WO2019198642A1 - 発泡成型体、及びその製造方法 - Google Patents
発泡成型体、及びその製造方法 Download PDFInfo
- Publication number
- WO2019198642A1 WO2019198642A1 PCT/JP2019/015160 JP2019015160W WO2019198642A1 WO 2019198642 A1 WO2019198642 A1 WO 2019198642A1 JP 2019015160 W JP2019015160 W JP 2019015160W WO 2019198642 A1 WO2019198642 A1 WO 2019198642A1
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- Prior art keywords
- foam
- layer
- mold
- resin
- compression
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- 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
- B32B5/32—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 at least two layers being foamed and next to each other
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- B29C67/205—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising surface fusion, and bonding of particles to form voids, e.g. sintering
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Definitions
- the present invention relates to a foam molded article and a method for producing the same.
- Foam molded bodies made of resin are used as structural materials for automobiles and electronic devices and containers as materials that replace conventional solid resin materials and metal materials. These foamed molded products have low density, high heat insulating properties, and buffering properties, and these characteristics are mainly used effectively. On the other hand, these foamed molded products have a low density, so that they are inferior to conventional solid resin materials in impact resistance and scratch resistance, and their range of use has been limited in the past.
- the foam molded body is formed by the bead foam molding method and the extrusion foam molding method, the surface of the bead trace in which the bead foam particles are fused and the structure of the water vapor hole introduced during foam molding are transferred. It was formed, and the surface smoothness generated by the solid resin material could not be expressed.
- Patent Document 1 As a technique for imparting impact resistance and scratch resistance to a foam molded article, a technique for melting the surface of the foam molded article and forming a non-foamed layer as shown in Patent Document 1 is known.
- this surface melt molding method the surface of the foamed layer is melted by a heated metal plate or a heated mold, and a non-foamed layer having a constant thickness is formed by bead foaming pressure or external pressurization. It is disclosed that scratch resistance and rigidity are improved and a design surface is obtained.
- Patent Document 2 As a technique for imparting surface smoothness, a technique for forming a compression layer on the surface of a foamed molded body as shown in Patent Document 2 is known.
- forming a compressed layer on the surface increases the strength, smoothes the surface, and improves the appearance quality. Further, as a technique for imparting design properties, a technique is disclosed in which a compression layer is formed at the interface between a skin material and a foam layer in combination with a skin material as shown in Patent Document 3.
- Patent Document 2 the formation of a compressed layer as shown in Patent Document 2 can provide good surface smoothness, while the molten layer is not formed, so that the turtle shell pattern at the interface between the pre-expanded particles constituting the expanded layer is formed. Remains on the surface of the foamed molded product, and the mold following ability is greatly reduced. Further, due to the influence of air bubbles existing inside the pre-expanded particles, the light scattering property of the foam layer appearance is strong, and a glossy surface cannot be obtained. Therefore, sufficient designability on the surface of the foam molded body is not obtained.
- the problem to be solved by the present invention is to provide a foamed molded article that has been difficult in the conventional molding process, has high surface smoothness, excellent mold followability on the design surface, and excellent rigidity. is there.
- the inventor preliminarily heated the surface mold for forming the design surface using the prefoamed particles having a predetermined hardness, and the foamed particles existing on the heated surface side are dissolved, and the foamed By compressing in a state where the part that softens the particles is formed, a compression deformation layer composed of selectively softened foam particles is formed, and the compression ratio applied to the compression deformation layer is controlled to a predetermined ratio.
- the compressive deformation layer plays the role of a buffer layer and can impart high mold followability to the design surface without propagating the shrinkage stress of the foam layer accompanying cooling of the foam particles that were not compressed to the surface layer. It was found that excellent rigidity can be maintained.
- a molded body comprising a resin, comprising a surface layer, a compression deformation layer, and a foam layer,
- the surface layer has a thickness of 0.1 to 5.0 mm;
- the compressive deformation layer is located between the surface layer and the foam layer;
- the average H / L (H is the length in the compression direction, L is the length in the direction perpendicular to the compression direction) of the expanded particles constituting the compression deformation layer is 0.5 or less
- a foamed molded article, wherein the foamed particles constituting the foamed layer have a foaming ratio of 3.0 times or more and less than 30 times.
- [8] A step of foaming and fusing pre-expanded particles containing a resin to form a foam comprising a foam layer composed of the expanded particles; Placing the foam inside a foam molding die heated to a temperature above the glass transition point (Tg) or melting point of the resin, and preheating; Compressing the foam to a mold size by a press mechanism to form a surface layer and a compression deformation layer; Cooling the mold and solidifying the surface layer to obtain a foam molded article;
- the present invention it is possible to provide a foamed molded article having high surface smoothness, excellent design surface mold followability, and excellent rigidity, and a method for producing the same.
- a (numerical value) to B (numerical value) mean A or more and B or less.
- FIG. 1 shows an example of a cross-sectional view of a foamed molded product according to an embodiment of the present invention cut in the compression direction Z.
- the foamed molded product of the present invention has a three-layer structure composed of a surface layer 1, a compression deformation layer 2 and a foamed layer 3.
- Each layer is composed of foamed particles containing a resin, and can be defined by the shape of the foamed particles to be formed, specifically, the presence or absence of a closed cell structure and H / L.
- the boundary surface B1 between the surface layer 1 and the compression deformation layer 2 and the boundary surface B2 between the compression deformation layer 2 and the foam layer 3 can be distinguished (FIG. 1).
- the total thickness of the foam molded article is preferably 3 mm or more and 5000 mm or less. Thickness here means the average value of the compression direction dimension of a foaming molding. When it is 3 mm or more, the foamed molded product is preferable in that it has self-supporting properties and can be used as a structural member, and more preferably 5 mm or more. Moreover, when it is 5000 mm or less, it is preferable at the point that a molded article is obtained with a hot press machine or a foam molding machine.
- the rigidity of the foam molded body can be evaluated by measuring the flexural modulus of the foam molded body. The larger the value of the flexural modulus, the better the rigidity.
- the flexural modulus of the foamed molded product can be measured according to JIS K7171 (2008).
- the flexural modulus of the foam molded body can be adjusted by adjusting the thickness and material of the surface layer 1 and the compressive deformation layer 2 so that the bending rigidity of the foam layer 3 is enhanced.
- the flexural modulus of the foam molded article is preferably 100 MPa or more, more preferably 120 MPa or more, and further preferably 130 MPa or more.
- the surface layer 1 is defined as a layer in which the closed cell structure of the expanded particles has disappeared by melting.
- the compressive deformation layer 2 is located between the surface layer 1 and the foamed layer 3, and H / L represented by the length (H) in the compression direction and the length (L) in the direction perpendicular to the compression direction is 0.5. It is defined as a layer composed of the following expanded particles.
- the foam layer 3 is defined as a layer composed of foam particles having the H / L exceeding 0.5.
- the compression direction Z can be specified by the method as described in the Example mentioned later.
- the closed cell ratio of the foamed molded article of the present invention is not particularly limited, but is preferably 30% or more and 99% or less. When the closed cell ratio is within this range, the elastic repulsion force is maintained during compression, the followability to the mold is improved, and a design surface with high surface smoothness can be formed.
- the closed cell ratio of the foamed molded product of the present embodiment improves the strength of the foamed molded product and makes it difficult for water to be taken into the resin that may occur in the open cell portion, thereby reducing the density of the foamed molded product. From the viewpoint of making it difficult, it is more preferably 80% or more and 99% or less, and further preferably 85% or more and 99% or less.
- the closed cell ratio S (%) is calculated by the equation represented by the following equation (1).
- S (%) ⁇ (Vx ⁇ W / ⁇ ) / (Va ⁇ W / ⁇ ) ⁇ ⁇ 100 ...
- Vx is the true volume (cm 3 ) of the foam molded body
- Va is the apparent volume (cm 3 ) of the foam molded body
- W is the weight (g) of the foam molded body
- ⁇ is the density (g / cm 3 ) of the base resin of the foam molded article.
- the expansion ratio of the expanded particles constituting the expanded layer of the expanded molded body of the present invention is preferably 3.0 times or more, more preferably 5.0 times or more. Moreover, it is preferable that it is less than 30 times from a viewpoint which can maintain the elastic repulsion force at the time of compression, and it is more preferable that it is 20 times or less.
- the expansion ratio means how much the volume has expanded from the state of the base resin through the inclusion (impregnation) of the foaming agent, preliminary foaming, and final stage foaming.
- the expansion ratio of the expanded particles constituting the foam layer of the foam molded product is obtained by dividing the density of the base resin (starting material) constituting the foam layer by the apparent density of the foam layer portion of the foam molded product that is the final product. It may be calculated by Alternatively, the density of the base resin may be calculated by dividing by the apparent density of the foam which is an intermediate product.
- the foamed particles constituting the foamed layer are not easily affected by pressure compression during the production process of the foamed molded product due to the presence of the foamed particles constituting the surface layer and the compression deformation layer, and maintain the foaming ratio immediately before the pressure compression. Because it can. More specifically, the expansion ratio can be calculated by the method described in the examples described later.
- the foamed molded product of the present invention contains a resin in the form of foamed particles.
- the expanded particles are particles constituting the expanded molded body and the expanded body of the present embodiment, and indicate expanded particles after the final expansion of the pre-expanded particles.
- the pre-expanded particles refer to expandable particles that have not been subjected to the final stage of foaming, and include states before and after the preliminary foaming that is not the final stage.
- thermoplastic resin is not particularly limited.
- Styrene polymers such as styrene-butadiene copolymer and high impact polystyrene; vinyl chloride polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, post-chlorinated polyvinyl chloride, ethylene or copolymers of propylene and vinyl chloride; Polyvinylidene chloride copolymer resins; Nylon-6, Nylon-6, 6, etc., and copolyamide resins; Polyethylene terephthalate, etc., mono and copolyethylene Tellurium resin; modified polyphenylene ether resin (phenylene ether-polystyrene alloy resin); polycarbonate resin; methacrylimide resin; polyphenylene sulfide resin; polysulfone resin; polyethersulfone resin; phenol resin; .
- vinyl chloride polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, post-chlorinated
- polystyrene resin examples include polypropylene, ethylene-propylene random copolymer, propylene-butene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-butene polymerized using a Ziegler catalyst or a metallocene catalyst.
- Polypropylene resins such as terpolymers, low density polyethylene, medium density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-methyl Examples include methacrylate copolymers and ionomer resins. These polyethylene resins are used alone or in admixture of two or more.
- thermoplastic resins include polyolefin resins, polyamide resins, polyester resins, polyether resins, methacrylic resins, modified polyether resins (phenylene ether-polystyrene alloy resins), and the like.
- polyamide resins are excellent as heat resistance, chemical resistance and solvent resistance, and are suitable for high heat resistant foam moldings, and modified polyether resins (phenylene ether-polystyrene alloy) as resins excellent in heat resistance and high temperature rigidity. Resin).
- the thermoplastic resin preferably has a surface tension at 20 ° C. of from 35 mN / m to 60 mN / m, more preferably from 36 mN / m to 57 mN / m, and even more preferably from 37 mN / m to 55 mN / m. is there.
- a foam molded article having high mechanical strength can be obtained, and rigidity can be imparted to the design surface.
- As the surface tension of the thermoplastic resin a value measured by changing the measurement temperature to 20 ° C. in the method described in JIS K6768: 1999 “Plastic-Film and Sheet-Wetting Tension Test Method” is used.
- thermoplastic resin may be used in an uncrosslinked state, or may be used after being crosslinked with peroxide or radiation.
- the resin may be a conventional compounding agent, for example, an antioxidant, a light stabilizer, an ultraviolet absorber, a flame retardant, a dye, a colorant such as a pigment, a plasticizer, a lubricant, a crystallization nucleating agent, talc,
- An inorganic filler such as calcium carbonate may be included depending on the purpose.
- brominated or phosphoric flame retardants can be used.
- antioxidant phenol-based, phosphorus-based, sulfur-based and the like antioxidants can be used.
- light stabilizer a light stabilizer such as a hindered amine or benzophenone can be used.
- a cell regulator may be added.
- the air conditioner include talc, silica, calcium silicate, calcium carbonate, aluminum oxide, titanium oxide, diatomaceous earth, clay, baking soda, alumina, barium sulfate, aluminum oxide, and bentonite. The amount is 0.005 to 2 parts by mass with respect to 100 parts by mass of the total amount of particles.
- the pre-expanded particles can be obtained by containing (impregnating) a foaming agent into the pelletized resin to cause foaming.
- This foaming is a prefoaming that is not the final foaming.
- a volatile foaming agent etc. are mentioned as a foaming agent used at the time of manufacture of the said pre-expanded particle.
- the volatile blowing agent include chain or cyclic lower aliphatic hydrocarbons such as methane, ethane, propane, butane, isobutane, pentane, isopentane, neopentane, hexane, heptane, cyclopentane, cyclohexane, and methylcyclopentane.
- Halogenated hydrocarbons such as dicyclodifluoromethane, trichloromonofluoromethane, 1-chloro-1,1-difluoroethane, 1-chloro-2,2,2-trifluoroethane, and inorganic such as nitrogen, air and carbon dioxide Examples thereof include a gas-based foaming agent.
