Classifications

• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
  • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
  • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09J127/18—Homopolymers or copolymers of tetrafluoroethene
• • 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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/04—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
• • 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
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/21—Paper; Textile fabrics
• • 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
  • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

• the present invention relates to an adhesive laminate sheet.
• An adhesive sheet has been developed that is designed to be exposed to a hot environment.
• Patent Document 1 discloses a heat-resistant tape that includes a base layer and an adhesive layer, the base layer being a glass fiber fabric impregnated with a fluorine-containing resin, and a silicon-containing agent being present between the glass fiber fabric and the fluorine-containing resin.
• Patent Document 1 The adhesive tape in Patent Document 1 is said to provide a heat-resistant tape with high productivity, but no consideration is given to heat insulation properties.
• the present invention aims to provide an adhesive laminated sheet with excellent heat insulation and heat resistance.
• the present invention is as follows.
• a first embodiment of the present invention is a double-sided pressure-sensitive adhesive laminate sheet having a first pressure-sensitive adhesive layer, a base layer, and a second pressure-sensitive adhesive layer laminated in this order,
• the first adhesive layer is made of a first adhesive component
• the second adhesive layer is made of a second adhesive component
• the base layer includes a nonwoven fabric sheet made of fluororesin fibers
• the substrate layer is a first mixed layer impregnated with the first adhesive component, the first mixed layer being provided in a range of 2% to 30% of a thickness of the base layer from the first adhesive layer side main surface toward the second adhesive layer side main surface of the base layer; a second mixed layer impregnated with the second adhesive component, the second mixed layer being provided in a range of 2% to 30% of the thickness of the base layer from the second adhesive layer side main surface of the base layer toward the first adhesive layer side main surface; an air layer including air, the air layer being provided in a range of 40% to 96% of the thickness of the base material layer from the first mixed layer toward
• the double-sided pressure-sensitive adhesive laminate sheet is characterized in that the change ratio ( A22 / A21 ) of the adhesive strength A22 of the second adhesive layer after heating at 200°C for 300 hours to the adhesive strength A21 of the second adhesive layer at 23°C and a humidity of 50% is 0.40 or more.
• first adhesive component and the second adhesive component are fluororesin-based adhesive components.
• a second aspect of the present invention is A double-sided adhesive laminate sheet having a first adhesive layer, a base layer, and a second adhesive layer laminated in this order,
• the first adhesive layer is made of a first adhesive component which is a fluororesin-based adhesive component
• the second adhesive layer is made of a second adhesive component which is a fluororesin-based adhesive component
• the base layer includes a nonwoven fabric sheet made of fluororesin fibers
• the substrate layer is a first mixed layer impregnated with the first adhesive component, the first mixed layer being provided in a range of 2% to 30% of a thickness of the base layer from the first adhesive layer side main surface of the base layer toward the second adhesive layer side main surface; a second mixed layer impregnated with the second adhesive component, the second mixed layer being provided in a range of 2% to 30% of the thickness of the base layer from the second adhesive layer side main surface of the base layer toward the first adhesive layer side main surface; an air layer including air, the air layer being provided in a range of 40% to 9
• the double-sided pressure-sensitive adhesive laminate sheet of the first embodiment and the double-sided pressure-sensitive adhesive laminate sheet of the second embodiment preferably have the following configuration.
• the thermal conductivity is preferably 0.20 W/(K ⁇ m) or less.
• the fluororesin fiber is preferably at least PTFE, PFA or FEP. It is preferable that the thickness of the first adhesive layer or the thickness of the second adhesive layer is equal to or less than the thickness of the base layer.
• the thickness of the substrate layer is preferably 20 ⁇ m to 1000 ⁇ m. It is preferable that the thickness of the first adhesive layer and the thickness of the second adhesive layer are each 5 ⁇ m to 500 ⁇ m.
• the present invention provides an adhesive laminated sheet with excellent heat insulation and heat resistance.
• FIG. 1 is a schematic diagram of a double-sided pressure-sensitive adhesive laminate sheet.
• FIG. 2 is a diagram summarizing the relationship between porosity and thermal conductivity in each of the examples and comparative examples.
• the double-sided adhesive laminate sheet 10 according to the present invention will be described below mainly with reference to FIG. 1, but the present invention is not limited thereto.
• a double-sided pressure-sensitive adhesive laminate sheet 10 is a double-sided pressure-sensitive adhesive laminate sheet in which a first pressure-sensitive adhesive layer 1, a base layer A, and a second pressure-sensitive adhesive layer 2 are laminated in this order.
• Another layer (e.g., a protective film, etc.) may be laminated on the surface of the double-sided adhesive laminate sheet 10.
• the first adhesive layer 1 is made of a first adhesive component.
• the first adhesive layer 1 is composed of a first adhesive component.
• the first adhesive component is preferably a heat-resistant adhesive component.
• the first adhesive layer 1 is preferably made of a first heat-resistant adhesive component.
