, and heating it for 2 minutes in an atmosphere at 85° C.
• the coating film was irradiated with ultraviolet light at 60% output for 6 to 12 seconds using a Fusion D bulb (90 mW/cm lamp) at 60° C. to form a polarization conversion layer.
• Example 9 A laminate having a structure of HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 8, except that Cellulose Acylate Film 6 was used as the resin substrate.
• the resin constituting the base material layer and the resin mixture for the adhesive layer were charged into each extruder, and the discharge rate of each extruder was adjusted (220°C) so that the base material layer thickness ratio was 96% and the adhesive layer thickness ratio was 4%, and the film thickness was set to 200 ⁇ m, to produce a two-layer laminated film, protect film 1.
• the protective film 1 was attached to the HC layer side of the above laminate so that the adhesive layer and the HC layer of the laminate were in contact with each other, thereby producing a laminate of Example 9 having a configuration of protective film 1/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer.
• Example 10 (Preparation of Protective Film 2)
• Protective film 2 was produced according to the same procedure as that for producing protective film 1, except that the extrusion rate of each extruder was adjusted so that the base layer thickness ratio was 97% and the adhesive layer thickness ratio was 3%, and the film thickness was 250 ⁇ m.
• a laminate of Example 10 having a structure of protective film 2/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 9, except that protective film 2 was used.
• the tensile modulus was measured in accordance with the method described in JIS K7127, and was calculated by the following method.
• a sample piece of 10 mm in width and 150 mm in length was cut out along the length direction in each direction rotated 45° clockwise from one in-plane direction as a reference, and the cut sample piece was placed in a tensile tester (manufactured by Toyo Seiki Co., Ltd., product name "Strograph-R2”) so that the chuck interval in the measurement direction was 100 mm, and stretched at a stretching speed of 300 mm/min under the condition of a measurement temperature of 25° C.
• the in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum tensile modulus of elasticity among the tensile moduli of the above-mentioned sample pieces was defined as the first direction, and the direction perpendicular to the first direction was defined as the second direction.
• the average value of the tensile modulus of elasticity in the first direction and the tensile modulus of elasticity in the second direction was defined as the average tensile modulus of elasticity of the laminate.
• ⁇ Film thickness measurement> The film thickness was measured by observation with a scanning electron microscope (SEM) according to the following method.
• SEM scanning electron microscope
• the cross sections of the laminates of the examples and comparative examples were exposed by a standard method such as ion beam or microtome, and the exposed cross sections were then observed by SEM.
• the laminate was divided into four equal parts in the width direction, and the thickness of the laminate was calculated as the arithmetic average of the thicknesses at three equal points excluding both ends.
• the heat shrinkage rate was measured as follows. In the laminates of the examples and comparative examples, a sample piece of 30 mm in width and 120 mm in length was cut out along each direction rotated 45° clockwise from one in-plane direction as a reference, and two reference lines were made in advance in the width direction of the cut-out test pieces so that the interval was 100 mm. The sample piece was left in a heating oven at 140° C. for 45 minutes under no tension, and then the sample piece was cooled to room temperature, and the interval between the two reference lines was measured. The interval after the treatment measured at this time was defined as A [mm].
• the numerical value [%] calculated from the interval of 100 mm before the treatment and the interval A mm after the treatment using the formula "100 ⁇ (100 ⁇ A)/100" was defined as the thermal shrinkage rate of the sample piece.
• the in-plane direction of the laminate corresponding to the length direction of the test piece showing the maximum thermal shrinkage rate among the thermal shrinkage rates of each sample piece was defined as the first direction, and the direction perpendicular to the first direction was defined as the second direction.
• the average value of the thermal shrinkage rates in the first direction and the second direction was defined as the average thermal shrinkage rate of the laminate.
• the wrinkles were evaluated as follows: The laminates of the examples and comparative examples, measuring 260 mm in length and 330 mm in width, were placed in the center of a glass substrate, with the surface on the heat seal layer side being the contact surface, on the concave side of a curved glass substrate measuring 330 mm in width and 260 mm in width, with a curvature of 1750 mm in the longitudinal direction of 330 mm and 1250 mm in the lateral direction of 260 mm. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atm) using a vacuum pump. The temperature was then raised to 115°C under reduced pressure, and after holding for 60 minutes, the temperature was returned to normal temperature and pressure.
• the laminate was then held in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, and a glass sample was produced in which the laminate and the glass substrate were bonded with a heat seal layer. Then, the protective film 1 was peeled off for Example 9, and the protective film 2 was peeled off for Example 10.
• the glass samples were evaluated according to the following criteria, with A to C being acceptable ranges. A: No wrinkles were present. B: There were wrinkles, but the number was two or less. C: There were more than 2 wrinkles and less than 10 wrinkles. D: There were more than 10 wrinkles.
• the evaluation of curved surface tracking is as follows.
• the glass samples prepared above were evaluated for wrinkle-free areas according to the following criteria, with A to C being acceptable ranges.
• D A floating was found between the laminate and the glass substrate, and it was more than 30% of the area.