- the average particle diameter of the pre-expanded particles can be measured by a classification method using 100 g of pre-expanded particles using a standard sieve defined in JIS Z8801-1: 2006.
- the pre-expanded particles preferably have an average particle size of 1.0 to 4.0 mm, more preferably 1.2 to 3.0 mm. If the average particle size is less than 1.0 mm, handling in the production process is difficult, and if it exceeds 4.0 mm, the surface accuracy of a complicated molded product tends to decrease, which is not preferable.
- the shape of the pre-expanded particle of this embodiment is not particularly limited, and may be various shapes.
- thermoplasticity of a thermoplastic resin As the method for producing the pre-expanded particles, a method using thermoplasticity of a thermoplastic resin, a method by post-processing such as cutting of resin particles in a solid state, and the like are possible, and a method capable of imparting a desired outer shape to the particles. Any are applicable. Among them, a modified extrusion method using a die having a discharge cross section can be suitably used as a method with excellent productivity and capable of producing particles having a stable shape. As a modified extrusion method, thermoplastic resin is melt-extruded by an extruder, and base resin pellets obtained by pelletizing by a method commonly used in industry such as strand cutting or underwater cutting are expanded to obtain pre-expanded particles.
- a base resin pellet is manufactured by extruding from a die having a shape, and then cooled to a predetermined length by a pelletizer.
- the base resin pellet is impregnated with a foaming agent and heated to foam at a predetermined expansion ratio.
- the method for incorporating (impregnating) the foaming agent into the resin is not particularly limited and may be a generally used method. Such a method is not particularly limited. For example, a method using an aqueous medium in a suspension system such as water (suspension impregnation), or a method using a thermally decomposable foaming agent such as sodium bicarbonate (decomposing foaming agent). ), A method in which the gas is brought into a liquid phase state in an atmosphere higher than the critical pressure and brought into contact with the base resin (liquid phase impregnation), a method in which the gas is brought into a gas phase state under the critical pressure and brought into contact with the base resin. (Gas phase impregnation).
- the arbitrary three-dimensional shape can be imparted to the particles or pellets of the base resin as the raw material of the pre-expanded particles.
- the three-dimensional shape is not particularly limited, and examples thereof include a solid bead shape and a bead shape having a hollow portion or a concave outer shape portion.
- the orthogonal projection image of the base resin particles or pellets can take any shape.
- a general solid bead shape means a substantially spherical shape in which an orthogonal projection image has a circular shape or an elliptical shape.
- Having a hollow part means that an orthogonal projection image of particles or pellets has a hollow region inside and an outer peripheral region surrounding the hollow circular region, and an orthogonal projection image with the hollow region and the outer peripheral region is present. It means that there is a direction to be obtained.
- An example of the hollow portion is shown in FIG.
- having a concave outer shape means that there is a direction in which an orthographic image in which the orthographic image of particles or pellets becomes a concave figure is obtained.
- a concave figure means that at least a part of a line segment (preferably the whole line segment) connecting two points on the outer surface of an orthographic image figure to be a concave figure is an external region of particles or pellets.
- FIGS. 4 (a) and 4 (b) Examples of concave figures are shown in FIGS. 4 (a) and 4 (b).
- the concave outer shape portion has a structure different from foamed bubbles formed during foaming.
- One or a plurality of the concave contours may be provided.
- the foamed particles of the foamed layer are defined by the compression direction length (H) and the length perpendicular to the compression direction (L), and the foamed layer in the present invention is composed of foamed particles with H / L exceeding 0.5.
- the thickness of the foamed layer is not particularly limited, but is preferably 1 mm or more and 5000 mm or less, more preferably 3 mm or more and 1000 mm or less, and further preferably 5 mm or more and 500 mm or less. When the thickness of the foamed layer is within this range, it is preferable from the viewpoint that the molded product can be self-supported as a structure, and that the molded product can be obtained by a practical hot press machine or foam molding machine.
- the thickness of the foam layer is determined by subtracting the thickness of the surface layer and compression deformation layer described later from the thickness of the entire molded body measured in the compression direction.
- the hardness of the foam layer is preferably durometer hardness of HDA 10 or more, and more preferably HDA 30 or more. When the durometer hardness is within this range, the repulsive force during compression is sufficiently high, and the mold following ability can be sufficiently exhibited. Further, from the viewpoint of imparting impact resistance to the foamed molded product, the durometer hardness is preferably HDA 89 or less, more preferably HDA 85 or less. If the HDA is higher than this, the foam layer having an apparent density that is too high has a too high hardness and cannot sufficiently absorb impact energy.
- the hardness of the foam layer is measured from the cross-sectional direction of the foam molded body, and the durometer hardness of the foam layer is a value measured within 1 second after pressurizing with a load of 1 kgf in accordance with JIS K7215: 1986. To do. And 30 durometer hardness is measured about a foam layer, and let the arithmetic mean value be durometer hardness of a foam layer.
- the durometer hardness can be measured using a hardness meter (for example, trade name “DUROMETER HARDNESS TYPE A” manufactured by ASKER).
- the compression deformation layer exists between the surface layer and the foamed layer, and the bubbles inside the foamed particles are deformed by compression, and the internal pressure of the cell rises due to closed cells, so the volume shrinkage due to temperature change during cooling It is adjusted so that it has no ability. Furthermore, by forming a compression-deformed layer with an appropriate thickness, it absorbs distortion caused by cooling and solidification of the surface layer and shrinkage deformation of the foam layer that has been softened unintentionally. It is possible to impart a function of expressing mold following ability.
- the average value of H / L (also referred to as “average H / L” in the present specification) of the expanded particles constituting the compression deformation layer is 0.50 or less, preferably 0.47 or less, 0 More preferably, it is .45 or less.
- the compression ratio of the expanded particles constituting the compression deformation layer can be expressed by H / L.
- H / L When the average H / L is 0.5 or less, the linear expansion change due to the air in the closed cells inside the expanded particles The phenomenon that the resin softened by heating follows and deforms does not occur.
- the melting temperature of a general resin is 100 ° C to 300 ° C, the volumetric shrinkage of air due to cooling to room temperature (300K) is expected to be 20 to 48%.
- the compression rate H / L is set to 0.50 or less. Further, if the average H / L of the expanded particles of the compression deformation layer is 0.1 or more, it is preferable because the compression elastic modulus is low and the mold followability at the time of foam molding can be improved.
- the thickness of the compressive deformation layer is preferably 0.2 mm or more. When the thickness is equal to or greater than this thickness, the shrinkage stress accompanying cooling of the foam particles in the foam layer can be absorbed, and the surface smoothness and the image clarity of the design surface can be maintained. More preferably, it is 0.5 mm or more, More preferably, it is 0.7 mm or more.
- the thickness of the compression deformation layer is preferably 10 mm or less, and more preferably 5 mm or less from the viewpoint of weight reduction. The thickness of the compression deformation layer is determined by the method described in the examples described later.
- the surface layer is a layer in which a plurality of independent cell structures do not exist continuously by the resin partition walls, and a single cell structure that occurs exceptionally in the process of forming the surface layer or the like may exist inside.
- the layer in which the independent cell structure is continuously present by the resin partition wall is a compression deformation layer or a foam layer.
- the thickness of a surface layer is not specifically limited, From a viewpoint of expressing mechanical characteristics, 0.1 mm or more is preferable. Impact resistance can be expressed as it is 0.1 mm or more.
- the thickness of the surface layer is preferably 0.2 mm or more from the viewpoint of bending strength and compressive strength, but is preferably 5 mm or less from the viewpoint of reducing the weight of the foamed molded product.
- the thickness of the surface layer is determined by the method described in the examples described later.
- the surface layer, the compression deformation layer, and the foam layer are preferably made of the same type of resin.
- the same type of resin means that resin components excluding additives such as plasticizers and heat stabilizers are composed of the same resins according to the classification according to JIS K-6899-1: 2006. More specifically, those classified as the same resin using a combination of “5. Abbreviations on homopolymer materials, copolymer materials and natural polymer materials” and “6. Symbols indicating properties” of the JIS standard. Are of the same type. For example, when the surface layer, the compression deformation layer, and the foam layer are all modified polyphenylene ether resins, they are the same type of resin.
- the polyamide 6 resin is also a polyamide 66 resin.
- the durometer hardness of the surface layer is preferably HDA 90 or more, more preferably HDA 92 or more. When the durometer hardness of the surface layer is not more than the above range, sufficient scratch resistance cannot be obtained.
- the durometer hardness of the surface layer is a value measured within 1 second after pressurizing the upper surface of the surface layer, that is, the design surface with a load of 1 kgf in accordance with JIS K7215: 1986. Then, 30 durometer hardnesses are measured in the surface layer, and the arithmetic average value is defined as the durometer hardness of the surface layer.
- the image clarity (%) evaluated using the image clarity measuring device can be used.
- the image clarity of the design surface is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
- the design surface has sufficient surface smoothness, and good image clarity can be imparted to the design surface.
- the surface smoothness when the design surface is flat can be evaluated by the above evaluation method.
- the design surface may be a curved surface shape, or a fine uneven shape such as a textured shape may be imparted to the design surface.
- These shapes can be imparted by appropriately selecting the mold shape.
- the image clarity of the design surface cannot be measured using the image clarity measuring apparatus as described above, but the mold followability is improved by the manufacturing method of the present embodiment similar to the case where the design surface is flat. It is possible to provide a foamed molded article excellent in design properties.
- First embodiment a step of foaming and fusing pre-foamed particles containing a resin to form a foam composed of a foam layer composed of the foamed particles, and the foam with a glass transition point (Tg) of the resin ) Or a foam molding mold heated to a temperature equal to or higher than the melting point, the foam is compressed to the mold dimensions by a preheating process of the foam and a press mechanism, and the surface layer and the compression deformation
- Second Embodiment Filling Pre-Expanded Particles Including Resin into Mold for Molding, and Heating Medium at Temperature to Fuse Pre-Expanded Particles into the Mold to Expand and Fusion
- a step of forming a foam comprising a foam layer composed of expanded particles, a step of preheating the foam by heating the mold to a temperature equal to or higher than the Tg or melting point of the resin, and a press.
- the foam is compressed to a mold size to form a surface layer and a compression deformation layer, the mold is cooled, and the surface layer is solidified to have a design surface in the present invention. Obtaining a foam-molded body.
- the first embodiment of the method for producing a foamed molded product of the present invention (hereinafter referred to as “manufacturing method of the first embodiment”) will be specifically described.
- the step of foaming and fusing pre-foamed particles containing a resin to form a foam made of a foam layer composed of the foam particles Placing the foam inside a foam molding die heated to a temperature above the glass transition point (Tg) or melting point of the resin, and preheating; Compressing the foam to a mold size by a press mechanism to form a surface layer and a compression deformation layer; Cooling the mold and solidifying the surface layer to obtain a foam molded article; It is characterized by including.
- the foam is a molded body in which pre-expanded particles are subjected to foaming in the final stage and fused to each other. That is, the foam of the present embodiment is a molded body having at least a portion where foamed particles obtained by subjecting at least two or more pre-foamed particles to foaming in the final stage are fused to each other.
- the method of forming the pre-expanded particles into a foam is not particularly limited.
- the pre-expanded particles are filled in the cavities of the molding die and heated to cause foaming and at the same time between the pre-expanded particles. After heat sealing, the product can be solidified by cooling and molded.
- the filling method of the pre-expanded particles is not particularly limited.
- the pre-expanded particles are filled into the cavities of the molding die from the viewpoint of uniforming the size (cell size) of the bubbles inside the particles by applying a certain gas pressure to the bubbles of the pre-expanded particles.
- pressure treatment with gas to the pre-expanded particles.
- gas used for a pressurization process It is preferable to use inorganic gas from a viewpoint of a flame retardance, heat resistance, and dimensional stability.
- the inorganic gas and the pressure treatment method are the same as those in the pressure treatment with the gas applied to the pre-foamed particles before foaming in the above-described method of causing foaming of the polyamide-based resin.
- the heat medium used when forming the pre-expanded particles into the foam may be a general-purpose heat medium, and is preferably saturated steam or superheated steam from the viewpoint of suppressing oxidative deterioration of the foam. In view of enabling uniform heating, saturated steam is more preferable.
- the foam is manufactured by filling the pre-expanded particles in a closed mold and foaming, or by filling the pre-expanded particles in a mold that cannot be sealed and heating to fuse the pre-expanded particles to each other. Any of these may be adopted. Depending on the resin type and molding conditions, a general-purpose in-mold foaming automatic molding machine can be used.
- the pre-foamed particles may be heated and foamed and fused in two stages to form a foam.
- the foam molded as described above may be cooled by supplying cooling water into the cavity with a water-cooling nozzle before taking it out of the mold.
- Each foam constituting one or two of the foam layer, the compression deformation layer, and the surface layer is molded separately, and the foams are laminated and arranged in a desired order in a mold, and compression described later. Molding may be performed. Alternatively, one foam constituting the foam layer or the foam layer and the compression deformation layer is preliminarily molded, and the foam is placed in another mold, and then used as a reserve for the compression deformation layer and the surface layer or the surface layer.