• the first adhesive component constituting double-sided adhesive laminate sheet 10 "has heat resistance" means that in double-sided adhesive laminate sheet 10, the change ratio ( A12 /A11) of the adhesive strength A12 of first adhesive layer 1 after heating at 200°C for 300 hours to the adhesive strength A11 of first adhesive layer 1 at 23 °C and 50% humidity is 0.40 or more.
• the resin that is the main component of the first adhesive component is not particularly limited.
• the first adhesive component include a fluororesin-based adhesive component or a silicone resin-based adhesive component.
• the first adhesive component is preferably a fluororesin-based adhesive component because it is compatible with the nonwoven fabric sheet composed of fluororesin fibers.
• fluororesins that make up the fluororesin-based adhesive component include copolymers containing fluorine-based monomers such as vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene.
• the adhesive component according to the present invention is a fluororesin-based adhesive component, it is possible to obtain an adhesive component that does not contain a silicone resin-based adhesive component (silicone-free), which is preferable because it can reduce environmental pollution and product defects caused by decomposition products.
• the first adhesive component may contain other additives to the extent that they do not impair the effects of the present invention.
• other additives include fillers, antioxidants, heat stabilizers, light stabilizers, antistatic agents, flame retardants, plasticizers, tackifiers, pigments, etc.
• the content of other additives in the first adhesive component is, for example, 10% by mass or less, 5% by mass or less, 1% by mass or less, etc., when the entire first adhesive component is taken as 100% by mass.
• the thickness T1 of the first adhesive layer 1 is not particularly limited, and is preferably 5 ⁇ m to 500 ⁇ m, 7 ⁇ m to 250 ⁇ m, or 10 ⁇ m to 100 ⁇ m.
• the ratio (T 1 /T 10 ) of the thickness T 1 of the first adhesive layer 1 to the total thickness T 10 of the double-sided adhesive laminate sheet 10 is preferably 0.01 or more, 0.02 or more, or 0.05 or more, and is preferably 0.40 or less, 0.30 or less, or 0.25 or less.
• the second adhesive layer 2 is made of a second adhesive component.
• the second adhesive layer 2 is composed of a second adhesive component.
• the second adhesive component is preferably a heat-resistant adhesive component.
• the second adhesive layer 2 is preferably made of a second heat-resistant adhesive component.
• the second adhesive component constituting double-sided adhesive laminate sheet 10 "has heat resistance" means that in double-sided adhesive laminate sheet 10, the rate of change (A22/ A21 ) of the adhesive strength A22 of second adhesive layer 2 after heating at 200°C for 300 hours to the adhesive strength A21 of second adhesive layer 2 at 23 °C and 50% humidity is 0.40 or more.
• the second adhesive component can be the same as that described as the first adhesive component, so the description will be omitted.
• the second adhesive component constituting the second adhesive layer 2 and the first adhesive component constituting the first adhesive layer 1 may be the same component or different components, but it is preferable that both have adhesiveness and heat resistance.
• the second adhesive component is preferably a fluororesin-based adhesive component, since it is easily compatible with the nonwoven fabric sheet composed of fluororesin fibers. It is more preferable that both the first adhesive component and the second adhesive component are fluororesin-based adhesive components.
• the thickness T2 of the second adhesive layer 2 is not particularly limited, and is preferably 5 ⁇ m to 500 ⁇ m, 7 ⁇ m to 250 ⁇ m, or 10 ⁇ m to 100 ⁇ m.
• the ratio ( T2 / T10 ) of the thickness T2 of the second adhesive layer 2 to the total thickness T10 of the double-sided adhesive laminate sheet 10 is preferably 0.01 or more, 0.02 or more, or 0.05 or more, and is preferably 0.40 or less, 0.30 or less, or 0.25 or less.
• the base material layer A includes a nonwoven fabric sheet (not shown) made of fluororesin fibers, and has regions where the nonwoven fabric sheet is impregnated with an adhesive component and regions where the nonwoven fabric sheet is not impregnated with an adhesive component.
• the base material layer A has a first mixed layer A1 which is formed from a first adhesive layer 1 side main surface S A1 (main surface in contact with the first adhesive layer 1) toward a second adhesive layer 2 side main surface S A2 (main surface in contact with the second adhesive layer 2) and is an area impregnated with a first adhesive component;
• a second mixed layer A2 is formed from the second adhesive layer 2 side main surface S A2 toward the first adhesive layer 1 side main surface S A1 and is an area impregnated with a second adhesive component;
• the air layer A0 is a layer made of a nonwoven fabric sheet containing air, formed between the first mixed layer A1 and the second mixed layer A2.
• the nonwoven fabric sheet constituting the base layer A is porous.
• the adhesive component penetrates into the holes in the nonwoven fabric sheet, forming a mixed layer containing fibers and the adhesive component.
