WO2022102778A1 - Stratifié - Google Patents

Stratifié Download PDF

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Publication number
WO2022102778A1
WO2022102778A1 PCT/JP2021/041955 JP2021041955W WO2022102778A1 WO 2022102778 A1 WO2022102778 A1 WO 2022102778A1 JP 2021041955 W JP2021041955 W JP 2021041955W WO 2022102778 A1 WO2022102778 A1 WO 2022102778A1
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WO
WIPO (PCT)
Prior art keywords
layer
silicone
laminate
polyimide
less
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PCT/JP2021/041955
Other languages
English (en)
Japanese (ja)
Inventor
香 谷山
純 松井
陽輔 濱
Original Assignee
三菱ケミカル株式会社
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Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to CN202180076372.0A priority Critical patent/CN116406333A/zh
Priority to KR1020237016307A priority patent/KR20230125172A/ko
Publication of WO2022102778A1 publication Critical patent/WO2022102778A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B32B2037/268—Release layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to a laminate having at least two resin layers, which is used for, for example, a mold release material, a cushioning material, a non-slip material, etc., and has a silicone layer and a polyimide layer.
  • silicones typified by silicone rubbers and silicone resins, especially silicone rubbers such as mirable type, have excellent heat resistance and electrical properties, and are therefore widely used in applications such as mold release materials, cushioning materials, and non-slip materials.
  • mold release materials such as press molding, a cushioning material, or the like.
  • non-slip material for transport carriers in reflow processes and the like.
  • silicone composed of a single silicone layer such as silicone rubber is used as it is as a release material for press molding, deformation occurs, assembly dimensional accuracy deteriorates, and wrinkles occur, which causes problems in workability. Therefore, it is known that silicone is used as a laminate by compositely integrating a plastic film.
  • the plastic film for example, as disclosed in Patent Document 1, a polyester resin film or the like is used. Further, the silicone is often laminated on the polyester resin film via an undercoat layer or the like in order to improve the adhesiveness.
  • press molding performed on all-solid-state batteries, semiconductors, etc. tends to have a high molding temperature and molding pressure.
  • press working may be performed at a temperature of about 100 to 300 ° C. and a pressure of about 50 to 1000 MPa.
  • the press molding temperature tends to be high also in the manufacturing process of FPC.
  • the silicone film (silicone layer) is integrated with another plastic film such as a polyester film and used repeatedly by press molding in a high temperature environment, the silicone film itself becomes brittle and has cushioning properties. Cannot be maintained, and problems such as being unable to be used repeatedly for a long period of time occur.
  • a silicone film laminated on a metal plate is often used, but from the viewpoint of weight reduction, a resin sheet is used instead of the metal plate.
  • a resin sheet is used instead of the metal plate.
  • the transport carrier is also heated to a high temperature, which makes the silicone film brittle and causes dimensional changes in the polyester film, making it difficult to use for a long period of time and practical use.
  • the present inventor has used a polyimide layer as a resin layer integrated with a silicone layer, or a resin layer (A) having a tensile storage elastic modulus that can be suitably used in a specific application.
  • a polyimide layer as a resin layer integrated with a silicone layer, or a resin layer (A) having a tensile storage elastic modulus that can be suitably used in a specific application.
  • B) and using a silicone layer or a resin layer (A) having a low weight loss rate even when heated at a high temperature and completed the following invention. That is, the present invention provides the following [1] to [16].
  • [1] A laminate having a silicone layer and a polyimide layer.
  • a laminate comprising a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • a laminate comprising a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • a laminate comprising a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • the cover film When used as a mold release material or a cushioning material at the time of molding, the cover film is peeled off, the polyimide layer side is arranged on the molding mold side, and the silicone layer side is arranged on the molded body side. ]. How to use the laminate according to any one of.
  • the present invention it is possible to provide a laminate having a silicone layer, which can be used for a long period of time without embrittlement of the silicone layer even when used in a high temperature environment. Further, according to the present invention, it is possible to provide a laminate that is suppressed from embrittlement even when used in a high temperature environment, can be used for a long period of time, and is suitably used for a specific application.
  • the term "main component” includes the meaning of allowing other components to be contained within a range that does not interfere with the function of the main component, unless otherwise specified.
  • the main component is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass in the composition. As mentioned above, it occupies 90% by mass or more (including 100%) particularly preferably.
  • X to Y when expressed as "X to Y" (X and Y are arbitrary numbers), unless otherwise specified, it means “X or more and Y or less", and “preferably larger than X” and “preferably larger than X”. Includes the meaning of "smaller than Y”. Further, in the present invention, when expressed as “X or more” (X is an arbitrary number), it includes the meaning of “preferably larger than X” and “Y or less” (Y is an arbitrary number) unless otherwise specified. When expressed as, it includes the meaning of "preferably smaller than Y” unless otherwise specified.
  • the laminate of the present invention is a laminate including a silicone layer and a polyimide layer.
  • the polyimide layer in addition to the silicone layer, wrinkles and bending are less likely to occur, and the heat resistance is improved. Therefore, for example, the productivity of the molded product when used as a mold release material such as press molding, vacuum forming, pressure forming, or a cushioning material is improved. Further, for example, when it is used as a carrier film for transporting, it is possible to appropriately transport the work even when it is used in a high temperature environment. Furthermore, the laminate can be used repeatedly for a long period of time in a high temperature environment.
  • the silicone layer of the present invention has a weight loss rate of 9% by mass or less at 380 ° C. by thermogravimetric analysis.
  • the weight reduction rate at 380 ° C. exceeds 9% by mass, the silicone layer becomes brittle when the laminate is used in a high temperature environment, the performance such as cushioning property cannot be maintained, and dimensional changes are likely to occur. Therefore, there are problems such as the laminated body cannot be used repeatedly for a long period of time in a high temperature environment. From the viewpoint of suppressing embrittlement of the silicone layer in a high temperature environment and enabling the laminated body to be used for a longer period of time, the weight reduction rate at 380 ° C.
  • the weight loss rate at 380 ° C. is preferably 7% by mass or less, more preferably 6% by mass or less. 5% by mass or less is more preferable.
  • the weight loss rate at 380 ° C. by thermal weight measurement indicates the ratio of the weight loss rate at 380 ° C. to the initial weight by heating the sample collected from the silicone layer at a constant temperature rise rate in the atmosphere. For details, the measurement can be performed by the method described in Examples.
  • the silicone layer preferably has a tensile fracture stress retention rate of 10% or more after being heat-treated at 300 ° C. for 3 hours, more preferably 20% or more, further preferably 30% or more, still more preferably 35%, and particularly preferably. Is 40% or more, most preferably 45% or more.
  • a tensile fracture stress retention rate of 10% or more after being heat-treated at 300 ° C. for 3 hours, more preferably 20% or more, further preferably 30% or more, still more preferably 35%, and particularly preferably. Is 40% or more, most preferably 45% or more.
  • the silicone layer preferably has a tensile fracture strain retention rate of 10% or more, more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more after being heat-treated at 300 ° C. for 3 hours. It is particularly preferably 60% or more, and most preferably 70% or more.
  • the tensile fracture strain retention rate during high-temperature heating becomes high as described above, the cushioning property of the silicone layer is maintained even after heating at high temperature for a long period of time, and the laminate can be used for a long period of time.
  • the tensile fracture stress retention rate and the tensile fracture strain retention rate were measured at the initial stage before the heat treatment and after heat treatment at 300 ° C. for 3 hours, and then a tensile test was performed at each to measure the stress and elongation at the time of tensile fracture before and after the heat treatment.
  • the ratio of the fracture stress and the fracture strain after the heat treatment to the initial fracture stress and the initial fracture strain before the heat treatment is shown as a percentage.
  • the tensile direction may be the resin flow direction (MD), but if the MD is unknown, the fracture stress and fracture strain are measured by pulling in the direction in which the initial fracture stress is highest. good.
