Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2266/00—Composition of foam
  • B32B2266/02—Organic
  • B32B2266/0214—Materials belonging to B32B27/00
  • B32B2266/025—Polyolefin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars

Definitions

• the present invention relates to a laminate of a suitable skin material and polyolefin resin foam in automotive interior materials such as instrument panels and door panels.
• Laminates consisting of a skin material and polyolefin resin foam are generally excellent in flexibility, heat resistance, heat insulation, light weight, and good design. It is used for automotive interior materials such as industrial materials, ceilings, door panels, instrument panels. In particular, the design of the skin material and the touch and feel of softness when touching a laminate made of polyolefin resin foam, and good design are added to bring out the luxury appearance and functionality of automotive interior materials. And demand is increasing. In automobile interior materials such as instrument panels and door panels, in order to ensure the safety of the driver and passengers when an automobile collides, there is an air bag inside the lid that has been processed, For example, when necessary, the lid is opened and the airbag is instantly inflated.
• the flexibility is improved by reducing the thickness of the skin material and increasing the expansion ratio of the polyolefin resin foam in order to facilitate the flexibility and the destruction in the thickness direction of the laminate, Since the mechanical strength is low, the laminate can be easily broken in the thickness direction, but the laminate is broken during compression molding such as vacuum molding or low-pressure injection molding, which causes a problem in appearance. Moreover, although the mechanical strength is improved by lowering the expansion ratio of the polyolefin resin foam, there is a problem that the flexibility is lowered.
• a resin, polyethylene-based resin, and thermoplastic elastomer-based material are added to obtain a crosslinked polyolefin-based resin foam with good heat resistance, flexibility and good design that enables secondary processing into complex shapes , (Meth) acrylic acid ester of methyl methacrylate and alcohol having 2 to 8 carbon atoms to thermoplastic polyurethane and acrylic soft resin.
• Patent Document 2 and Patent Document 3 Has been proposed (see Patent Document 2 and Patent Document 3).
• a skin material for an automobile airbag a skin layer made of a thermoplastic resin layer and a two-layer structure made of a polyolefin foam layer, or a skin layer made of a thermoplastic resin layer, a polyolefin foam layer, polypropylene, etc. It has also been proposed to improve the appearance of the airbag storage part and facilitate the inflation of the airbag by allowing the skin material to have a needle hole that cannot be visually confirmed using a three-layer structure consisting of the barrier layer. (See Patent Document 4).
• the polyolefin resin foam is susceptible to brittle fracture in the low temperature region. Further, there is a possibility that one part of the foam is scattered and the strength of the laminated body is temporarily increased, and the airbag may not be easily opened. Furthermore, it is not easy to process a needle hole that cannot be visually confirmed on the skin material. If the needle hole is enlarged, there is a problem in appearance, and if it is too small, the effect may be limited.
• the present invention is suitable for instrument panels, door panels, and the like, and is excellent in flexibility and soft touch, and aims to promote easy tearing of an airbag in a range from a low temperature to a high temperature region.
• Another object of the present invention is to solve the problem that one part of the skin material and the foam is scattered at the time of air bag tearing and the problem that the appearance defect that the skin layer and the foam layer are separated does not occur.
• the polyolefin resin foam (A) used in the laminate of the present invention is composed of 30% by mass to 60% by mass of the polypropylene resin (a1) and 100% by mass of the polyethylene resin (a2) in 100% by mass of the polyolefin resin. 1 mass% or more and 20 mass% or less and 30 mass% or more of thermoplastic elastomer-type resins (a3).
• the tensile elongation of the laminate is 30% or more under a temperature environment at ⁇ 35 ° C.
• the laminate is a laminate of a polyolefin resin foam (A) and a skin material (B), and the polyolefin resin foam (A) is a differential scanning calorimeter.
• DSC differential scanning calorimeter
• the skin material (B) has at least one endothermic peak by a differential scanning calorimeter (DSC) in a region of 95 ° C. or higher and 110 ° C. or lower and each region of 130 ° C. or higher and 160 ° C. or lower.
• the preferable aspect of the laminated body of this invention is an automotive interior material use.
• the laminate of the present invention when used as an automobile interior material equipped with a resin base material having an airbag storage structure, that is, in applications such as instrument panels and door panels, flexibility when contacting the laminate, and It has an excellent effect on the tactile sensation of feeling softness, and facilitates easy tearing of the airbag in a range from a low temperature to a high temperature region. Further, when the airbag is torn, the problem that one part of the skin material and the foam is scattered and the appearance defect that the skin layer and the foam layer are peeled off are not caused, and the characteristics are exhibited particularly in a low temperature region.