• the areas of the nonwoven fabric sheet that have not been penetrated by the adhesive component maintain the porous state inherent to the nonwoven fabric sheet, and an air layer containing air is formed.
• the base layer A includes a mixed layer and an air layer.
• the first adhesive component constituting the first adhesive layer 1 and the first adhesive component constituting the first mixed layer A1 are integrated (continuous).
• the second adhesive component constituting the second adhesive layer 2 and the second adhesive component constituting the second mixed layer A2 are integrated (continuous).
• the nonwoven fabric sheet that constitutes the base layer A can be any conventionally known material.
• the fluororesin fibers constituting the nonwoven fabric sheet are not particularly limited, and examples include fibers made from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.
• PTFE polytetrafluoroethylene
• PVDF polyvinylidene fluoride
• PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
• FEP tetrafluoroethylene-hexafluoropropylene copolymer
• the fiber diameter and fiber length of the fluororesin fibers and the density of the nonwoven fabric sheet can be appropriately adjusted taking into consideration the porosity of the base layer A (or the porosity of the air layer A0), strength, ease of impregnation with the adhesive component, etc.
• the thickness T A of the base layer A is not particularly limited, and is preferably 20 ⁇ m to 1000 ⁇ m, 50 ⁇ m to 800 ⁇ m, or 100 ⁇ m to 500 ⁇ m.
• the thickness T1 of the first adhesive layer 1 is preferably equal to or less than the thickness TA of the base layer A.
• the ratio ( T1 / TA ) of the thickness T1 of the first adhesive layer 1 to the thickness TA of the base layer A is preferably equal to or less than 1.00, equal to or less than 0.90, or equal to or less than 0.80.
• the lower limit of this ratio ( T1 / TA ) is not particularly limited, but is, for example, 0.05, 0.08, or 0.10.
• the thickness T2 of the second adhesive layer 2 is equal to or less than the thickness TA of the base layer A.
• the ratio ( T2 / TA ) of the thickness T2 of the second adhesive layer 2 to the thickness TA of the base layer A is equal to or less than 1.00, equal to or less than 0.90, or equal to or less than 0.80.
• the lower limit of this ratio ( T1 / TA ) is not particularly limited, but is, for example, 0.05, 0.08, or 0.10.
• the air layer A0 is a layer formed by a nonwoven fabric sheet and in which air is held by the nonwoven fabric sheet.
• the air layer A0 usually contains air and a nonwoven fiber sheet.
• the air layer A0 is provided in the range of 40% to 96% of the thickness of the base layer A.
• the ratio of the thickness T A0 of the air layer A0 to the thickness T A of the base layer A ([T A0 /T A ] ⁇ 100) is 40% to 96%.
• [T A0 /T A ] ⁇ 100 is preferably 50% or more, 60% or more, 70% or more, or 80% or more, and is preferably 95% or less, or 94% or less.
• the thickness T A0 of the air layer A0 is not particularly limited, but is preferably 10 ⁇ m to 500 ⁇ m, 50 ⁇ m to 500 ⁇ m, or 100 ⁇ m to 500 ⁇ m.
• the nonwoven fabric sheet constituting the first mixed layer A1 is the same as the nonwoven fabric sheet constituting the air layer A0, and therefore a description thereof will be omitted.
• the first adhesive component constituting the first mixed layer A1 is the same as the first adhesive component constituting the first adhesive layer 1, so a description thereof will be omitted.
• the first mixed layer A1 is provided in a range of 2% to 30% of the thickness of the base layer A.
• the upper limit is preferably 25% or less, 20% or less, 15% or less, or 10% or less.
• the thickness T A1 of the first mixed layer A1 is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, 2 ⁇ m to 50 ⁇ m, or 5 ⁇ m to 20 ⁇ m.
• the nonwoven fabric sheet constituting the second mixed layer A2 is the same as the nonwoven fabric sheet constituting the air layer A0, and therefore a description thereof will be omitted.
• the second adhesive component constituting the second mixed layer A2 is the same as the second adhesive component constituting the second adhesive layer 2, so a description thereof will be omitted.
• the second mixed layer A2 is provided in the range of 2% to 30% of the thickness of the base layer A.
• the upper limit is preferably 25% or less, 20% or less, 15% or less, or 10% or less.
• the thickness T A2 of the second mixed layer A2 is not particularly limited, but is preferably 1 ⁇ m to 100 ⁇ m, 2 ⁇ m to 50 ⁇ m, or 5 ⁇ m to 20 ⁇ m.
• the porosity of the double-sided adhesive laminate sheet 10 is 20% or more, and preferably 25% or more, or 30% or more.
• the upper limit of the porosity of the double-sided adhesive laminate sheet 10 is not particularly limited, and is preferably, for example, 60%, 70%, or 80%.
• the porosity of the double-sided adhesive laminate sheet 10 is calculated as ([volume of air layer A0]/[volume of double-sided adhesive laminate sheet 10]) x [volume % of air in air layer A0], or ([volume of air layer A0] x [volume % of air in air layer A0])/[volume of adhesive laminate sheet 10].
