WO2012090802A1 - Mousse, mousse renforcée par un matériau en surface et corps moulé - Google Patents

Mousse, mousse renforcée par un matériau en surface et corps moulé Download PDF

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Publication number
WO2012090802A1
WO2012090802A1 PCT/JP2011/079584 JP2011079584W WO2012090802A1 WO 2012090802 A1 WO2012090802 A1 WO 2012090802A1 JP 2011079584 W JP2011079584 W JP 2011079584W WO 2012090802 A1 WO2012090802 A1 WO 2012090802A1
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Prior art keywords
foam
face material
resin
glass fiber
mass
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PCT/JP2011/079584
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English (en)
Japanese (ja)
Inventor
透 板谷
正廣 古澤
貢 才丸
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旭ファイバーグラス株式会社
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Priority to JP2012550870A priority Critical patent/JP5830470B2/ja
Publication of WO2012090802A1 publication Critical patent/WO2012090802A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • B32B2419/00—Buildings or parts thereof
    • 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
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
    • 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
    • B32B2607/00—Walls, panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

Definitions

  • the present invention is a lightweight, high-rigidity, and dimensioned product in which a deep drawing with a high expansion ratio, a foam excellent in moldability with a high compression ratio, and a glass fiber-containing thermoplastic resin sheet are laminated on the surface of the foam.
  • the present invention relates to a face material reinforced foam excellent in stability and moldability, and a molded product obtained from the face material reinforced foam.
  • linear polypropylene is a hard resin
  • a highly rigid foam can be obtained by using linear polypropylene as the foamed resin.
  • linear polypropylene is a crystalline resin and has a very high speed from the plasticized state until it is completely melted. It was inferior to.
  • Patent Document 1 discloses that a foamed resin including a polypropylene resin and a polyethylene resin is foamed and crosslinked to produce a crosslinked foam. Is disclosed.
  • Patent Document 2 discloses producing a foam by foaming a mixed resin of a polypropylene resin and an ethylene / ⁇ -olefin copolymer.
  • Patent Document 1 As shown in Patent Document 1, by cross-linking a polypropylene resin, the elongation of the foam can be improved and the occurrence of tearing due to molding can be reduced, but a cross-linking treatment step is required. In short, productivity was inferior.
  • Patent Document 2 by adding a soft olefin elastomer resin such as an ethylene / ⁇ -olefin copolymer to a polypropylene resin, the flexibility of the foam and the extensibility at the time of molding can be improved. Although it could be increased, rigidity was insufficient and dimensional stability was easily lost.
  • a soft olefin elastomer resin such as an ethylene / ⁇ -olefin copolymer
  • an object of the present invention is to provide a foam and a face material reinforced foam made of a non-crosslinked resin, which are excellent in moldability and capable of obtaining a molded article having excellent rigidity and dimensional stability, and rigidity and dimensional stability.
  • the object is to provide a good molded article.
  • the foam of the present invention is obtained by foaming a foam raw material composition containing a polypropylene-based foamed resin containing 5 to 70 parts by mass of block polypropylene with respect to 100 parts by mass of linear polypropylene. It is characterized by comprising a non-crosslinked resin.
  • the foam of the present invention is preferably a foamed strand converging body obtained by extruding and concentrating the foam raw material composition into a strand shape.
  • the foam of the present invention has a tensile elongation in the TD direction at 180 ° C. relative to the MD direction when the direction of the strand of the foam strand bundle is the MD direction and the direction orthogonal to the strand direction is the TD direction. It is preferably 1.5 to 2.5 times.
  • the foam of the present invention has a melt flow rate of 3 to 30 g / min at 230 ° C. and a melt tension of 0.5 to 30 g at a take-off speed of 3.1 m / min at 230 ° C. It is preferable.
  • a reinforcing face material comprising a glass fiber-containing thermoplastic resin sheet having a tensile elastic modulus of 10 to 45 kgf / mm 2 in an atmosphere at 180 ° C. is provided on at least one surface of the foam.
  • the glass fiber content in the laminated face material reinforced foam is 10 to 20% by mass.
  • the glass fiber-containing thermoplastic resin sheet of the face material-reinforced foam of the present invention preferably contains 20-40% by mass of the glass fiber.
