Laminated molded body and method for manufacturing the laminated molded body

Abstract

To provide a laminated molded article in which a phenolic resin molding layer is lightweight and has high heat insulation, excellent dimensional stability under high temperature and high humidity, and excellent wear durability, and to provide a method for manufacturing the laminated molded article.SOLUTION: A laminated molded article comprises a phenolic resin molding layer and a base material adjacently, in which the cross-sectional porosity of the phenolic resin molding layer is 6.0 to 30.0% and the density of the laminated molded article is 200 to 1,100 kg / m3. A method for manufacturing the laminated molded article comprises arranging phenol foam powder adjacent to a base material, and thermopress-molding the phenol foam powder and the base material at 130 to 240°C and 1,000 to 5,000 kPa.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated molded product and a method for producing the laminated molded product. [Background technology]

[0002] Phenolic resins are known for their excellent mechanical strength, heat resistance, solvent resistance, acid resistance, and electrical properties, and are widely used as molding materials in the fields of electronics, automobiles, construction, and medicine. Phenolic resins are classified into novolac-type phenolic resins and resol-type phenolic resins. With resol-type phenolic resins, crosslinking (curing reaction) can be promoted by heating or adding acid, resulting in the production of thermosetting resin molded products.

[0003] However, because resol-type phenolic resins have methylol groups as crosslinking groups, when cured by heating or adding acid, depending on the molding conditions, they may shrink due to the ongoing reaction even after molding, or may expand due to moisture absorption, so dimensional stability under high temperature and high humidity is required. Therefore, substrates may be laminated on the top and bottom surfaces, but this does not provide the required light weight and heat insulation properties in addition to dimensional stability.

[0004] Furthermore, there are techniques for imparting heat resistance to a resol-type phenolic resin cured body, such as adding phenolic resin powder or using a phenolic resin powder compression molded plate instead of a resol-type phenolic resin cured body. However, when a physical impact is applied to the powder portion, particularly the powder portion on the surface of the molded plate, the phenolic resin powder may fall off, or so-called powder fall, which makes it difficult to apply to components of precision instruments, etc.

[0005] As a cured product of phenolic resin, for example, Patent Document 1 discloses a curable composition in which the amount of acid elution and impact resistance are improved by blending a specific aromatic sulfonic acid as a curing agent with a resol-type phenolic resin. However, the curable composition obtained by this technique has high thermal conductivity and is poor in dimensional stability and weight reduction in high-temperature, high-humidity environments, making it insufficient for practical use.

[0006] In Patent Document 2, an attempt is made to heat and pressurize a sheet-shaped molding material obtained by dispersing phenolic resin powder and reinforcing fibers in a liquid and then forming the material into a sheet. However, when the sheet-forming material is subjected to physical impact, powder tends to fall off, making the material unsuitable for practical use.

[0007] Furthermore, Patent Document 3 attempts to coat a porous inorganic fiber sheet with phenolic resin and laminate the decorative sheet together, but this method is not practical because of its high thermal conductivity and poor lightness. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 149652 / 1983 [Patent Document 2] Patent No. 3440809 [Patent Document 3] Patent No. 3180036 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, the present invention aims to provide a laminated molded body in which the phenolic resin molded layer is lightweight, has high thermal insulation properties, excellent dimensional stability under high temperature and high humidity conditions, and excellent abrasion resistance, and a method for manufacturing such a laminated molded body. [Means for solving the problem]

[0010] That is, the present invention is as follows. [1] A laminated molded body including a phenolic resin molded layer and a substrate adjacent to each other, The cross-sectional porosity of the phenolic resin molding layer is 6.0% or more and 30.0% or less, The density of the laminated compact is 200 kg / m 3 More than 1,100kg / m 3 The laminated molded body is as follows. [2] The phenolic resin molding layer has a volume average particle size of 20 μm or more and 550 μm or less and a bulk density of 5 kg / m 3 More than 150kg / m 3 The laminated molded body according to [1], which is made of the following phenol foam powder: [3] The laminated molded product according to [1] or [2], wherein the substrate is a thermosetting resin or a thermoplastic resin having a melting point of 60°C or higher. [4] The laminated molded product according to any one of [1] to [3], wherein the substrate is at least one selected from the group consisting of nonwoven fabric, woven fabric, and urethane foam. [5] The laminated molded product according to any one of [1] to [4], wherein the base material, the phenolic resin molded layer, and a second base material are laminated adjacently in this order. [6] The laminated molded product according to any one of [1] to [5], wherein the thermal conductivity of the laminated molded product at 30°C is 0.12 W / (m·K) or less. [7] The laminated molded article according to any one of [1] to [6], wherein the average dimensional change rate of the laminated molded article after 48 hours at 80°C and humidity of 95% is -0.20% or more and 0.60% or less. [8] placing a phenolic foam powder adjacent to the substrate; A method for producing a laminated molded product, comprising: heat-pressing the adjacently arranged phenol foam powder and the substrate at a temperature of 130°C or higher and 240°C or lower and a pressure of 1,000 kPa or higher and 5,000 kPa or lower. [9] The phenol foam powder has a volume average particle size of 20 μm or more and 550 μm or less and a bulk density of 5 kg / m 3 More than 150kg / m 3 The method for producing a laminated molded product according to [8], which is as follows: [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a laminated molded body and a method for manufacturing a laminated molded body, in which the phenolic resin molded layer is lightweight, has high thermal insulation properties, excellent dimensional stability under high temperature and high humidity conditions, and excellent abrasion resistance. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a scanning electron microscope photograph of a cross section of the laminate molded body of Example 1. [Figure 2] This is a binarized image of the photograph in Figure 1. [Figure 3] 1 is a scanning electron microscope photograph of a cross section of the laminate molded body of Comparative Example 5. [Figure 4] This is a binarized image of the photograph in Figure 3. [Figure 5] FIG. 2 is a schematic diagram showing measurement points for measuring dimensional change rates in an example. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail.