- the foamed particles may be stacked and filled and subjected to foam molding, and the newly obtained foam may be subjected to compression molding described later.
- the foam layer or one foam constituting the foam layer and the compression deformation layer is preliminarily molded, and the foam is placed in a mold, and then the pre-expanded particles for the compression deformation layer and the surface layer or the surface layer.
- In-mold foam molding and compression molding which will be described later for the second embodiment, may be performed.
- each base resin is a mixture classified as the same type of resin, but the mixing ratio If they are significantly different, or if they are different types of resins, the above method may be effective.
- the foam is subjected to the following preheating step, compression step, and cooling step, and the foam is compression-molded to obtain a foam-molded product.
- preheating step compression step
- cooling step compression-molded to obtain a foam-molded product.
- a preheating step of heating the foam above the glass transition temperature of the amorphous thermoplastic resin or above the melting point temperature of the crystalline thermoplastic resin is performed before the compression step. It is preferable.
- the surface portion of the foam can be melted and fluidized, and the portion where the compression deformation layer is to be formed can be selectively heated and softened. Thereafter, by carrying out the compression and the rapid cooling process of the mold, it is possible to obtain a foamed molded article in which a smooth surface layer having good image clarity and a compression deformation layer are formed on the surface portion.
- the heating temperature of the foam in the preheating step is preferably Tg ° C. or more and less than (Tg + 100) ° C., with the glass transition temperature being “Tg (° C.)”. It is more preferable that the temperature is not lower than (° C.) and lower than (Tg + 90) ° C. If the heating temperature of the foam is too low, the fluidity of the molten resin is poor, the bubbles generated on the resulting design surface are not lost, and the design property of the design surface of the foamed molded product may be reduced. Further, if the heating temperature of the foam is too high, the foam is heated up to the inside of the foam layer and contracts during cooling, so that no elastic repulsion can be obtained during compression and the surface smoothness may be reduced.
- the glass transition temperature of the amorphous resin refers to a value measured by differential scanning calorimetry (DSC) according to JIS K7121.
- the peak indicating endotherm that appears in the measurement is defined as a peak indicating melting of the resin, and the temperature at the peak indicating endotherm that appears on the highest temperature side is defined as the glass transition temperature.
- a commercially available differential scanning calorimeter may be used, and a trade name “DSC6220 type” is available from SII Nano Technology.
- the glass transition temperature of the amorphous resin is measured by the method described in JIS K7121: 1987 “Method for measuring plastic transition temperature”.
- the sampling method and temperature conditions are as follows. Using a differential scanning calorimeter device, about 6 mg of the sample is filled so that there is no gap in the bottom of the aluminum measurement container, and the sample is heated from 30 ° C. to 290 ° C. under a nitrogen gas flow rate of 20 mL / min (1st Heating) The temperature was lowered from 290 ° C. to 30 ° C. after being held at 290 ° C. for 10 minutes, held at 30 ° C. for 10 minutes and then heated from 30 ° C. to 290 ° C. (2nd Heating) A DSC curve was obtained. In addition, all the temperature increase rates and temperature decrease rates are performed at 10 ° C./min, and alumina is used as a reference material.
- the melting point temperature is “Tm (° C.)”
- Tm melting point temperature
- Tm + 100 melting point temperature
- Tm + 10 preferably Tm + 10 ° C. or higher and lower than (Tm + 90) ° C.
- the heating temperature of the foamed molded product is too low, the fluidity of the molten resin is poor, and bubbles generated on the resulting design surface are not lost, which may reduce the designability of the foamed molded product.
- the heating temperature of the foam molding is too high, the inside of the foam layer is heated and contracts during cooling, so that no elastic repulsion can be obtained during compression and the surface smoothness may be reduced.
- the melting point of the crystalline resin is measured according to the following procedure. Take 6 mg of resin as a sample. Using a differential scanning calorimeter device, the sample was heated from 30 ° C. to 290 ° C. at a rate of temperature increase of 10 ° C./min in a nitrogen gas flow at a flow rate of 20 mL / min. Hold for a minute. Thereafter, the sample is quickly taken out from the apparatus and cooled to 30 ° C., and then the sample is heated again to 290 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen gas flow at a flow rate of 20 mL / min. The melting point (midpoint) is calculated from the DSC curve obtained at the time.
- alumina is used as a reference material.
- the differential scanning calorimeter apparatus marketed by the SII nanotechnology company by the brand name "DSC6220 type
- the temperature in the preheating step is within the above range, the temperature may be increased at an arbitrary temperature increase rate of two or more stages.
- the surfaces to be designed are molds on both sides, a plurality of molds may be set at different temperatures and preheated to suppress warping of the molded product after cooling.
- the heat source of the mold is preferably water vapor from the viewpoint of the heating rate.
- saturated steam is preferable from the viewpoint of heating uniformity, superheated steam obtained by heating saturated steam may be used.
- the compression process includes a hydraulic press mechanism or an electric press mechanism using a servo drive mechanism.
- a compression operation is performed step by step according to the cooling rate, and the mold repulsive force is always obtained by the elastic repulsive force of the foam layer. It is preferable from the viewpoint of being able to be compressed in a wet state and improving flatness.
- Adjustment of the compression rate of a foam can be performed by adjusting the pressurization degree to a foam.
- a method for adjusting the compressive deformation rate of the foam a method in which the foam is sandwiched between pressing members in the thickness direction and the pressing force applied to the foam by these pressing members is used.
- the spacers on the outer side of the foam, for example, outside both ends in the width direction or the length direction of the foam.
- the spacer may be disposed outside the foam.
- the spacer may be disposed at least outside both ends in the width direction or the length direction of the foam, and both ends in the width direction of the foam. You may arrange
- a servo mechanism that can pressurize the press mechanism in a stepwise manner is preferable from the viewpoint of being able to arbitrarily adjust the compression rate and performing compression in accordance with the cooling rate.
- a special compression molding die having a movable die as disclosed in Japanese Patent Application Laid-Open No. 2015-112827 can be preferably used.
- the cooling process can suitably implement a cooling method using a refrigerant.
- This cooling step is preferably performed simultaneously with the compression step from the viewpoint of adjusting the thickness of the compression deformation layer. Further, it is preferable that the cooling rate is high, and it is preferable to use a heat and cool die that can be rapidly heated and rapidly cooled, which includes a cooling medium and a heating medium, as the mold on the side on which the design surface is formed.
- the cooling temperature is preferably equal to or lower than the Tg of the resin, and more preferably equal to or lower than Tg ⁇ 10 ° C.
- the cooling temperature is preferably Tm or less of the resin, and more preferably Tm-10 ° C. or less.
- a second embodiment of the method for producing a foam molded article of the present invention (hereinafter referred to as “manufacturing method of the second embodiment”) will be described.
- pre-expanded particles are foamed and fused in a foam molding die to form a foam
- a compression deformation layer is formed by pressing and a surface layer is formed by heating and cooling.
- This method gives a heat and cool function to the inside of the mold for foam molding, and further gives the mold a compression mechanism as shown in the manufacturing method of the first embodiment, thereby molding the foam molded body.
- the surface layer and the compression deformation layer can be formed, which is desirable from the viewpoint of greatly reducing the manufacturing cost.
- the manufacturing method of the second embodiment is: 1) A step of filling pre-expanded particles containing a resin into a foam molding die; 2) A step of introducing a heating medium having a temperature for fusing the pre-foamed particles into the mold, foaming and fusing, and forming a foam composed of a foam layer composed of the foam particles; 3) A step of melting the mold surface resin by heating the mold to a temperature equal to or higher than the Tg or melting point of the resin and preheating the foam; 4) a step of compressing the foam to a mold size by a press mechanism to form a surface layer and a compression deformation layer; and 5) cooling the mold and solidifying the surface layer to obtain a foam molded body.
- Obtaining step including.
- in-mold foam molding may be performed by heating the pre-foamed particles in two stages in the foam molding mold, thereby obtaining a foam.
- the temperature distribution in the whole aggregate of the pre-foamed particles is further increased by preliminarily heating the pre-foamed particles with water vapor below the heat fusion temperature of the pre-foamed particles. It can be made uniform. Then, by the preliminary heating in the first stage, when the pre-expanded particles are heated in the second stage with water vapor having a temperature equal to or higher than the heat fusion temperature, the foam in the pre-expanded particles becomes more uniform. Can be easily formed into a foam. Further, according to this method, in the crystalline resin foam molded body obtained using the crystalline resin, the crystallite size of the resin becomes larger, the degree of crystallinity becomes higher, and thus the heat resistance is excellent. A foamed molded product can be obtained.
- the temperature at which the pre-expanded particles of the thermoplastic resin are heated is preferably in the vicinity of the thermal fusing temperature (Tf) of the pre-expanded particles of the thermoplastic resin.
- the heat fusion temperature refers to a temperature at which the pre-foamed particles are heated in saturated steam and the pre-foamed particles are fused.
- the method for measuring the heat fusion temperature is as follows. The pre-expanded particles are brought into a state where the pressure inside the bubbles is atmospheric pressure and does not contain a foaming agent such as hydrocarbon.
- the pre-expanded particles 10 g are put in a metal mesh container so that the pre-expanded particles come into contact with each other, and then heated with saturated steam at a predetermined temperature for 30 seconds. Then, the lowest temperature (° C.) of the temperatures at which the pre-expanded particles are fused by 80% or more after the heating is defined as the heat-fusion temperature of the pre-expanded particles.
- the heating temperature in the first stage is desirably lower than Tf (° C.), preferably Tf ⁇ 20 ° C. or more, more preferably Tf ⁇ 15 ° C. or more, and Tf ⁇ 2 ° C.
- the temperature is preferably below, and more preferably below Tf ⁇ 5 ° C.
- the heating time of the first stage is preferably 2 seconds or more, more preferably 3 seconds or more, preferably 20 seconds or less, and more preferably 15 seconds or less.
- the heating temperature in the second stage is higher than Tf (° C.), preferably Tf + 15 ° C. or less, more preferably Tf + 10 ° C. or less, and particularly preferably Tf + 5 ° C. or less.
- the heating time for the second stage is desirably 10 seconds or more, more desirably 15 seconds or more, desirably 60 seconds or less, and more desirably 45 seconds or less.
- the pre-foamed particles of the crystalline resin can be sufficiently foamed and heat-sealed, and the resin can be further crystallized. An accelerated foamed molded product can be obtained.
- the foam formed by the in-mold foam molding steps 1) and 2) is described above for the preheating step of the manufacturing method of the first embodiment. What is necessary is just to heat according to heating conditions. By this heating, the surface portion of the foam can be melted and fluidized, and the part where the compression deformation layer is to be formed can be selectively heated and softened. Thereafter, by performing the compression step of 4) and the rapid cooling step of the mold of 5), a foamed molded article having a smooth surface layer with good image clarity and a compression deformation layer is obtained on the surface portion. Can do.
- Step 4) of the manufacturing method of the second embodiment may be performed in the same manner as the compression step described above for the manufacturing method of the first embodiment.
- the press mechanism is used in combination with a frame part of a normal in-mold foam molding machine that pushes cracking after filling, and a mold having a movable piece for forming a compression deformation layer by compression. be able to.
- the mold cooling in the step 5) of the manufacturing method of the second embodiment may be performed in the same manner as the cooling step of the manufacturing method of the first embodiment.
- it is preferable to cool the foam molding by supplying cooling water into the foam molding die with a water cooling nozzle or the like simultaneously with the cooling of the die.
- [Mold for foam molding]] Although it does not specifically limit as a metal mold
- the heat and cool mold only needs to be provided in a mold on the side forming the design surface of at least two molds (for example, a core mold and a cavity mold) used at the time of molding, Two molds may be provided. Other than that, it is not particularly limited, and a mold having a general material or shape used for the production of a foam molded article can be used.
- the surface of the mold for foam molding can have an inverted shape such that the surface of the foam molded body has a desired shape such as a mirror surface shape, a polyhedral lens cut shape, a conical wrinkle shape, or a glossy layer.
- the foamed molded product of the present embodiment may further include a skin material on the upper surface (that is, the design surface) of the surface layer. Moreover, in the foaming molding of this embodiment, the skin material adhere
- the foam molded body provided with the skin material is not particularly limited. For example, in the manufacturing method of the first embodiment and the manufacturing method of the second embodiment, in the foam molding mold in which the skin material is arranged in advance, It may be obtained by placing foam or filling pre-expanded particles and foam molding.
- a decorative film in which the film surface or the lower surface of the hard coat layer is a printed surface, or a metal glossy surface with vapor deposition, sputtering or plating can be suitably used.
- nonwoven fabric bodies, such as a flocking film and a felt, may be sufficient.
- the printing pattern layer is formed by printing various patterns using ink and a printing machine.
- Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns, fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as patchwork. These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.
- a film having a metal layer formed by vapor deposition, sputtering, plating, or the like can be used as a design surface.