• the present invention is a laminate of a polyolefin resin foam (A) and a skin material (B), wherein the polyolefin resin foam (A) constitutes the polyolefin resin foam (A).
• the polyolefin resin foam (A) constitutes the polyolefin resin foam (A).
• polystyrene resin In 100% by mass of polyolefin resin, 30% to 60% by mass of polypropylene resin (a1), 1% to 20% by mass of polyethylene resin (a2), thermoplastic elastomer resin (a3) If it contains 30% by mass or more, it has an excellent effect on the softness and touch feeling when touching the laminate, and particularly in a low temperature region, one part of the skin material or foam is present when the airbag is opened. The problem of scattering and the appearance defect that the skin layer and the foam layer are peeled off can be prevented.
• the polyolefin resin foam (A) used in the laminate of the present invention must be composed of at least a polypropylene resin (a1), a polyethylene resin (a2), and a thermoplastic elastomer resin (a3).
• the polypropylene resin (a1) include homopolypropylene, ethylene-propylene random copolymer, and ethylene-propylene block copolymer. Copolymerization of propylene monomer with other copolymerizable monomers as necessary. A polymer can also be used.
• the polypropylene resin (a1) may be used alone or in a blend of two or more.
• the polypropylene resin (a1) has an ethylene-propylene random copolymer and an ethylene-propylene random copolymer having a melting point of 135 ° C. or more and less than 160 ° C. and an MFR (230 ° C.) of 0.5 g / 10 min or more and less than 5.0 g / 10 min.
• An ethylene-propylene block copolymer or homopolypropylene having an ethylene content of 1% by mass or more and less than 15% by mass of 0 g / 10 min or more and less than 7.0 g / 10 min is particularly preferably used.
• the “block” of the ethylene-propylene random block copolymer and the ethylene-propylene block copolymer here means that ethylene-propylene rubber is mixed with the ethylene-propylene random copolymer or homo-polypropylene. This is different from the block structure in general polymer chemistry.
• polyethylene resin (a2) examples include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate.
• HDPE high density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene
• EOA ethylene-ethyl acrylate copolymer
• ethylene-butyl acrylate ethylene-butyl acrylate.
• a polymer (EBA) etc. are mentioned, The copolymer of an ethylene monomer and another copolymerizable monomer can also be used as needed.
• the polyethylene resin (a2) may be a single type or a blend of two or more types.
• the polymerization method of these polypropylene resins is not particularly limited, and any of a high pressure method, a slurry method, a solution method, and a gas phase method may be used, and the polymerization catalyst is particularly limited, such as a Ziegler catalyst or a metallocene catalyst. It is not a thing.
• the polyethylene resin (a2) those having a density of 890 to 950 kg / m 3 and an MFR (190 ° C.) in the range of 1 g / 10 min to less than 15 g / 10 min are preferably used, and in particular, the density is 920 to 940 kg / m. 3.
• thermoplastic elastomer-based resin (a3) examples include polystyrene-based thermoplastic elastomer (SBC, TPS), polyolefin-based thermoplastic elastomer (TPO), vinyl chloride-based thermoplastic elastomer (TPVC), and polyurethane-based thermoplastic elastomer (TPU).
• Polyester-based thermoplastic elastomers (TPEE, TPC), polyamide-based thermoplastic elastomers (TPAE, TPA), polybutadiene-based thermoplastic elastomers, hydrogenated styrene butadiene rubber (HSBR), styrene / ethylene butylene / olefin crystal block polymer (SEBC) , Olefin Crystal / Ethylene Butylene / Olefin Crystal Block Polymer (CEBC), Styrene / Ethylene Butylene / Styrene Block Polymer (SEBS), Olefin Block Block copolymers such as polymers (OBC) and polyolefin-vinyl graft copolymers, polyolefin-amide graft copolymers, polyolefin-acrylic graft copolymers, and polyolefin-cyclodextrin graft copolymers, and particularly preferred are olefin block copolymers
• thermoplastic elastomer resins (a3) may be blended in at least one kind or two or more kinds. Moreover, there is no restriction
• the thermoplastic elastomer resin (a3) has a melting point of 150 ° C.