[0014] For the laminated molded article of this embodiment, the cross-sectional porosity of the phenolic resin molded layer, as well as the density, thermal conductivity, and average dimensional change rate of the laminated molded article are determined by the methods described in the Examples. Unless otherwise specified, the density of the laminated molded article refers to the apparent overall density measured according to JIS K7222. Unless otherwise specified, the thermal conductivity refers to the thermal conductivity at 30°C. Unless otherwise specified, the average dimensional change rate refers to the average dimensional change rate after 48 hours at a temperature of 80°C and a humidity of 95%. In addition, the volume average particle size and bulk density of the phenolic foam powder are determined by the methods described in the Examples.

[0015] In this embodiment, a laminated molded body having a thickness of less than 30 mm is specifically referred to as a "laminated molded plate." The "thickness" direction refers to the direction of the shortest of the three dimensions of the laminated molded body: length, width, and height. In this embodiment, terms such as "first" and "second" may be used, but these are intended only to distinguish one element from another and do not limit the position, size, etc. of the element. Figure 5 of the accompanying drawings is a schematic diagram prioritized for ease of understanding of the present invention, and therefore the scale of each layer in the figure is not accurate.

[0016] Laminated molding The laminated molded body of this embodiment is a laminated molded body including a phenolic resin molded layer and a substrate adjacent to each other, The cross-sectional porosity of the phenolic resin molding layer is 6.0% or more and 30.0% or less, The density of the laminated compact is 200 kg / m 3 More than 1,100kg / m 3 The laminated molded body is as follows: The phenolic resin molded layer and the substrate, which are essential elements of the laminated molded body, will be exemplified below.

[0017] Phenolic resin molding layer The phenolic resin molded layer is a layer that imparts high heat insulation to the laminated molded article of this embodiment, and also has excellent dimensional stability under high temperature and high humidity conditions.

[0018] The phenolic resin molded layer is made of a cured phenolic resin. The phenolic resin can be appropriately selected from known phenolic resins. As the phenolic resin, a resol-type phenolic resin is preferable, and for example, "phenolic foam crushed powder" obtained by crushing phenolic foam can be used.

[0019] The phenolic resin molded layer may contain additives such as binders (binding agents), extenders, surfactants, urea, acids, nonwoven fabrics, etc. in addition to the cured phenolic resin, as long as a cross-sectional porosity of 6% or more and 30% or less can be ensured.

[0020] In the laminated molded body of this embodiment, the phenolic resin molded layer has voids, and the cross-sectional porosity of the phenolic resin molded layer is 6.0% or more and 30.0% or less. The voids are usually present throughout the phenolic resin molded layer. The cross-sectional porosity of the phenolic resin molded layer represents the proportion of irregular recesses resulting from voids present on the cut surface of the phenolic resin molded layer when the laminated molded body is cut parallel to the stacking direction of the laminated molded body.

[0021] The cross-sectional porosity of the phenolic resin molded layer is 6.0% or more and 30.0% or less, preferably 6.0% or more and 20.0% or less, and more preferably 10.0% or more and 15.0% or less. A cross-sectional porosity of the phenolic resin molded layer of 30.0% or less provides excellent dimensional stability under high temperature and high humidity conditions and ensures mechanical strength, thereby preventing damage to the phenolic resin molded layer during handling. Meanwhile, a cross-sectional porosity of the phenolic resin molded layer of 6.0% or more provides the laminated molded body with lightweight properties and high thermal insulation.

[0022] The voids in the phenolic resin molded layer can be formed by hot-press molding using phenolic foam powder as the raw material for the phenolic resin molded layer. Therefore, the cross-sectional porosity of the phenolic resin molded layer can be adjusted by changing the volume average particle size, bulk density, and amount of the phenolic foam powder, as well as the compression molding conditions (e.g., temperature, pressure, and time) of the phenolic foam powder.