• the porosity of the double-sided adhesive laminate sheet 10 can be adjusted by adjusting the thickness of each layer, etc.
• the double-sided adhesive laminate sheet 10 preferably has a thermal conductivity of 0.20 W/(K ⁇ m) or less, 0.18 W/(K ⁇ m) or less, or 0.15 W/(K ⁇ m) or less.
• a thermal conductivity 0.20 W/(K ⁇ m) or less, 0.18 W/(K ⁇ m) or less, or 0.15 W/(K ⁇ m) or less.
• the thermal conductivity (k) of the double-sided adhesive laminate sheet 10 is calculated by the non-steady-state method from the "thermal diffusivity", "density” and "specific heat” using the following formula.
• the thermal diffusivity is measured using a thin film ultra-high sensitivity thermal diffusivity measurement device (ai-Phase Mobile M3 Type 1, manufactured by Ai-Phase Co., Ltd.) on the double-sided adhesive laminate sheet 10 cut into 5 cm squares in accordance with ISO 22007-3.
• the specific heat is measured using a differential scanning calorimeter (DSC) (DSC6200, manufactured by Hitachi, Ltd.) on the double-sided adhesive laminate sheet 10 cut into 5 cm squares in accordance with JIS K 7123.
• DSC differential scanning calorimeter
• the density is calculated from the weight of the double-sided adhesive laminate sheet 10 cut into 5 cm squares measured by a scale and the volume value of the double-sided adhesive laminate sheet 10 calculated in the above "void ratio calculation".
• k ⁇ C P (k: thermal conductivity [W/(m ⁇ K)], ⁇ : thermal diffusivity [m 2 /s], ⁇ : density [kg/m 3 ], C P : specific heat (specific heat at constant pressure) [J/(Kg ⁇ K)])
• the double-sided pressure-sensitive adhesive laminate sheet 10 preferably satisfies at least one of the following (1) or (2), and preferably satisfies both of the following (1) and (2).
• the change ratio ( A12 /A11) of the adhesive strength A12 of the first adhesive layer 1 after heating at 200°C for 300 hours to the adhesive strength A11 of the first adhesive layer 1 at 23°C and a humidity (relative humidity ) of 50 % is 0.40 or more (more preferably, 0.60 or more, or 1.00 or more).
• the change ratio ( A22 /A21) of the adhesive strength A22 of the second adhesive layer 2 after heating at 200°C for 300 hours to the adhesive strength A21 of the second adhesive layer 2 at 23°C and a humidity ( relative humidity ) of 50% is 0.40 or more (more preferably, 0.60 or more, or 1.00 or more).
• the double-sided adhesive laminate sheet 10 has this adhesive strength, it is likely to function adequately as a heat-resistant adhesive sheet.
• the adhesive strength of the double-sided adhesive laminated sheet 10 was evaluated by first polishing the surface of an aluminum alloy (A5052) plate with sandpaper, and then bonding the adhesive layer surface of a double-sided adhesive laminated sheet 10 cut to a size of 5 cm x 5 mm to the polished surface with a hand roller.
• the measurement is performed by dividing the evaluation objects into two conditions, "(1) immediately after lamination” and "(2) after lamination, heated in an oven at 200°C for 300 hours, and then cooled at room temperature for 1 hour", using a Tensilon universal testing machine (RTC-1210, manufactured by A&D Manufacturing Co., Ltd.) at a peel angle of 90° and a peel speed of 50 mm/min.
• the measurement is performed a total of five times under each of the above conditions (1) and (2), and the average value is taken as the adhesive strength.
• the adhesive strength A11 of the first adhesive layer 1 and the adhesive strength A21 of the second adhesive layer 2 are not particularly limited, and are preferably 0.05 [N/5 mm] or more, 0.1 [N/5 mm] or more, or 0.2 [N/5 mm] or more.
• the adhesive strength A12 of the first adhesive layer 1 and the adhesive strength A22 of the second adhesive layer 2 are not particularly limited, and are preferably 0.05 [N/5 mm] or more, 0.1 [N/5 mm] or more, 0.2 [N/5 mm] or more, 0.3 [N/5 mm] or more, or 0.5 [N/5 mm] or more.
• the double-sided pressure-sensitive adhesive laminated sheet 10 can be produced according to a conventionally known method as long as the method is capable of maintaining the air layer A0 within the layer.
• a specified adhesive paint (a composition containing an adhesive and a solvent) is applied to a specified nonwoven fabric sheet and dried, or a previously prepared adhesive paint film is placed adjacent to it and pressed, and a double-sided adhesive laminate sheet 10 including a substrate layer A can be obtained by controlling the air layer derived from the nonwoven fabric sheet and the mixed layer, which is the area impregnated with the adhesive component, to have an appropriate shape.