• the melting point is less than 150 ° C., the required heat resistance may not be sufficiently obtained, and if the crystal melting energy is 30 J / g or more, the crystallinity is high and sufficient flexibility may not be obtained. There is sex. More preferably, the melting point is 160 ° C. or higher, and the crystal melting energy is less than 25 J / g. Further, the crystallization temperature is preferably 50 ° C. or higher. More preferably, it is 60 degreeC or more. If the crystallization temperature is less than 50 ° C., the cycle time when molding the foam may not be shortened.
• the glass transition temperature of the thermoplastic elastomer resin (a3) is preferably less than ⁇ 20 ° C., more preferably less than ⁇ 30 ° C., and most preferably less than ⁇ 40 ° C. When the glass transition temperature is ⁇ 40 ° C. or higher, the desired flexibility may not be obtained, which may adversely affect the airbag deployment characteristics at low temperatures that the present invention intends to achieve.
• the thermoplastic elastomer resin (a3) preferably has a density of 850 to 920 kg / m 3 and an MFR (230 ° C.) in the range of 1 g / 10 min to less than 15 g / 10 min.
• thermoplastic elastomer resins (a3) used in the present invention include Mitsui Chemicals “Toughmer” (registered trademark) PN-3560, polyolefin-based thermoplastic elastomer (TPO) as olefin block copolymer (OBC). Includes "Prime TPO” (registered trademark) M142E manufactured by Prime Polymer.
• the polyolefin resin foam (A) used in the laminate of the present invention may be mixed with other thermoplastic resins as long as the effects of the invention are not impaired.
• the thermoplastic resin herein include conventionally known polyester, polyamide, polylactic acid, polyether, polyvinyl chloride, polyurethane, polystyrene and the like.
• phenolic, phosphorus-based, amine-based and sulfur-based antioxidants, and metal damage prevention are within the range not impairing the effects of the present invention.
• the polyolefin resin foam used in the laminate of the present invention is produced by mixing a polyolefin resin mixture with a foaming agent capable of generating gas, and the production method thereof is a polyolefin resin mixture.
• a foaming agent a pyrolytic chemical foaming agent is added and melt kneaded, and then the normal pressure foaming method in which foaming is performed by heating at normal pressure.
• the pyrolytic chemical foaming agent is thermally decomposed in an extruder and extruded under high pressure.
• Extrusion foaming while foaming heat decomposable chemical foaming agent is thermally decomposed in a press mold, press foaming method foaming while reducing pressure, and gas or vaporized solvent is melted and mixed in an extruder and extruded under high pressure
• Examples thereof include an extrusion foaming method for foaming.
• the thermal decomposition type chemical foaming agent used here is a chemical foaming agent that decomposes by applying heat and releases a gas.
• azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, P, P examples thereof include organic foaming agents such as' -oxybenzenesulfonylhydrazide, and inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and calcium azide.
• a foaming agent can be used individually or in combination of 2 types or more, respectively.
• a normal pressure foaming method using azodicarbonamide as a foaming agent is preferably used.
• the polyolefin resin foam (A) used in the laminate of the present invention has a thickness of 0.50 mm to 5.0 mm.
• the thickness of the polyolefin resin foam is preferably 1.0 mm or more and 4.0 mm or less, and promotes destruction in a low temperature environment of ⁇ 40 to ⁇ 10 ° C. Considering this, a more preferable aspect is a range of 2.0 mm to 3.0 mm.
• the polyolefin resin foam used in the laminate of the present invention preferably has an apparent density in the range of 30 kg / m 3 or more and 150 kg / m 3 or less from the viewpoint that both moldability and flexibility are excellent.
• a more preferable embodiment is a range of 50 kg / m 3 or more and 100 kg / m 3 or less.
• the polyolefin-based resin foam used in the laminate of the present invention can be either a crosslinked resin foam (referred to as a crosslinked foam) or an uncrosslinked resin foam (referred to as a non-crosslinked foam). What is necessary is just to select a suitable resin foam according to a use.
• a chemical crosslinking method in which a raw material contains a crosslinking agent having a chemical structure such as a silane group, a peroxide, a hydroxyl group, an amide group, and an ester group
• a radiation crosslinking method in which electron beams, ⁇ rays, ⁇ rays, ⁇ rays, and ultraviolet rays are irradiated to a polyolefin resin for crosslinking.