[0023] The shape of the phenolic resin molded layer is not particularly limited and can be any shape. Examples of the shape of the phenolic resin molded layer include a rectangular parallelepiped (e.g., a plate), a polyhedron other than a rectangular parallelepiped (e.g., a regular polyhedron such as a regular tetrahedron, a regular octahedron, a regular dodecahedron, or a regular icosahedron), a sphere, a pyramid, a cone, a torus, a hollow cylinder, a solid cylinder (cylinder), and an irregular shape. In one embodiment, the phenolic resin molded layer is a rectangular parallelepiped. In a preferred embodiment, the phenolic resin molded layer is a phenolic resin molded plate having a thickness of less than 30 mm.

[0024] The thickness of the phenolic resin molding layer is not particularly limited, but is preferably 0.5 mm or more and less than 30 mm, more preferably 1 mm or more and 20 mm or less, even more preferably 1 mm or more and 10 mm or less, particularly preferably 1 mm or more and 5 mm or less, and most preferably 1.5 mm or more and 5 mm or less. If it is 0.5 mm or more, the mechanical strength is increased and handling is easy. Also, if it is less than 30 mm, it is lightweight and handling is easy.

[0025] The volume ratio of the phenolic resin layer in the laminated molded product is not particularly limited, but is, for example, 20 to 95%. In other words, the volume ratio of the base material in the laminated molded product is, for example, 5 to 80%.

[0026] When there are two or more separate phenolic resin molding layers in a laminated molding, such as an alternating laminate of a substrate and a phenolic resin molding layer, each phenolic resin molding layer may have the same or different cross-sectional porosity, dimensions, shape, density, etc.

[0027] ·Base material In the laminated molded article of this embodiment, the phenolic resin molded layer and the substrate are adjacent to each other. The substrate protects the phenolic resin molded layer from friction, imparts abrasion resistance to the laminated molded article, and reduces powder shedding. The laminated molded article of this embodiment, which has improved abrasion resistance due to the substrate, can be suitably used in high-temperature environments such as automobile parts and aircraft parts. The laminated molded article of this embodiment can also be suitably used in places where physical impacts such as vibration or friction may occur.

[0028] The substrate may be laminated adjacent to at least a portion of the surface of the phenolic resin molded layer, or may be laminated on the entire surface of the phenolic resin molded layer. When the phenolic resin molded layer is a rectangular parallelepiped, polyhedron, or the like, the substrate may be laminated on a portion or all of one or more surfaces of the phenolic resin molded layer. For example, when the phenolic resin molded layer is a rectangular parallelepiped, polyhedron, or the like, the substrate may be laminated on two opposing surfaces of the phenolic resin molded layer, on two adjacent surfaces of the phenolic resin molded layer, on any two or more surfaces of the phenolic resin molded layer, or on all surfaces of the phenolic resin molded layer. When there are multiple substrates (e.g., when separate substrates are laminated on the surface of the phenolic resin molded layer, or when substrates and phenolic resin molded layers are alternately laminated), the substrates may be the same or different in material, size, shape, melting point, etc.

[0029] When the substrate and the phenolic resin molding layer are alternately stacked in the laminated molded body, the substrate may be stacked adjacent to at least a portion of the surface of the phenolic resin molding layer. For example, the substrate may be located in the two outermost layers of the laminated molded body, such as first substrate / first phenolic resin molding layer / second substrate; first substrate / first phenolic resin molding layer / second substrate / second phenolic resin molding layer / third substrate, or the substrate may be located in only one of the outermost layers of the laminated molded body, such as first substrate / first phenolic resin molding layer / second substrate / second phenolic resin molding layer, or the substrate may be sandwiched between the phenolic resin molding layers, such as first phenolic resin molding layer / first substrate / second phenolic resin molding layer.

[0030] The substrate is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, nonwoven fabrics, paper, felt, films, sheets, plates, boards, foams, and composites thereof. The composite may be a laminate of woven fabrics, knitted fabrics, nonwoven fabrics, paper, felt, films, sheets, plates, boards, foams, or the like, or may be a molded product obtained by impregnating woven fabrics, knitted fabrics, or nonwoven fabrics with resin, or a fiber-reinforced plastic molded by kneading short fibers or long fibers into a resin. In one embodiment, the substrate is at least one selected from the group consisting of nonwoven fabrics, woven fabrics, and urethane foams.

[0031] The shape of the substrate is not particularly limited and can be any shape. Examples of the shape of the substrate include a rectangular parallelepiped (e.g., a plate), a polyhedron other than a rectangular parallelepiped (e.g., a regular polyhedron such as a regular tetrahedron, a regular octahedron, a regular dodecahedron, and a regular icosahedron), a sphere, a pyramid, a cone, a torus, a hollow cylinder, a solid cylinder (cylinder), and an irregular shape. In one embodiment, the substrate is a rectangular parallelepiped.

[0032] The thickness of the substrate is not particularly limited and is, for example, 1 μm or more and 20 mm or less. The thickness of the substrate is preferably 1 μm or more and 10 mm or less, more preferably 1 μm or more and 7 mm or less, even more preferably 1 μm or more and 5 mm or less, particularly preferably 1 μm or more and 3 mm or less, and most preferably 1 μm or more and 2 mm or less. If the thickness of the substrate is 1 μm or more, dimensional stability and abrasion resistance under high temperature and high humidity conditions tend to be improved, and if the thickness is 20 mm or less, heat insulation tends to be improved.