  • the measurement may be performed on a test piece cut out from the silicone layer of the laminated body, and if it is difficult to cut out, a sample prepared by the same method as the method for forming the silicone layer in the laminated body (thickness is also the same as that of the laminated body). It may be measured for the same as the silicone layer).
  • the tensile storage elastic modulus which will be described later, may be measured in the same manner.
  • the initial fracture stress of the silicone layer is not particularly limited, but is preferably 3 MPa or more, more preferably 5 MPa or more, further preferably 8 MPa or more, and for example, 25 MPa or less, preferably 20 MPa or less, more preferably 15 MPa or less.
  • the initial fracture strain of the silicone layer is not particularly limited, but is preferably 200% or more, more preferably 250% or more, further preferably 300% or more, particularly preferably 350% or more, and for example, 1400% or less. It is preferably 1300% or less.
  • the silicone layer of the present invention is a layer containing silicone as a main component.
  • the silicone preferably contains a silicone having a siloxane skeleton represented by the following formula (1).
  • a silicone having a siloxane skeleton represented by the following formula (1) in addition to polydimethylsiloxane in which all Rs in the formula are methyl groups, a part of the methyl group (for example, about 30 mol% or less, preferably about 20 mol% or less) is another.
  • Various polydimethylsiloxanes substituted with one or more of an alkyl group, a vinyl group, a phenyl group, a fluoroalkyl group and the like can also be appropriately selected.
  • n in the equation is a positive integer of 1 or more, preferably 3 to 5000.
  • the silicone is preferably a silicone elastomer resin. Therefore, the silicone layer preferably contains a silicone elastomer resin, and more preferably contains a silicone elastomer resin as a main component. As an example of the silicone elastomer resin, a silicone elastomer resin containing polydimethylsiloxane as a main component is preferably mentioned.
  • the silicone elastomer resin particularly polydimethylsiloxane, preferably contains a vinyl group.
  • a vinyl group By containing a vinyl group, the compression set becomes smaller, the thickness tends to be less likely to change even after repeated use during press molding, etc., sufficient cushioning property is maintained, and durability tends to be excellent.
  • the content of the vinyl group with respect to the total amount of the silicone elastomer resin is preferably 0.05 to 5 mol%, more preferably 0.5 to 4 mol%, and 1 to 3 mol. % Is more preferable.
  • the content of the vinyl group is at least the above lower limit value, it becomes easy to adjust the crosslink density of the silicone elastomer resin, and it tends to be easy to obtain a silicone elastomer resin having a desired compression set.
  • it is at least the above upper limit value it is preferable because the silicone elastomer resin is not excessively crosslinked.
  • the silicone elastomer resin may contain a silicone elastomer resin containing no vinyl group from the viewpoint of adjusting the cross-linking point, and the silicone elastomer resin containing a vinyl group and the silicone elastomer resin containing no vinyl group may be contained. It may be used together.
  • the silicone elastomer resin is preferably a mirabable type.
  • the mirabable silicone elastomer resin is a non-liquid (for example, solid or paste) having no self-fluidity at room temperature (25 ° C.) in an uncrosslinked state, but is mixed with other components in a kneader or the like. It can be mixed uniformly with additives and the like described later. Further, since the silicone elastomer resin is a mirable type, the productivity is improved.
  • the silicone elastomer resin is crosslinked in the silicone layer.
  • the silicone elastomer layer By cross-linking the silicone elastomer layer, cushioning properties and the like are easily imparted, and compression set and the like are improved, so that the silicone elastomer layer can be suitably used as a mold release material, a cushioning material, etc. at the time of press molding.
  • the silicone layer is more preferably a radiation crosslinked body crosslinked by radiation.
  • the silicone layer of the present invention preferably contains a metal oxide.
  • the metal oxide include titanium oxide, iron oxide, cerium oxide and the like, and among these, titanium oxide and iron oxide are preferable. Further, in particular, iron oxide is more preferable from the viewpoint of maintaining a high tensile fracture strain retention rate, and titanium oxide is more preferable from the viewpoint of appearance such as coloring.
  • the metal oxide may be used alone or in combination of two or more.
  • the content of the metal oxide in the silicone layer is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, further preferably 0.5 to 5% by mass, and 0.7 to 3% by mass. Is particularly preferable.
  • the heat resistance is appropriately improved, and the weight loss rate at the above-mentioned 380 ° C. is sufficiently lowered.
  • the value can be improved without impairing the performance such as the cushioning property of the silicone layer.
  • the silicone layer of the present invention preferably contains carbon black.
  • carbon black By containing carbon black in the silicone layer, the heat resistance is improved and the weight loss rate at 380 ° C. described above is lowered. Then, the tensile fracture stress retention rate and the tensile fracture strain retention rate after the above heat treatment can be increased. In addition, flame resistance can be improved.
  • Examples of carbon black include graphitized carbon, furnace black, acetylene black, and ketjen black, and among these, furnace black is preferable from the viewpoint of availability and price.
  • One type of carbon black may be used alone, or two or more types may be used in combination.
  • the content of carbon black in the silicone layer is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, further preferably 0.2 to 3% by mass, and 0.3 to 2% by mass. Especially preferable.
  • the heat resistance is appropriately improved, and the weight loss rate at the above-mentioned 380 ° C. is sufficiently lowered.
  • the value is set to the upper limit or less, the heat resistance and the flame resistance can be improved without impairing the performance such as the cushioning property of the silicone layer.
  • the silicone layer contains reinforcing fillers such as fumed silica, precipitated silica, diatomaceous earth, and quartz powder, various processing aids, heat resistance improvers, and various additives that give functionality to the elastomer. It may be contained. These can be used alone or in combination of two or more. Examples of the additive include a flame retardant-imparting agent, a heat-dissipating filler, a conductive filler and the like.
  • reinforcing fillers such as fumed silica, precipitated silica, diatomaceous earth, and quartz powder, various processing aids, heat resistance improvers, and various additives that give functionality to the elastomer. It may be contained. These can be used alone or in combination of two or more. Examples of the additive include a flame retardant-imparting agent, a heat-dissipating filler, a conductive filler and the like.
  • the type A durometer hardness of the silicone layer is preferably 3 or more, more preferably 5 or more, further preferably 15 or more, particularly preferably 25 or more, and 35 or more. Is particularly preferable, and 45 or more is most preferable. Further, the type A durometer hardness is preferably 90 or less, more preferably 80 or less, further preferably 70 or less, and particularly preferably 60 or less.
  • the hardness of the type A durometer can be measured according to JIS K6253-3: 2012.
  • Examples of the method for adjusting the hardness of the Type A durometer include a method of adjusting the filling amount of a filler such as silica to be blended in the silicone layer as a filler, a method of appropriately selecting the type of the raw material silicone, and the like.
  • the silicone layer has a tensile storage elastic modulus of, for example, 100 MPa or less at 23 ° C., preferably 100 MPa or less, from the viewpoints of followability to the molded body during press molding, adhesion, and surface tackiness of the silicone layer. It is 70 MPa or less, more preferably 50 MPa or less, still more preferably 30 MPa or less, and particularly preferably 10 MPa or less. Further, it is preferably 0.1 MPa or more, more preferably 0.5 MPa or more, and further preferably 1 MPa or more.
  • silicone elastomer resin a commercially available silicone elastomer resin containing a metal oxide as a heat resistance improver can also be used.
  • Commercially available products include “X-30-3888-U” manufactured by Shin-Etsu Chemical Industry Co., Ltd., which contains about 1 to 3% by mass of iron oxide as a metal oxide, and about 1 to 10% by mass of titanium oxide as a metal oxide. Examples thereof include “TSE2323-5U” manufactured by Momentive Performance Materials Co., Ltd., and “TSE2323-7U” manufactured by Momentive Performance Materials Co., Ltd. containing about 0.1 to 1% by mass of titanium oxide.