- Nonwoven fabrics include polyamide fibers, polyester fibers, polyacrylonitrile fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, phenol fibers, recycled fibers, etc., and wood pulp, hemp pulp, cotton linter Fibers selected from natural fibers such as pulp and inorganic fibers such as glass fibers can be used alone or in combination.
- the foamed molded product was cut in a direction perpendicular to the surface, and the resulting cross section was observed with a microscope (VHX-2000 Keyence Corporation). Specifically, an image of a sectional view as shown in FIG. 1 is acquired. The cross-sectional shape of the expanded particles is observed on the cross-sectional image, and the boundary between the surface layer and the compression deformation layer is specified based on the presence or absence of closed cells.
- the surface layer is a layer in which a plurality of independent cell structures do not exist continuously by the resin partition walls, and a single cell structure that occurs exceptionally in the process of forming the surface layer or the like may exist inside.
- the layer in which the independent cell structure is continuously present by the resin partition wall is a compression deformation layer or a foam layer.
- the cross-sectional shape of the expanded particles constituting the compression deformation layer is observed, and the short axis direction in which the aspect ratio (major axis diameter / minor axis diameter) takes the maximum value is specified as the compression direction.
- first foam particles in which the foamed form is observed inside the bead shape when viewed in the inner I direction from an arbitrary point on the surface S of the foamed molded body.
- a rectangle surrounding the first bead is created by two straight lines in the compression direction of the beads and two straight lines in a direction perpendicular to the compression direction.
- points where two straight lines in a direction perpendicular to the compression direction are in contact with the first bead are a bead upper point (foamed particle upper point U) and a bead lower point (foamed particle lower point D), respectively.
- the surface layer thickness is obtained by similarly averaging 30 points from the first bead upper point to the surface S measured in parallel with the compression direction.
- the thickness of the compression deformation layer is an average of 30 points of the distance between the upper point of the first bead and the lower point of the lowermost bead having H / L of 0.5 or less as viewed from the surface. It is calculated by doing.
- the closed cell ratio S (%) is calculated by the following equation (1).
- S (%) ⁇ (Vx ⁇ W / ⁇ ) / (Va ⁇ W / ⁇ ) ⁇ ⁇ 100 ...
- Vx is the true volume (cm 3 ) of the foam molded body
- Va is the apparent volume (cm 3 ) of the foam molded body
- W is the weight (g) of the foam molded body
- ⁇ is the density (g / cm 3 ) of the base resin of the foam molded article.
- the apparent volume means the volume calculated from the external dimensions of the foam molded article
- the true volume means the actual volume excluding the voids of the foam molded article.
- the true volume of the foamed molded product can be obtained by measuring using a pycnometer.
- Foaming magnification of the foamed particles constituting the foamed layer is defined as the foamed layer by observing the foamed molded product that is the final product in the cross-sectional direction. cut out portion, the density of the base resin (g / cm 3) of was calculated by dividing the apparent density of the foamed layer portion (g / cm 3). The apparent density of the foamed layer portion can be measured according to JIS K7222: 2005.
- the expansion ratio of the expanded particles constituting the expanded layer of the expanded molded body is determined by determining the density (g / cm 3 ) of the base resin and the apparent density (g / cm 3 ) of the expanded foam (also referred to as “resin foam”) before compression molding. It may be calculated by dividing by 3 ). The expansion ratio of the pre-expanded particles described later was calculated by dividing the apparent density of the pre-expanded particles by the density of the base resin.
- Mold followability of foam molded article Visual evaluation of the surface layer side of the foam molded article was performed, and mold followability was evaluated according to the following criteria. ⁇ : No defects are confirmed, and the surface of the molded body having an inverted shape of the mold is formed. ⁇ : Defects are not confirmed, but surface waviness different from the mold surface is observed. Xx: Holes. Observed defects such as
- Durometer-Hardness The durometer hardness is measured using a hardness meter (for example, “DUROMETER HARDNESS TYPE A” manufactured by ASKER). The value measured within 1 second after pressurizing with. And 30 places of durometer hardness were measured about the foam layer, and the arithmetic mean value was made into the durometer hardness of the foam layer.
- the durometer hardness of the surface layer is a value measured within 1 second after pressing from the surface side with a load of 1 kgf. And 30 places of durometer hardness were measured about the surface layer, and the arithmetic mean value was made into the durometer hardness of a foaming layer.
- the pellet had a surface tension of 37 mN / m and a glass transition temperature Tg of 150 ° C.
- the pellets as the base resin are placed in a pressure-resistant container, the gas in the container is replaced with dry air, and then carbon dioxide ( Gas), 7 mass% of carbon dioxide is impregnated into the pellet as the base resin over 3 hours under the conditions of a pressure of 3.2 MPa and a temperature of 11 ° C., and the base resin pellet is stirred in a foaming furnace Foaming was performed with pressurized steam while winging.
- Pre-expanded particles A-1 had an expansion ratio of 4.3 times, and pre-expanded particles A-2 had an expansion ratio of 8.7 times.
- the obtained pre-expanded particles were transferred to a pressure vessel, and the internal pressure was increased to 0.5 MPa over 1 hour with compressed air, and then maintained at 0.5 MPa for 8 hours, followed by pressure treatment.
- the obtained foam is provided with a heating and cooling mechanism in addition to a normal press mechanism as disclosed in JP-A-2015-112827 so that the foam can be efficiently preheated before compression.
- a foam-molded article was produced by compression molding using an apparatus equipped with a simple heat and cool mold mechanism. As the compression mechanism of the apparatus, a hydraulic cylinder type or servo motor type was used.
- Example 1 The resin foam A-1 was set in advance in a mold having a heating mechanism, and preheated in a state where the foam was in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 30 seconds. After heating, the upper die is compressed 10 mm by a hydraulic cylinder type compression mechanism, cooling is started at the same time as the compression starts, and after 90 seconds, when the upper die temperature reaches 100 ° C., the die is opened and the surface is designed. The foamed molded product was taken out. Table 1 shows the evaluation results of the foamed molded product.
- Example 2 to 4 In Examples 2 to 4, the amount of compression was set to 7.5 mm, 5.0 mm, and 2.5 mm, respectively, and the other conditions were processed under the same conditions as in Example 1. Each evaluation result is shown in Table 1.
- Examples 5 to 8 In Examples 5 to 8, processing was carried out under the same conditions as in Examples 1 to 4 except that the foam A-2 was processed. The evaluation results are shown in Table 1.
- Example 9 In advance, the resin foam A-1 was set in a mold having a heating mechanism, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 30 seconds. After the heating, the upper mold was compressed 1 mm by a servo motor type compression mechanism, and the compression cycle was held 10 times for 10 seconds, and compressed 10 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out. The evaluation results are shown in Table 1.
- Example 10 to 12 After the resin foam A-1 was heated in the same procedure as in Example 9, a compression cycle of holding for 4 seconds was performed 10 times at equal intervals by a servo motor type compression mechanism, and the upper molds were respectively 7.5 mm and 5 mm. , Compressed 2.5 mm. Moreover, cooling was started simultaneously with the start of compression. After 40 seconds, when the upper mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out. The evaluation results are shown in Table 1.
- Example 13 In advance, the resin foam A-1 was set in a mold having a heating mechanism, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 180 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 30 seconds. After heating, the upper mold was compressed 1.5 mm by a servo motor type compression mechanism, and the compression cycle was held 5 times, and compressed by 7.5 mm over 20 seconds. Cooling was started simultaneously with the start of compression, and after 20 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foam molded body having a surface design was taken out. The results are shown in Table 1.
- Example 14 In advance, the resin foam A-1 was set in a mold having a heating mechanism, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 60 seconds. After the heating, the upper mold was compressed 1 mm by a servo motor type compression mechanism, and the compression cycle was held 10 times for 10 seconds, and compressed 10 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out. The results are shown in Table 1.
- Example 15 In advance, the resin foam A-1 was set in a mold having a heating mechanism, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 60 seconds. After the heating, the upper mold was compressed by 0.75 mm by a servo motor type compression mechanism, and the compression cycle of holding for 4 seconds was performed 10 times, and compressed by 7.5 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out. The evaluation results are shown in Table 1.
- the carbon dioxide-impregnated pellets were transferred to a foaming apparatus, and air at 240 ° C. was blown in for 20 seconds to obtain an aggregate of polyamide pre-expanded particles.
- the obtained polyamide pre-expanded particles had an expansion ratio of 4.2 times and an average particle size of 2.0 mm.
- the pre-expanded particles that had been subjected to the pressure treatment were filled into cavities (cavity dimensions: length: 300 mm, width: 300 mm, height: 25 mm) of the in-mold molding die, and then clamped. And this metal mold
- Example 16 In advance, the resin foam A-3 was set in a mold having a heating mechanism, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 30 seconds. After the heating, the upper mold was compressed 1 mm by a servo motor type compression mechanism, and the compression cycle was held 10 times for 10 seconds, and compressed 10 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out. The results are shown in Table 2.
- Example 17 After heating the resin foam A-3 in the same procedure as in Example 16, the upper mold was compressed by 7.5 mm, 5.0 mm, and 2.5 mm in 10 compression cycles by a servo motor type compression mechanism, respectively. . Further, cooling was started simultaneously with the compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foam molded body having a surface design was taken out. The results are shown in Table 2.
- Example 20 and Comparative Example 5 regarding the manufacturing method of the second embodiment will be described.
- Example 20 Polyamide 666 resin (2430A, manufactured by DSM Co., Ltd.), surface tension of 46 mN / m at 20 ° C., 0.8% talc was melted using an extruder, and the strand discharged from the die was pelletized with a pelletizer. A solid bead-shaped pellet having a particle diameter of 1.4 mm was obtained. The melting point of this pellet was 193 ° C. The obtained pellets were put into a 10 ° C. pressure kettle, and 4 MPa carbon dioxide gas was blown in and absorbed for 3 hours. Next, the carbon dioxide impregnated mini-pellets were transferred to a foaming apparatus, and air at 240 ° C.
- the obtained polyamide pre-expanded particles had an expansion ratio of 4.2 times and an average particle size of 2.0 mm.
- the pre-expanded particles were subjected to pressure treatment.
- the pre-expanded particles that had been subjected to the pressure treatment were filled into cavities (cavity dimensions: length: 300 mm, width: 300 mm, height: 25 mm) of the in-mold molding die, and then clamped.
- the core mold was compressed by 2 mm by a servo motor type compression mechanism attached to the core mold, and the compression cycle of holding for 4 seconds was performed 5 times, and the compression was performed by 10 mm over 20 seconds. Simultaneously with the compression, the core mold was cooled with cooling water for 20 seconds, and cooling water was supplied into the cavity to cool the obtained molded body for 20 seconds. Thereafter, the mold was opened and the foamed molded product A-4 was taken out. The results are shown in Table 2.
- Example 21 The resin foam A-1 was set in advance in a mold having a heating mechanism, and preheated in a state where the foam was in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 210 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 100 ° C. The heating time was 15 seconds. After heating, the upper die is compressed by 7.5 mm by a hydraulic cylinder type compression mechanism, and cooling starts at the same time as compression starts. After 90 seconds, when the upper die temperature reaches 100 ° C., the die is opened and the surface The designed foamed molded article was taken out. The evaluation results of this foamed molded product are shown in Table 2.
- Example 22 to 23 In Examples 22 to 23, the compression was set to 5.0 mm and 2.5 mm, respectively, and the other conditions were the same as in Example 21. The respective evaluation results are shown in Table 2.
- the carbon dioxide-impregnated pellets were transferred to a foaming apparatus, and air at 220 ° C. was blown for 20 seconds to obtain an aggregate of polyamide pre-expanded particles.
- the obtained polyamide pre-expanded particles had an expansion ratio of 4.2 times and an average particle size of 2.0 mm.
- the pre-expanded particles that had been subjected to the pressure treatment were filled into cavities (cavity dimensions: length: 300 mm, width: 300 mm, height: 25 mm) of the in-mold molding die, and then clamped. And this metal mold
- Example 24 The resin foam B-1 was set in advance in a mold having a heating mechanism, and preheated in a state where the foam was in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side where the surface layer was formed was 210 ° C., and the temperature of the lower mold on the side where the surface layer was not formed was 100 ° C. The heating time was 30 seconds. After heating, the upper die is compressed by 7.5 mm by a hydraulic cylinder type compression mechanism, cooling is started simultaneously with the start of compression, 90 seconds later, when the upper die temperature reaches 100 ° C., the die is opened, and the resin The foamed molded product was taken out. The evaluation results of this foamed molded product are shown in Table 2.
- Example 25 P-block (JSP) whose base resin is non-crosslinked foamed polypropylene (melting point 142 ° C., surface tension 25 mN / mm at 20 ° C., indicated as “PP” in the table) as a resin foam in a mold having a heating mechanism in advance. (Foaming ratio: 15 times) 25 mm was set, and the foam was heated in contact with the upper mold and the lower mold. At this time, the temperature of the upper mold on the side on which the design surface was formed was 180 ° C., and the temperature of the lower mold on the side on which the design surface was not formed was 70 ° C. The heating time was 30 seconds.