  • the glass fiber-containing thermoplastic resin sheet of the face material reinforced foam of the present invention is preferably one in which the glass fiber is impregnated with a polyolefin resin.
  • the molded body of the present invention is obtained by molding the face material reinforced foam.
  • the molded product of the present invention is preferably shaped at a development rate of 130 to 200%.
  • the foam By producing a foam using a polypropylene-based foamed resin containing 5 to 70 parts by weight of block polypropylene with respect to 100 parts by weight of linear polypropylene, the foam is rigid and formable without any crosslinking treatment. It can be set as an excellent foam. Then, a glass fiber-containing thermoplastic resin sheet having a tensile elastic modulus of 10 to 45 kgf / mm 2 under an atmosphere of 180 ° C. is laminated on at least one surface of the foam, and the glass fiber content in the face material-reinforced foam By setting the content to 10 to 20% by mass, it is possible to obtain a face material reinforced foam that is lightweight, has rigidity and dimensional stability, and can be deep drawn with a high expansion ratio.
  • the foam of the present invention is made of a non-crosslinked resin obtained by foaming a foam raw material composition containing a polypropylene-based foamed resin containing linear polypropylene and block polypropylene.
  • Linear polypropylene is greatly related to the foaming characteristics of the resin in the foam production process.
  • a propylene-based multistage polymer comprising the following resin component [A] and resin component [B] is preferably used, and the following resin component [A] is contained in 8 to 18 in the entire polymer. More preferably, the resin component [B] described below is contained in an amount of 82 to 92% by mass in the entire polymer.
  • Resin component [A] a copolymer component of propylene and an ⁇ -olefin having 2 to 8 carbon atoms is contained in the total polymer in an amount of 5 to 20% by weight, and the others are propylene homopolymer components.
  • the density of the linear polypropylene is preferably 0.89 to 0.92 g / cc.
  • the melt flow rate (hereinafter referred to as MFR) at 230 ° C. of linear polypropylene is preferably 5 to 30 g / 10 min, and more preferably 6.5 to 20 g / 10 min. If the MFR exceeds 30 g / 10 min, the resin fluidity becomes too high and the resin pressure suitable for foaming cannot be maintained, and the cells do not grow sufficiently, so the foaming ratio is lowered or foaming property is controlled. It becomes difficult. If it is less than 5 g / 10 min, the fluidity of the resin required for foaming is significantly reduced, the cell membrane is immediately torn after foaming and the foaming ratio is reduced, or the foaming pressure is too high, which places a heavy burden on the device. .
  • the melting point of the linear polypropylene is preferably 160 to 170 ° C, more preferably 162 to 167 ° C.
  • the resin price increases because it falls outside the category of so-called general-purpose linear polypropylene, and when it is less than 160 ° C., the rigidity and heat resistance peculiar to the linear polypropylene are impaired.
  • the resulting molded product tends to be unsuitable for use in heat-resistant containers, automobile interior parts, and the like.
  • the block polypropylene used in the present invention is a polymer alloy blend obtained by polymerizing propylene and other olefins, mainly ethylene, in multiple stages.
  • the polymer alloy blend obtained by block copolymerization of propylene and ethylene is a composition comprising a propylene-ethylene block copolymer and mainly composed of polypropylene, polyethylene, ethylene-propylene rubber or the like.
  • a block polypropylene in which a dispersed phase having a core-shell structure in which polypropylene is wrapped with ethylene-propylene rubber is dispersed in a polypropylene matrix is preferably used.
  • Such block polypropylene is, for example, “BJS-MU” (trade name) and “J-750HP” (trade name) sold by Prime Polymer Co., Ltd. Examples thereof include “BC8” (trade name) and “BC6C” (trade name) which are impact grade resins.
  • the MFR at 230 ° C. of the block polypropylene is preferably 0.3 to 30 g / 10 min, more preferably 1.0 to 10 g / 10 min. If the MFR exceeds 30 g / 10 min, the resin pressure at the time of foaming is too low, making it difficult to control foaming, or the cells do not grow sufficiently at the time of foaming, and the foaming ratio is lowered. If it is less than 0.3 g / 10 min, the fluidity of the resin required for foaming is significantly reduced, the cell membrane is immediately torn after foaming, the foaming ratio is reduced, and the foaming pressure becomes too high, resulting in a heavy burden on the apparatus. It takes.