[0033] In a substrate having a melting point, the melting point is preferably 60°C or higher. In one embodiment, the melting point of the substrate is 100°C or higher. In another embodiment, the melting point of the substrate is 100°C or higher and 400°C or lower. If the melting point of the substrate is 100°C or higher, the substrate is less likely to burn during hot press molding, and the appearance of the laminated molded product is likely to be good. The melting point of the substrate is preferably 110°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, and particularly preferably 150°C or higher.

[0034] The material constituting the substrate is not particularly limited, and examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyacrylonitrile, polyurethane, polyisocyanurate, polyvinyl chloride, cellulose, glass, silicone rubber, natural rubber, synthetic rubber, calcium hydroxide, calcium sulfate, aluminum, iron, and the like. Polyethylene terephthalate and polyurethane are preferred materials constituting the substrate. In one embodiment, the substrate is a thermosetting resin. In another embodiment, the substrate is a thermoplastic resin. In yet another embodiment, the substrate is a thermoplastic resin having a melting point of 60°C or higher.

[0035] A portion of the phenolic resin molded layer or the substrate is cut out from the laminate, and the cut sample is subjected to infrared spectroscopy (IR) to observe the peak of the absorption wavelength, thereby identifying the material, such as phenolic resin, polyethylene terephthalate, polyurethane, etc. For other materials, the material of the phenolic resin molded layer or the substrate can be identified by appropriate IR, nuclear magnetic resonance analysis (NMR), pyrolysis gas chromatography / mass spectrometry (GC / MS), etc.

[0036] In one embodiment, a substrate (first substrate), a phenolic resin molded layer, and a second substrate are laminated in this order adjacent to each other. This allows both opposing surfaces of the phenolic resin molded layer to be protected. When the laminated molded product is an alternating laminate of substrates and phenolic resin molded layers, the number of layers is not particularly limited and may be an odd number such as 3, 5, 7, 9 or more layers, and it is preferable that the substrate is located in the outermost two layers.

[0037] The density of the laminated compact of this embodiment is 200 kg / m 3 More than 1,100kg / m 3 or less, preferably 300 kg / m 3 More than 900kg / m 3 Less than or equal to 400 kg / m 3 More than 800kg / m 3 The density of the laminated compact is 200 kg / m or less. 3If the density of the laminated compact is 1,100 kg / m or more, mechanical strength such as impact resistance can be ensured, and breakage of the laminated compact during handling can be prevented. 3 The density of the laminated compact can be adjusted mainly by changing the density of the raw material phenol foam powder, the amount used, the density of the substrate, and the compression molding conditions of the phenol foam powder (for example, temperature, pressure, and time).

[0038] The thermal conductivity of the laminated molded body in this embodiment at 30°C is preferably 0.12 W / (m·K) or less, more preferably 0.030 W / (m·K) or more and 0.10 W / (m·K) or less, even more preferably 0.030 W / (m·K) or more and 0.09 W / (m·K) or less, and particularly preferably 0.030 W / (m·K) or more and 0.08 W / (m·K) or less. The thermal conductivity can be adjusted, for example, by the density and moisture content of the phenolic resin, the temperature and pressure during production of the laminated molded body, the composition, bulk density, volume average particle size, and material, density, and thickness of the substrate of the phenolic foam powder used as the raw material for the phenolic resin molded layer of the laminated molded body.

[0039] The average dimensional change rate of the laminated molded body of this embodiment is preferably -0.20% or more and 0.60% or less, more preferably -0.20% or more and 0.40% or less, even more preferably -0.20% or more and 0.20% or less, and most preferably -0.20% or more and 0.10% or less. A positive average dimensional change rate indicates that the laminated molded body has expanded, and a negative value indicates that the laminated molded body has shrunk.

[0040] The average dimensional change rate of the laminated molded body depends mainly on the properties of the raw material phenol foam powder, the properties of the substrate, and the manufacturing method of the laminated molded body, and can be adjusted, for example, by the volume average particle size and bulk density of the phenol foam powder, the material, density, and thickness of the substrate, and if the substrate is a fiber, the fiber length and the heat press molding conditions of the phenol foam powder (e.g., temperature, pressure, time), etc.

[0041] The thickness of the laminated molded body is not particularly limited and may be adjusted as appropriate. The thickness of the laminated molded plate is sufficient as long as it is less than 30 mm, preferably 0.5 mm or more and less than 30 mm, more preferably 1 mm or more and 20 mm or less, even more preferably 1 mm or more and 10 mm or less, particularly preferably 1 mm or more and 5 mm or less, and most preferably 1.5 mm or more and 5 mm or less. If it is 0.5 mm or more, it has excellent mechanical strength and is easy to handle. If it is 30 mm or less, it is lightweight and easy to handle.