- the upper mold was compressed by 0.75 mm by a servo motor type compression mechanism, and the compression cycle of holding for 4 seconds was performed 10 times, and compressed by 7.5 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out.
- the evaluation results of this foamed molded product are shown in Table 2.
- the upper mold was compressed by 0.75 mm by a servo motor type compression mechanism, and the compression cycle of holding for 4 seconds was performed 10 times, and compressed by 7.5 mm over 40 seconds. Cooling was started simultaneously with the start of compression, and after 40 seconds, when the mold temperature reached 100 ° C., the mold was opened, and the foamed molded body having a surface design was taken out.
- the evaluation results of this foamed molded product are shown in Table 2.
- the foamed molded product of the present embodiment can be provided as a structural member having both designability, lightness, and rigidity.
- Examples of applications of the foamed molded product of the present embodiment include members such as automobiles, trains, trains, and other vehicles that require lightness, design, and rigidity, and members that cover aircraft, particularly as interior materials. Etc. can be suitably used.
- the foamed molded article of the present invention takes advantage of its characteristics, and heat insulating materials and automobile parts used under high temperature conditions, such as oil pans, engine covers, engine under covers and cylinder head covers, other cover-shaped parts, intake manifolds, and It can be suitably used for such integrated parts, vehicle body structures, ducts, electrical component cases, battery cases and the like.
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Abstract
Description
また、発泡成型体は、ビーズ発泡成形法、押出発泡成形法により形成されるため、それぞれビーズ発泡粒子が融着したビーズ痕、発泡成形の際に投入する水蒸気孔の構造が転写された表面が形成されており、中実の樹脂材料が発する表面平滑を発現することができなかった。
また、表面平滑性を付与する手法として、特許文献2に示されるような、発泡成型体表面に圧縮層を形成する手法が知られている。この手法では、圧縮層を表面に形成することにより、強度が高く、表面が平滑で外観品質がよくなることが開示されている。
また、意匠性を付与する手法として、特許文献3に示されるような表皮材と組み合わせて、表皮材と発泡層との界面に圧縮層を形成する手法が開示されている。
[1]
樹脂を含み、表面層と、圧縮変形層と、発泡層とを備える成型体であって、
前記表面層の厚みが0.1~5.0mmであり、
前記圧縮変形層が、前記表面層と前記発泡層との間に位置し、
前記圧縮変形層を構成する発泡粒子の平均H/L(Hは圧縮方向長さ、Lは圧縮方向に対する垂直方向長さ)が0.5以下であり、
前記発泡層を構成する発泡粒子の発泡倍率が3.0倍以上30倍未満であることを特徴とする、発泡成型体。
[2]
表面層と発泡層が同一種類の樹脂からなる[1]に記載の発泡成型体
[3]
前記表面層の上面の写像性が30%以上である、[1]~[2]のいずれかに記載の発泡成型体。
[4]
前記表面層にシボ形状が付与されている、[1]~[3]のいずれかに記載の発泡成型体。
[5]
エンジンカバー、またはエンジンアンダーカバーとして用いられる[1]~[4]のいずれかに記載の発泡成型体。
[6]
前記樹脂が、融点145℃以上の結晶性樹脂、またはガラス転移温度145℃以上の非晶性樹脂である[1]~[5]のいずれかに記載の発泡成型体。
[7]
前記樹脂がポリアミドである[1]~[6]のいずれかに記載の発泡成型体。
樹脂を含む予備発泡粒子を発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、
前記発泡体を、前記樹脂のガラス転移点(Tg)又は融点以上の温度に加熱した発泡成形用金型の内部に配置し、予備加熱する工程と、
プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、
前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程と、
を含むことを特徴とする、[1]~[7]のいずれかに記載の発泡成型体の製造方法。
[9]
樹脂を含む予備発泡粒子を発泡成型用金型の内部に充填する工程と、
前記予備発泡粒子を融着せしめる温度の熱媒を前記金型の内部に投入し発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、
前記金型を前記樹脂のTg又は融点以上の温度まで加熱して、前記発泡体を予備加熱する工程と、
プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、
前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程と
を含むことを特徴とする、[1]~[7]のいずれかに記載の発泡成型体の製造方法。
なお、本発明の実施の形態において、A(数値)~B(数値)は、A以上B以下を意味する。
本発明の一実施形態の発泡成型体を圧縮方向Zに切断した断面図の一例を図1に示す。
本発明の発泡成型体は、図1に示されるように、表面層1と圧縮変形層2と発泡層3とから構成される3層構造を有している。
各層は、樹脂を含む発泡粒子で構成されており、構成する発泡粒子の形状、具体的には、独立気泡構造の有無と、H/Lとで規定することができる。例えば、図1の断面図では、表面層1と圧縮変形層2との境界面B1、圧縮変形層2と発泡層3との境界面B2が判別できる(図1)。
3mm以上であると、発泡成型体が自立性を持ち、構造部材として使用できる点で好ましく、さらに好ましくは5mm以上である。
また、5000mm以下であると、加熱プレス機や発泡成型機により成型品が得られるという点で好ましい。
発泡成型体の曲げ弾性率は、JIS K7171(2008)に従って測定できる。発泡成型体の曲げ弾性率は、発泡層3の曲げ剛性が強化されるよう、表面層1や圧縮変形層2の厚みや材質の調節で調整することができる。
発泡成型体の曲げ弾性率は、100MPa以上であることが好ましく、より好ましくは120MPa以上、さらに好ましくは130MPa以上である。
圧縮変形層2は、表面層1と発泡層3との間に位置し、圧縮方向長さ(H)と、圧縮方向に対する垂直方向長さ(L)で表されるH/Lが0.5以下である発泡粒子で構成されている層として規定される。
また、発泡層3は、上記H/Lが0.5を超える発泡粒子で構成されている層として規定される。
本発明の発泡成型体の独立気泡率は、特に限定されないが、30%以上99%以下であることが好ましい。独立気泡率がこの範囲であることにより、圧縮時に弾性反発力が維持され、金型への追従性が向上し、表面平滑性が高い意匠面を形成することができる。
本実施形態の発泡成型体の独立気泡率は、発泡成型体の強度を向上させると共に、連続気泡部分において生じ得る樹脂中への水の取り込みを生じにくくして、発泡成型体の密度を低下しにくくする観点から、80%以上99%以下であることがより好ましく、85%以上99%以下であることが更に好ましい。
なお、独立気泡率S(%)は、下記式(1)で表される式により算出される。
S(%)={(Vx-W/ρ)/(Va-W/ρ)}×100
・・・(1)
式中、Vxは、発泡成型体の真の体積(cm3)であり、Vaは、発泡成型体の見かけの体積(cm3)であり、Wは、発泡成型体の重量(g)であり、ρは、発泡成型体の基材樹脂の密度(g/cm3)である。
発泡成型体の発泡層を構成する発泡粒子の発泡倍率は、発泡層を構成する基材樹脂(出発材料)の密度を、最終製品である発泡成型体の発泡層部分の見掛け密度で除することによって算出すればよい。
あるいは、基材樹脂の密度を、中間製品である発泡体の見掛け密度で除することによって算出してもよい。発泡層を構成する発泡粒子は、表面層および圧縮変形層を構成する発泡粒子の存在により、発泡成型体の製造過程の加圧圧縮の影響を受け難く、加圧圧縮直前の発泡倍率を維持することができるためである。
発泡倍率は、より具体的には、後述する実施例記載の方法で算出することができる。
本発明の発泡成型体は、発泡粒子の形態で、樹脂を含む。
ここで、本発明において、発泡粒子とは、本実施形態の発泡成型体及び発泡体を構成する粒子であり、予備発泡粒子に最終段階の発泡を行った後の膨張した粒子を指す。
また、本発明において、予備発泡粒子とは、最終段階の発泡を行っていない発泡性の粒子を指し、最終段階でない予備的な発泡の実施前から実施後の状態を含む。
上記樹脂としては、特に限定されないが、例えば、熱可塑性樹脂等が挙げられる。
上記熱可塑性樹脂としては、特に限定されないが、例えば、ポリスチレン、ポリα-メチルスチレン、スチレン無水マレイン酸コポリマー、ポリフェニレンオキサイドとポリスチレンとのブレンド又はグラフトポリマー、アクリロニトリル-スチレンコポリマー、アクリロニトリル-ブタジエン-スチレンポリマー、スチレン-ブタジエンコポリマー、ハイインパクトポリスチレンなどのスチレン系重合体;ポリ塩化ビニル、塩化ビニル-酢酸ビニルコポリマー、後塩素化ポリ塩化ビニル、エチレン又はプロピレンと塩化ビニルのコポリマーなどの塩化ビニル系重合体;ポリ塩化ビニリデン系共重合樹脂;ナイロン-6、ナイロン-6,6等の、単独および共重合ポリアミド樹脂;ポリエチレンテレフタレート等の、単独および共重合ポリエステル系樹脂;変性ポリフェニレンエーテル樹脂(フェニレンエーテル-ポリスチレンアロイ樹脂);ポリカーボネート樹脂;メタクリルイミド樹脂;ポリフェニレンスルフィド樹脂;ポリスルホン樹脂;ポリエーテルスルホン樹脂;フェノール樹脂;ウレタン樹脂;ポリオレフィン系樹脂;などが挙げられる。
熱可塑性樹脂の表面張力は、JIS K6768:1999「プラスチック-フィルム及びシート-ぬれ張力試験方法」記載の方法において測定温度を20℃に変更して測定される値を用いる。
上記樹脂は必要に応じて、通常の配合剤、たとえば、酸化防止剤、光安定剤、紫外線吸収剤、難燃剤、染料、顔料などの着色剤、可塑剤、滑剤、結晶化核剤、タルク、炭酸カルシウム等の無機充填剤等を目的に応じて含んでいてもよい。
上記予備発泡粒子の製造時に用いる発泡剤としては、揮発性発泡剤等が挙げられる。上記揮発性発泡剤としては、メタン、エタン、プロパン、ブタン、イソブタン、ペンタン、イソペンタン、ネオペンタン、ヘキサン、へプタン、シクロペンタン、シクロヘキサン、メチルシクロペンタン等の鎖状または環状低級脂肪族炭化水素類、ジシクロジフルオロメタン、トリクロロモノフルオロメタン、1-クロロ-1、1-ジフルオロエタン、1-クロロ-2,2,2-トリフルオロエタン等のハロゲン化炭化水素類、窒素、空気、二酸化炭素等の無機ガス系発泡剤等が挙げられる。
なお、本実施形態の予備発泡粒子の形状は、特に限定されず、様々な形状としてよい。
かかる方法としては、特に限定されないが、例えば、水等の懸濁系で水性媒体を用いて行う方法(懸濁含浸)や、重炭酸ナトリウム等の熱分解型発泡剤を用いる方法(発泡剤分解)、ガスを臨界圧力以上の雰囲気とし液相状態にして、基材樹脂に接触させる方法(液相含浸)、ガスを臨界圧力未満の雰囲気とし気相状態にして、基材樹脂に接触させる方法(気相含浸)等が挙げられる。
予備発泡粒子の原料としての基材樹脂の粒子またはペレットには、任意の3次元形状を付与することができる。かかる3次元形状としては、特に限定されないが、中実のビーズ形状、中空部又は凹外形部を有するビーズ形状などが挙げられる。
基材樹脂の粒子またはペレットの正射影像は、任意の形状を取ることができる。一般的な中実のビーズ形状は、正射影像が、円形状もしくは楕円形状を有している略球状のものを意味する。中空部を有するとは、粒子またはペレットの正射影像が内部に中空領域を有しつつ該中空円領域を取り囲む外周領域を有することを意味し、かかる中空領域及び外周領域がある正射影像が得られる方向が存在することを意味する。中空部の例を図4(c)に示す。
また、凹外形部を有するとは、粒子またはペレットの正射影像が凹図形となる正射影像が得られる方向が存在することを意味する。また、本明細書において凹図形とは、凹図形となる正射影像図形の外表面上の2点間を結んだ線分の少なくとも一部(好ましくは全線分)が粒子またはペレットの外部領域を通る線分となる2点を選ぶことが可能であることを言う。凹図形の例を図4(a)、(b)に示す。凹外形部は、発泡時に形成される発泡気泡と異なる構造である。上記凹外形部は、一個でも複数個でもよい。
発泡層の発泡粒子は、圧縮方向長さ(H)、圧縮方向に対する垂直方向長さ(L)により規定され、本発明における発泡層は、H/Lが0.5を超える発泡粒子から構成される。