  • the deflection temperature under load according to JIS K7161 of block polypropylene is preferably 85 to 110 ° C, more preferably 90 to 105 ° C.
  • the deflection temperature under load is higher than 110 ° C.
  • the rigidity and heat-resistant dimensional stability are excellent, but the extensibility is lowered. Therefore, the foamed layer is torn during the deep drawing or becomes a special grade resin, which increases the price. If it is less than 90 ° C., the elongation characteristics at the time of molding are improved, but the rigidity and heat-resistant dimensional stability are poor, and the resulting molded product tends to be unsuitable for use in heat-resistant containers or automobile interior parts. .
  • the tensile modulus of elasticity in accordance with JIS K7161 of block polypropylene is preferably 900 to 2000 MPa, more preferably 1000 to 1700 MPa.
  • the foam has good extensibility and moldability is improved, but rigidity and heat-resistant dimensional stability are easily impaired.
  • the tensile modulus exceeds 2000 MPa, the rigidity and heat-resistant dimensional stability are good, but the stretchability is insufficient and tearing tends to occur during molding.
  • the polypropylene-based foamed resin used in the present invention is composed of linear polypropylene and block polypropylene, and contains 5 to 70 parts by mass, preferably 7 to 65 parts by mass of block polypropylene with respect to 100 parts by mass of linear polypropylene. More preferably, the content is 10 to 60 parts by mass.
  • the gel fraction of the polypropylene-based foamed resin is infinitely close to 0, has high crystallinity, and has rigidity equivalent to that of linear polypropylene. Meanwhile, a foam having improved extensibility and excellent moldability can be obtained.
  • the foam When the content of block polypropylene is less than 5 parts by mass, the foam does not have sufficient stretchability, and the stress of the foam cannot be sufficiently dispersed at the time of molding. This makes it easier to cause swelling. Moreover, it is difficult to adjust to the target product thickness. Furthermore, when the foamed body is a foamed strand converging body to be described later, buckling tends to occur at the interface between the foamed strands during molding, and physical properties such as rigidity are likely to be impaired. When the content of the block polypropylene exceeds 70 parts by mass, the rigidity is impaired.
  • the MFR of the polypropylene-based foamed resin at 230 ° C. is preferably 3 to 30 g / 10 min, and more preferably 5 to 25 g / 10 min. If the MFR exceeds 30 g / 10 min, the resin fluidity becomes too high and the resin pressure suitable for foaming cannot be maintained, and the cells do not grow sufficiently, so the foaming ratio is lowered or foaming property is controlled. It becomes difficult. If it is less than 3 g / 10 min, the fluidity of the resin required for foaming is significantly reduced, and the cell membrane is immediately broken after foaming, the foaming ratio is lowered, or the foaming pressure becomes too high, which places a heavy burden on the apparatus. .
  • the melt tension (MT) at 230 ° C. of the polypropylene-based foamed resin is preferably 0.5 to 30 g at a take-up speed of 3.1 m / min.
  • the value of MT and the value of MFR satisfy
  • the foam material composition used in the present invention contains at least the above polypropylene-based foamed resin.
  • polypropylene-based foamed resins ethylene / ⁇ -olefin copolymers, propylene / ⁇ -olefin copolymers, acrylonitrile / styrene copolymers, polypropylene resins, polyethylene resins, etc. You may contain another thermoplastic resin.
  • the ethylene / ⁇ -olefin copolymer is a copolymer of ethylene and an ⁇ -olefin other than ethylene copolymerizable with ethylene.
  • the ⁇ -olefin is not particularly limited, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. It is done.
  • These ⁇ -olefins other than ethylene may be used alone or in combination of two or more.
  • the propylene / ⁇ -olefin copolymer is a copolymer of propylene and an ⁇ -olefin other than propylene copolymerizable with propylene.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. It is done. These may be used alone or in combination of two or more.
  • the foam raw material composition used in the present invention is a phenol-based, phosphorus-based, amine-based, sulfur-based antioxidant (anti-aging agent), heat stabilizer, and the like as long as the physical properties of the foam are not impaired.