[0042] The laminated molded body may include a phenolic resin molded layer and a substrate adjacent to each other. Preferably, the laminated molded body is manufactured by hot-press molding using a phenolic foam powder and a substrate, as described below. However, the laminated molded body may also be manufactured by methods other than hot-press molding. For example, the phenolic resin molded layer and the substrate may be prepared, and then laminated and fixed with a fixing means such as an adhesive or a fixing tool to form a laminated molded body. In one embodiment, the laminated molded body consists of only one or more phenolic resin molded layers and one or more substrates. In another embodiment, the laminated molded body includes one or more phenolic resin molded layers, one or more substrates, and one or more other layers or fixing means.

[0043] ·Method of manufacturing laminated molded body The method for manufacturing a laminated molded body of this embodiment includes arranging phenol foam powder adjacent to a substrate; The method for producing a laminated molded product includes hot press molding the phenol foam powder and the substrate at a temperature of 130°C or higher and 240°C or lower and a pressure of 1,000 kPa or higher and 5,000 kPa or lower.

[0044] In a preferred example, the raw material phenolic foam powder is pulverized phenolic foam. Because the cross-linked structure of phenolic foam is destroyed in the phenolic foam powder, its shape within the optimal volume average particle size range has three-dimensional angular protrusions, similar to those of wave-dissipating blocks. These angular protrusions intertwine with each other, creating a physical bonding effect that allows the phenolic resin molded layer to be integrally molded.

[0045] The method for pulverizing the phenol foam is not particularly limited, and the phenol foam can be obtained using a pulverizer such as a cutter mill, hammer mill, pin mill, roller mill, jet mill, rolling ball mill, rolling rod mill, vibrating ball mill, vibrating rod mill, etc. In consideration of the environment, it is more preferable to use scraps generated during cutting processing.

[0046] The phenol foam powder is placed adjacent to the substrate. In this case, the phenol foam powder may be placed adjacent to at least a portion of one surface of the substrate, or the phenol foam powder may be placed adjacent to the entire surface of the substrate, or the phenol foam powder may be placed adjacent to some or all of multiple surfaces of the substrate. An adhesive or pressure-sensitive adhesive may be placed at the interface between the phenol foam powder and the substrate as appropriate. In addition, additives such as a binder (binding agent), adhesive, pressure-sensitive adhesive, and extender may be added to or mixed with the phenol foam powder as appropriate.

[0047] Next, the adjacently arranged phenol foam powder and substrate are subjected to heat press molding to obtain a laminated molded body.

[0048] The means for heat press molding is not particularly limited, and examples thereof include a heat press device. The heat press device is not particularly limited, and examples thereof include an oil heat type, a heater type, and a cold press type, but it is preferable to use an oil heat type in consideration of temperature control and productivity.

[0049] The temperature during heat press molding is 130°C or higher and 240°C or lower, preferably 140°C or higher and 230°C or lower, more preferably 140°C or higher and 220°C or lower, even more preferably 150°C or higher and 210°C or lower, and particularly preferably 160°C or higher and 210°C or lower. A temperature of 130°C or higher during heat press molding is preferable because a laminate molded product with excellent handleability can be obtained. Furthermore, a temperature of 240°C or lower during heat press molding is preferable because a laminate molded product with good appearance can be obtained without scorching the surface of the laminate molded product.

[0050] The pressure during heat press molding is 1,000 kPa or more and 5,000 kPa or less, preferably 1,000 kPa or more and 3,000 kPa or less, and more preferably 1,500 kPa or more and 3,000 kPa or less. A pressure of 1,000 kPa or more during heat press molding is preferable because a laminate molded product with excellent handleability can be obtained. Furthermore, a pressure of 5,000 kPa or less during heat press molding is preferable because the cross-sectional porosity of the phenolic resin molded layer falls within the desired range.

[0051] The volume average particle size of the phenol foam powder is preferably 20 μm or more and 550 μm or less, more preferably 20 μm or more and 250 μm or less, even more preferably 20 μm or more and 150 μm or less, and particularly preferably 20 μm or more and 100 μm or less. A volume average particle size of 20 μm or more and 550 μm or less is preferable because it is easy to handle and the bonding effect due to the entanglement of the phenol foam powder particles with each other is easily exhibited, making it easy to form a phenol resin molded layer.

[0052] The bulk density of phenol foam powder is 5 kg / m 3 More than 150kg / m 3 It is preferable that the density is less than 5 kg / m 3 More than 100kg / m 3 More preferably, it is 5 kg / m or less. 3 More than 80kg / m 3 More preferably, it is 10 kg / m or less. 3 More than 50kg / m 3It is particularly preferable that the bulk density is 5 kg / m or less. 3 More than 150kg / m 3 If the temperature is below this, the bonding effect due to the entanglement of the phenol foam powder particles with each other is easily exhibited, and the phenol resin molded layer is easily formed. [Example]

[0053] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these.