  • the thickness of the silicone layer may be appropriately selected depending on the intended use, but is preferably 3 mm or less, more preferably 1 mm or less, further preferably 800 ⁇ m or less, and particularly preferably 600 ⁇ m or less. It is particularly preferably 400 ⁇ m or less. Further, from the viewpoint of appropriate elasticity, long-term use and repeated use, the lower limit is preferably 10 ⁇ m, more preferably 20 ⁇ m, further preferably 30 ⁇ m, and particularly preferably 50 ⁇ m. ..
  • the polyimide layer of the present invention contains polyimide as a main component.
  • the polyimide layer of the present invention preferably has a temperature of 2% weight loss by thermogravimetric analysis of 260 ° C. or higher.
  • the temperature is 260 ° C. or higher, the heat resistance of the polyimide layer is improved, and when used in combination with the above-mentioned silicone layer, the heat resistance of the laminated body is further improved. Therefore, in various applications used in a high temperature environment, the laminated body can be repeatedly used for a long period of time without deteriorating the performance of the laminated body.
  • the temperature of 2% weight reduction by thermogravimetric analysis is more preferably 275 ° C or higher, further preferably 350 ° C or higher, further preferably 400 ° C or higher, still more preferably 450 ° C or higher, from the viewpoint of heat resistance, durability and the like. Preferably, 500 ° C. or higher is particularly preferable, and 540 ° C. or higher is most preferable.
  • the temperature of the 2% weight reduction by thermogravimetric measurement of the polyimide layer is not particularly limited, but is, for example, 750 ° C. or lower, and may be 700 ° C. or lower.
  • the temperature of 2% weight loss by thermogravimetric analysis is a temperature at which the sample collected from the polyimide layer is heated in the atmosphere and the weight loss with respect to the initial weight is 2%, and the details can be measured by the method described in Examples. ..
  • the polyimide layer of the present invention preferably has a tensile storage elastic modulus of 2 GPa or more at 300 ° C.
  • the tensile storage elastic modulus at 300 ° C. is 2 GPa or more, dimensional changes such as the laminated body extending in the plane direction are suppressed even if pressure is applied to the laminated body by press molding or the like at a high temperature. Therefore, even if distortion occurs with the silicone layer, it does not peel off, and the laminated body can be easily used repeatedly in a higher temperature environment. From the viewpoint of reducing dimensional changes even when pressure is applied in a high temperature environment, the tensile storage elastic modulus at 300 ° C.
  • the tensile storage elastic modulus at 300 ° C. is not limited with respect to the upper limit, and may be, for example, 10 GPa or less, 7 GPa or less, or 6 GPa or less.
  • the polyimide layer preferably has a tensile storage elastic modulus at 23 ° C. higher than that of the silicone layer at 23 ° C. Further, the polyimide layer preferably has a tensile storage elastic modulus at 23 ° C. of 3.7 GPa or more.
  • the tensile storage elastic modulus of the polyimide layer at room temperature is high as described above, the handling property becomes good, and for example, it becomes easy to set the molded body at the time of molding. Further, when manufacturing a laminate by a laminating method or the like, tension is likely to act even if it is thin, the production is easy, and the obtained laminate tends to have less wrinkles and the like.
  • the tensile storage elastic modulus at 23 ° C. is preferably 4 GPa or more, more preferably 4.5 GPa or more, still more preferably 5 GPa or more, particularly preferably 6 GPa or more, and most preferably 7 GPa or more. be.
  • the tensile storage elastic modulus at 23 ° C. is not limited with respect to the upper limit, and may be, for example, 15 GPa or less, 13 GPa or less, or 11 GPa or less.
  • the tensile storage elastic modulus of the silicone layer at 23 ° C. may also be measured by using a viscoelastic spectrometer to measure the tensile storage elastic modulus with respect to the single layer of the silicone layer.
  • the tensile storage elastic modulus may be a value measured in the resin flow direction (MD: Machine Direction), but when the MD is unknown, the value in the direction in which the tensile storage elastic modulus is highest is used. You can adopt it.
  • the polyimide layer preferably has a coefficient of linear expansion of 33 ⁇ 10 -6 / ° C. or less.
  • the linear expansion coefficient of the polyimide layer is 33 ⁇ 10 -6 / ° C. or less, the dimensional change is small even after the temperature is changed from a low temperature to a high temperature and repeated use, and the dimensional stability is improved. Therefore, it can be suitably used for various applications used in a high temperature environment.
  • the coefficient of linear expansion of the polyimide layer is preferably 27 ⁇ 10 -6 / ° C or less, more preferably 22 ⁇ 10 -6 / ° C or less, even more preferably 18 ⁇ 10 -6 / ° C or less, and 14 ⁇ 10 -6 / ° C.
  • the coefficient of linear expansion of the polyimide layer is not particularly limited, but may be, for example, 5 ⁇ 10 -6 / ° C. or higher, and may be 8 ⁇ 10 -6 / ° C. or higher.
  • the outermost surface of the laminate composed of the polyimide layer preferably has an arithmetic mean roughness (Ra) of 26 nm or less.
  • Ra arithmetic mean roughness
  • the polyimide layer comes into contact with the molding die side of the press plate or the like, but if the arithmetic average roughness (Ra) is 26 nm or less, the polyimide layer is in contact with the molding die such as the press plate when an initial pressure is applied. It becomes difficult to shift, and the moldability becomes good when it is used as a mold release material, a cushioning material, or the like.
  • the arithmetic average roughness (Ra) of both outermost surfaces is 26 nm or less. Is preferable.
  • both outermost surfaces of the laminated body are polyimide layers, for example, one is in contact with a molding die such as a press plate and the other is in contact with the molded body. Therefore, when the arithmetic mean roughness of both outermost surfaces becomes smaller, not only the molding die such as a press plate but also the molded body is less likely to be displaced, and the moldability when used as a mold release material, a cushioning material, etc. is further improved.
  • the arithmetic mean roughness (Ra) is more preferably 20 nm or less, still more preferably 17 nm or less, still more preferably 13 nm or less, and particularly preferably 10 nm or less, from the viewpoint of preventing deviation from the molded product or a mold such as a press plate. Is.
  • the lower limit of the arithmetic mean roughness (Ra) is not particularly limited, but is, for example, 0.5 nm, preferably 1 nm, more preferably 1.5 nm, and even more preferably 2 nm.
  • the arithmetic average roughness is 0.5 nm or more
  • the convex portions are in point contact with each other, so that the laminated bodies are suppressed from adhering to each other, and a laminated body having excellent peelability can be obtained. Easy to get rid of.
  • the handleability tends to be excellent when the laminated bodies are taken out one by one. Further, after press molding, when the molding die such as a press plate is opened and the molded body is taken out, the problem that the laminated body adheres to the molding die side such as the press plate is improved, and the productivity tends to be improved.
  • both outermost surfaces of the laminated body are polyimide layers, there is an advantage that the contact state with the molded body can be appropriately improved and the alignment on the molded body becomes easy.
  • the surface roughness (Ra) is measured by a three-dimensional non-contact surface shape measuring machine, and may be measured under the measurement conditions described in the examples.
  • the method for adjusting the arithmetic average roughness is not particularly limited, but for example, in a casting process in which a polyimide layer is applied onto a support, dried, and heat-treated, a mirror-polished metal roll or an endless metal belt used as the support is used. A method of appropriately adjusting the surface roughness of the polymer film or the like is preferably mentioned.
  • the polyimide contained in the polyimide layer of the present invention may be any as long as it is obtained by polymerizing a tetracarboxylic acid or a tetracarboxylic acid dianhydride with a diamine, and an aromatic polyimide is preferably used, specifically, the polyimide is used.
  • the aliphatic diamine contains an alicyclic diamine.
  • the polyimide contained in the polyimide layer of the present invention for example, the polyimide represented by the following general formula (2) is used.