  • Light stabilizers, UV absorbers, Phosphorus, Nitrogen, Halogen, Antimony and other flame retardants, Lubricants, Metal damage inhibitors, Antistatic agents, Fillers, Colorants, Cell nucleating agents, Crystal nucleating agents 1 type, or 2 or more types of various additives, such as, may be added.
  • the cell nucleating agent and filler are not particularly limited, but include talc, mica, shirasu balloon, calcium carbonate, clay, kaolin, mica, magnesium oxide, zinc oxide, carbon black, glass powder, and milled fiber. And glass fibers such as needle, spherical silica, alumina, novaculite, hydrated alumina, iron, iron oxide, silicon dioxide, titanium oxide, and the like.
  • the cell nucleating agent and the filler may be used so as not to impair the foaming property, but the content thereof is preferably 20% by mass or less in the foam raw material composition, and more preferably 10% by mass or less.
  • the crystal nucleating agent is not particularly limited, and generally includes a sorbitol-based crystal nucleating agent, a phosphate ester-based crystal nucleating agent, and a rosin-based crystal nucleating agent.
  • the phosphoric acid ester salt nucleating agent is not particularly limited, and examples thereof include “NA-11” (trade name) sold by Asahi Denka Kogyo.
  • the rosin-based crystal nucleating agent is not particularly limited as long as it is a rosin-based resin, and examples thereof include “dibenzylidene sorbitol” (trade name) and the like sold by Shin Nippon Rika. .
  • These crystal nucleating agents may be contained alone or in combination.
  • the crystal nucleating agent may be used so as not to impair the foaming property, but the content thereof is preferably 5% by mass or less, more preferably 1% by mass or less in the foam raw material composition.
  • the foam of the present invention comprises a non-crosslinked resin obtained by foaming the above-mentioned foam raw material composition.
  • the foaming ratio of the foam material composition is preferably 10 to 40 times, more preferably 20 to 30 times. If the expansion ratio is less than 10 times, the foam tends to be heavy. When the expansion ratio exceeds 40 times, the foam tends to be inferior in rigidity and dimensional stability.
  • the foam of the present invention is preferably a foamed strand converging body obtained by extruding and concentrating the foam raw material composition into a strand shape.
  • a foamed strand bundle is a material in which the tensile elongation in the TD direction (direction orthogonal to the strand direction) is larger than the tensile elongation in the MD direction (strand direction), and the tensile elongation is anisotropic. It becomes. For this reason, a sufficient elongation characteristic can be imparted to the foam by arranging and molding the direction in which higher development is required in the TD direction.
  • molded products with different vertical and horizontal molding development ratios include headlining, undercovers, package trays, door trims, and other automotive interior parts, and heat insulating panels with irregularities on the surfaces used for transfer trays, refrigerators, hot water tanks, etc. Etc. are mentioned as an example.
  • the tensile elongation in the TD direction at 180 ° C. is preferably 1.5 to 2.5 times that in the MD direction. One time is more preferable.
  • the value of tensile elongation is a value measured by the method described in Examples described later.
  • the foam of the present invention preferably has a basis weight of 200 to 550 g / m 2 , and more preferably 280 to 4500 g / m 2 . If it is less than 200 g / m 2 , it is preferable in terms of light weight, but the rigidity is remarkably impaired. If it exceeds 550 g / m 2 , it is preferable in terms of rigidity, but light weight is impaired and the cost increases.
  • the tensile elastic modulus of the foam of the present invention can be adjusted by the foaming magnification (density) of the foam and the content of the block polypropylene resin, but it is a face material reinforced foam in which both surfaces of the foam are reinforced with reinforcing face materials.
  • the tensile elastic modulus of the reinforcing face material has a greater influence on the elongation at the time of molding than the tensile elastic modulus of the foam core layer, and is not particularly specified.
  • the tensile elastic modulus of the reinforcing face material will be described later.
  • the foam of the present invention preferably has a closed cell ratio of 20 to 90%, more preferably 30 to 80%.
  • the closed cell ratio is desired to be less than 20%, it is necessary to remarkably increase the resin pressure at the time of foaming, which increases the burden on the extrusion foaming apparatus and the mold. If it exceeds 90%, the repulsion of air will be large at the time of molding, the product thickness will not be able to be obtained or the product thickness will be restored over time, and as a result, the surface smoothness will be impaired, and the air will not smoothly escape. Swelling tends to occur in the foam core layer of the product.