[0054] The materials and devices used in the examples are as follows. Phenolic foam: Asahi Kasei Construction Materials Corporation, product name "Neoma (registered trademark) Foam", 80 mm x 910 mm x 45 mm, with PET nonwoven fabric surface material on the top and bottom surfaces Urethane foam: Inoac Corporation, product name "Malt Filter CFH-13" open-cell structure, soft, filter urethane foam Nonwoven fabric: DFK Co., Ltd., product name "Meyuka Paper XP81213-1", DFK resin-processed nonwoven fabric, polyethylene terephthalate content 43-56%, resorcinol resin content 44-57% Cutter mill: Manufactured by Horai Co., Ltd., product name "PC3-3060LGS." The cutter mill's outlet is equipped with a screen with a diameter of 8 mm, allowing pulverized phenol foam powder with a diameter of less than 8 mm to be discharged. Laser diffraction light scattering particle size distribution analyzer: Nikkiso Co., Ltd., product name "Microtrac HRA 9320-X100" Tumbling ball mill: dry type, diameter 900mm x 1,500mm Vibration ball mill: dry type, inner diameter 150 mm, 15.5 L per cylinder x 2 cylinders High stainless steel double-edged or single-edged blade: Made by FEATHER Tabletop scanning electron microscope: JEOL Ltd., product name "JCM-7000 NeoScope" Thermal conductivity measuring device: Advance Riko Co., Ltd., steady-state thermal conductivity measuring device, product name "GH-1" Vernier caliper: Mitutoyo Corporation Constant temperature and humidity chamber: Manufactured by Kusumoto Kasei Co., Ltd., product name "SXN412" Taber abrasion tester: Toyo Seiki Seisakusho Co., Ltd.

[0055] Example 1 ·Phenol foam powder manufacturing The upper and lower surface materials were peeled off, and multiple pieces of phenol foam were prepared and crushed in a cutter mill to obtain phenol foam powder. The phenol foam powder was removed and sieved through a sieve with 500 μm openings, and the phenol foam powder recovered below the sieve was designated as phenol foam powder A. When the obtained phenol foam powder A was measured using a laser diffraction particle size distribution analyzer, the volume average particle size of phenol foam powder A was found to be 81 μm. The bulk density of phenol foam powder A was also found to be 30 kg / m 3 It was.

[0056] - Manufacturing of laminated molded products Phenol foam powder A was sandwiched between two layers of urethane foam to form a layer, and then hot-pressed using an oil-heated hot press at a temperature of 180°C and a pressure of 3,000 kPa. Five minutes after the start of hot-press molding, the molded body was removed and air-cooled for five minutes to obtain a 2 mm-thick laminated molded body (laminated molded plate). The thickness of the urethane foam substrate of the laminated molded body was 700 μm or more and 900 μm or less.

[0057] Example 2 Plural pieces of phenolic foam with the top and bottom surface materials peeled off and phenolic foam with the top and bottom surface materials attached were prepared so that the surface material content in the phenolic foam pulverized powder was 15% by weight, and then pulverized to obtain phenolic foam powder B. The same treatment as in Example 1 was carried out except that phenolic foam powder B was used instead of phenolic foam powder A, and a thickness of 2 mm and a density of 490 kg / m were obtained. 3 The phenol foam powder B had a volume average particle size of 102 μm and a bulk density of 12 kg / m 3 It was.

[0058] Examples 3 to 6 The laminated molded bodies of Examples 3 to 6 were obtained in the same manner as in Example 1, except that the temperature or pressure during hot press molding was changed as shown in Table 1. The thickness of the laminated molded bodies of Examples 3, 4, 5 and 6 was all 2 mm. The densities of the laminated molded bodies are also shown in Table 1.

[0059] Example 7 The thickness was 4 mm and the density was 270 kg / m in the same manner as in Example 1, except that the two substrates in Example 1 were changed from urethane foam to PET nonwoven fabric. 3 The thickness of the PET nonwoven fabric substrate of the laminated molded product was 50 μm or more and 150 μm or less.

[0060] Example 8 A laminated molded body was obtained in the same manner as in Example 1, except that the pressure during hot press molding was changed as shown in Table 1 and the thickness was changed to 5 mm.

[0061] Example 9 A laminated molded body was obtained in the same manner as in Example 1, except that the pressure during hot press molding was changed as shown in Table 1 and the thickness was changed to 1 mm.

[0062] (Comparative Example 1) Instead of phenol foam powder A, volume average particle size 30 μm, bulk density 152 kg / m 3 An attempt was made to produce a 2 mm thick laminated molded body in the same manner as in Example 1, except that phenol foam powder C was used. However, the obtained product was not integrated and could not be handled as a molded product. Phenol foam powder C was obtained by peeling off the surface material from phenol foam equivalent to that in Example 1 using a tumbling ball mill and coarsely pulverizing it, then removing the surface material using a 1.2 mm mesh sieve, consolidating and pulverizing it using a vibrating ball mill, and removing large particle size phenol foam powder using a 0.5 mm mesh sieve.

[0063] (Comparative Example 2) Instead of phenol foam powder A, volume average particle size 19 μm, bulk density 59 kg / m3 An attempt was made to produce a 2 mm thick laminated molded product in the same manner as in Example 1, except that phenol foam powder D was used. However, the product obtained was not integrated and could not be handled as a molded product. Phenol foam powder D was obtained by peeling off and coarsely pulverizing the surface material from phenol foam equivalent to that in Example 1 using a tumbling ball mill, removing the surface material with a 1.2 mm mesh sieve, and then further removing the surface material with a 0.063 m mesh sieve.