• the glass sample prepared above was placed indoors on an imager (iPad (registered trademark) manufactured by APPLE) fixed and installed on a horizontal floor surface while adjusting the image projection angle, and the glass sample was placed using a pedestal so that the distance between the center of the glass sample (image display unit) and the center of the imager was 1.0 m. At this time, the glass sample was tilted so that the angle between the floor surface and the surface of the glass sample was 30°. The laminate side of the glass sample was visually observed from a distance of 1.0 m from the glass sample so that the gray background simulating a road and the HUD display image were superimposed.
• an imager iPad (registered trademark) manufactured by APPLE
• the luminance LB of the gray background and the luminance LI of the white display of the imager were measured with a spectroradiometer (SR-3AR, manufactured by Topcon Technohouse Corporation), and the LI/LB was 3.0.
• the HUD display image used displayed characters in white and was evaluated according to the following criteria. A: I was able to read the letters clearly. B: The letters were distorted, but I was able to read them. C: The letters were faint and difficult to read. D: The letters were faint and badly distorted with wrinkles and raised areas, making them impossible to read.
• the above glass sample was conditioned at a temperature of 25° C. and a relative humidity of 60% for 2 hours, and then the haze (HA) before the abrasion test was measured using a haze meter (NDH2000N, manufactured by Nippon Denshoku Co., Ltd.).
• the surface of the hard coat layer was subjected to 100 cycles of testing using a Taber abrasion tester (Rotary Abrasion Tester, manufactured by Toyo Seiki Co., Ltd.) at a rotation speed of 72 rpm under a load of 500 gf using a CS-10F abrasion wheel.
• the haze (HB) of the test portion of the laminate was measured.
• the ⁇ haze (HB-HA) before and after the test was calculated and evaluated according to the following criteria.
• the column “Resin substrate” indicates the type of cellulose acylate film used, and each numerical value indicates the number of the cellulose acylate film. For example, “1" in Example 1 indicates cellulose acylate film 1.
• the column “Flexural rigidity coefficient (x 10 6 GPa ⁇ m 3 )" indicates the magnitude of the flexural rigidity coefficient. For example, “6” in Example 1 indicates “6 x 10 6 [GPa ⁇ m 3 ]”.
• the laminate of the present invention exhibits predetermined effects. Furthermore, a comparison of Examples 1 to 3 confirmed that a bending stiffness coefficient of 15 ⁇ 10 6 [GPa ⁇ m 3 ] or more provides a superior effect, and a bending stiffness coefficient of 25 ⁇ 10 6 [GPa ⁇ m 3 ] or more provides an even superior effect. Furthermore, a comparison between Examples 1, 4 and 5 confirmed that the effect was superior when the heat shrinkage rate was 0.4% or more, and was even superior when the heat shrinkage rate was 0.6% or more. Moreover, as shown in Examples 6 to 10, the laminate has a reflective layer, which improves the visibility of the projected image.
• the laminate has a protective film, which suppresses the transfer of the unevenness of the rubber bag when the laminate is placed in the rubber bag and heat-pressed, thereby improving the visibility of the projected image.
• the laminate of the present invention has a hard coat layer, which improves the abrasion resistance. From the above results, the effects of the present invention are clear.
• Example 101> (Preparation of Protective Film 3)
• Protective film 3 was produced according to the same procedure as that for producing protective film 1, except that the extrusion rate of each extruder was adjusted so that the base layer thickness ratio was 97% and the adhesive layer thickness ratio was 3%, and the film thickness was 230 ⁇ m.
• a laminate of Example 101 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 9, except that protective film 3 was used.
• Example 102 to 106 Except for using HS-2 to HS-6 as the heat seal layer forming composition, the laminates of Examples 102 to 106 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer were prepared in the same manner as in Example 101.
• Example 107 A laminate of Example 107 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 106, except that the coating was performed so that the thickness of the heat seal layer after drying would be 3.0 ⁇ m.
• Example 108 A laminate of Example 108 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 106, except that the coating was performed so that the film thickness of the heat seal layer after drying was 4.0 ⁇ m.
• Example 109 A laminate of Example 109 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer was prepared in the same manner as in Example 106, except that the coating was performed so that the heat seal layer had a film thickness of 5.0 ⁇ m after drying.
• Examples 1010 to 14> Except for using HS-7 to HS-11 as the heat seal layer forming composition, the laminates of Examples 110 to 114 having a structure of protective film 3/HC layer/resin substrate/retardation layer/reflective layer/polarization conversion layer/heat seal layer were prepared in the same manner as in Example 109.
• the evaluation of wrinkles after vacuum heating and pressing at 90° C. is as follows.
• the adhesion after vacuum heating and pressing at 90° C. was evaluated as follows. For the glass samples prepared above, the areas where no wrinkles were formed were evaluated according to the following criteria. A: There was no portion of the laminate peeled off from the glass substrate. B: The laminate was partially peeled off from the glass substrate, and the peeled off accounted for 5% or less of the area. C: The laminate was partially peeled off from the glass substrate, and the peeled off accounted for more than 5% and not more than 10% of the area. D: There were some areas where the laminate had peeled off from the glass substrate, and the area was larger than 10%.