  • a foaming agent that melts the above-mentioned foam raw material composition in an extruder and is easy to mix with liquefied carbon dioxide, supercritical carbon dioxide, supercritical nitrogen, and their mixed fluids or polypropylene resins such as hydrocarbon gases. Pour and mix thoroughly.
  • the hydrocarbon gas is not particularly limited, but aliphatic hydrocarbon gases such as propane, n-butane, iso-butane, n-pentane, iso-pentane, cyclopentane, and benzene, and partially halogen-substituted.
  • Halogenated hydrocarbon gases such as 1,2-dichlorotetrafluoroethane, 1-chlorotetrafluoroethane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, HFC152a, HCFC142b, HFC134a, etc.
  • At least one selected from halogenated hydrocarbon compounds mainly composed of alternative chlorofluorocarbons, ethers, and alcohols is preferably used.
  • iso-butane and iso-butane / n-butane mixtures are particularly preferably used because they are hydrocarbon gases that are not halogenated in terms of environment and have high affinity with polyolefin resins.
  • the mixed fluid While sufficiently mixing the molten foamed resin and the foaming agent, the mixed fluid is adjusted to a temperature suitable for foaming, and then extruded from the nozzle of the extruder at a pressure of 3 to 20 MPa. By releasing to a medium pressure, foaming occurs at a foaming ratio of 10 to 40 times to obtain a foam.
  • the foam raw material composition extruded into the strand shape by extruding the foam raw material composition from each die nozzle into a strand shape by using a die nozzle having a plurality of holes arranged at equal intervals as an extruder.
  • the foamed strands are bundled while foaming strands are foamed to obtain a foamed body of foamed strands.
  • An extruder having a die nozzle opening diameter of 0.5 to 3 mm and a die nozzle numerical aperture of 50 to 5000 is used, and at a melt extrusion temperature of 160 to 250 ° C., There is a method in which the discharge amount per opening is 0.03 to 0.5 kg / h, and the resin pressure at the die nozzle opening is released to the atmosphere at 3 to 20 MPa and extruded. By doing in this way, the foam which consists of a foamed strand bundling body is obtained.
  • the reinforcing face material examples include a thermoplastic resin sheet or a thermoplastic resin containing an inorganic substance such as glass fiber or talc.
  • the thermoplastic resin sheet As a reinforcing face material, and in order to improve high rigidity and dimensional stability, it is possible to use a glass fiber-containing thermoplastic resin sheet. preferable.
  • the glass fiber-containing thermoplastic resin sheet it is preferable that glass fibers are impregnated with a thermoplastic resin, and a gap between the glass fibers is filled with the thermoplastic resin.
  • the average fiber length of the glass fibers is preferably 10 to 100 mm, more preferably 13 to 85 mm. If the average fiber length is shorter than 10 mm, it is easy to tear during molding, and if it exceeds 100 mm, the homogeneity of the fabric weight is impaired, the processability is reduced, or the resin is removed from the gap between the fibers when impregnating the thermoplastic resin. There is a tendency for seepage to increase.
  • the fiber diameter of the glass fiber is preferably 3 to 20 ⁇ m, more preferably 4 to 15 ⁇ m.
  • the fiber diameter is shorter than 3 ⁇ m, it is easy to tear during molding. If it exceeds 20 ⁇ m, the distribution of the glass fibers in the reinforcing face material tends to be non-uniform and the strength tends to vary. Further, when the glass fiber is used in the form of a nonwoven fabric, the glass fiber tends to drop off, so that the processability is lowered, the thermoplastic resin is easily impregnated unevenly, and the strength is likely to vary.
  • the glass fiber may be treated with various coupling agents such as a silane coupling agent.
  • various coupling agents such as a silane coupling agent.
  • the glass fiber may be used in any form of a woven fabric or a nonwoven fabric, but in the case of a woven fabric, a nonwoven fabric in which fibers are dispersed in a random direction is more preferable because the tensile elongation in the fiber orientation direction is poor. .
  • the glass fiber nonwoven fabric contains a binder.
  • the binder is not particularly limited, and various binder resins such as urethane resin, acrylic resin, vinyl acetate resin, and a mixture of two or more thereof can be used.