[0064] (Comparative Example 3) A curable composition was obtained by blending xylene sulfonic acid as a curing agent with a resol-type phenolic resin (corresponding to phenolic resin AU in paragraph

[0064] of JP 2008-024868 A). The curable composition was poured into a mold, and urethane sheets were attached to two opposing surfaces of the curable composition, followed by preforming in an oven at a temperature of 70°C for 20 minutes. The mold was then removed, and the preformed plate was sandwiched between punched metals from above and below to prevent warping during oven molding. This was further molded in an oven at a temperature of 70°C for 24 hours, resulting in a product with a thickness of 2 mm and a density of 1130 kg / m. 3 A laminated molded body of this size was obtained.

[0065] Comparative Example 4 In Comparative Example 3, the same treatment as in Comparative Example 3 was carried out except that the urethane foam substrate was not attached. The thickness was 2 mm and the density was 1,150 kg / m 3 A molded body of the above formula was obtained.

[0066] (Comparative Example 5) In Example 1, the same treatment as in Example 1 was carried out except that the urethane foam substrate was not bonded. 3 A phenolic resin molded article of the above formula was obtained.

[0067] The volume average particle size and bulk density of the phenolic foam powders of the examples and comparative examples; the density, thermal conductivity, average dimensional change, and weight loss of the laminated molded articles and molded articles; and the cross-sectional porosity of the phenolic resin molded layer were measured as follows. The results are shown in Table 1. However, for Comparative Examples 1 and 2, as mentioned above, the molded articles could not be handled as molded articles, so the cross-sectional porosity, density, thermal conductivity, average dimensional change, and weight loss were not measured. For the molded articles of Comparative Examples 4 and 5, the laminated molded articles used in the measurements of the density, thermal conductivity, average dimensional change, and weight loss of the laminated molded articles below were replaced with molded articles, and the measurements were performed in the same manner.

[0068] Volume average particle size of phenolic foam powder The volume average particle size of the phenol foam powder was measured using a laser diffraction light scattering particle size distribution measuring device after treating the phenol foam powder with ultrasound for 1 minute to disperse it uniformly in water.

[0069] ·Bulk density of phenolic foam powder The bulk density of the phenol foam powder was measured as "loose bulk density" in accordance with JIS Z 2504, using phenol foam powder instead of metal powder.

[0070] Density of laminated compact Using a 200 mm square laminated molded body as a sample, the apparent overall density was measured in accordance with JIS K7222.

[0071] - Cross-sectional porosity of the phenolic resin molding layer The laminated molded bodies obtained in the Examples and Comparative Examples were used as samples. Five 2mm x 2mm specimens were obtained by cutting the phenolic resin molded layer and substrate parallel to the lamination direction on the pair of opposite sides of the laminated molded body, which represented the largest area, using a high-quality stainless steel double-edged or single-edged blade. The surfaces of the specimens were metal-coated for 1 minute using a JEOL DII-29010SCTR Smart Coater. The phenolic resin molded layer region on the cut surface of the specimen was observed using a tabletop scanning electron microscope and "SEM Operation EZ" software under the following conditions: high vacuum mode, accelerating voltage of 5 kV, signal: SED, observation magnification: 200x, and working distance: 12.9mm-13.3mm. SEM image data was captured for impurity-free regions. The SEM images were imported into Image-J image analysis software, and the image brightness was binarized using a threshold value of 80, so that the areas occupied by the phenolic foam powder and the resol-type phenolic resin and curing agent composition were white and the void areas were black. In the binarized image, 0.09 mm 2 The black area ratio in the field of view was calculated. The black area ratios of the five measurement samples were averaged, and this average value was used as the cross-sectional porosity. SEM images of the cross-section of the phenolic resin molded layer in Example 1, where the cross-sectional porosity was measured, and the binarized image thereof are shown in Figures 1 and 2, respectively. SEM images of the cross-section of the phenolic resin molded layer in Comparative Example 5, where the cross-sectional porosity was measured, and the binarized image thereof are shown in Figures 3 and 4, respectively.

[0072] -Thermal conductivity of laminated compacts Thermal conductivity through the thickness was measured at 30°C in accordance with ASTM E 1530-04. The specific procedure is as follows: The laminate was cut into 25mm square specimens and placed in an atmosphere at 23±1°C and 50±2% humidity. The weight change of the specimen was measured every 24 hours, and the specimen's condition was monitored and adjusted until the weight change after 24 hours was 0.2% by mass or less. The specimen was then placed in a thermal conductivity measuring device at 23±1°C and 50±2% humidity. Thermal conductivity at 30°C was measured using a single specimen with a symmetrical configuration, with a low temperature plate at 18°C ​​and a high temperature plate at 42°C.