  • R 1 is a tetravalent organic group containing an aromatic ring
  • R 2 is a divalent organic group containing an aromatic ring
  • m is an integer of 1 or more.
  • the tetravalent organic group of R 1 may have an aromatic ring, and examples thereof include organic groups having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of R 1 include tetracarboxylic acid residues having an aromatic substance, and specific examples thereof include the following formulas (3-1) to (3-5).
  • any of the formulas (3-1) and (3-2) is preferable, and among them, the organic group represented by any of the following (3-1') and (3-2') is preferable. It is more preferable that it is an organic group represented by the following (3-1').
  • the polyimide represented by the general formula (2) contains, for example, 50 mol% or more, preferably 70, of the organic group represented by any of the above (3-1') and (3-2') in R1 . It is contained in a proportion of mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%.
  • the divalent organic group of R2 may have an aromatic ring, and examples thereof include organic groups having 6 to 24 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 6 to 15 carbon atoms.
  • the divalent organic group of R2 is preferably an organic group represented by any of the following formulas (4) and (5).
  • R 3 and R 4 are independently one of a hydrogen atom, a methyl group, and a halogen atom.
  • the group represented by X is a single bond or oxygen.
  • Atom, sulfur atom, C O, -CH 2- , -CH (CH 3 )-, -C (CH 3 ) 2- , -SO 2- , and -C (CF 3 ) 2- .
  • R 5 , R 6 , R 7 and R 8 are each independently one of a hydrogen atom, a methyl group, and a halogen atom.
  • R 2 of the polyimide represented by the general formula (2) is an organic group represented by the formula (4). Since at least a part of R 2 of the polyimide represented by the general formula (2) is an organic group represented by the formula (4), the heat resistance is high and the temperature of 2% weight loss is also high. Become. Further, the tensile storage elastic modulus at 300 ° C. becomes high, and further, the linear expansion coefficient of the polyimide layer becomes easy to be lowered.
  • the above formula (4) preferably has a bond position at the 1st or 4th position from the viewpoint of heat resistance and low coefficient of linear expansion, and R 3 and R 4 are both hydrogen atoms. It is preferable to have. Therefore, it is more preferable that at least a part of R 2 in the formula (2) is an organic group represented by the following formula (4-1).
  • the polyimide represented by the general formula (2) contains, for example, 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% of the organic group represented by the above formula (4-1) in R2 . It may be contained in the above ratio, 70 mol% or more, or 100 mol% or more.
  • R 2 is an organic group represented by the above formula (4) (preferably the formula (4-1)), and a part of R 2 is the above formula (4).
  • R 2 May be an organic group having an aromatic ring.
  • R 2 other than the above formula (4) include divalent organic groups having 12 to 24 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 15 carbon atoms.
  • the organic group represented by the above formula (5) is preferable.
  • X is preferably an oxygen atom
  • R 5 , R 6 , R 7 and R 8 are all preferably hydrogen atoms.
  • the bonding position in the formula (5) is preferably the 4,4'position. Therefore, the organic group represented by the formula (5) is more preferably the organic group represented by the following formula (5-1).
  • at least a part of R 2 is an organic group represented by the above formula (4) (preferably the formula (4-1)), and the rest are as follows. It is an organic group represented by the formula (5-1).
  • the polyimide is preferably obtained by polymerizing 3,3', 4,4'-biphenyltetracarboxylic acid or its acid dianhydride with 1,4-phenylenediamine, and more specifically, the following.
  • the polyimide represented by the formula (6) is preferable.
  • the heat resistance is good and the temperature at which the weight of the polyimide layer is reduced by 2% is increased. Further, it becomes easy to obtain a polyimide layer having a low linear expansion coefficient and a high tensile storage elastic modulus at 300 ° C.
  • a commercially available product can also be used, and specific examples thereof include "UPIREX-S" manufactured by Ube Kosan Co., Ltd.
  • the polyimide a polyamide obtained by copolymerizing pyromellitic acid or an acid dianhydride thereof with paraphenylenediamine and 4,4'-diaminodiphenyl ether is also preferable, and specifically, the above formula (specifically, the above formula ( In 2), R 1 is an organic group of the formula (3-2'), a part of R 2 is an organic group of the formula (4-1), and the rest is an organic group of the formula (5-1). It is preferably a copolymer polyimide. By controlling the combination of monomers (sequence control), the copolymer polyimide can be a polyimide having relatively good heat resistance while lowering the coefficient of linear expansion.
  • the coefficient of linear expansion is low and the heat resistance is excellent.
  • Polyimide can be obtained. Therefore, the tensile storage elastic modulus of the polyimide layer at 300 ° C. and the temperature of 2% weight loss are likely to be increased.
  • the copolymer polyimide a commercially available product can also be used, and examples thereof include "Apical NPI" manufactured by Kaneka Corporation.
  • the polyimide does not need to have at least a part of R 2 an organic group represented by the above formula (4), and R 2 is a polyimide having the above formula (5), preferably the above formula (5-1). In that case, it is more preferable that R 1 is of the formula (3-2').
  • a polyimide a commercially available product may be used, and specific examples thereof include "Apical AH” manufactured by Kaneka Corporation and "Kapton” manufactured by Toray DuPont.
  • the polyimide layer of the present invention includes other resins, fillers, and various additives such as heat stabilizers, ultraviolet absorbers, light stabilizers, nucleating agents, and coloring agents, as long as the gist of the present invention is not exceeded. Agents, lubricants, flame retardants and the like may be appropriately blended.
  • the content of the other resin is not particularly limited, but may be, for example, about 50 parts by mass or less, 30 parts by mass or less, or 10 parts by mass or less with respect to 100 parts by mass of the polyimide.
  • the resin in the polyimide layer is preferably made of polyimide.
  • the thickness of the polyimide layer may be appropriately selected depending on the intended use, but it should be 150 ⁇ m or less from the viewpoint of imparting desired heat resistance and dimensional stability to the laminate without impairing the cushioning property imparted by the silicone layer. It is more preferably 130 ⁇ m or less, further preferably 100 ⁇ m or less, particularly preferably 80 ⁇ m or less, particularly preferably 60 ⁇ m or less, and preferably 3 ⁇ m or more, 5 ⁇ m. It is more preferably 10 ⁇ m or more, and particularly preferably 15 ⁇ m or more.
  • the thickness of the polyimide layer is the thickness of each polyimide layer provided on both sides of the silicone layer when the polyimide layers are provided on both sides of the silicone layer.
  • the thickness ratio of the silicone layer: polyimide layer is preferably 99: 1 to 20:80.
  • the thickness ratio of the laminated body is within the above range, heat resistance is improved and appropriate elasticity is obtained, so that the laminated body can be suitably used as a mold release material and a cushioning material.
  • the thickness ratio is more preferably 95: 5 to 30:70, further preferably 90:10 to 40:60, and particularly preferably 85:15 to 50:50.
  • the thickness of the polyimide layer referred to here means the thickness of the polyimide layer provided on one side of the silicone layer, and when the polyimide layers are provided on both sides of the silicone layer, they are provided on both sides of the silicone layer.
  • the thickness of the polyimide layer is preferably within the above range.
  • the laminate of the present invention may include a polyimide layer and a silicone layer, and may have a laminate structure in which the polyimide layer is provided on only one side of the silicone layer. That is, the laminated body of the present invention may have a laminated structure of a polyimide layer / a silicone layer. In the laminated structure, the polyimide layer may form one outermost surface of the laminated body, and the silicone layer may form the other outermost surface. More specifically, the laminate may have a two-kind two-layer structure, or may have a structure in which a primer layer described later is provided between the polyimide layer and the silicone layer in addition to the two-kind two-layer structure. ..