• the glass sample was tilted so that the angle between the floor surface and the surface of the glass sample was 30°.
• the laminate side of the glass sample was visually observed from a distance of 1.0 m from the glass sample so that the gray background simulating a road and the HUD display image were superimposed.
• the luminance LB of the gray background and the luminance LI of the white display of the imager were measured with a spectroradiometer (SR-3AR, manufactured by Topcon Technohouse Corporation), and the LI/LB was 3.0.
• the HUD display image used displayed characters in white and was evaluated according to the following criteria. A: I was able to read the letters clearly. B: The letters were wrinkled or distorted and some were unreadable. C: The letters were wrinkled or distorted and some parts were unreadable. D: The letters were very distorted due to wrinkles or lifting, and many parts were unreadable.
• the above glass sample was conditioned at a temperature of 25° C. and a relative humidity of 60% for 2 hours, and then the haze (HA) before the abrasion test was measured using a haze meter (NDH2000N, manufactured by Nippon Denshoku Co., Ltd.).
• the surface of the hard coat layer was subjected to 100 cycles of testing using a Taber abrasion tester (Rotary Abrasion Tester, manufactured by Toyo Seiki Co., Ltd.) at a rotation speed of 72 rpm under a load of 500 gf using a CS-10F abrasion wheel.
• the haze (HB) of the test portion of the laminate was measured.
• the ⁇ haze (HB-HA) before and after the test was calculated and evaluated according to the following criteria.
• Example 109 The laminate of Example 109 was evaluated by sandwiching a rubber sheet or film between the laminate and the rubber bag, and then vacuum heating and pressing as described below.
• Example 109 measuring 260 mm in length and 330 mm in width, was placed in the center of the glass substrate on the concave side of a curved glass substrate measuring 330 mm in width and 260 mm in width, with a curvature of 330 mm in length, R1750 mm, and 260 mm in width, R1250 mm, with the surface on the heat seal layer side being the contact surface.
• a rubber sheet EB360E2 (2 mm thick, EPDM rubber, manufactured by Maxell Kureha Co., Ltd.) having a size of 260 mm length ⁇ 330 mm width was laminated on the three-layered protective film side of the laminate of Example 109 described above. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atm) using a vacuum pump. The rubber sheet was then removed, and the glass sample in which the laminate and the glass substrate were bonded with a heat seal layer was heated to 115°C under reduced pressure, held for 60 minutes, and then returned to room temperature and pressure.
• the glass sample was then held in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, and a glass sample in which the laminate and the glass substrate were bonded with a heat seal layer was produced.
• the protective film 3 was then peeled off.
• the glass samples were evaluated according to the following criteria, with A to C being acceptable ranges. A: No wrinkles were present. B: There were wrinkles, but the number was two or less. C: There were more than 2 wrinkles and less than 10 wrinkles. D: There were more than 10 wrinkles.
• Example 109 measuring 260 mm in length and 330 mm in width, was placed in the center of the glass substrate on the concave side of a curved glass substrate measuring 330 mm in width and 260 mm in width, with a curvature of 330 mm in length, R1750 mm, and 260 mm in width, R1250 mm, with the surface on the heat seal layer side being the contact surface.
• a PET film 60 ⁇ m thick, manufactured by Fuji Film Corporation
• having a size of 260 mm length ⁇ 330 mm width was laminated on the three-layered protect film side of the laminate of Example 109 described above.
• Example 109 measuring 260 mm in length and 330 mm in width, was placed in the center of the glass substrate on the concave side of a curved glass substrate measuring 330 mm in width and 260 mm in width, with a curvature of 330 mm in length, R1750 mm, and 260 mm in width, R1250 mm, with the surface on the heat seal layer side being the contact surface.
• a PET film 60 ⁇ m thick, manufactured by Fuji Film Corporation
• having a size of 260 mm length ⁇ 330 mm width was laminated on the three-layered protect film side of the laminate of Example 109 described above.
• a rubber sheet EB360E2 (2 mm thick, EPDM rubber, manufactured by Maxell Kureha Co., Ltd.) measuring 260 mm length x 330 mm width was laminated on the PET film. This was placed in a rubber bag and the pressure was reduced to 10 kPa (0.1 atm) using a vacuum pump. The rubber sheet and PET film were then removed, and the glass sample in which the laminate and the glass substrate were bonded by a heat seal layer was heated to 115°C under reduced pressure, held for 60 minutes, and then returned to room temperature and pressure.
• the glass sample was held in an autoclave (manufactured by Kurihara Seisakusho) at 140°C and 1.3 MPa (13 atm) for 60 minutes to remove air bubbles, and a glass sample in which the laminate and the glass substrate were bonded by a heat seal layer was produced. Then, the protective film 3 was peeled off.
• the glass samples were evaluated according to the following criteria, with A to C being acceptable ranges. A: No wrinkles were present. B: There were wrinkles, but the number was two or less. C: There were more than 2 wrinkles and less than 10 wrinkles. D: There were more than 10 wrinkles.

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• 2024
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