Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/14—Layered products comprising a layer of metal 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • 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
  • B32B27/28—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
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of 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
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
  • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2009/00—Layered products
• • 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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—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
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—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
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/02—Synthetic macromolecular fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/101—Glass fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/302—Conductive
• • 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
  • B32B2605/00—Vehicles

Definitions

• the present invention relates to a molding base material in which a prepreg layer of a fiber reinforced resin and a fiber paper layer are combined, a molded product molded using the molding base material, and a method for manufacturing the molded product.
• Fiber reinforced resin molded products are widely used in various applications, taking advantage of their characteristics of being lightweight, high strength, and high rigidity.
• prepreg which is an uncured or semi-cured molding base material obtained by impregnating reinforced fibers such as carbon fiber and glass fiber with a matrix resin, is often used for molding (for example).
• Patent Document 1 is an uncured or semi-cured molding base material obtained by impregnating reinforced fibers such as carbon fiber and glass fiber with a matrix resin, is often used for molding (for example).
• Heat resistance may be required for fiber-reinforced resin molded products, but the heat resistance of fiber-reinforced resin molded products is determined by the heat resistance of the matrix resin.
• the following methods have been conventionally adopted, for example. (1) Select a resin having high heat resistance as the matrix resin. (2) Prevent the temperature of the molded product from rising. (I) Keep a distance from high heat sources.
• a cooling device is installed between the high heat source and the air (for example, blast air cooling).
• the cooling mechanism is directly incorporated into the molded product (for example, water-cooled piping, cooling fins).
• a heat insulating material is used in combination to suppress heat conduction to a small value (for example, ceramic material, foam material).
• a reflective material is used in combination to suppress radiant heat to a small value (for example, metal plate, metal foil).
• any of the above methods has the following problems.
• In the above method (1) there is a limit to the heat resistance of the resin.
• In the above method (2) ⁇ Additional costs will be incurred. ⁇ The structure becomes complicated. ⁇ Weight will increase. ⁇ Space is needed.
• synthetic resin fiber paper fiber paper made of non-woven fabric, especially polyimide fiber paper
• synthetic resin fiber paper has been proposed as a heat insulating material for suppressing heat conduction in the above methods (2) and (iv), instead of ceramics material and foam material.
• This polyimide fiber paper has excellent properties such as high heat resistance, thinness, and light weight as well as high heat insulation. That is, this polyimide fiber paper is made by microslitting a polyimide resin fiber having high heat resistance or a polyimide resin film having high heat resistance into fibers, and then making paper by making the same method as the Japanese paper manufacturing method. Since it has voids (air layer between fibers) inside, it can exhibit high heat insulating properties.
• the polyimide fiber paper having such high heat insulating performance can be formed into a thin layer while ensuring the desired heat insulating performance as compared with a foaming material (for example, Patent Document 3) which is generally widely used as a heat insulating material. It is particularly suitable when improvement of space efficiency and weight reduction are required when the installation space is narrow as a whole including the heat insulating material.
• JP-A-2015-143343 Japanese Patent No. 6580643 Japanese Unexamined Patent Publication No. 2002-18993
• the subject of the present invention is to strengthen the fiber in order to achieve both the high heat resistance and heat insulating property of the fiber-reinforced resin molded product and the improvement of the space efficiency and the weight reduction as a whole in view of the above-mentioned background technology.
• a molding base material having at least a prepreg layer of a fiber reinforced resin, a fiber paper layer, and a partition layer interposed between the prepreg layer and the fiber paper layer.
• the partition layer is provided on at least one surface of the fiber paper layer, and a fiber paper layer different from the fiber paper layer is provided between the partition layer and the prepreg layer, (1) to (1).
• (6) The molding substrate according to any one of (1) to (5), wherein the partition layer is made of a thermosetting resin.
• the molded product according to (7) which has a gap of 30 to 90% in the fiber paper layer.
• the prepreg layer and the fiber paper layer of the fiber reinforced resin can be integrated via a partition layer interposed between them, and the molding is integrally formed.