  • the polyimide layer side is arranged on the molding mold side such as a press plate, and the silicone layer side is the molded body side. It is good to place it in. According to such an arrangement, the polyimide layer makes it difficult for the laminate to be displaced from the mold, while the silicone layer improves the mold releasability to the mold.
  • the laminated body of the present invention may have a laminated structure in which polyimide layers are provided on both sides of the silicone layer. That is, the laminated body of the present invention may have a laminated structure of a polyimide layer / a silicone layer / a polyimide layer. In the laminated structure, the polyimide layer may form both outermost surfaces of the laminated body. More specifically, the laminate may have a two-kind three-layer structure, or in addition to the two-kind three-layer structure, one or both of the polyimide layer and the silicone layer have a primer layer described later. It may be a structure.
  • the polyimide layer makes it difficult for the molded body and the molded body to be displaced, and the surface is smooth. It becomes easy to obtain a highly high-quality molded product.
  • a low molecular weight siloxane component such as a low molecular weight cyclic siloxane may be precipitated by heating and adhere to a molding die or a obtained molded body to be contaminated.
  • a polyimide layer should be provided on both sides.
  • the precipitation of the low molecular weight siloxane component is prevented, and the contamination by the low molecular weight siloxane component is suppressed.
  • the silicone film is used as a mold release material or a cushioning material
  • the low molecular weight siloxane component adhering to the mold may be removed by heat treatment or the like, but the polyimide layers are provided on both sides. It is also possible to reduce the frequency of heat treatment.
  • a laminate in which the polyimide layer is provided on only one side of the silicone layer is used.
  • a method may be adopted in which the silicone layer side is arranged on the molding die side such as a press plate, and the polyimide layer side is arranged on the molded body side.
  • the polyimide layer may be laminated directly on the silicone layer, or may be laminated via a primer layer.
  • the primer layer preferably contains a silicone resin, and more preferably contains a silicone resin as a main component, from the viewpoint of ensuring adhesiveness to the silicone layer.
  • the silicone resin that can be used for the primer layer include an addition type silicone resin, a condensation type silicone resin, a UV curable silicone resin, and the like, and among them, the addition type silicone resin is preferable. These can be used alone or in combination of two or more.
  • Examples of the addition type silicone resin include those obtained by using polydimethylsiloxane containing a vinyl group as a base polymer, blending polymethylhydrogensiloxane as a cross-linking agent, and reaction-curing in the presence of a platinum catalyst.
  • Examples of the condensed silicone resin include those obtained by using polydimethylsiloxane containing a silanol group at the terminal as a base polymer, blending polymethylhydrogensiloxane as a cross-linking agent, and heat-curing in the presence of an organic tin catalyst. ..
  • the UV curable silicone resin includes a polydimethylsiloxane containing an acryloyl group or a methacryloyl group as a base polymer, a polydimethylsiloxane containing a mercapto group and a vinyl group as a base polymer, and the above-mentioned addition type silicone resin.
  • a photopolymerization initiator may be added to a polydimethylsiloxane base polymer containing an epoxy group that is cured by a cationic curing mechanism, and the polymer may be cured by irradiating with UV light.
  • the primer layer may appropriately contain a silane coupling agent, an adhesion improver and the like, if necessary.
  • Examples of the silane coupling agent include compounds represented by the general formula ZSiX 3 .
  • Z is an organic group having a functional group such as a vinyl group, an epoxy group, an amino group and a mercapto group and having about 1 to 20 carbon atoms
  • X is a hydrolyzable group such as a methoxy group and an ethoxy group. It is a functional group or an alkyl group.
  • the silane coupling agent is preferably a compound represented by the general formula YRSiX 3 , where Y is a functional group such as a vinyl group, an epoxy group, an amino group or a mercapto group, and R is a methylene, ethylene, propylene or the like.
  • the alkylene group and X are preferably a hydrolyzable functional group such as a methoxy group or an ethoxy group or an alkyl group.
  • silane coupling agent examples include vinyl triethoxysilane, vinyl trimethoxysilane, ⁇ -glycidylpropyltrimethoxysilane, ⁇ -glycidylpropyltriethoxysilane, and N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane. , N- ⁇ (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane and the like. These can be used alone or in combination of two or more.
  • siloxane having an epoxy group at the end of the molecular chain or the side chain is preferably mentioned.
  • the thickness of the primer layer is preferably 0.01 to 1 ⁇ m, more preferably 0.03 to 0.7 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m.
  • the thickness is at least the above lower limit value, a cured film having a uniform thickness can be obtained, and a sufficient adhesive force with the silicone layer tends to be obtained.
  • the silicone resin constituting the primer layer is generally not so strong in film strength, but if the thickness is not more than the upper limit value, it is easy to suppress the cohesive failure of the primer layer and increase the strength of the laminated body.
  • the laminate of the present invention may have a cover film attached to the surface of the silicone layer on which the polyimide layer is not provided.
  • the cover film may be made of a resin film other than the polyimide layer and the silicone layer.
  • the material of the cover film is not particularly limited, but for example, a polyolefin resin, a styrene resin, a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene sulfide resin, a polyphenylene ether resin, and a polyaryl ether ketone type. Examples thereof include resins and liquid crystal polymer resins. Among these, from the viewpoint of heat resistance and mechanical strength, it is preferable to contain a polyester resin, and it is more preferable to contain the polyester resin as a main component.
  • polyester resins it is preferable to use a crystalline polyester resin, and examples of the crystalline polyester resin include polyethylene terephthalate and polyethylene naphthalate. Of these, polyethylene terephthalate is preferable from the viewpoints of heat resistance, film strain, smoothness, availability for commercial use, and the like. These can be used alone or in combination of two or more.
  • the cover film may contain additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, a nucleating agent, a lubricant, a pigment, and a dye as long as the effects of the present invention are not impaired. From the viewpoint of mechanical strength, it is preferably stretched to at least one axis, and more preferably to two axes.
  • the cover film may be a process film used when forming the silicone layer during manufacturing, or may be a protective film that protects the silicone layer during transportation, storage, and the like. The cover film may be removed from the laminate before it is used as a release material, cushioning material, non-slip material, carrier film and the like.
  • the thickness of the cover film is not particularly limited, but is preferably 10 to 350 ⁇ m, more preferably 15 to 300 ⁇ m, and even more preferably 20 to 250 ⁇ m.
  • the method for producing the laminated body of the present invention is not particularly limited as long as the polyimide layer can be laminated on at least one surface of the silicone layer, and a known method can be used as the laminating method.
  • a polyimide layer may be prepared, a silicone layer may be separately prepared and laminated, or a polyimide layer may be prepared, a silicone layer may be prepared on the polyimide layer, and these may be laminated.
  • a silicone layer may be prepared, a polyimide layer may be formed and laminated on the silicone layer, or the polyimide layer and the silicone layer may be laminated while being formed.
  • a cover film may be appropriately laminated on the surface of the silicone layer where the polyimide layer is not provided.
  • the polyimide layer and the silicone layer are laminated with the silicone layer uncrosslinked to form a laminated body, and then the silicone layer is crosslinked.
  • the silicone layer is crosslinked.
  • the polyimide layer and the silicone layer can be laminated by a coextrusion method, a laminating method, or the like.
  • the coextrusion method the polyimide layer and the silicone layer may be kneaded at the same time by a feed block method, a multi-manifold method, or the like, and coextruded and laminated.
  • a laminating method there is a method in which a polyimide layer and a silicone layer are separately produced to obtain a polyimide layer and a silicone layer, and then the polyimide layer and the silicone layer are laminated and laminated.
  • a silicone layer may be formed and laminated on the polyimide layer prepared in advance.
  • a primer layer may be provided between the polyimide layer and the silicone layer as described above.
  • a primer agent is applied to the polyimide layer, and the primer agent is appropriately dried and cured. It is advisable to form a primer layer with. Then, it is preferable that the silicone layer is laminated on the polyimide layer on which the primer layer is formed.