• Polyolefin-based because the foam cells are made uniform and the destruction of the laminate is promoted in a low temperature environment of ⁇ 40 ° C.
• the resin foam (A) into a crosslinked foam radiation crosslinking with an electron beam is preferred.
• the polyolefin resin foam (A) used for the laminate of the present invention when it is difficult to construct a crosslinked structure by electron beam crosslinking, the polyolefin resin foam (A) is produced.
• a crosslinking aid in the raw material By containing a crosslinking aid in the raw material, a crosslinked foamed body by an electron beam can be obtained.
• a crosslinking adjuvant It is preferable to use a polyfunctional monomer.
• polyfunctional monomer examples include divinylbenzene, trimethylolpropane trimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimellitic acid triallyl ester , Triallyl isocyanurate, ethyl vinyl benzene and the like can be used. These polyfunctional monomers may be used alone or in combination of two or more.
• the polyolefin resin foam (A) used in the laminate of the present invention is crosslinked, that is, when the foam of the present invention is a crosslinked foam, the gel fraction indicating the crosslinked state is 20% or more and 65%.
• the gel fraction is less than 20%, the foaming agent gas is dissipated from the foaming surface, making it difficult to obtain a product with the desired expansion ratio. On the other hand, if the gel fraction exceeds 65%, excessive crosslinking occurs. It may be difficult to obtain a product with a high surface expansion ratio and a high expansion ratio, and mechanical strength such as elongation at break may be lowered, and moldability may be lowered.
• the polyolefin resin foam (A) used in the laminate of the present invention preferably has a 25% compression hardness of 30 kPa or more and 120 kPa or less, more preferably 50 kPa or more and 100 kPa or less as an index indicating flexibility. It is an aspect.
• the polyolefin resin foam (A) used in the laminate of the present invention preferably has two or more endothermic peaks in the differential scanning calorimetry. Specifically, it is preferable that endothermic peaks by a differential scanning calorimeter (DSC) exist at 100 ° C. or higher and 130 ° C. or lower and 145 ° C. or higher. The first endothermic peak is more preferably 110 ° C.
• the second endothermic peak is more preferably 150 ° C. or more, and most preferably 155 ° C. or more.
• the first endothermic peak is 130 ° C. or higher, the softening temperature at the time of molding the laminate may be too high, and the molding cycle may be too long.
• the second endothermic peak is less than 145 ° C. In the current situation where the heating rate tends to be increased in order to increase the molding temperature, heat resistance is often insufficient.
• the total crystal melting energy per unit mass in the differential scanning calorimetry of the polyolefin resin foam (A) used in the laminate of the present invention is preferably less than 80 J / g.
• the polyolefin resin foam (A) used for the laminate of the present invention preferably has a crystal melting energy per unit mass of 145 ° C. or higher of less than 20 J / g. When it is 20 J / g or more, a large amount of propylene-based resin may be contained, and in that case, sufficient flexibility that is the object of the present invention may not be obtained.
• the polyolefin resin foam (A) used in the laminate of the present invention preferably has a heat shrinkage of less than 40% at 180 ° C. for 10 minutes.
• the molding draw ratio of the polyolefin resin foam (A) used in the laminate of the present invention is preferably 0.4 or more and less than 0.8. If it is less than 0.4, there is insufficient moldability, and tearing may occur during shaping. On the other hand, if it is 0.8 or more, there is a possibility that deviation from the skin material when the laminate is formed is not preferable. More preferably, it is 0.5 or more and less than 0.7.
• the polyolefin resin foam (A) used in the laminate of the present invention preferably has a closed cell structure.
• a foam having a closed cell structure it is possible to form a complicated shape, for example, air can be sufficiently drawn by vacuum forming because of the structure.
• the bubbles are fine and uniform since the surface of the foam or a molded product obtained by molding the foam becomes smooth.
• the polyolefin resin foam (A) used for the laminate of the present invention can be produced in the form of a long sheet. By making it into a long sheet shape, it is possible to supply a large amount at a low cost.
• thermoplastic resin which comprises the skin material (B) which comprises the laminated body of this invention.
• thermoplastic resin constituting the skin material (B) include polyethylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate copolymer.
• thermoplastic polyolefin elastomer containing an elastomer component such as ethylene-propylene rubber, vinyl resin such as polyvinyl chloride and polyvinylidene chloride, polyurethane resin, polystyrene resin, polyether resin, polyamide resin, And copolymers composed of monomers copolymerizable with these resins.