• the partition layer prevents the softened or melted prepreg layer from entering the fiber paper layer of the matrix resin, or at least a part of the fiber paper layer. It is possible to prevent the gaps between the fibers inside the fiber paper layer from being filled with the invading resin, the presence of the air layer inside the fiber paper layer is maintained, and the excellent heat insulation of the fiber paper layer is maintained. The sex is maintained.
• the integrally formed molding base material for molding molding into a complicated shape can be easily performed, and the fiber paper is surely prevented from peeling off from the molded product. It is possible to form a high-strength, high-rigidity molded product in a desired form by using a fiber-reinforced resin, and a fiber paper layer in which the presence of an air layer is maintained is formed into a desired form together with a prepreg layer. As a result, the molded product can exhibit the target high heat insulating property. Further, since the fiber paper layer can be formed into a thin layer, the molded product can be improved in space efficiency and reduced in weight as a whole including the fiber paper layer as a heat insulating material. Further, when the fiber paper layer is made of a polyimide fiber paper layer having high heat resistance, the high heat resistance of the molded product can also be exhibited.
• a base material similar to the conventional molding using only a prepreg base material can be obtained.
• a desired highly heat-insulating molded product can be easily manufactured through a shaping step and a heating / pressurizing step of the shaped base material.
• the molding base material according to the present invention is characterized by having at least a prepreg layer of a fiber reinforced resin, a fiber paper layer, and a partition layer interposed between the prepreg layer and the fiber paper layer. be. By laminating these layers, it is preferable that the base material for molding is formed into an integrated base material.
• the fiber-reinforced resin constituting the prepreg layer is composed of a reinforcing fiber and a matrix resin impregnated with the reinforcing fiber, and the matrix resin is in an uncured or semi-cured state (so-called B stage state). ..
• Both discontinuous fibers and continuous fibers can be used as the reinforcing fibers of the prepreg layer, but if it is desired to have strength and rigidity higher than the level of the fiber reinforced resin layer of the molded product, the continuous reinforcing fibers can be used. It is preferable to use it. Further, when the continuous reinforcing fiber is used, it is preferable to use the continuous reinforcing fiber aligned in one direction from the viewpoint of ease of designing the strength and rigidity of the molded product.
• a single layer fiber reinforced resin prepreg layer composed of continuously reinforced fibers aligned in one direction and a matrix resin, or unidirectionally It is possible to adopt a configuration of a plurality of layers of prepreg layers composed of aligned continuous reinforcing fibers and a matrix resin, and a plurality of layers of fiber reinforced resin prepreg layers in which each layer is laminated so as to have a desired reinforcing fiber orientation direction.
• the type of reinforcing fiber is not particularly limited, and examples thereof include inorganic fiber such as carbon fiber and glass fiber, metal fiber, and organic fiber. Two or more of these may be used.
• the carbon fiber examples include PAN-based carbon fiber made from polyacrylonitrile (PAN) fiber, pitch-based carbon fiber made from petroleum tar or petroleum pitch, and cellulose-based carbon made from viscose rayon or cellulose acetate. Examples thereof include vapor-phase growth-based carbon fibers made from fibers and hydrocarbons, and these graphitized fibers. Among these carbon fibers, PAN-based carbon fibers are preferably used because they have an excellent balance between strength and elastic modulus.
• PAN-based carbon fibers are preferably used because they have an excellent balance between strength and elastic modulus.
• glass fiber examples include E glass fiber (for electricity), C glass fiber (for corrosion resistance), S glass fiber, and T glass fiber (high strength and high elasticity).
• metal fibers include fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel.
• the organic fiber examples include fibers made of organic materials such as aramid, polybenzoxazole (PBO), polyphenylene sulfide, polyester, polyamide, and polyethylene.
• the aramid fiber examples include a para-based aramid fiber having excellent strength and elastic modulus, and a meta-based aramid fiber having excellent flame retardancy and long-term heat resistance.
• the para-aramid fiber examples include polyparaphenylene terephthalamide fiber and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber, and examples of the meta-type aramid fiber include polymethaphenylene isophthalamide fiber. Can be mentioned.
• a para-type aramid fiber having a higher elastic modulus than the meta-type aramid fiber is preferably used.
• Examples of other inorganic fibers include fibers made of inorganic materials such as basalt, silicon carbide, and silicon nitride.