  • the primer agent contains a base polymer for forming a primer layer, a cross-linking agent, a photopolymerization initiator, a catalyst, a silane coupling agent, an adhesion improver, etc., which are blended as necessary, and is diluted with a solvent. It is good.
  • the surface of the silicone layer and / or the polyimide layer coated with the primer agent may be subjected to surface treatment such as corona treatment in advance.
  • the primer is not particularly limited, but may be cured by heating at a temperature of, for example, about 50 to 150 ° C.
  • the laminated body of the present invention is preferably manufactured by the laminating method.
  • silicone mixed with a metal oxide or other additives as needed by a kneader or the like, preferably a silicone elastomer resin is uncrosslinked, and is fed out from two directions, respectively. It is put into a pair of polyimide films to be a polyimide layer, or between a polyimide film and a cover film.
  • the silicone may be inserted between the films by extruding it from a T-die or the like using, for example, an extruder.
  • the thickness is adjusted in the gaps between the rolls to obtain a laminated body in which a silicone layer, preferably a non-crosslinked silicone layer, is formed between the films.
  • the cover film may be omitted as appropriate.
  • uncrosslinked silicone it is preferable to crosslink the silicone, but it is preferable that the crosslinking is performed after laminating the silicone layer and the polyimide layer as described above.
  • the method of cross-linking include a method of adding a cross-linking agent or the like to silicone in advance and cross-linking with light such as heat or ultraviolet rays, moisture in the air, or the like, and a method of cross-linking by irradiation with radiation.
  • the silicone layer is crosslinked by irradiation.
  • Cross-linking by irradiation is preferable because there is no concern that the heat resistance due to the residue of the cross-linking agent or the like is impaired, and wrinkles or the like do not occur at the time of cross-linking unlike the cross-linking by heating. It is also preferable to ensure the adhesion between the silicone layer and the polyimide layer.
  • Examples of radiation include electron beams, X-rays, ⁇ -rays, and the like. These radiations are also widely used industrially, are readily available and are energy efficient methods. Among them, it is preferable to use ⁇ -rays from the viewpoint of almost no absorption loss and high transparency.
  • the irradiation dose of ⁇ -rays can be appropriately selected and determined depending on the type of resin, the amount of cross-linking groups, and the type of radiation source.
  • the irradiation dose of ⁇ -rays is preferably 20 to 150 kGy, more preferably 30 to 120 kGy, further preferably 40 to 110 kGy, and particularly preferably 50 to 100 kGy.
  • the irradiation dose is at least the above lower limit value, the silicone layer can be sufficiently crosslinked, and as a result, the desired compression set and durometer hardness tend to be easily obtained.
  • the irradiation dose is not more than the upper limit value, the decomposition reaction does not occur and the increase of the low molecular weight siloxane component can be suppressed.
  • the laminate of the present invention can be used for various purposes by taking advantage of the characteristics of silicone, for example, in the case of a silicone elastomer resin, characteristics such as appropriate adhesion to various parts and followability.
  • the laminate of the present invention is preferably used, for example, in the manufacturing process of various molded bodies, particularly in press molding, vacuum forming, pneumatic molding, etc., in which case, a mold release material, a cushioning material, a non-slip material (sealing material), etc. It is good to use as.
  • the laminated body can also be used as a carrier film for transporting the work, a protective film for protecting the work, and the like.
  • the laminate is preferably used as a mold release material or a cushioning material in various molding steps such as press molding, vacuum forming, and compressed air forming. Specifically, in the molding process, it is placed between the molding die (mold) and the molded body and used as a cushioning material that evenly disperses the pressure applied to the molded body, or from the molding die of the molded body. It is recommended to use it for the purpose of ensuring releasability. Further, among the above, the laminated body is more preferably used as a cushioning material for press molding and a mold release material. In press molding, the laminate may be arranged between the work and the press plate when the molded body (work) is pressed by the press plate.
  • the polyimide layer side is arranged on the press plate side and the silicone layer side is arranged on the work side.
  • the temperature during press molding is not particularly limited, but is, for example, 50 to 350 ° C, preferably 100 to 350 ° C, more preferably 200 to 350 ° C, and even more preferably 250 to 320 ° C.
  • press molding include hydraulic / hydraulic press molding, roll press molding, and belt press molding.
  • the laminate of the present invention is preferably used when molding a circuit board, a semiconductor, other electronic components, etc. incorporated in an electric or electronic product as a molded body.
  • the press molding is not particularly limited, but is preferably a step performed in the process of manufacturing, for example, an FPC and further, a component constituting an all-solid-state battery, and an ACF (anisotropic conductive film). It is also preferable that the process is performed when crimping the circuit board.
  • the laminate of the present invention has a polyimide layer, it is less likely to wrinkle or bend and has high heat resistance, so that it can be used in various molding processes to improve the productivity of the molded product.
  • the silicone layer has high heat resistance, is less likely to be embrittled, can maintain good cushioning properties for a long period of time under high temperature heating, and can suppress dimensional changes. Therefore, the laminate of the present invention can be repeatedly used for a long period of time as a mold release material, a cushioning material, and the like.
  • the laminate of the present invention is used as a carrier film.
  • the laminate When the laminate is used as a carrier film, it preferably has a laminated structure of a silicone layer / polyimide layer, and when the conveyed material is placed on the silicone layer constituting the outermost surface and the conveyed material is conveyed. good. Since the silicone layer has a slight adhesiveness particularly when the silicone is a silicone elastomer resin, it can be used as a non-slip material by using it as the outermost surface of the carrier film.
  • the laminate (carrier film) is not particularly limited, but is conveyed by, for example, a belt conveyor.
  • the polyimide layer may be used as a support for the silicone layer.
  • a carrier film having a silicone layer as the outermost surface generally uses a metal plate as a support, but by using a polyimide layer instead of the metal plate, the weight of the transport carrier can be reduced.
  • the polyimide layer has high rigidity, it can be appropriately used as a support instead of a metal plate.
  • the polyimide layer of the present invention is used as described above, which has high heat resistance, is not easily deformed by heating, and has a low coefficient of linear expansion, it can be used in a high temperature environment (for example, about 200 to 350 ° C.).
  • the carrier film is preferably a reflow carrier in which a reflow process is performed with a conveyed object (work) mounted on the carrier film.
  • the laminate may be heated to 200 ° C. or higher, but as described above, the laminate of the present invention can be repeatedly used even in a high temperature environment, and can be particularly preferably used as a reflow carrier.
  • the present invention provides a laminate (X1) used as any of a release material, a cushioning material, and a non-slip material.
  • the laminate (X1) is a laminate including a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • the weight loss rate of the resin layer (A) at 380 ° C. by thermal weight measurement is 9% by mass or less.
  • the resin layer (A) since the resin layer (A) has a tensile storage elastic modulus of 100 MPa or less at 23 ° C., it has good followability, adhesion, and surface tackiness to the molded body during press molding and the like. It becomes. Further, when the tensile storage elastic modulus of the resin layer (B) at 23 ° C. is 1 GPa or more, the handleability is improved. Therefore, the present laminated body (X1) can be suitably used as a mold release material, a cushioning material, and a non-slip material.
  • the details of the mold release material, the cushioning material, and the non-slip material are as described above, and it is preferable to use the resin layer (A) instead of the silicone layer and the resin layer (B) instead of the polyimide layer.
  • the weight loss rate of the resin layer (A) at 380 ° C. is 9% by mass or less, so that the resin layer (A) is prevented from becoming embrittlement, and the above-mentioned applications are used.
  • the laminated body (X1) can be repeatedly used for a long period of time in a high temperature environment.
  • the weight loss rate at 380 ° C. is low.
  • the resin layer (A) has a tensile storage elastic modulus of preferably 70 MPa or less at 23 ° C. from the viewpoint of followability to the molded body during press molding, adhesion, and surface tackiness of the resin layer (A). It is more preferably 50 MPa or less, further preferably 30 MPa or less, and particularly preferably 10 MPa or less. Further, it is preferably 0.1 MPa or more, more preferably 0.5 MPa or more, and further preferably 1 MPa or more.