• the thermoplastic resin constituting these skin materials (B) may be mixed with at least one or two or more.
• the thermoplastic resin constituting the skin material (B) preferably has at least an endothermic peak by a differential scanning calorimeter in a region of 95 ° C. or higher and 110 ° C. or lower and a region of 130 ° C.
• the skin material (B) preferably has at least an endothermic peak by a differential scanning calorimeter in a region of 95 ° C. or higher and 110 ° C. or lower and a region of 130 ° C. or higher and 155 ° C. or lower.
• inorganic fillers, antioxidants, hydrocarbon oils and the like may be added.
• the skin material (B) contains a block copolymer elastomer having a polyolefin hard segment and a polyolefin soft segment, and contains a polyolefin resin, such as a thermoplastic polyolefin elastomer
• Lamination processing with the polyolefin resin foam (A) is simplified, and it is preferable because of its flexibility when contacted.
• the thickness of the skin material (B) which comprises the laminated body of this invention is not specifically limited, It can process and use for the thickness according to the intended purpose.
• the thickness of the skin material (B) is preferably in the range of 0.1 mm to 1.5 mm.
• the thickness of the skin material (B) is preferably 0.3 mm or more and 0.6 mm or less.
• the thickness of the skin material (B) is preferably 0.3 mm or more and 0.6 mm or less.
• the surface of the polyolefin resin foam (A) or skin material (B) that contacts the adhesive is subjected to electrical discharge machining, and hydroxyl groups are introduced into the surface to improve the adhesion.
• a urethane-based solvent-based adhesive or an emulsion-based adhesive may be applied to the polyolefin-based resin foam (A) and bonded together.
• the adhesive examples include “Pandex T-5265” manufactured by Dainippon Ink & Chemicals, Inc. and “Desmocol # 500” manufactured by Bayer Co., Ltd.
• a heat-sealing method of heating and laminating the polyolefin resin foam (A) and the skin material (B) is preferably used.
• the laminate of the present invention preferably has a tensile elongation of 30% or more under an environment of ⁇ 35 ° C. If the tensile elongation of the laminate under an environment of ⁇ 35 ° C. is less than 30%, the polyolefin resin foam (A) is scattered when the airbag is opened, which is not preferable.
• the polyolefin resin foam (A) and the skin material (B) peel off and cause poor appearance when broken. There is a concern that a part of the resin-based resin foam (A) or the skin material (B) may be scattered. Especially in automobile interior materials equipped with airbags, when the polyolefin resin foam (A) is peeled off from the skin material (B) due to the impact of the airbag destroying the laminate, only the polyolefin resin foam (A) is produced. There is a concern that the skin material (B) breaks, and the skin material (B) does not break, and the speed at which the airbag is cleaved is slow.
• the maximum peel strength of interfacial delamination or material delamination between the polyolefin resin foam (A) and the skin material (B) of the laminate is 25 N / 25 mm or more.
• the maximum peeling strength of interfacial peeling or material breaking peeling between the polyolefin resin foam (A) and the skin material (B) of the laminate of the present invention is 20 N / 25 mm or more in both the MD direction and the TD direction. It is preferable that The upper limit of the maximum peel strength between the polyolefin resin foam (A) and the skin material (B) of the present invention is not limited, but is preferably 150 N / 25 mm or less.
• the laminated body of this invention When using the laminated body of this invention as a motor vehicle interior material, there is no restriction
• “Pandex T-5265” manufactured by Dainippon Ink and Chemicals, “Desmocol # 500” manufactured by Bayer Co., Ltd. can be used as an adhesive on the polyolefin resin foam side.
• the difference in low temperature tensile elongation between the polyolefin resin foam (A) and the skin material used in the laminate of the present invention is preferably less than 150%. More preferably, it is 10% or more and less than 100%, More preferably, it is 25% or more and less than 80%.
• the automobile interior material comprising the laminate of the present invention generally has at least three layers of a skin material (B), a polyolefin resin foam (A), and a resin base material.
• the composition of the resin base material used for the automobile interior material in the present invention is not particularly limited, and includes polypropylene resin, ABS resin, polycarbonate resin, talc, mica, wollastonite, glass beads, glass fiber, carbon fiber and the like. It is common to use a composite reinforced with an inorganic filler.