• Basalt fiber is a fiber made from basalt, which is a mineral, and has extremely high heat resistance.
• thermosetting resin either a thermosetting resin or a thermoplastic resin can be used. It is easy to control the glass transition temperature as high as possible, and when the molded product is used in a high temperature atmosphere, the structure can be maintained without softening the molded product, and in the unlikely event that it is carbonized, it is heat.
• curable resin is preferred.
• thermosetting resin as the matrix resin of the prepreg layer examples include unsaturated polyester, vinyl ester, epoxy, phenol (resole type), urea melamine, polyimide, etc., and copolymers, modified products thereof, and the like. A resin obtained by blending two or more of these can be used. Further, for example, in order to improve impact resistance, an elastomer or a rubber component may be added to the thermosetting resin. Of these, epoxy resin is particularly preferable from the viewpoint of strength and rigidity of the molded product.
• the thickness of the prepreg layer of the fiber reinforced resin in the present invention and the base material for molding using the prepreg layer is not particularly limited. However, it is not preferable that the base material for molding is too thick in consideration of shaping of the base material for molding, ease of molding, and good followability to a complicated shape. Therefore, the thickness of the molding substrate is preferably in the range of 0.1 to 5 mm, more preferably in the range of 0.1 to 4 mm, and further preferably in the range of 0.1 to 3 mm.
• the ratio of the reinforcing fibers in the prepreg layer of the fiber reinforced resin in the present invention is preferably 55 to 65% by volume, more preferably about 60% by volume in the case of a one-way prepreg (UD prepreg) from the viewpoint of formability and mechanical properties. preferable. In the case of a woven prepreg, 45 to 55% by volume is preferable, and about 50% by volume is more preferable.
• the fiber paper layer in the present invention is preferably a dry or wet non-woven fabric made of synthetic fibers from the viewpoint of providing heat insulating properties to the molding base material.
• the fiber paper layer is made from synthetic fibers.
• the synthetic resin constituting the fiber paper layer is made of a polyimide resin, and the fiber paper layer is preferably made of a polyimide fiber paper layer.
• the polyimide fiber paper the fiber paper proposed in the above-mentioned Patent Document 2 can be used.
• aramid fiber paper, polyphenylene sulfide paper, or fiber paper in which these fibers are mixed can be used.
• the fiber paper used preferably has 45 to 90% porosity (porosity at the molding substrate stage) in the fiber paper layer, more preferably 60 to 90%, from the viewpoint of heat insulating performance.
• the range more preferably 70-90%. It is preferable that this porosity is maintained as much as possible as a molded product after molding in order to secure high heat insulating properties of the molded product after molding.
• the molded product after molding preferably has 30 to 90% porosity (porosity at the molded product stage) in the fiber paper layer, more preferably in the range of 45 to 90%, and further preferably 60 to 90. It is in the range of%.
• the thickness of the fiber paper layer in the present invention is not particularly limited, but if it is too thin, the thickness of the internal air layer may also be thin, so that the desired heat insulating performance as a molded product may not be obtained. Since the layer is not expected to have a function that essentially bears the strength and rigidity of the molded product, the strength and hardness of the surface layer of the molded product may become too small. Therefore, the thickness of the fiber paper layer is preferably in the range of 0.05 to 3.0 mm, more preferably in the range of 0.1 to 2.5 mm, both in the stage of the base material for molding and in the stage of the molded product. , More preferably in the range of 0.5 to 2.0 mm.
• a partition layer is interposed between the prepreg layer of the fiber reinforced resin and the fiber paper layer.
• the matrix resin of the prepreg layer of the fiber reinforced resin is heated and pressed for molding.
• the matrix resin of the softened or melted prepreg layer invades (impregnates) the inside of the fiber paper layer, and at least a part of the voids inside the fiber paper layer is filled (the air layer is formed). It disappears or is greatly reduced), and has a function of suppressing the deterioration of the excellent heat insulating properties of the fiber paper.
• the partition layer in the present invention is a layer having a function of preventing the prepreg layer from invading at least a part of the fiber paper layer of the matrix resin.