• the double-sided pressure-sensitive adhesive laminate sheet 10 can be produced, for example, by the following method. An adhesive paint containing an adhesive that is the first adhesive component and an appropriate solvent is applied onto a release film (such as a PET film), and the adhesive paint is then dried to form a film provided with an adhesive layer made of the first adhesive component.
• the adhesive layer made of the first adhesive component provided on the release film is brought into contact with one of the main surfaces (the main surface S A1 on the side of the first adhesive layer 1) of the nonwoven fabric sheet, and while applying pressure (and heating as necessary), the adhesive layer made of the first adhesive component is pressed into the nonwoven fabric sheet to impregnate a part of the adhesive component into the nonwoven fabric sheet, thereby forming a first mixed layer A1.
• the part of the adhesive layer that is not impregnated into the nonwoven fabric sheet becomes the first adhesive layer 1.
• a pressure-sensitive adhesive layer made of a second adhesive component provided on a release film is brought into contact with the other main surface (main surface S A2 on the second adhesive layer 2 side) of the nonwoven fabric sheet, and a part of the adhesive component is impregnated into the nonwoven fabric sheet while applying pressure (and heating as necessary), thereby forming a second mixed layer A2 and a second adhesive layer 2.
• the pressing depth of each adhesive layer is adjusted to form an air layer A0, which is a region in which no adhesive component exists, between the first mixed layer A1 and the second mixed layer A2 in the nonwoven fabric sheet.
• the release film is removed as necessary to obtain a double-sided adhesive laminated sheet 10.
• the thickness of the nonwoven fabric sheet at the raw material stage may differ from that of the nonwoven fabric sheet at the double-sided adhesive laminated sheet 10 stage.
• the nonwoven fabric sheet may be compressed in advance, or a nonwoven fabric sheet with a thickness that takes into account the deformation of the nonwoven fabric sheet may be used.
• the method for manufacturing the double-sided adhesive laminate sheet 10 is not limited to this.
• the method for manufacturing the double-sided adhesive laminate sheet 10 may be a method in which an adhesive paint before drying is directly applied to a nonwoven fabric sheet, and the adhesive coating is dried while adjusting the impregnation of the adhesive paint into the nonwoven fabric sheet so that an air layer remains within the layer of the double-sided adhesive laminate sheet 10, to form a mixed layer and an adhesive layer.
• the double-sided pressure-sensitive adhesive laminate sheet 10 has a predetermined air layer and is therefore excellent in heat insulation and conformability, and can therefore be suitably used for various heat insulation or heat resistance applications.
• a double-sided pressure-sensitive adhesive laminate sheet was produced as follows. The measurement methods used in this production are as follows.
• ⁇ Adhesive layer thickness measurement> The thickness of the adhesive layer was measured using a micrometer (MDH-25MC, manufactured by Mitutoyo Corporation) by averaging measurements taken at five points on each of the four corners of the main surface of a 5 cm square cut adhesive layer.
• the adhesive strength of the adhesive layer was evaluated by using an aluminum alloy (A5052) aluminum plate with a surface that had been polished with sandpaper in advance, and a piece of adhesive layer with PET film on both sides that had been cut to 5 cm x 5 mm had one of the PET films peeled off to expose the adhesive layer surface, which was then bonded to the polished surface with a hand roller.
• the measurement was performed using a Tensilon universal testing machine (RTC-1210, manufactured by A&D Manufacturing Co., Ltd.) at a peel angle of 90° and a peel speed of 50 mm/min. The measurement was performed five times in total, and the average value was taken as the adhesive strength.
• Example 1 Coating material 1 was prepared by dispersing a copolymer resin made of TFE and propylene in tetrahydrofuran (THF) to a concentration of 20 wt %. Next, the coating material 1 was applied onto the treated surface of a 38 ⁇ m-thick release PET film 1 using an applicator, and then dried at 90° C. for 3 minutes to obtain a composition 1 with a PET film on one side. Furthermore, the treated surface of release PET film 2, which has an easier release property than release PET film 1, was laminated to the composition 1 surface of composition 1 with a single PET film using a laminator at room temperature and 0.1 MPa to obtain adhesive layer 1 with double-sided PET films.
• THF tetrahydrofuran
• the adhesive layer 1 had a thickness of 25 ⁇ m and an adhesive strength of 0.1 N/5 mm.
• the adhesive layer 1 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 1 with PET films on both sides will be referred to as adhesive layer 1a with PET films on both sides, and that adhesive layer 1 will be referred to as adhesive layer 1a, the second adhesive layer 1 with PET films on both sides will be referred to as adhesive layer 1b with PET films on both sides, and that adhesive layer 1 will be referred to as adhesive layer 1b).