  • the binder may contain a crosslinked resin.
  • the content of the crosslinked resin is preferably 0.1 to 3% by mass, particularly preferably 0.2 to 2% by mass, based on the solid content of the binder.
  • the cross-linked resin is not particularly limited, but it is preferable to use polyvinyl alcohol (PVA) or polyfunctional acrylic polyol in terms of cost and workability.
  • PVA polyvinyl alcohol
  • the glass fiber nonwoven fabric binder (loss on ignition) is a solid content in the glass fiber nonwoven fabric, preferably 5 to 20 mass%, more preferably 7 to 16 mass%. If the binder gloss is less than 5% by mass, the binding force of the glass fibers will be weakened, resulting in an increase in fiber dropout during processing, impairing the workability when impregnating the thermoplastic resin into the nonwoven fabric, and desired reinforcement The effect is weakened, and tearing and dimensional change during molding increase. When the gloss of the binder exceeds 20% by mass, the binding force between the glass fibers becomes strong, so that the tensile elastic modulus of the reinforcing face material is lowered and it becomes difficult to mold, and the nonwoven fabric becomes expensive and is not economical.
  • the glass fiber nonwoven fabric preferably has a tensile strength at room temperature of 0.4 to 1.0 kgf / mm, more preferably 0.45 to 0.95 kgf / mm, and particularly preferably 0.5 to 0.9 kgf / mm. preferable. If the tensile strength of the glass fiber non-woven fabric is less than 0.4 kgf / mm, the strength for suppressing unevenness on the surface of the strand-bound foamed layer as the rigidity of the face-reinforced foam is impaired or the residual strain is reduced by molding. As a result, the surface smoothness of the product tends to be impaired. Moreover, when the tensile strength of a glass fiber nonwoven fabric exceeds 1.0 kgf / mm, the extensibility at the time of shaping
  • the glass fiber nonwoven fabric preferably has a tensile modulus at 180 ° C. of 0.8 to 2.0 kgf / mm 2 , more preferably 0.9 to 1.5 kgf / mm 2 , and 0.9 to 1.2 kgf / mm 2.
  • mm 2 is particularly preferred. If the tensile modulus is less than 0.8 kgf / mm 2 , the glass fiber tends to fall off, the handleability and workability deteriorate, and the residual strain increases when the material is stretched more than necessary during molding. Depending on the type, when handling a molded product in a high temperature (low temperature) and high humidity environment, the dimensional stability of the face material reinforced foam may be impaired or the surface smoothness of the molded product may be impaired due to relaxation of distortion during molding. It may be lost. On the other hand, if the tensile modulus exceeds 2.0 kgf / mm 2 , the stretchability of the squeezed portion is insufficient at the time of molding, and it tends to be broken.
  • the thermoplastic resin impregnated into the glass fiber is not particularly defined, but is preferably a polyolefin resin in consideration of the adhesiveness to the foam and the material cost, for example, polypropylene resin, polyethylene resin, ethylene-propylene -Olefin elastomers (TPO) typified by diene rubber (EPDM), ethylene-propylene rubber (EPR), butyl rubber graft polyethylene and the like.
  • a polypropylene resin the linear polypropylene used for this invention can be used, it is excellent in rigidity and dimensional stability (heat resistance), and also the adhesiveness of a foam and a reinforcement
  • a dispersibility modifying resin such as an unsaturated carboxylic acid-modified polyolefin resin that is relatively familiar to glass fibers may be added.
  • a polyvinyl chloride resin can be used to transfer the uneven shape of the inner surface of the mold to the surface of the reinforcing face material to give a design.
  • the MFR at 230 ° C. of the thermoplastic resin is preferably 3 to 50 g / 10 min, more preferably 5 to 45 g / 10 min.
  • thermoplastic resin As a method for efficiently infiltrating the thermoplastic resin into the gaps between the glass fibers, there is a method in which the thermoplastic resin is applied to the glass fibers in a high-temperature molten state that does not decompose the thermoplastic resin.
  • the method for applying the thermoplastic resin is not particularly limited. For example, it can apply
  • the glass fiber nonwoven fabric when it is a sheet, it is preferably applied on both surfaces of the sheet.