• a small amount of the matrix resin of the prepreg layer invades the fiber paper layer during molding, so that the prepreg layer and the fiber paper layer after molding are firmly adhered to each other and prevent each layer from peeling off when the molded product is used. It is preferable because it can be used.
• the porosity of the fiber paper layer in the molded product is at least 30%. It is more preferably 45% or more, still more preferably 60% or more.
• the material and thickness of the intervening partition layer are not particularly limited as long as they have a function of preventing the matrix resin of the prepreg layer from invading at least a part of the fiber paper layer, but the material of the partition layer is not particularly limited.
• Examples include thermosetting adhesive sheets of polyimide-based, polyamide-imide-based, epoxy-based, acrylic-based, urethane-based, polyester-based, phenol-based, urea-based, and melamine-based resins, and adhesive sheets of silicone-based resins. It can be used.
• An elastomer or a rubber component may be added to the thermosetting adhesive.
• an epoxy resin is particularly preferable from the viewpoint of adhesiveness to the prepreg, but it is preferable to select an adhesive mainly containing the same kind of component as the resin component of the prepreg.
• the thickness of the partition layer is not particularly limited, but if it is too thick, the heat insulating performance may be deteriorated, and conversely, if it is too thin, the matrix resin of the prepreg layer as described above may be inserted into at least a part of the fiber paper layer. Since the intrusion prevention function becomes too low, the range of 0.01 to 0.1 mm is preferable, and more preferably the range of 0.015 to 0.075 mm, both at the stage of the base material for molding and at the stage of the molded product. More preferably, it is in the range of 0.015 to 0.05 mm.
• the partition layer interposed between the prepreg layer and the fiber paper layer of the fiber reinforced resin preferably satisfies the following conditions.
• the prepreg layer and the textile paper layer must be integrated (it is not necessary to completely integrate them).
• the molding base material according to the present invention has a basic laminated form (integrated form) of a prepreg layer of a fiber reinforced resin, a fiber paper layer, and a partition layer interposed between them.
• a basic laminated form integrated form
• each of the following forms can be adopted as a more detailed concrete form.
• a form in which another layer is provided may be provided.
• a partition layer is provided on at least one surface of the fiber paper layer (here, referred to as a first fiber paper for convenience), and the fiber paper layer is formed between the partition layer and the prepreg layer of the fiber reinforced resin.
• the second fiber paper preferably has high heat insulation and high heat resistance, and as the second fiber paper, the same polyimide fiber paper as described above can be used, or another fiber paper can be used. You can also.
• the other fiber paper for example, a fiber paper made of aramid fiber paper, polyphenylene sulfide paper, ceramic fiber paper, or a fiber paper in which these fibers are mixed can be used.
• the prepreg layer of the fiber reinforced resin is cured and the molded product according to the present invention can be obtained.
• voids in the range of 30 to 90%, preferably 45 to 90%, more preferably 60 to 90% are formed in the fiber paper layer. It is desirable to have. That is, the porosity of the fibrous paper layer of the molding base material before molding is suppressed as much as possible by the partition layer during molding, and the porosity of the fibrous paper layer in the molded product after molding is maintained in the above range. It is preferable to be able to exhibit excellent heat insulating properties.
• the glass transition temperature of the molded product after molding is preferably in the range of 90 to 400 ° C, preferably 120 to 390 ° C, and more preferably 150 to 380 ° C.
• the thermal conductivity of the textile paper in the present invention is 0.1 W / mK or less, preferably 0.07 W / mK or less, and more preferably 0.04 W / mK or less as measured by the stationary method.
• the molded article according to the present invention as described above, it is possible to add a specific layer particularly on the surface in order to add further functions.
• it can be a molded product in which a metal layer is provided on at least one surface layer.
• the metal layer include a layer made of aluminum, silver, gold, nickel, chromium and the like.
• the surface layer of the molded product can be provided with functions such as radiant heat reflection and electromagnetic wave shielding.
• the molded article according to the present invention as described above can be produced by a production method having at least the following steps A to C.
• A. The step of preparing the molding base material according to the present invention as described above, B.
• B. The process of shaping the molding substrate into the desired shape, C.
• the high heat insulating performance makes it possible to thermally protect peripheral parts from high-temperature heat source parts (for example, around the exhaust pipe of an internal combustion engine). ..