• the release PET film 2 of the first double-sided PET film-attached adhesive layer 1a was peeled off to expose the adhesive layer 1a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 1a surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 1 with a PET film on one side, in which the adhesive of the adhesive layer 1a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• the release PET film 2 of the second adhesive layer 1b with PET film on both sides was peeled off to expose the adhesive layer 1b side, and then the other side of the nonwoven fabric sheet of single-sided adhesive laminate sheet 1 with PET film on one side was thermally laminated to the exposed adhesive layer 1b side using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a double-sided adhesive laminate sheet 1 with PET film on both sides in which some of the adhesive of adhesive layer 1b has impregnated inside from the other side of the nonwoven fabric sheet of single-sided adhesive laminate sheet 1 with PET film on one side.
• Example 2 Two pieces of the double-sided PET film-attached adhesive layer 1 prepared in Example 1 were prepared. Next, the release PET films 2 of each of the two prepared adhesive layers 1 with PET films on both sides were peeled off to expose the adhesive layer 1 surface, and then the two exposed adhesive layer 1 surfaces were laminated together using a laminator at room temperature and 0.1 MPa to obtain an adhesive layer 2 with PET films on both sides.
• the adhesive layer 2 had a thickness of 50 ⁇ m.
• the adhesive layer 2 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 2 with PET films on both sides will be referred to as adhesive layer 2a with PET films on both sides, and that adhesive layer 2 will be referred to as adhesive layer 2a, the second adhesive layer 2 with PET films on both sides will be referred to as adhesive layer 2b with PET films on both sides, and that adhesive layer 2 will be referred to as adhesive layer 2b).
• one of the release PET films 1 of the first double-sided PET film-attached adhesive layer 2a was peeled off to expose the adhesive layer 2a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fibers as a substrate was thermally laminated to the exposed adhesive layer 2a surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 2 with a PET film on one side, in which the adhesive of the adhesive layer 2a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• one of the release PET films 1 of the second double-sided PET film-attached adhesive layer 2b was peeled off to expose the adhesive layer 2b surface, and then the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 2 with a PET film on one side was thermally laminated to the exposed adhesive layer 2b surface using a laminator at 120°C and 0.3 MPa to obtain a double-sided adhesive laminate sheet 2 with a PET film on both sides in which some of the adhesive of the adhesive layer 2b has impregnated inside from the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 2 with a PET film on one side.
• Example 3 An adhesive layer 1 with a double-sided PET film prepared in Example 1 and an adhesive layer 2 with a double-sided PET film prepared in Example 2 were prepared. Next, the release PET film 2 of the prepared double-sided PET film-attached adhesive layer 1 and the release PET film 1 of the double-sided PET film-attached adhesive layer 2 were peeled off to expose the adhesive layer 1 and adhesive layer 2 surfaces, and then the two exposed adhesive layer surfaces were laminated together using a laminator under conditions of room temperature and 0.1 MPa to obtain an adhesive layer 3 with double-sided PET films.
• the adhesive layer 3 had a thickness of 75 ⁇ m.
• the adhesive layer 3 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 3 with PET films on both sides will be referred to as adhesive layer 3a with PET films on both sides, and that adhesive layer 3 will be referred to as adhesive layer 3a, the second adhesive layer 3 with PET films on both sides will be referred to as adhesive layer 3b with PET films on both sides, and that adhesive layer 3 will be referred to as adhesive layer 3b).
• one of the release PET films 1 of the first double-sided PET film-attached adhesive layer 3a was peeled off to expose the adhesive layer 3a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 3a surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 3 with a PET film on one side, in which the adhesive of the adhesive layer 3a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• one of the release PET films 1 of the second double-sided PET film-attached adhesive layer 3b was peeled off to expose the adhesive layer 3b surface, and then the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 3 with a PET film on one side was thermally laminated to the exposed adhesive layer 3b surface using a laminator at 120°C and 0.3 MPa to obtain a double-sided adhesive laminate sheet 3 with a PET film on both sides in which some of the adhesive of the adhesive layer 3b has impregnated inside from the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 3 with a PET film on one side.
• Example 4 Two pieces of the double-sided PET film-attached adhesive layer 2 prepared in Example 2 were prepared. Next, the release PET film 1 of each of the two prepared adhesive layers 2 with PET films on both sides was peeled off to expose the adhesive layer 2 surface, and the two exposed adhesive layer 2 surfaces were then laminated together using a laminator at room temperature and 0.1 MPa to obtain an adhesive layer 4 with PET films on both sides.
• the adhesive layer 4 had a thickness of 100 ⁇ m.
• the adhesive layer 4 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 4 with PET films on both sides will be referred to as adhesive layer 4a with PET films on both sides, and that adhesive layer 4 will be referred to as adhesive layer 4a, the second adhesive layer 4 with PET films on both sides will be referred to as adhesive layer 4b with PET films on both sides, and that adhesive layer 4 will be referred to as adhesive layer 4b).