  • the thermoplastic resin having a temperature suitable for processing and an appropriate viscosity characteristic and the thermoplastic resin to be permeated in the thickness direction of the glass fiber nonwoven fabric, only from one side surface of the glass fiber nonwoven fabric You can just cast it.
  • thermoplastic resin when seeking a reinforcing surface material having excellent extensibility by deep drawing or the like, it is preferable to infiltrate so that the thermoplastic resin is homogeneously present in the glass fiber nonwoven fabric. As the permeability is higher, the reinforcing effect of the foam layer by the glass fiber is increased, and as a result, the amount of the thermoplastic resin required is small.
  • the reinforcing face material preferably has a glass fiber content of 20 to 40% by mass, more preferably 25 to 35% by mass. If the glass fiber content exceeds 40% by mass, the tensile elastic modulus of the reinforcing face material is lowered, the elongation at the time of molding is insufficient, and the molded body may be torn. When the glass fiber content is less than 20% by mass, the product weight increases and the price increases, such being undesirable.
  • Basis weight of the reinforcing surface material is preferably 70 ⁇ 200g / m 2, more preferably 120 ⁇ 170g / m 2. If the basis weight of the reinforcing face material is less than 70 g / m 2 , the reinforcing effect as a reinforcing face material is insufficient, but the rigidity and heat-resistant dimensional stability of the face material-reinforced foam are likely to be impaired. If it exceeds 200 g / m 2 , the rigidity and heat-resistant dimensional stability of the face material-reinforced foam will increase, but the lightness and elongation at the time of molding will be impaired, and the material will be expensive.
  • the reinforcing face material needs to have a tensile elastic modulus of 10 to 45 kgf / mm 2 under an atmosphere of 180 ° C., and preferably 10 to 35 kgf / mm 2 .
  • a tensile elastic modulus 10 to 45 kgf / mm 2 under an atmosphere of 180 ° C., and preferably 10 to 35 kgf / mm 2 .
  • the tensile elastic modulus is less than 10 kgf / mm 2 , the dimensional change and shape deformation of the molded body increase, and when the tensile elastic modulus exceeds 45 kgf / mm 2 , the extensibility of the reinforced face material decreases and strengthens during molding.
  • the face material tends to tear.
  • a tensile elasticity modulus is the value measured by the method described in the Example mentioned later.
  • the face material reinforced foam of the present invention is formed by laminating the above-described reinforcing face material as a surface material layer on at least one surface of the above-described foam.
  • the glass fiber is pressed by pressing the foam and the reinforced face material in a state where the glass fiber is heated and melted and then further heat plasticized.
  • the reinforcing face material and the foam can be bonded to each other using the adhesive property of the thermoplastic resin while allowing the thermoplastic resin to moderately penetrate to the back surface of the nonwoven fabric.
  • a reinforcing face material in which a thermoplastic resin is sufficiently infiltrated into a glass fiber nonwoven fabric and a foam to be bonded thereto are prepared in advance, and in the next step, both are bonded by a hot roll,
  • a method of laminating in the process of extrusion foaming line molding by the type lamination is a method of laminating in the process of extrusion foaming line molding by the type lamination.
  • the extrusion laminating method has a disadvantage that the apparatus is large and requires a wide space, and the apparatus cost is very high, but there is an advantage that a high basis weight thermoplastic resin can be easily applied with a relatively uniform basis weight.
  • the spray-type hot melt laminating method can be processed at a relatively low cost, but has a demerit that the basis weight of the thermoplastic resin is not uniform or is not suitable for application of a high basis weight resin.
  • a reinforcing face material when prepared in advance, it can be suitably processed by the above extrusion laminating method or spray hot melt laminating method.
  • thermoplastic resin that has penetrated the foam and reinforced face material is heated and melted simultaneously. Therefore, even when the extrusion foaming speed is high, there is an advantage that the bonding process can be sufficiently performed even in the same process.
  • the thickness of the face material reinforced foam is not particularly limited.
  • it may be a board shape having a thickness of 5 to 15 mm, or a sheet shape having a thickness of 3 to 5 mm. It can be suitably adjusted according to the application.
  • the face material reinforced foam contains 10 to 20% by mass of glass fiber, and preferably 12 to 18% by mass.
  • the glass fiber content is less than 10% by mass, the rigidity and dimensional stability of the molded product are impaired.