発泡層の厚みは、特に限定されないが、1mm以上5000mm以下であることが好ましく、3mm以上1000mm以下であることがより好ましく、さらに好ましくは5mm以上500mm以下である。発泡層の厚みがこの範囲であると、成形品が構造体としての自立が可能であり、また、実用的な加熱プレス機や発泡成形機により成形品が得られるという観点で好ましい。
なお、発泡層の厚みは、圧縮方向に測定される成型体全体の厚みから、後述の表面層及び圧縮変形層の厚みを差し引くことにより求める。
発泡層の硬度は、発泡成型体を切り出した断面方向から測定され、発泡層のデュロメータ硬度は、JIS K7215:1986に準拠して、荷重1kgfで加圧してから1秒以内に測定された値とする。そして、発泡層についてデュロメータ硬度を30箇所測定し、その相加平均値を発泡層のデュロメータ硬度とする。デュロメータ硬度の測定は、硬度計(例えば、ASKER社製 商品名「DUROMETER HARDNESS TYPE A」など)を用いて行うことができる。
圧縮変形層は、表面層と発泡層との間に存在し、圧縮により、発泡粒子内部の気泡が変形し、また独立気泡体によりセル内圧が上昇するために、冷却時の温度変化による体積収縮能をもたないよう調整される。
さらに、適切な厚みの圧縮変形層を形成することにより、表面層の冷却固化における歪や、意図せずして軟化した発泡層の収縮変形による歪を吸収し、表面の意匠面に良好な金型追従性を発現させる機能を付与させることができる。
圧縮変形層を構成する発泡粒子の圧縮率はH/Lで表すことができ、平均H/Lが0.5以下であると、発泡粒子内部の独立気泡内の空気による線膨張変化に対して、加熱により軟化した樹脂が追従し、変形する現象が生じない。
一般的な樹脂の溶融温度が100℃~300℃である場合、室温(300K)までの冷却による空気の体積収縮が20~48%見込まれるため、この体積収縮分である加圧圧縮を発泡粒子へ加えることにより、冷却過程での空気の体積収縮にともなう発泡成型体の収縮変形を抑制することが可能となる。したがって、圧縮率H/Lを0.50以下とする。
また、圧縮変形層の発泡粒子の平均H/Lが0.1以上であれば、圧縮弾性率が低く、発泡成型時の金型追従性を高めることができるため好ましい。
圧縮変形層の厚みは、軽量化の観点から、10mm以下であることが好ましく、5mm以下がより好ましい。
なお、圧縮変形層の厚みは、後述する実施例記載の方法によって求める。
表面層は、樹脂隔壁により独立した複数の気泡構造が連続して存在しない層であり、表面層を形成する過程などで例外的に生じる単独の気泡構造が内部に存在していてもよい。樹脂隔壁により独立した気泡構造が連続して存在する層は、圧縮変形層または発泡層とする。
表面層の厚みは、特に限定されないが、機械特性を発現する観点から、0.1mm以上が好ましい。0.1mm以上であると、耐衝撃性を発現できる。また、曲げ強度、圧縮強度の観点から、表面層の厚みは、0.2mm以上であることが好ましいが、発泡成型体の軽量化の観点から5mm以下が好ましい。
なお、表面層の厚みは、後述する実施例記載の方法によって求める。
たとえば、表面層と圧縮変形層と発泡層がともに、変性ポリフェニレンエーテル樹脂である場合は同一種類の樹脂である。
また、たとえば、表面層と圧縮変形層と発泡層がいずれも、ポリアミド6樹脂とポリアミド66樹脂との混合物を基材樹脂とする発泡粒子で構成されている場合は、ポリアミド6樹脂もポリアミド66樹脂もポリアミドのホモポリマーとして分類されるため、同一種類の樹脂からなるものである。この場合、上記3層を構成する樹脂混合物の間でポリアミド6樹脂とポリアミド66樹脂との混合比率が異なっていても、同一種類の樹脂からなるとする。
表面層のデュロメータ硬度は、表面層の上面、すなわち、意匠面に対して、JIS K7215:1986に準拠して、荷重1kgfで加圧してから1秒以内に測定された値とする。そして、表面層においてデュロメータ硬度を30箇所測定し、その相加平均値を表面層のデュロメータ硬度とする。
本実施形態の発泡成型体の表面層の上面(意匠面)の平滑性を示す指標として、写像性測定装置を用いて評価した写像性(%)を使用することができる。写像性が高い程、表面平滑性に優れる。
本実施形態の発泡成型体では、特に限定されないが、意匠面の写像性が30%以上であることが好ましく、50%以上であることがより好ましく、更に好ましくは70%以上である。意匠面の写像性が上記範囲であると、十分な表面平滑性を有し、意匠面に良好な写像鮮明性を付与することができる。
意匠面が平坦である場合の表面平滑性は以上のような評価方法で評価することができる。
この場合、上記のような写像性測定装置を用いて意匠面の写像性を測定することができないが、意匠面が平坦である場合と同様の本実施形態の製造方法によって、金型追従性が良く、意匠性に優れた発泡成型体を提供することができる。
本実施形態の発泡成型体の製造方法としては、特に限定されないが、例えば、以下の第一実施形態、第二実施形態などが挙げられる。
第一実施形態:樹脂を含む予備発泡粒子を発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、前記発泡体を、前記樹脂のガラス転移点(Tg)又は融点以上の温度に加熱した発泡成型用金型の内部に配置し、発泡体を予備加熱する工程と、プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、前記金型を冷却し、前記表面層を固化せしめて、本発明における意匠面を有する発泡成型体を得る工程と、を含む方法。
第二実施形態:樹脂を含む予備発泡粒子を発泡成型用金型の内部に充填する工程と、前記予備発泡粒子を融着せしめる温度の熱媒を前記金型の内部に投入し発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、前記金型を前記樹脂のTg又は融点以上の温度まで加熱して、前記発泡体を予備加熱する工程と、プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、前記金型を冷却し、前記表面層を固化せしめて、本発明における意匠面を有する発泡成型体を得る工程と、を含む方法。
以下、本発明の発泡成型体の製造方法の第一実施形態(以下、「第一実施形態の製造方法」と称する)について具体的に述べる。
第一実施形態の製造方法では、樹脂を含む予備発泡粒子を発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、
前記発泡体を、前記樹脂のガラス転移点(Tg)又は融点以上の温度に加熱した発泡成形用金型の内部に配置し、予備加熱する工程と、
プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、
前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程と、
を含むことを特徴とする。
発泡体は、予備発泡粒子が最終段階の発泡を行われ相互に融着した成形体である。即ち、本実施形態の発泡体は、少なくとも2個以上の予備発泡粒子が最終段階の発泡に供されてなる発泡粒子が互いに融着した部分を少なくとも有する成形体である。
予備発泡粒子を発泡体へ成形する方法としては、特に限定されないが、例えば、予備発泡粒子を成形用金型のキャビティ内に充填し、加熱することによって、発泡を生じさせると同時に予備発泡粒子同士を熱融着させた後、冷却により生成物を固化し、成形することができる。ここで、予備発泡粒子の充填方法は、特には限定されないが、例えば、金型を多少開けた状態で予備発泡粒子を充填するクラッキング法、金型を閉じたままの状態で加圧圧縮した予備発泡粒子を充填する圧縮法、金型に加圧圧縮した予備発泡粒子を充填した後に上記クラッキング法を行う圧縮クラッキング法等が挙げられる。
上記発泡体の製造は、上記予備発泡粒子を閉鎖した金型内に充填、発泡させて得る方法、密閉し得ない金型内に充填して加熱し、予備発泡粒子を相互に融着させる方法のいずれを採用してもよい。樹脂種と成形条件によっては汎用の型内発泡自動成形機を使用することができる。
上述のように成形した発泡体は、金型から取り出す前に、水冷ノズルでキャビティ内に冷却水を供給することによって、冷却してもよい。
あるいは、発泡層または発泡層および圧縮変形層を構成する1の発泡体を予め成形し、当該発泡体を別の金型内に配置した上に圧縮変形層および表面層用または表面層用の予備発泡粒子を積層充填し発泡成形し、新たに得られた発泡体に後述する圧縮成型を行ってもよい。
あるいは、発泡層または発泡層および圧縮変形層を構成する1の発泡体を予め成形し、当該発泡体を金型内に配置した上に圧縮変形層および表面層用または表面層用の予備発泡粒子を積層充填して、第二実施形態について後述する型内発泡成形および圧縮成型を行ってもよい。
例えば、発泡成型体の各層を構成する各基材樹脂の融点又はガラス転移温度が互いに異なる場合、具体的には、各基材樹脂が、同一種類の樹脂として分類される混合物であるが混合比率が大幅に異なる場合、または、互いに異なる種類の樹脂である場合は、上記のような手法が有効であり得る。
以下、第一実施形態の製造方法における圧縮成型の各工程について説明する。
第一実施形態の製造方法では、圧縮工程の前に、発泡体を、非晶性熱可塑性樹脂のガラス転移温度以上、または結晶性熱可塑性樹脂の融点温度以上で加熱する予備加熱工程を実施することが好ましい。予備加熱工程を実施することによって、発泡体の表面部を溶融流動化させ、また圧縮変形層を形成させたい部位を選択的に加熱、軟化させることができる。その後に圧縮と金型の急冷却工程を実施することによって、表面部に写像鮮明性の良い平滑な表面層と圧縮変形層とが形成された発泡成型体を得ることができる。
樹脂が非晶性樹脂の場合、予備加熱工程における発泡体の加熱温度は、ガラス転移温度を「Tg(℃)」として、Tg℃以上で且つ(Tg+100)℃未満であることが好ましく、(Tg+10)℃以上で且つ(Tg+90)℃未満であることがより好ましい。発泡体の加熱温度が低過ぎると、溶融した樹脂の流動性が悪く、得られる意匠面に発生した気泡が消失せず、発泡成型体の意匠面の意匠性が低下する虞れがある。また、発泡体の加熱温度が高過ぎると、発泡層内部まで加温され、冷却時に収縮するため、圧縮時に弾性反発力が得られず、表面の平滑性が低下する虞れがある。
圧縮工程は、油圧式によるプレス機構、またはサーボ駆動機構による電動式によるプレス機構などがある。特に、圧縮変形層を形成する際に、位置制御による駆動機構を使用することで、冷却速度に合わせて段階的に圧縮動作を行い、常時発泡層の持つ弾性反発力により金型追従性を得た状態で圧縮でき、平坦性が向上するという観点で好ましい。
圧縮工程における発泡体の圧縮は、得られる発泡成型体の圧縮変形層の平均H/Lが0.5以下となるように調整することが好ましい。
発泡体の圧縮率の調整は、発泡体への加圧度を調整することによって行うことができる。例えば、発泡体の圧縮変形率を調整する方法としては、発泡体をその厚み方向に押圧部材によって挟持し、これらの押圧部材によって発泡体に付加する押圧力を調整する方法などが用いられる。この時、発泡体の外方、例えば、発泡体の幅方向又は長さ方向における両端部外側にスペーサを配置することが好ましい。スペーサの高さを調整することによって発泡体への加圧度や発泡体の圧縮変形率を容易に調整することが可能となる。
また、プレス機構そのものを段階的に加圧できるようなサーボ機構を具備することにより、任意に圧縮率を調整でき、冷却速度に合わせた圧縮ができる観点から好ましい。
このような圧縮機構を備えた装置として、特開2015-112827号公報に開示されているような可動金型を備えた特殊な圧縮成型用金型を好適に使用することができる。
冷却工程は、冷媒を使用した冷却方法を好適に実施することができる。
この冷却工程は圧縮工程と同時に行うことが、圧縮変形層の厚みを調整できる観点から好ましい。
また、冷却速度が速いほど好ましく、少なくとも意匠面を形成する側の金型として、冷却媒体と加熱媒体を具備した急速加熱と急速冷却が可能なヒートアンドクール金型を用いることが好ましい。
樹脂が非晶性樹脂である場合、冷却温度は、樹脂のTg以下であることが好ましく、さらに好ましくはTg-10℃以下である。
樹脂が結晶性樹脂である場合、冷却温度は、樹脂のTm以下であることが好ましく、さらに好ましくはTm-10℃以下である。
以下、本発明の発泡成型体の製造方法の第二実施形態(以下、「第二実施形態の製造方法」と称する)について述べる。
第二実施形態の製造方法は、発泡成型用金型内で予備発泡粒子を発泡及び融着させ、発泡体形成を行うと同時に、プレス駆動による圧縮変形層の形成と、加熱、冷却による表面層形成とを行う方法である。この方法は、発泡成型用金型内部にヒートアンドクール機能を付与し、さらに上記第一実施形態の製造方法で示したような圧縮機構を前記金型に付与することにより、発泡成型体の成型と同時に、表面層、圧縮変形層を形成でき、製造コストを大幅に低減できる観点から、望ましい。
1)樹脂を含む予備発泡粒子を、発泡成型用金型の内部に充填する工程;
2)予備発泡粒子を融着せしめる温度の熱媒を前記金型の内部に投入し発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程;
3)前記金型を前記樹脂のTg又は融点以上の温度まで加熱して、前記発泡体を予備加熱することにより、金型表面樹脂を溶融する工程;
4)プレス機構で前記発泡体を金型寸法へ圧縮し、表面層と圧縮変形層とを形成する工程;及び
5)前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程;
を含む。
なお、上記第二実施形態の製造方法において、工程5)と同時に、水冷ノズルで前記金型内に冷却水を供給して、発泡成型体を冷却してもよい。
予備発泡粒子を発泡成形用金型のキャビティ内に充填する工程と、
キャビティ内に予備発泡粒子の熱融着温度以下の水蒸気を5~30秒間供給して、予備発泡粒子を予備的に加熱する、前加熱工程(第一段階の加熱)と、
キャビティ内に予備発泡粒子の熱融着温度以上の水蒸気を20~120秒間供給して、予備発泡粒子を発泡させ、且つ熱融着させることによって、樹脂発泡体を得る、後加熱工程(第二段階の加熱)と、を含んでもよい。
言い換えると、第二実施形態の製造方法では、発泡成型用金型内で、予備発泡粒子を二段階で加熱することによって、型内発泡成形を行い、発泡体を得てもよい。
また、この方法によれば、結晶性樹脂を用いて得られる結晶性樹脂発泡成型体において、樹脂の結晶子サイズがより大きくなり、また、結晶化度がより高くなり、ひいては、耐熱性に優れた発泡成型体を得ることができる。
なお、熱融着温度とは、予備発泡粒子を飽和水蒸気内において加熱し、予備発泡粒子同士が融着する温度を指す。熱融着温度の測定方法は、次の通りである。予備発泡粒子を、気泡内部の圧力が大気圧であり、炭化水素等の発泡剤を含んでいない状態にする。この予備発泡粒子10gを金属メッシュの容器に予備発泡粒子同士が接触するように入れ、次いで、所定温度の飽和蒸気で30秒間加熱する。そして、加熱後に予備発泡粒子同士が全体で80%以上融着していた温度のうちの最低の温度(℃)を、予備発泡粒子の熱融着温度とする。