• one of the release PET films 1 of the first double-sided PET film-attached adhesive layer 4a was peeled off to expose the adhesive layer 4a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 4a surface using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 4 with a PET film on one side, in which the adhesive of the adhesive layer 4a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• one of the release PET films 1 of the second double-sided PET film-attached adhesive layer 4b was peeled off to expose the adhesive layer 4b surface, and then the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 4 with a PET film on one side was thermally laminated to the exposed adhesive layer 4b surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a double-sided adhesive laminate sheet 4 with a double-sided PET film in which some of the adhesive of the adhesive layer 4b has impregnated inside from the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 4 with a PET film on one side.
• the adhesive layer 5 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 5 with PET films on both sides will be referred to as adhesive layer 5a with PET films on both sides, and that adhesive layer 5 will be referred to as adhesive layer 5a, the second adhesive layer 5 with PET films on both sides will be referred to as adhesive layer 5b with PET films on both sides, and that adhesive layer 5 will be referred to as adhesive layer 5b).
• one of the release PET films 1 of the first double-sided PET film-attached adhesive layer 5a was peeled off to expose the adhesive layer 5a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 5a surface using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 5 with a PET film on one side, in which the adhesive of the adhesive layer 5a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• one of the release PET films 1 of the second double-sided PET film-attached adhesive layer 5b was peeled off to expose the adhesive layer 5b surface, and then the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 5 with a PET film on one side was thermally laminated to the exposed adhesive layer 5b surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a double-sided adhesive laminate sheet 5 with a double-sided PET film in which some of the adhesive of the adhesive layer 5b has impregnated inside from the other surface of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 5 with a PET film on one side.
• the adhesive layer 6 had a thickness of 25 ⁇ m and an adhesive strength of 2.0 N/5 mm.
• the adhesive layer 6 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 6 with PET films on both sides will be referred to as adhesive layer 6a with PET films on both sides, and that adhesive layer 6 will be referred to as adhesive layer 6a, the second adhesive layer 6 with PET films on both sides will be referred to as adhesive layer 6b with PET films on both sides, and that adhesive layer 6 will be referred to as adhesive layer 6b).
• the release PET film 2 of the first double-sided PET film-attached adhesive layer 6a was peeled off to expose the adhesive layer 6a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 6a surface using a laminator at 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 6 with a PET film on one side, in which the adhesive of the adhesive layer 6a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• the release PET film 2 of the second adhesive layer 6b with PET film on both sides was peeled off to expose the adhesive layer 6b side, and then the other side of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 6 with PET film on one side was thermally laminated to the exposed adhesive layer 6b side using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a double-sided adhesive laminate sheet 6 with PET film on both sides in which some of the adhesive of the adhesive layer 6b has impregnated inside from the other side of the nonwoven fabric sheet of the single-sided adhesive laminate sheet 6 with PET film on one side.
• ⁇ Comparative Example 3> A resin consisting of a styrene-based copolymer, an aromatic hydrocarbon resin, and a polyolefin-based resin was dispersed in toluene to a concentration of 30 wt %, to prepare paint 3. Next, the coating material 3 was applied onto the treated surface of a 38 ⁇ m-thick release PET film 1 using an applicator, and then dried at 90° C. for 3 minutes to obtain a composition 3 having a PET film on one side.
• the treated surface of release PET film 2, which has an easier release property than release PET film 1 was laminated to the composition 3 surface of composition 3 with a PET film on one side using a laminator at room temperature and 0.1 MPa to obtain adhesive layer 7 with PET films on both sides.
• the adhesive layer 7 had a thickness of 27 ⁇ m and an adhesive strength of 0.9 N/5 mm.
• the adhesive layer 7 with PET films on both sides was cut into a total of two pieces (hereinafter, the first adhesive layer 7 with PET films on both sides will be referred to as adhesive layer 7a with PET films on both sides, and that adhesive layer 7 will be referred to as adhesive layer 7a, the second adhesive layer 7 with PET films on both sides will be referred to as adhesive layer 7b with PET films on both sides, and that adhesive layer 7 will be referred to as adhesive layer 7b).
• the release PET film 2 of the first double-sided PET film-attached adhesive layer 7a was peeled off to expose the adhesive layer 7a surface, and then one side of a nonwoven fabric sheet (Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.) composed of fluororesin fiber as a substrate was thermally laminated to the exposed adhesive layer 7a surface using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a single-sided adhesive laminate sheet 7 with a PET film on one side, in which the adhesive of the adhesive layer 7a is partially impregnated into the interior from one side of the nonwoven fabric sheet.
• a nonwoven fabric sheet Tommy Phylec F, manufactured by Tomoegawa Paper Works, Ltd.
• the release PET film 2 of the second adhesive layer 7b with PET film on both sides was peeled off to expose the adhesive layer 7b side, and then the other side of the nonwoven fabric sheet of single-sided adhesive laminate sheet 7 with PET film on one side was thermally laminated to the exposed adhesive layer 7b side using a laminator under conditions of 120°C and 0.3 MPa, thereby obtaining a double-sided adhesive laminate sheet 7 with PET film on both sides in which some of the adhesive of adhesive layer 7b has impregnated into the interior from the other side of the nonwoven fabric sheet of single-sided adhesive laminate sheet 7 with PET film on one side.