[0073] Average dimensional change rate of laminated molded body Two samples of approximately 100 mm × 100 mm laminated compact were each placed in an environment at 23 ± 2°C and 50 ± 10% RH for at least 24 hours. The samples were then removed and immediately measured using calipers at two locations (a, b, c, and d) in the vertical and horizontal directions, as shown in Figure 5. The measured values ​​L0 before heating and humidification were calculated. The upper and lower figures in Figure 5 are schematic perspective and plan views of the laminated compact 1, respectively. The samples were then placed in a thermo-hygrostat chamber at 80°C and 95% RH. After 48 hours, the samples were removed and placed in an environment at 23 ± 2°C and 50 ± 10% RH. The measured values ​​L1 after heating and humidification were calculated using the following formula: The dimensional change rate was calculated from these measurement results using the following formula: (L1-L0) / L0×100(%) (1) The average value of the dimensional change rates at a total of eight locations (a×2, b×2, c×2, and d×2) of two samples was taken as the average dimensional change rate.

[0074] Weight loss of laminated compact In Examples 1 to 9 and Comparative Example 3, which had a substrate, one side of the opposing substrate of a 100 mm × 200 mm laminated molded product sample was designated Side A, and the other side was designated Side B. Next, two 100 mm × 100 mm samples (i.e., a first sample and a second sample) were taken from the 100 mm × 200 mm sample. Side A of the first sample was placed as the measurement surface in a Taber abrasion tester, and a test was conducted under the following conditions: load 4.9 N, abrasion wheel H-18, rotation speed 60 rpm, ambient temperature 23°C ± 2°C, and 300 abrasion cycles, and the weight loss was measured. Next, a similar test was conducted using Side B of the second sample as the measurement surface, and the weight loss was measured. The average weight loss of Side A of the first sample and Side B of the second sample was then calculated. The abrasion durability of the sample was evaluated based on the weight loss of the test. The smaller the weight loss of the sample, the better the abrasion durability. In Comparative Examples 4 and 5, which did not have a substrate, an abrasion test was carried out on one of the main flat surfaces (the surface with the largest area) of the test specimen, and the amount of weight loss was measured.

[0075] [Table 1] In Table 1, "N / A" indicates that data was not available.

[0076] The laminated molded articles of Examples 1 to 9 had smaller densities, thermal conductivities, and dimensional change rates, and the phenolic resin molded layer had a smaller density and was lighter, had higher heat insulation, and were excellent in dimensional stability under high temperature and high humidity conditions compared to the laminated molded article of Comparative Example 3. Furthermore, the laminated molded articles of Examples 1 to 8 had smaller densities, thermal conductivities, dimensional change rates, and weight loss rates compared to the molded articles of Comparative Examples 4 and 5, and were excellent in abrasion resistance. Furthermore, the laminated molded article of Example 9 had smaller thermal conductivities and dimensional change rates, smaller weight loss in the abrasion test, and were excellent in abrasion resistance compared to the molded articles of Comparative Examples 4 and 5. Examples 1 to 6, 8, and 9, which used urethane foam as the substrate, had better abrasion resistance than Example 7, which used PET nonwoven fabric as the substrate. [Explanation of symbols]

[0077] 1. Laminated molded body 10 Phenolic resin molding layer 20 Base material [Industrial Applicability]

[0078] According to the present invention, it is possible to provide a laminated molded body and a method for manufacturing a laminated molded body, in which the phenolic resin molded layer is lightweight, has high thermal insulation properties, excellent dimensional stability under high temperature and high humidity conditions, and excellent abrasion resistance.

Claims

1. A laminated molded body including a substrate, a phenolic resin molded layer, and a second substrate, arranged adjacent to each other in this order, The cross-sectional porosity of the phenolic resin molding layer is 6.0% or more and 30.0% or less, The density of the laminated molded body is 200 kg / m ３ 1,100kg / m or more ３ is as follows: The laminated molded article, wherein the substrate and the second substrate are each at least one selected from the group consisting of a nonwoven fabric and a urethane foam.

2. 2. The laminated molded body according to claim 1, wherein the thermal conductivity of the laminated molded body at 30°C is 0.12 W / (m·K) or less.

3. 3. The laminated molded article according to claim 1, wherein the average dimensional change rate of the laminated molded article after 48 hours at 80° C. and humidity of 95% is −0.20% or more and 0.60% or less.

4. A laminated molded body described in any one of claims 1 to 3, wherein the nonwoven fabric is a polyethylene terephthalate nonwoven fabric.

5. The laminated molded body according to any one of claims 1 to 4, wherein the substrate and the second substrate are made of the same material.

6. The phenolic resin molding layer has a volume average particle size of 20 μm or more and 550 μm or less and a bulk density of 5 kg / m ３ More than 150kg / m ３ The laminated molded body according to any one of claims 1 to 5, which is made of a phenol foam powder having the following properties:

7. A method for producing the laminated molded body according to any one of claims 1 to 6, comprising: disposing a phenolic foam powder between the substrate and the second substrate adjacent to each other; The method for producing the laminated molded body according to any one of claims 1 to 6, comprising hot press molding the adjacently arranged base material, the phenol foam powder, and the second base material at a temperature of 130°C or higher and 240°C or lower and a pressure of 1,000 kPa or higher and 5,000 kPa or lower.

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