第一段階の加熱時間は、2秒以上であることが望ましく、3秒以上であることが更に望ましく、20秒以下であることが望ましく、15秒以下であることが更に望ましい。
第二段階の加熱時間は、10秒以上であることが望ましく、15秒以上であることが更に望ましく、60秒以下であることが望ましく、45秒以下であることが更に望ましい。
なお、プレス機構は、充填時の片開き、充填後にクラッキングを押す通常の型内発泡成形機のフレーム部位と圧縮により圧縮変形層を形成するための可動駒を備えた金型を組み合わせて使用することができる。
また、金型の冷却と同時に、水冷ノズル等で発泡成型用金型内に冷却水を供給して、発泡成型体を冷却することが好ましい。
発泡成型に使用される発泡成型用金型としては、特に限定されないが、少なくとも1つはヒートアンドクール金型であることが好ましい。
ヒートアンドクール金型は、成型時に使用される、少なくとも2つ(例えば、コア金型、キャビ金型)の金型のうちの意匠面を形成する側の金型に具備されていればよく、2つの金型に具備されてもよい。
それ以外は、特に限定されず、発泡成型体の製造に使用される一般的な材質や形状の金型を用いることができる。
本実施形態の発泡成型体は、表面層の上面(すなわち、意匠面)に表皮材を更に備えていてもよい。また、本実施形態の発泡成型体において、表面層と接着した表皮材が意匠面を形成してもよい。
表皮材を備える発泡成型体は、特に限定されないが、例えば、上記第一実施形態の製造方法、上記第二実施形態の製造方法において、表皮材を予め配置した発泡成型用金型の内部に、発泡体を配置し又は予備発泡粒子を充填して、発泡成形することによって得てもよい。
また植毛フィルムやフェルトなどの不織布体でもよい。
実施例及び比較例で用いた評価方法について以下に説明する。
発泡成型体を表面に対して垂直方向に切断し、得られた断面をマイクロスコープ(VHX-2000 キーエンス株式会社)で観察した。具体的には、図1のような断面図の画像を取得する。断面図の画像上で発泡粒子の断面形状を観察して、独立気泡の有無によって表面層と圧縮変形層との境界を特定する。表面層は、樹脂隔壁により独立した複数の気泡構造が連続して存在しない層であり、表面層を形成する過程などで例外的に生じる単独の気泡構造が内部に存在していてもよい。樹脂隔壁により独立した気泡構造が連続して存在する層は、圧縮変形層または発泡層とする。圧縮変形層を構成する発泡粒子の断面形状を観察し、アスペクト比(長軸径/短軸径)が最大値をとる短軸方向を、圧縮方向として特定する。
図2の模式図のように、発泡成型体の表面S上の任意の1点から内側I方向に見て、ビーズ形状の内部に発泡形態が観察される最初の発泡粒子(以下、「第1ビーズ」と称する)を特定し、ビーズの圧縮方向に2直線と、圧縮方向に対して垂直な方向の2直線とで、第1ビーズを囲む長方形を作成する。その長方形において、圧縮方向に対して垂直な方向の2直線が第1ビーズと接する点を、各々、ビーズ上部点(発泡粒子上部点U)、ビーズ下部点(発泡粒子下部点D)とする。その第一ビーズ上部点から圧縮方向と平行に計測した表面Sまでの距離を、同様に30点加算平均したものを表面層厚みとする。
発泡成型体の断面をマイクロスコープVHX-2000付随の解析ソフトの測長機能を用いて観察した。上記(1)表面層厚みを求める方法と同様にして、複数のビーズの上部と下部を求め、さらに表面Sから内側Iへの法線方向とビーズが接する2点の距離をビーズ幅(L)とし、ビーズ上部と下部の距離を(H)とし、H/Lを算出した。H/Lが0.5以下となるビーズを圧縮変形ビーズとした。
圧縮変形層の厚みは、表面からみて上記第1ビーズの上部点とH/Lが0.5以下の最下部のビーズの下部点の距離の30点加算平均することにより算出される。
なお、独立気泡率S(%)は、下記式(1)で表される式により算出される。
S(%)={(Vx-W/ρ)/(Va-W/ρ)}×100
・・・(1)
式中、Vxは、発泡成型体の真の体積(cm3)であり、Vaは、発泡成型体の見かけの体積(cm3)であり、Wは、発泡成型体の重量(g)であり、ρは、発泡成型体の基材樹脂の密度(g/cm3)である。見かけの体積は発泡成型体の外形寸法から算出される体積、真の体積は発泡成型体の空隙部を除いた実体積をそれぞれ意味する。
発泡成型体の真の体積はピクノメータを用いて測定することにより得られる。
発泡成型体の発泡層を構成する発泡粒子の発泡倍率は、最終製品である発泡成型体を断面方向に観察して、発泡層と定義される部分を切り出し、基材樹脂の密度(g/cm3)を当該発泡層部分の見掛け密度(g/cm3)で除することにより算出した。発泡層部分の見掛け密度は、JIS K7222:2005に準拠して測定することができる。
発泡成型体の発泡層を構成する発泡粒子の発泡倍率は、基材樹脂の密度(g/cm3)を圧縮成型前の発泡体(「樹脂発泡体」とも称する)の見掛け密度(g/cm3)で除することにより算出してもよい。
また、後述する予備発泡粒子の発泡倍率は、予備発泡粒子の見掛け密度を、基材樹脂の密度で除して算出した。
発泡成型体の表面層側の目視評価を行い、下記基準に従って、金型追従性を評価した。
○:欠陥は確認されず、金型の反転形状の成型体表面が形成されているもの
×:欠陥は確認されないが、金型表面とは異なる、表面うねりが観察されるもの
××:空孔などの陥没欠陥が観察されるもの
写像性測定器(スガ試験機(株)製ICM-1T)を用いて、発泡成型体の意匠面の写像性を評価した。
写像性は以下の式で評価した。
C(n)=(M-m)/(M+m)×100
ここで、nはスリットの幅であり、Mは受光側スリットの透過光量であり、mは受光側スリット遮光部の漏れ光量である。
発泡成型体の意匠面の写像性は、受光側のスリット幅=0.125mmで評価した。
写像性(%)の数値が大きい程、写像性に優れる。例えば、完全な写像性が得られる光学ミラーの場合、受光側スリットで完全に遮光されて漏れ光量m=0となるため、写像性は100%となる。
デュロメータ硬度の測定は、硬度計(例えば、ASKER社製 商品名「DUROMETER HARDNESS TYPE A」など)を用いて、発泡層のデュロメータ硬度は、JIS K7215に準拠して、荷重1kgfで加圧してから1秒以内に測定された値とする。そして、発泡層についてデュロメータ硬度を30箇所測定し、その相加平均値を発泡層のデュロメータ硬度とした。
表面層のデュロメータ硬度は、表面側から荷重1kgfで加圧してから1秒以内に測定された値とする。そして、表面層についてデュロメータ硬度を30箇所測定し、その相加平均値を発泡層のデュロメータ硬度とした。
発泡成型体の曲げ弾性率の測定は、JIS K7171(2008)に従って実施した。発泡成型体を、あらかじめ真空下で40℃、24時間以上乾燥させたのち、島津製作所製オートグラフ(AG-5000D)型を用いて、表面層側から荷重をかけることで曲げ弾性率(MPa)を計測した。
曲げ弾性率が130MPaより大きいものを剛性◎、100MPa以上130MPa以下のものを剛性〇、100MPaより小さいものを剛性×と評価した。曲げ弾性率の数値が大きい程、剛性に優れる。
ポリフェニレンエーテル系樹脂(PPE)(商品名:ザイロンTYPES201A、旭化成(株)製、20℃における表面張力40mN/m)を60質量%、汎用ポリスチレン樹脂(PS)(商品名:GP685、PSジャパン(株)製)を40質量%加え、押出機にて加熱溶融混練押し出しダイから吐出させたストランドをペレタイザーでペレタイズし、中実ビーズ形状のペレットを得た。このペレットの表面張力は37mN/m、ガラス転移温度Tgは150℃であった。特開平4-372630号公報の実施例1に記載の方法に準じ、基材樹脂としての上記ペレットを耐圧容器に収容し、容器内の気体を乾燥空気で置換した後、発泡剤として二酸化炭素(気体)を注入し、圧力3.2MPa、温度11℃の条件下で3時間かけて基材樹脂としてのペレットに対して二酸化炭素を7質量%含浸させ、基材樹脂ペレットを発泡炉内で攪拌羽させながら加圧水蒸気により発泡させた。予備発泡粒子A-1は、4.3倍、予備発泡粒子A-2は8.7倍の発泡倍率を有した。
得られた予備発泡粒子を耐圧容器に移し、圧縮空気により内圧を0.5MPaまで1時間かけて昇圧し、その後0.5MPaで8時間保持し、加圧処理を施した。これを、型内発泡成形装置の水蒸気孔を有する金型内に充填し、加圧水蒸気0.37MPaで加熱して予備発泡粒子を相互に膨張・融着させた後、冷却し、成形金型より取り出し、発泡体A-1(発泡倍率5.0倍、25mm厚み)及びA-2(発泡倍率10.0倍、25mm厚み)の樹脂発泡体を得た。
なお、前記装置の圧縮機構としては、油圧シリンダー式又はサーボモーター式のものを用いた。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で予備加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。
加熱時間は30秒とした。
加熱後、油圧シリンダー式の圧縮機構により上金型を10mm圧縮し、圧縮開始と同時に冷却を開始し、90秒後上金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
この発泡成型体の評価結果を表1に示す。
実施例2~4では圧縮量をそれぞれ7.5mm、5.0mm、2.5mmとし、それ以外は実施例1と同一の条件で加工した。それぞれの評価結果を表1に示す。
実施例5~8では、A-2の発泡体を加工した以外は、それぞれ実施例1~4と同一の条件で加工を実施した。評価結果を表1に示す。
上金型による予備加熱時間を10秒とした以外は実施例4と同一の条件で加工した。評価結果を表1に示す。
圧縮量を0mmとした(すなわち、圧縮しなかった)以外は、実施例4と同一の条件で加工した。評価結果を表1に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は30秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を1mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて10mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
評価結果を表1に示す。
実施例9と同様の手順で樹脂発泡体A-1を加熱後、サーボモーター式の圧縮機構により、4秒保持する圧縮サイクルを等間隔で10回行い、上金型をそれぞれ7.5mm、5mm、2.5mm圧縮した。また、圧縮開始と同時に冷却を開始した。40秒後上金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
評価結果を表1に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を180℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は30秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を1.5mm圧縮し、4秒保持する圧縮サイクルを5回行い、20秒かけて7.5mm圧縮した。
圧縮開始と同時に冷却を開始し、20秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表1に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は60秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を1mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて10mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表1に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は60秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を0.75mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて7.5mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
評価結果を表1に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は90秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を0.75mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて7.5mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表1に示す。
ポリアミド666樹脂(2430A、(株)DSM製、20℃における表面張力46mN/m、表中「PA666」と表記する)タルク0.8%を、押出し機を用いて溶融し、ダイから吐出させたストランドをペレタイザーでペレタイズし、平均粒子径1.4mmの中実ビーズ形状のペレットを得た。このペレットの表面張力は46mN/m、融点は193℃であった。得られたペレットを10℃の圧力釜に投入し、4MPaの炭酸ガスを吹き込み3時間吸収させた。次いで炭酸ガス含浸ペレットを発泡装置に移し、240℃の空気を20秒間吹き込み、ポリアミド予備発泡粒子の集合体を得た。得られたポリアミド予備発泡粒子は、4.2倍の発泡倍率を有し、平均粒子径は2.0mmであった。
得られた予備発泡粒子をオートクレーブ中に封入し、オートクレーブ内の圧力が0.4MPaとなるまで、圧縮空気を1時間かけて導入し、その後、圧力を0.4MPaに24時間保持することによって、予備発泡粒子に加圧処理を施した。
加圧処理した予備発泡粒子を、型内成形金型のキャビティ(キャビティ寸法は、縦:300mm、横:300mm、高さ:25mm)内に充填し、その後、型締めした。そして、この金型を型内発泡成形機に取り付けた。
その後、キャビティ内に105℃の飽和水蒸気を10秒間供給し、その後、キャビティ内に116℃の飽和水蒸気を30秒間供給して、予備発泡粒子を発泡させ、且つ熱融着させることによって、予備発泡粒子を発泡体へ成形した。金型のキャビティ内に冷却水を供給することによって、得られた発泡体を冷却し、その後、型開きを行い、樹脂発泡体A-3を取り出した。樹脂発泡体A-3の発泡倍率は5.0倍であった。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-3をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は30秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を1mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて10mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表2に示す。