• Examples 5 and 6 Comparative Examples 4 to 7> Except for changing the thickness of the air layer, the thickness of the adhesive layer, the volume ratio of the mixed layer, the total thickness, and the porosity, etc., as shown in Table 1, double-sided adhesive laminated sheets 4 with double-sided PET films for Examples 5 and 6 and Comparative Examples 4-7 were obtained in the same manner as in Example 1.
• each of the double-sided adhesive laminate sheets with PET films on both sides cut into 5 cm squares was cut in a direction perpendicular to the main surface to expose the cross section of each of the double-sided adhesive laminate sheets with PET films on both sides.
• the exposed cross section was subjected to image analysis using a microscope (VHX-8000 manufactured by Keyence Corporation) to measure the total thickness of each double-sided adhesive laminate sheet and the thicknesses of the "two adhesive layers (hereinafter referred to as adhesive layer A and adhesive layer B)", “air layer”, and “two mixed layers (hereinafter referred to as mixed layer A and mixed layer B)" therein.
• each thickness was measured at 20 arbitrary locations in the width direction (direction perpendicular to the perpendicular direction) of the exposed cross section of the double-sided adhesive laminate sheet with double-sided PET film, and the average value was calculated.
• the void ratio was calculated as the ratio of air to the volume of the air layer relative to the volume of the double-sided pressure-sensitive adhesive laminate sheet.
• the void ratio of the substrate was calculated from the following formula: Note that the apparent density of the substrate was measured by a geometric measurement method in accordance with JIS Z 8807.
• Substrate porosity (%) (1-(apparent density of substrate/true density of substrate fiber material)) ⁇ 100
• the substrate porosity was calculated from the above formula, and the volume of air in the air layer was calculated by multiplying the substrate porosity by the apparent volume of the air layer calculated using the thickness of the air layer in the above "Thickness measurement.”
• the volume value of the double-sided pressure-sensitive adhesive laminate sheet was calculated using the thickness of the double-sided pressure-sensitive adhesive laminate sheet in the above "Thickness Measurement”. From the above, the ratio of the volume of air in the air layer to the volume of the obtained double-sided pressure-sensitive adhesive laminate sheet was calculated as the void ratio.
• the thermal conductivity (k) was calculated by the unsteady method from the "thermal diffusivity”, “density”, and “specific heat” using the following formula.
• the "thermal diffusivity” and “specific heat” were measured by the method described below.
• the "density” was calculated from the weight of the double-sided pressure-sensitive adhesive laminated sheet cut into 5 cm squares measured on a scale and the volume value of the double-sided pressure-sensitive adhesive laminated sheet calculated in the "void ratio calculation” above.
• the thermal diffusivity measurement was performed on a double-sided adhesive laminated sheet cut into a 5 cm square using an ultra-high sensitivity thermal diffusivity measurement device for thin films (ai-Phase Mobile M3 Type 1, manufactured by Ai-Phase Co., Ltd.) in accordance with ISO 22007-3.
• the specific heat measurement was carried out in accordance with JIS K 7123 using a differential scanning calorimeter (DSC) (DSC6200, manufactured by Hitachi, Ltd.) on a double-sided pressure-sensitive adhesive laminate sheet cut into a 5 cm square.
• DSC differential scanning calorimeter
• the adhesive strength of the double-sided adhesive laminate sheet was evaluated by first polishing the surface of an aluminum alloy (A5052) aluminum plate with sandpaper, and then using a hand roller to bond a double-sided adhesive laminate sheet with PET film on both sides that had been cut to 5 cm x 5 mm in size to the polished surface, with one side of the PET film peeled off to expose the adhesive layer.
• A5052 aluminum alloy
• a hand roller to bond a double-sided adhesive laminate sheet with PET film on both sides that had been cut to 5 cm x 5 mm in size to the polished surface, with one side of the PET film peeled off to expose the adhesive layer.
• the measurement was performed on the evaluation objects divided into "(1) immediately after lamination” and "(2) after lamination, heated in an oven at 200°C for 300 hours, and then cooled at room temperature for 1 hour” using a Tensilon universal testing machine (RTC-1210, manufactured by A&D Manufacturing Co., Ltd.) at a peel angle of 90° and a peel speed of 50 mm/min.
• the measurement was performed a total of five times under each of the above conditions (1) and (2), and the average value was taken as the adhesive strength.
• this embodiment has produced an adhesive laminate sheet with excellent heat insulation properties (for example, thermal conductivity of 0.20 W/(K ⁇ m) or less) and heat resistance.
• Adhesive laminated sheet 1 Adhesive layer A: Base material layer A0: Air layer A1, A2: Mixed layer

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