• the fiber paper layer which is responsible for the heat insulating performance, is lighter than the current heat insulating materials (glass cloth and ceramic sheet), so that it can be made lighter as a molded product.
• the molded base material (molded product) after molding can have high heat insulation performance, high strength and high rigidity while being thin. Further, since the base material for molding can be formed to be thin, a compact heat insulating structure and a heat resistant structure can be realized, and the gap with the high temperature source can be minimized in combination with excellent heat insulating and heat resistant properties.
• the matrix resin type is an epoxy resin
• prepreg F6343B-05P manufactured by Toray Co., Ltd. is used, and when the matrix resin is a cyanate ester resin, Delta-Preg S. p. A.
• a prepreg GG200T (T800-DT350CN) manufactured by Uninominale was used.
• continuous carbon fiber fibers are used as the reinforcing fibers.
• Polyimide fiber paper manufactured by Toray DuPont Co., Ltd. was used as the fiber paper layer.
• An epoxy-based adhesive sheet (AU type) manufactured by Arisawa Mfg. Co., Ltd. was used as the partition layer.
• Glass transition temperature stage after molding: The glass transition temperature of the cured portion of the prepreg layer of the fiber reinforced resin in the molded product was measured at ASTM D7028 Modulus Tangent Intercept, 5 ° C./min.
• the base materials are laminated in advance so as to have a structure of a fiber paper layer / a partition layer / a fiber paper layer / a partition layer / a fiber paper layer / a partition layer / a fiber paper layer, and the partition is heated at 160 ° C. for 60 minutes.
• the layers were cured and the fiber paper layers were bonded to each other (the base material bonded and integrated is called the base material 4).
• a partition layer (uncured) was laminated on one surface of the base material 4, and the partition layer (uncured) was adhered and laminated while maintaining the semi-cured (B stage) state using an iron heated to 120 ° C. (based on this).
• Material 5 ).
• the fiber reinforced resin prepreg was placed on the flat plate-shaped molding mold and placed along the molding mold. Then, on the prepreg, the semi-cured partition layer of the base material 5 was brought into contact with the prepreg, and similarly formed into the shape of the molding die (this is called the base material 6).
• the base material 6 was bagged with a sealing film together with the molding die, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of the molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 130 ° C.
• Example 2 The base materials were laminated in advance so as to form a fiber paper layer / partition layer / fiber paper layer, and heated at 160 ° C. for 60 minutes to cure the partition layer and bond the fiber paper layers to each other ().
• the base material that is adhered and integrated is called the base material 1).
• partition layers (uncured) were laminated on both surfaces of the base material 1, and using an iron heated to 120 ° C., they were adhered and laminated while maintaining the semi-cured (B stage) state (based on this).
• Material 2 The base materials were laminated in advance so as to form a fiber paper layer / partition layer / fiber paper layer, and heated at 160 ° C. for 60 minutes to cure the partition layer and bond the fiber paper layers to each other ().
• the base material that is adhered and integrated is called the base material 1).
• partition layers (uncured) were laminated on both surfaces of the base material 1, and using an iron heated to 120 ° C., they were adhered and laminated while maintaining the semi-cured (B stage) state (
• the fiber reinforced resin prepreg was placed on the hat-shaped molding mold and placed along the molding mold. Then, the base material 2 was similarly placed on the prepreg in the shape of the mold, and then the prepreg was further placed on the base material 2 and similarly followed in the mold (this is referred to as the base material 3). ).
• the base material 3 was bagged with a sealing film, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of a molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave and then post-treated in an oven to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 355 ° C.
• Post-treatment conditions The entire molded product taken out of the autoclave is placed in an oven, heated from room temperature to 125 ° C. at 2 ° C./min, then heated from 125 ° C. to 200 ° C. at 0.3 ° C./min, and then heated at 200 ° C. 2 I kept it for a while. Then, after lowering the temperature to 70 ° C. at 2 ° C./min, the entire molded product was taken out from the oven.
• Example 3 The base materials are laminated in advance so as to form a fiber paper layer / partition layer / fiber paper layer / partition layer / fiber paper layer, and heated at 160 ° C. for 60 minutes to cure the partition layer and fiber.