  • the resin constituting the resin layer (A) is not particularly limited, and for example, silicone, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, urethane-based resin, epoxy-based resin, fluoroelastomer, or the like is used.
  • silicone it is preferable to use silicone as a main component in the resin layer (A) from the viewpoint of excellent electrical properties such as heat resistance and insulating properties, and mold releasability.
  • silicone it is preferable to use the silicone as described above, and the resin layer (A) is the same as the silicone layer described above.
  • the resin layer (B) has a tensile storage elastic modulus at 23 ° C., preferably 3 GPa or more, from the viewpoint of improving handleability and dimensional accuracy such as suppressing deformation of the laminate when used as a mold release material during press molding. It is more preferably 3.7 GPa or more, further preferably 4.5 GPa or more, particularly preferably 5 GPa or more, particularly preferably 6 GPa or more, and most preferably 7 GPa or more. Further, it is preferably 15 GPa or less, more preferably 13 GPa or less, and further preferably 11 GPa or less.
  • the resin constituting the resin layer (B) is not particularly limited, and is, for example, a curable resin such as polyimide, bismaleimide, or benzoxazine, a thermoplastic polyimide, a polyamideimide, an olefin resin, a styrene resin, or a polyester.
  • Resins polycarbonate resins, polyamide resins, polyetherimide resins, polyphenylene sulfide resins, polyphenylene ether resins, polyether ketone resins such as polyether ether ketones, polytetrafluoroethylene resins (PTFE), tetrafluoroethylene pers
  • thermoplastic resins such as fluoroalkoxyethylene copolymer resin (PFA) and liquid crystal polymers.
  • curable resins such as polyimide, bismaleimide and benzoxazine, and non-crystalline thermoplastic resins having a glass transition temperature (Tg) of 300 ° C. or higher such as thermoplastic polyimides and polyamideimides.
  • Polyether ketone resin such as polyether ether ketone, polytetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkoxyethylene copolymer resin (PFA), crystal melting temperature (Tm) of liquid crystal polymer, etc.
  • PTFE polytetrafluoroethylene resin
  • PFA tetrafluoroethylene / perfluoroalkoxyethylene copolymer resin
  • Tm crystal melting temperature of liquid crystal polymer, etc.
  • a crystalline thermoplastic resin having a temperature of 300 ° C. or higher is preferable, and among them, it is more preferable to use polyimide as the main component resin from the viewpoint of excellent heat resistance, rigidity and the like.
  • Tg and Tm are values obtained from the DSC curve at the time of re-heating measured by a differential scanning calorimeter according to JIS K7121: 2012.
  • the resin layer (B) is the same as the above-mentioned polyimide layer.
  • Various characteristics such as average roughness (Ra) and thickness are the same as those of the polyimide layer described above, and the description thereof will be omitted.
  • the resin layer (A) the tensile fracture stress retention rate after heat treatment at 300 ° C. for 3 hours, the tensile fracture strain retention rate after heat treatment at 300 ° C. for 3 hours, initial fracture stress, initial fracture strain, type A durometer.
  • the resin layer (B) may be laminated directly on the resin layer (A), or may be laminated via another layer such as a primer layer.
  • the primer layer preferably contains a silicone resin from the viewpoint of ensuring adhesiveness to the primer layer (A), and contains a silicone resin as a main component. Is more preferable.
  • the details of the primer layer containing the silicone resin are as described above.
  • the resin layer (B) may be provided on only one surface of the resin layer (A) or may be provided on both sides. When the resin layer (B) is provided on only one surface of the resin layer (A), the cover film described above may be provided on the other surface.
  • the present invention provides a laminate (X2) used for any of press molding, vacuum forming, and compressed air forming.
  • the laminate (X2) is a laminate including a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • the weight loss rate of the resin layer (A) at 380 ° C. by thermal weight measurement is 9% by mass or less.
  • the resin layer (A) has a tensile storage elastic modulus of 100 MPa or less at 23 ° C., the followability and adhesion to the molded body in press molding, vacuum forming, and pressure forming.
  • the surface tackiness is good.
  • the tensile storage elastic modulus of the resin layer (B) at 23 ° C. is 1 GPa or more, the handleability is improved, and it can be suitably used as a mold release material or a cushioning material in each of these moldings.
  • the details of press molding, vacuum forming, pressure forming, mold release material or cushioning material are as described above, and the resin layer (A) is used instead of the silicone layer, and the resin layer (B) is used instead of the polyimide layer. Should be used.
  • the weight loss rate of the resin layer (A) at 380 ° C. by thermogravimetric analysis is 9% by mass or less, so that the resin layer (A) is prevented from becoming embrittlement.
  • the laminate can be used repeatedly for a long period of time in a high temperature environment.
  • the configuration of the laminated body (X2) in this embodiment is as described in the above-mentioned laminated body (X1), and detailed description thereof will be omitted.
  • the present invention provides, as yet another aspect, a laminate (X3) used for a carrier film.
  • the laminate (X3) is a laminate including a resin layer (A) having a tensile storage elastic modulus of 100 MPa or less at 23 ° C. and a resin layer (B) having a tensile storage elastic modulus of 1 GPa or more at 23 ° C.
  • the weight loss rate of the resin layer (A) at 380 ° C. by thermal weight measurement is 9% by mass or less.
  • the resin layer (A) has a tensile storage elastic modulus of 100 MPa or less at 23 ° C., the surface tackiness of the resin layer (A) is improved and the resin layer (B) is formed.
  • the tensile storage elastic modulus of is 1 GPa or more, a certain strength can be secured, and it can be suitably used as a carrier film.
  • the details of the carrier film are as described above, and it is preferable to use the resin layer (A) instead of the silicone layer and the resin layer (B) instead of the polyimide layer.
  • the weight loss rate of the resin layer (A) at 380 ° C.
  • the laminated body (X) can be repeatedly used for a long period of time in a high temperature environment, and is also suitable as a reflow carrier or the like.
  • the configuration of the laminated body (X3) in this embodiment is as described in the above-mentioned laminated body (X1), and detailed description thereof will be omitted.
  • Weight loss rate at 380 ° C A sample collected from the silicone layer is heated using a differential thermal weight simultaneous measuring device (TG-DSC) under the following conditions, and the weight loss at 380 ° C. is measured. The rate of weight loss at 380 ° C. to the initial weight was calculated.
  • Measuring device "STA200RV", manufactured by Hitachi High-Tech Science Corporation Measurement conditions: Measured by raising the temperature from 35 ° C to 800 ° C at 20 ° C / min. Conducted in an atmospheric atmosphere.
  • the ratio of the tensile fracture stress after the heat treatment to the initial tensile fracture stress was defined as the tensile fracture stress retention rate after the heat treatment at 300 ° C. for 3 hours.
  • the ratio of the tensile fracture strain after the heat treatment to the initial tensile fracture strain was defined as the tensile fracture strain retention rate after the heat treatment at 300 ° C. for 3 hours.
  • the content of the low molecular weight cyclic siloxane was measured by gas chromatography (GC) under the following measurement conditions.