実施例16同様の手順で樹脂発泡体A-3を加熱後、サーボモーター式の圧縮機構により、10回の圧縮サイクルで、上金型をそれぞれ7.5mm、5.0mm、2.5mm圧縮した。また、圧縮と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表2に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-3をセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。加熱時間は60秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を0.25mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて2.5mm圧縮した。
圧縮と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
結果を表2に示す。
ポリアミド666樹脂(2430A、(株)DSM製)、20℃における表面張力46mN/m)タルク0.8%を、押出し機を用いて溶融し、ダイから吐出させたストランドをペレタイザーでペレタイズし、平均粒子径1.4mmの中実ビーズ形状のペレットを得た。このペレットの融点は193℃であった。得られたペレットを10℃の圧力釜に投入し、4MPaの炭酸ガスを吹き込み3時間吸収させた。次いで炭酸ガス含浸ミニペレットを発泡装置に移し、240℃の空気を20秒間吹き込み、ポリアミド予備発泡粒子を得た。得られたポリアミド予備発泡粒子は、4.2倍の発泡倍率を有し、平均粒子径は2.0mmであった。
得られた予備発泡粒子をオートクレーブ中に封入し、オートクレーブ内の圧力が0.4MPaとなるまで、圧縮空気を1時間かけて導入し、その後、圧力を0.4MPaに24時間保持することによって、予備発泡粒子に加圧処理を施した。
加圧処理した予備発泡粒子を、型内成形金型のキャビティ(キャビティ寸法は、縦:300mm、横:300mm、高さ:25mm)内に充填し、その後、型締めした。そして、この金型を型内発泡成形機に取り付けた。
その後、キャビティ内に105℃の飽和水蒸気を10秒間供給し、その後、キャビティ内に116℃の飽和水蒸気を30秒間供給して、予備発泡粒子を発泡させ、且つ熱融着させることによって、予備発泡粒子を発泡体へ成形した。
その後コア金型に200℃の過熱蒸気を入れ、10秒後に金型温度が210℃になった状態で30秒間保持した。
その後、コア金型に取付けられたサーボモーター式の圧縮機構により、コア金型を2mm圧縮し、4秒保持する圧縮サイクルを5回行い、20秒かけて10mm圧縮した。
圧縮と同時にコア金型を冷却水により20秒間冷却し、また、キャビティ内に冷却水を供給することによって、得られた成型体を20秒間冷却した。
その後、型開きを行い、発泡成型体A-4を取り出した。結果を表2に示す。
実施例20と同様の方法で発泡体までの成形を行い、コア金型を210℃になった状態で30秒間保持後、圧縮せずに冷却を開始した。コア金型を冷却水により20秒間冷却し、また、キャビティ内に冷却水を供給することによって、得られた成型体を20秒間冷却した。
その後、型開きを行い、発泡成型体A-5を取り出した。結果を表2に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で予備加熱した。この際、意匠面を形成する側である上金型の温度を210℃とし、意匠面を形成しない側である下金型の温度は100℃とした。
加熱時間は15秒とした。
加熱後、油圧シリンダー式の圧縮機構により上金型を7.5mm圧縮し、圧縮開始と同時に冷却を開始し、90秒後上金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
この発泡成型体の評価結果を表2に示す。
実施例22~23では圧縮をそれぞれ5.0mm、2.5mmとし、それ以外は実施例21と同一の条件で加工した。それぞれの評価結果を表2に示す。
ポリアミド666樹脂(2430A、(株)DSM製、20℃における表面張力46mN/m、表中「PA666」と表記する)タルク0.8%を、押出し機を用いて溶融し、異形押し出しダイから吐出させたストランドをペレタイザーでペレタイズし、平均粒子径1.4mmの図4(c)記載の中空断面形状のペレットを得た。このペレットの融点は193℃であった。得られたペレットを10℃の圧力釜に投入し、4MPaの炭酸ガスを吹き込み12時間吸収させた。次いで炭酸ガス含浸ペレットを発泡装置に移し、220℃の空気を20秒間吹き込み、ポリアミド予備発泡粒子の集合体を得た。得られたポリアミド予備発泡粒子は、4.2倍の発泡倍率を有し、平均粒子径は2.0mmであった。
得られた予備発泡粒子をオートクレーブ中に封入し、オートクレーブ内の圧力が0.4MPaとなるまで、圧縮空気を1時間かけて導入し、その後、圧力を0.4MPaに24時間保持することによって、予備発泡粒子に加圧処理を施した。
加圧処理した予備発泡粒子を、型内成形金型のキャビティ(キャビティ寸法は、縦:300mm、横:300mm、高さ:25mm)内に充填し、その後、型締めした。そして、この金型を型内発泡成形機に取り付けた。
その後、キャビティ内に105℃の飽和水蒸気を10秒間供給し、その後、キャビティ内に116℃の飽和水蒸気を30秒間供給して、予備発泡粒子を発泡させ、且つ熱融着させることによって、予備発泡粒子を発泡体へ成形した。金型のキャビティ内に冷却水を供給することによって、得られた発泡体を冷却し、その後、型開きを行い、樹脂発泡体B-1を取り出した。樹脂発泡体B-1の発泡倍率は5.5倍であった。
あらかじめ、加熱機構をもつ金型に樹脂発泡体B-1をセットし、発泡体が上金型及び下金型と接触した状態で予備加熱した。この際、表面層を形成する側である上金型の温度を210℃とし、表面層を形成しない側である下金型の温度は100℃とした。加熱時間は30秒とした。
加熱後、油圧シリンダー式の圧縮機構により上金型を7.5mm圧縮し、圧縮開始と同時に冷却を開始し、90秒後上金型温度が100℃になったところで、金型を開き、樹脂発泡成型体を取り出した。
この発泡成型体の評価結果を表2に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体として基材樹脂が無架橋発泡ポリプロピレン(融点142℃、20℃における表面張力25mN/mm、表中「PP」と表記する)であるピーブロック(JSP製 発泡倍率15倍)25mmをセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を180℃とし、意匠面を形成しない側である下金型の温度は70℃とした。加熱時間は30秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を0.75mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて7.5mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
この発泡成型体の評価結果を表2に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体として基材樹脂が無架橋発泡ポリプロピレン(融点142℃、20℃における表面張力25mN/mm、表中「PP」と表記する)であるピーブロック(JSP製 発泡倍率30倍)25mmをセットし、発泡体が上金型及び下金型と接触した状態で加熱した。この際、意匠面を形成する側である上金型の温度を180℃とし、意匠面を形成しない側である下金型の温度は70℃とした。加熱時間は30秒とした。
加熱後、サーボモーター式の圧縮機構により、上金型を0.75mm圧縮し、4秒保持する圧縮サイクルを10回行い、40秒かけて7.5mm圧縮した。
圧縮開始と同時に冷却を開始し、40秒後金型温度が100℃になったところで、金型を開き、表面意匠化された発泡成型体を取り出した。
この発泡成型体の評価結果を表2に示す。
あらかじめ、加熱機構をもつ金型に樹脂発泡体A-1をセットし、発泡体が上金型及び下金型と接触した状態で予備加熱した。この際、意匠面を形成する側である上金型の温度を140℃とし、意匠面を形成しない側である下金型の温度は100℃とした。
加熱時間は30秒とした。
加熱後、油圧シリンダー式の圧縮機構により上金型を7.5mm圧縮し、圧縮開始と同時に冷却を開始し、40秒後上金型温度が100℃になったところで、金型を開き、発泡成型体を取り出した。
意匠面を形成する側である上金型の温度(140℃)が基材樹脂PPの融点(142℃)より低かったため、得られた発泡成型体には表面層が形成されなかった。そのため、圧縮変形層の上面を表面層の上面とみなして、表面層の硬度、意匠面金型追従性、および意匠面写像性を測定し評価した。この発泡成型体の評価結果を表2に示す。
本実施形態の発泡成型体の用途例としては、軽量性と意匠性と剛性が求められる自動車、電車、汽車などの車両および航空機などの部材が挙げられ、特に内装材として、部品を被覆するカバー等に好適に使用できる。
本発明の発泡成型体は、その特徴を生かし、高温条件下で使用される断熱材や自動車部材、例えば、オイルパン、エンジンカバー、エンジンアンダーカバーやシリンダーヘッドカバー、その他カバー形状の部品、インテークマニホールド及びその集積部品、車体構造体、ダクト類、電装品ケース、電池ケース等に好適に用いることができる。
2:圧縮変形層
3:発泡層
B1:表面層と圧縮変形層との実際の境界
B2:圧縮変形層と発泡層との実際の境界
S:発泡成型体表面
O:発泡成型体外側
I:発泡成型体内側
T:表面層厚み
U:発泡粒子上部点
D:発泡粒子下部点
H:発泡粒子の圧縮方向長さ
L:発泡粒子の圧縮方向に対する垂直方向長さ
Z:圧縮方向
Claims (9)
- 樹脂を含み、表面層と、圧縮変形層と、発泡層とを備える成型体であって、
前記表面層の厚みが0.1~5.0mmであり、
前記圧縮変形層が前記表面層と前記発泡層との間に位置し、
前記圧縮変形層を構成する発泡粒子の平均H/L(Hは圧縮方向長さ、Lは圧縮方向に対する垂直方向長さ)が0.5以下であり、
前記発泡層を構成する発泡粒子の発泡倍率が3.0倍以上30倍未満であることを特徴とする、発泡成型体。 - 表面層と発泡層が同一種類の樹脂からなる請求項1に記載の発泡成型体。
- 前記表面層の上面の写像性が30%以上である、請求項1または2に記載の発泡成型体。
- 前記表面層にシボ形状が付与されている、請求項1~3のいずれか1項に記載の発泡成型体。
- エンジンカバー、またはエンジンアンダーカバーとして用いられる請求項1~4のいずれか1項に記載の発泡成型体。
- 前記樹脂が、融点145℃以上の結晶性樹脂、またはガラス転移温度145℃以上の非晶性樹脂である請求項1~5に記載の発泡成型体。
- 前記樹脂がポリアミドである請求項1~6のいずれか1項に記載の発泡成型体。
- 樹脂を含む予備発泡粒子を発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、
前記発泡体を、前記樹脂のガラス転移点(Tg)又は融点以上の温度に加熱した発泡成形用金型の内部に配置し、予備加熱する工程と、
プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、
前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程と、
を含むことを特徴とする、請求項1~7のいずれか1項に記載の発泡成型体の製造方法。 - 樹脂を含む予備発泡粒子を、発泡成型用金型の内部に充填する工程と、
前記予備発泡粒子を融着せしめる温度の熱媒を前記金型の内部に投入し発泡及び融着させて、発泡粒子で構成される発泡層からなる発泡体を形成する工程と、
前記金型を前記樹脂のTg又は融点以上の温度まで加熱して、前記発泡体を予備加熱する工程と、
プレス機構により、前記発泡体を金型寸法へ圧縮して、表面層と圧縮変形層とを形成する工程と、
前記金型を冷却し、前記表面層を固化せしめて、発泡成型体を得る工程と
を含むことを特徴とする、請求項1~7のいずれか1項に記載の発泡成型体の製造方法。
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| CN201980007839.9A CN111587172B (zh) | 2018-04-09 | 2019-04-05 | 发泡成型体及其制造方法 |
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| WO2022106319A1 (en) * | 2020-11-17 | 2022-05-27 | Basf Se | Composite article comprising a structured porous body and a foam and a process the production of a structured porous body and a particle foam |
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| US12275822B2 (en) | 2021-12-28 | 2025-04-15 | Industrial Technology Research Institute | Foam, composite material, and foaming composition |
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| US20210039352A1 (en) | 2021-02-11 |
| EP3778177A1 (en) | 2021-02-17 |
| KR20200067184A (ko) | 2020-06-11 |
| EP3778177A4 (en) | 2021-07-28 |
| CN111587172A (zh) | 2020-08-25 |
| JPWO2019198642A1 (ja) | 2020-12-03 |
| EP3778177B1 (en) | 2022-04-27 |
| KR102323648B1 (ko) | 2021-11-09 |
| CN111587172B (zh) | 2021-11-19 |
| JP6844065B2 (ja) | 2021-03-17 |
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