• the paper layers are bonded to each other (the base material bonded and integrated is called the base material 7).
• a partition layer uncured was laminated on both surfaces of the base material 7, and using an iron heated to 120 ° C., the base material 7 was adhered and laminated while maintaining the semi-cured (B stage) state (this was used as the base material). Called 8).
• the fiber reinforced resin prepreg was placed on the hat-shaped molding mold and placed along the molding mold. Then, the base material 8 was similarly placed on the prepreg in the shape of the mold, and then the prepreg was further placed on the base material 8 and similarly formed in the mold (this is referred to as the base material 9).
• the base material 9 was bagged with a sealing film, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of a molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave and then post-treated in an oven to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 355 ° C.
• Post-treatment conditions The entire molded product taken out of the autoclave is placed in an oven, heated from room temperature to 125 ° C. at 2 ° C./min, then heated from 125 ° C. to 200 ° C. at 0.3 ° C./min, and then heated at 200 ° C. 2 I kept it for a while. Then, after lowering the temperature to 70 ° C. at 2 ° C./min, the entire molded product was taken out from the oven.
• the base materials are laminated in advance so as to have a structure of a partition layer / fiber paper layer / partition layer / fiber paper layer / partition layer / fiber paper layer / partition layer, and heated at 160 ° C. for 60 minutes to form a partition layer.
• the base material bonded and integrated is called the base material 10.
• partition layers (uncured) were laminated on both surfaces of the base material 10, and using an iron heated to 120 ° C., they were adhered and laminated while maintaining the semi-cured (B stage) state (this was used as the base material). Called 11).
• the fiber reinforced resin prepreg was placed on the hat-shaped molding mold and placed along the molding mold. Then, the base material 11 was similarly placed on the prepreg in the shape of the molding die, and then the prepreg was further placed on the base material 11 in the same manner in the molding die (this is called the base material 12). ..
• the base material 12 was bagged with a sealing film, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of a molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave and then post-treated in an oven to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 355 ° C.
• Post-treatment conditions The entire molded product taken out of the autoclave is placed in an oven, heated from room temperature to 125 ° C. at 2 ° C./min, then heated from 125 ° C. to 200 ° C. at 0.3 ° C./min, and then heated at 200 ° C. 2 I kept it for a while. Then, after lowering the temperature to 70 ° C. at 2 ° C./min, the entire molded product was taken out from the oven.
• the base material 13 was bagged with a sealing film together with the molding die, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of the molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 130 ° C.
• the obtained molded product had a porosity of 0% in the fiber paper, so that the target heat insulating performance could not be expected.
• the base material 14 was bagged with a sealing film together with the molding die, and the inside was depressurized with a vacuum pump to prepare a precursor (preform) of the molded product. Then, under the following conditions, the entire precursor of the molded product was cured by an autoclave to obtain a molded product.
• the glass transition temperature of the prepreg portion of the obtained molded product was 130 ° C.
• a polyimide fiber paper adhesive tape prepared separately and coated with an acrylic adhesive was cut and pasted according to the shape of the molded product to form a heat insulating layer made of polyimide fiber paper on the surface.
• the void ratio in the polyimide fiber paper on the surface could be maintained high, the polyimide fiber paper could not follow the curved surface shape of the molded product, and floating from the molded product and wrinkles of the fiber paper occurred. In addition, the adhesive strength between the fiber paper and the molded product was unstable.
• Table 1 summarizes the conditions and results of each example and comparative example.
• Example 5 Aluminum metal is heated and melted and evaporated on both surfaces of the molded product obtained in Example 2 in a vacuum vapor deposition apparatus, aluminum is coagulated and deposited on both surfaces of the molded product, and a 50 nm vapor deposition film is attached to the surface layer. A molded product in which an aluminum layer was added was obtained.
• the present invention can be applied to all applications in which high strength and high rigidity characteristics of fiber reinforced plastic and high heat insulation performance of lightweight and thin layer materials are required, and in particular, lightweight and compact heat insulation and heat resistant structure are required. It is suitable for various types of mobility, and is also suitable for members having complicated shapes.

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• 2021
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