• the molding method is not limited, but generally, the above-mentioned laminate of polyolefin resin foam (A) and skin material (B) is extruded.
• Polyolefin resin foam (A) by producing a molded product of a laminate that becomes the shape of the interior material by a known molding process such as vacuum molding, stamping molding, blow molding, etc., and interposing an adhesive or a heat medium And a resin base material are bonded.
• a known molding process such as vacuum molding, stamping molding, blow molding, etc.
• interposing an adhesive or a heat medium And a resin base material are bonded.
• These moldings may be subjected to secondary processing into a shape as required by thermal welding, vibration welding, ultrasonic welding, laser welding, or the like.
• the laminate of the present invention is laminated on a resin base material having an airbag function of an automobile interior material
• a punching machine or the like is used so long as the appearance of the skin material (B) is not deteriorated.
• a laser machine can be used to have holes.
• the holes in the resin base material and the polyolefin resin foam (A) are preferably opened in the direction from the resin base material side to the skin material (B) side so that the airbag can be more easily cleaved.
• a thermal decomposable foaming agent such as azodicarbonamide is further added to the polypropylene resin (a1), polyethylene resin (a2), and thermoplastic elastomer resin (a3), and a mixing device such as a Henschel mixer or tumbler is used. Mix evenly. Then, using melt-kneading equipment such as an extruder or a pressure kneader, melt and knead uniformly below the decomposition temperature of the pyrolytic foaming agent, and after forming into a sheet shape with a T-type die, irradiate with ionizing radiation. Crosslink.
• melt-kneading equipment such as an extruder or a pressure kneader
• the temperature of the obtained sheet is raised above the decomposition temperature of the pyrolytic foaming agent by the method of floating on a salt bath as a heat medium or the method of throwing it in an atmosphere such as hot air.
• the polyolefin resin foam (A) of the present invention can be obtained.
• thermoplastic resin constituting the skin material (B) is melt-kneaded using a melt-kneading device such as an extruder or a pressure kneader, and is molded into a sheet shape with a T-type die or a calender roll to a predetermined thickness To control.
• the obtained sheet having a predetermined thickness is air-cooled or water-cooled to obtain the skin material (B).
• the manufacturing method of the laminated body of this invention is illustrated and demonstrated.
• the surface side of the polyolefin resin foam (A) obtained by the foam production method and the skin material (B) obtained by the skin material production method is laminated.
• a laminated body having a three-layer structure is obtained by a heat-sealing method through a nip roll whose gap is adjusted.
• MFR of polyolefin resin means JIS K7210 (1999) “Plastics – Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics”.
• the polyethylene resin (a2) has a temperature of 190 ° C. and a load of 2.16 kgf
• the polypropylene resin (a1) and the thermoplastic elastomer resin (a3) have a temperature of 230 ° C.
• melt mass flow rate meter melt indexer model F-B01 manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the manual cut-off method was adopted, and the weight of the resin that came within 10 minutes from the die was measured.
• Density of polyolefin resin The density of the polyolefin resin was measured according to JIS K7112 (1999) “Plastics—Method of measuring density and specific gravity of non-foamed plastic”.
• the melting point of the polyolefin resin is the maximum obtained from the endothermic peak of the DSC curve obtained when the vertical axis obtained by differential scanning calorimetry is calorie (J / g) and the horizontal axis is temperature.
• Temperature. 2 mg of each sample was prepared using a differential scanning calorimeter (DSC: RDC220-Robot DSC manufactured by Seiko Denshi Kogyo Co., Ltd.) and measured in a nitrogen environment. The measurement conditions were that the sample was heated to a temperature of 200 ° C.
• the exothermic peak obtained when cooled to a temperature of ⁇ 100 ° C. at a rate of 10 ° C./min was the crystallization temperature.
• the glass transition temperature is the middle point of the step-like displacement point.
• the temperature was increased at a rate of 10 ° C./min, and the endothermic peak per unit mass was measured.
• the endothermic peak obtained at the second temperature increase was taken as the melting point.
• the thickness of the foam is a value measured in accordance with ISO 1923 (1981) “Method for measuring foamed plastic and rubber alignment”. Specifically, using a dial gauge with a circular probe having an area of 10 cm 2 , the foam cut to a certain size was allowed to stand on a flat table and then contacted with the foam surface at a certain pressure. And measure.