  • GC gas chromatography
  • Tension storage elastic modulus Compliant with JIS K7244-4: 1999 for a polyimide film forming a polyimide layer or a film (thickness 100 ⁇ m) made of a silicone resin raw material forming a silicone layer produced by the method described below. Then, the tensile storage elastic modulus at 23 ° C. and 300 ° C. was measured under the following conditions using a viscoelastic spectrometer. Measuring device name: "DVA-200", manufactured by IT Measurement Control Co., Ltd. Chuck distance: 25 mm Distortion: 0.07% Width: Approximately 4 mm Temperature: -50 to 350 ° C Frequency: 1Hz Measurement method: Tensile temperature rise rate: 3 ° C / min Measurement direction: MD
  • thermogravimetric measurement temperature of 2% weight loss
  • TG-DSC differential thermal weight simultaneous measuring device
  • the polyimide film forming the polyimide layer was measured under the following measurement conditions using a thermomechanical analyzer. Measuring device: "TMA / SS7100", manufactured by Hitachi High-Tech Science Corporation Width of test piece: 3 mm Distance between chucks: 10 mm Mode: Tension Measurement direction: MD Temperature conditions: When the temperature was raised from 15 to 330 ° C. at a rate of 5 ° C./min and then lowered to 15 ° C. at a rate of 5 ° C./min, the sample lengths at 300 ° C. and 30 ° C. at the time of temperature reduction were measured. The coefficient of linear expansion (1 / ° C.) was calculated. The measurement direction was MD.
  • Arithmetic mean roughness (Ra) of the polyimide layer The arithmetic average roughness (Ra) of the polyimide layer constituting the outermost surface of the laminated body is 5 times by using a three-dimensional non-contact surface shape measuring instrument (trade name "VertScan2.0 R5200G” manufactured by Ryoka System Co., Ltd.). The measurement was performed under the conditions of an objective lens and a measurement range of 948.76 ⁇ m ⁇ 711.61 ⁇ m.
  • Silicone resin shown in Table 1 between two cover films (biaxially stretched PET film, "Diafoil T-100" manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m) supplied along two 100 mm diameter calendars. Each raw material of the layer was supplied, and a bank was formed on the roll under the condition of a roll temperature of 80 ° C. to prepare a laminate composed of a cover film / silicone layer / cover film.
  • the obtained laminate with a cover film is irradiated with ⁇ -rays so that the absorption dose is 50 kGy to crosslink the silicone elastomer resin of the silicone layer, the cover film is peeled off from the crosslinked laminate, and the silicone for evaluation is used. It was made into a film.
  • Example 1 A polyimide film (“UPIREX-S” manufactured by Ube Kosan Co., Ltd., thickness: 25 ⁇ m) contains an add-on silicone resin, an adhesion improver, and a curing catalyst, and a primer agent diluted with solvent toluene is dried by a roll coat method. After coating to a thickness of 0.3 ⁇ m, the film was dried at 120 ° C. for 30 seconds and heat-treated to obtain a polyimide film having a primer layer on one side.
  • UPIREX-S manufactured by Ube Kosan Co., Ltd., thickness: 25 ⁇ m
  • a primer agent diluted with solvent toluene is dried by a roll coat method. After coating to a thickness of 0.3 ⁇ m, the film was dried at 120 ° C. for 30 seconds and heat-treated to obtain a polyimide film having a primer layer on one side.
  • a spontaneous silicone elastomer resin (“TSE2323-5U” manufactured by Momentive Performance Materials Co., Ltd., contains titanium oxide as a metal oxide (1.1% by mass), and has a tensile storage elasticity of 2. Using 6 MPa (23 ° C), type A durometer hardness 50 (manufacturer's nominal value)), and supplied along a two calendar with a diameter of 100 mm, on the primer layer of the polyimide film and on the biaxial as a cover film.
  • the above silicone elastomer resin is supplied between the stretched PET film (“Diafoil T-100” manufactured by Mitsubishi Chemical Co., Ltd., thickness: 100 ⁇ m), and a bank is formed on the roll under the condition of a roll temperature of 80 ° C. to form a polyimide layer / silicone. A laminate consisting of layers was produced. A cover film was attached to the silicone layer.
  • the obtained laminate with a cover film was irradiated with ⁇ -rays so that the absorbed dose was 50 kGy, and the silicone elastomer resin was crosslinked to obtain a laminate in which the polyimide layer and the silicone layer were integrated.
  • the thickness of the silicone layer was 100 ⁇ m.
  • the cover film was peeled off from the obtained laminate to obtain a laminate for evaluation.
  • the weight loss rate at 380 ° C., the tensile fracture stress retention rate and the tensile fracture strain retention rate after heat treatment at 300 ° C. for 3 hours were evaluated for the laminate. The results are shown in Table 1. Further, when the polyimide layer was evaluated, the tensile storage elastic modulus at 300 ° C.
  • the arithmetic average roughness (Ra) of the outermost surface composed of the polyimide layer of the laminated body was 2.6 nm.
  • Example 2 As a raw material for the silicone resin layer, a spontaneous silicone elastomer resin (“TSE2323-7U” manufactured by Momentive Performance Materials Co., Ltd.) contains titanium oxide as a metal oxide (0.8% by mass), and has a tensile storage elastic modulus of 5. A laminate was produced in the same manner as in Example 1 except that 7 MPa (23 ° C.) and a type A durometer hardness of 70 (manufacturer's nominal value) were used.
  • TSE2323-7U manufactured by Momentive Performance Materials Co., Ltd.
  • Example 3 As a raw material for the silicone resin layer, a spontaneous silicone elastomer resin (“X-30-3888-U” manufactured by Shin-Etsu Chemical Industry Co., Ltd. (iron oxide (2.4% by mass) as a metal oxide) and carbon black 0.3 to 1 are used. A laminate was produced in the same manner as in Example 1 except that (contained in% by mass), the tensile storage elasticity was 5.2 MPa (23 ° C.), and the type A durometer hardness was 60 (manufacturer's nominal value)).
  • Example 4 instead of the cover film, a polyimide film having a primer layer formed in the same manner as in Example 1 on one side is used, a silicone layer is formed between the primer layers of the two polyimide films, and the polyimide layer / silicone layer / polyimide layer is used. It was carried out in the same manner as in Example 1 except that the laminated body was obtained.
  • Example 5 Laminated in the same manner as in Example 4 except that a spontaneous silicone elastomer resin (“TSE2233-7U” manufactured by Momentive Performance Materials, containing 0.8% by mass of titanium oxide) was used as a raw material for the silicone resin layer. The body was made.
  • a spontaneous silicone elastomer resin (“TSE2233-7U” manufactured by Momentive Performance Materials, containing 0.8% by mass of titanium oxide) was used as a raw material for the silicone resin layer. The body was made.
  • Example 6 As a raw material for the silicone resin layer, a spontaneous silicone elastomer resin (“X-30-3888-U” manufactured by Shin-Etsu Chemical Co., Ltd., containing 2.4% by mass of iron oxide and 0.3 to 1% by mass of carbon black) was used. A laminated body was produced in the same manner as in Example 4 except for the points.
  • Comparative Example 1 A laminate was produced in the same manner as in Example 1 except that a spontaneous silicone elastomer resin (“TSE2571-5U” manufactured by Momentive Performance Materials, no metal oxide) was used as a raw material for the silicone resin layer. ..
  • the thickness (dimensional change) due to press molding was larger than that in the examples. Therefore, it is difficult to repeatedly use it as a mold release material, a cushioning material, a carrier film, etc. in a high temperature environment for a long period of time.

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Abstract

L'invention concerne un stratifié comprenant une couche de silicone et une couche de polyimide, le taux de réduction de poids de la couche de silicone à 380°C, mesuré par thermogravimétrie, n'étant pas supérieur à 9 % en masse.
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JP2012077128A (ja) * 2010-09-30 2012-04-19 Unitika Ltd オルガノシロキサン共重合樹脂
JP2015170690A (ja) * 2014-03-06 2015-09-28 信越化学工業株式会社 Ｌｅｄチップ圧着用熱伝導性複合シート及びその製造方法
WO2017073507A1 (fr) * 2015-10-29 2017-05-04 東レ株式会社 Film stratifié pour collage temporaire, pièce de travail formant substrat utilisant un film stratifié pour le collage temporaire, procédé de production d'une pièce de travail formant substrat stratifié, et procédé de production d'un dispositif semi-conducteur l'utilisant
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