• Apparent density of foam The apparent density of the foam is a value measured and calculated according to JIS K6767 (1999) “Foamed plastics-polyethylene test method”. The thickness of the foam cut into 10 cm square is measured, and the mass of the test piece is weighed. The value obtained by the following equation is the apparent density, and the unit is kg / m 3 .
• 25% compression hardness of the foam is a value measured based on JIS K6767 (1999) “Foamed plastics-polyethylene test method”. Specifically, the foam is cut into 50 mm ⁇ 50 mm, stacked so that the thickness is 20 mm or more and 30 mm or less, and the initial thickness is measured. A sample was placed on a flat plate, and stopped by compressing at a speed of 10 mm / min up to 25% of the initial thickness, the load after 20 seconds was measured, and 25% compression hardness (kPa) was calculated by the following formula.
• 25% compression hardness (kPa) 25% compression and load (N) / 25 (cm 2 ) / 10 after 20 seconds.
• the endothermic peak of the foam means a peak on the endothermic side in the DSC curve obtained when the vertical axis obtained by differential scanning calorimetry is calorie (J / g) and the horizontal axis is temperature.
• a differential scanning calorimeter DSC: RDC220-Robot DSC, manufactured by Seiko Denshi Kogyo Co., Ltd.
• the peak obtained from the DSC curve obtained at the second temperature increase is called an endothermic peak.
• the total crystal melting energy is calculated by the area surrounded by the DSC curve and the baseline at this time. Further, the endothermic amount per unit mass of 130 ° C. or higher is calculated by the area of the portion higher than this temperature by further dividing the portion surrounded by the DSC curve and the base line by a 130 ° C. line. .
• Measuring method of heat shrinkage rate of foam As a method for measuring the heat shrinkage rate, it is carried out according to JIS K6767 (1999) “Foamed plastic-polyethylene test method”. Specifically, a test piece with a 100 mm square marked line was left in a hot air oven adjusted to 180 ° C. for 10 minutes, and the amount of decrease in the distance between marked lines was divided by the original distance between marked lines of 100 mm. It is a value expressed as a percentage of the thing.
• Molding ratio means that when a foam is heated and straight molded using a vacuum molding machine on a vertical cylindrical female mold with a diameter D and depth H, the foam does not break and expands into a cylindrical shape. It is the value of H / D at the limit of elongation.
• Examples 1 to 20 [Comparative Examples 1 to 10]
• the foams prepared in Examples 1 to 20 and Comparative Examples 1 to 10 are as follows. Mixing the polypropylene resin (a1), the polyethylene resin (a2), the thermoplastic elastomer resin (a3), the foaming agent, the crosslinking aid and the antioxidant shown in Table 1 in respective ratios using a Henschel mixer, Using a twin screw extruder, melt extrusion was performed at a temperature of 170 ° C., and a polyolefin resin sheet having a predetermined thickness was produced using a T die.
• the polyolefin resin sheet thus obtained was irradiated with an electron beam having an acceleration voltage of 800 kV and a predetermined absorbed dose from one side to obtain a crosslinked sheet, and then the crosslinked sheet was placed on a salt bath at a temperature of 220 ° C. Floating and heated from above with an infrared heater to cause foaming.
• the foam is cooled with water at a temperature of 60 ° C., the foam surface is washed with water and dried, the thickness is 1.5 to 3.0 mm, the apparent density is 50 to 100 kg / m 3 , and the gel fraction is 35.
• a long roll of ⁇ 45% polyolefin resin foam (A) was obtained.
• the skin material (B) was produced as follows.
• the skin material (B) is a thermoplastic polyolefin elastomer having endothermic peaks at 95 ° C. and 138 ° C. with a differential scanning calorimeter, melt kneaded with an extruder, and has a thickness shown in Table 1 from the T-type die. A sheet was obtained.
• the laminated body it produced as follows.
• the surface heated on the side of the radiation heater at the time of foaming is heated to 146 ° C., and the gap between the rolls is changed to the thickness of the skin material (B) and the thickness of the polyolefin resin foam (A).
• the heated surface side and the skin material (B) were heat-sealed to obtain a laminate.
• Table 1 shows each physical property and evaluation status of the polyolefin resin foam (A), the skin material (B), and the laminate.
• the present invention is suitable for automobile interior materials such as instrument panels and door panels.

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• Laminated Bodies (AREA)
• Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2016
  • 2016-08-03 WO PCT/JP2016/072766 patent/WO2018025343A1/ja active Application Filing
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