  • problems such as shrinkage and collapse of shape occur.
  • the residual stress increases, so that the dimensional stability is significantly impaired. If it exceeds 20% by mass, the lightness is impaired, or the tensile elastic modulus of the reinforced face material becomes too high and tearing is likely to occur during molding.
  • Basis weight of the surface material reinforced foam preferably 450 ⁇ 650g / m 2, more preferably 500 ⁇ 600g / m 2. If it is less than 450 g / m 2 , the lightness is very excellent, but the rigidity and dimensional stability of the face material reinforced foam are impaired, or if the thickness of the face material reinforced foam is reduced, Prone to tearing. If it exceeds 650 g / m 2 , the rigidity and heat-resistant dimensional stability will be good, but the lightness specific to the foamed core laminate material will not be sufficiently exhibited, and the material cost will be high.
  • the expansion rate of the face material reinforced foam is not particularly defined because the required value varies depending on the mold shape, but is preferably 130% or more, more preferably 170% or more in order to ensure a certain degree of mold elongation. preferable.
  • the tensile elongation in the TD direction at 180 ° C. is preferably 1.5 to 2.5 times that in the MD direction. More preferably, it is 7 to 2.3 times.
  • the tensile elongation in the TD direction is preferably 200% or more, more preferably 200 to 300%, and the tensile elongation in the MD direction is preferably 130% or more, more preferably 170 to 190%.
  • the expansion rate necessary for the face material reinforced foam in a mold having a specific shape in consideration of the tensile elongation characteristics in the MD direction and the TD direction of the foam is preferable to mold the direction that requires molding at a higher development rate as the TD direction of the foam.
  • the adhesive strength between the foam and the reinforcing face material is 0.05 kgf / mm 2 or more, more preferably 0.1 to 5 kgf / mm 2 in the state of the substrate temperature at the time of molding. If the adhesive strength between the foam and the reinforced face material is insufficient, the strength of the face material reinforced foam decreases, the reinforced face material peels off from the foam during molding, and the resulting molded product Does not have sufficient dimensional stability.
  • Adhesive strength is sufficient when the adhesive strength is 0.05 kgf / mm 2 or more, more preferably 0.5 kgf / mm 2 or more, and most preferably 2 kgf / mm 2 or more.
  • the adhesive strength means a 180 ° peel test value at room temperature at a peel rate of 200 mm / min, measured by the method of JIS K6854-2.
  • the molded body of the present invention is formed by molding the above-mentioned face material reinforced foam.
  • the molding method of the face material reinforced foam There is no particular limitation on the molding method of the face material reinforced foam. It can be formed by a conventionally known method. For example, stamping molding, vacuum molding, etc. are mentioned.
  • the face material reinforced foam is softened and melted by preheating and molded into a specific shape by a cooling press.
  • An adhesive layer is laminated on the surface of the face material reinforced foam, and simultaneously with pressing, felt, ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPR), butyl rubber graft on the surface of the face material reinforced foam.
  • Cosmetic materials made of various olefin resin materials such as polyethylene can be bonded together.
  • a decorative material can be bonded to the molded product simultaneously with the forming.
  • the molded product of the present invention is preferably shaped by pressing the face material reinforced foam and having a development rate of preferably 130% or more, more preferably 170% or more. Moreover, it is preferable that it is shaped with a development rate of 200% or less. Since the face material reinforced foam of the present invention is excellent in moldability, it is preferably used for molding a molded product that requires highly developed molding.
  • the molded product of the present invention preferably has a molding compression rate of 75% or less, more preferably 50% or less. If the molding compression ratio of the foam exceeds 50%, bulges are likely to occur in the foam. This is particularly noticeable when the closed cell ratio of the foam is high.
  • the molding compression rate of a foam is the value measured by the method as described in the Example mentioned later.
  • the bending maximum load of the molded body is preferably 20 N or more, more preferably 30 to 40 N. If it is 20N or more, for example, it can be applied to a member that is relatively non-touchable, such as an interior ceiling material of an automobile, but the strength is insufficient when used as a member that is frequently touched, such as a door panel or a sunshade. In this case, the maximum bending load of at least 30N is required.
  • the dimensional change rate after the thermal cycle test of the molded body is 1 ⁇ (1/1000) or less.
  • the dimensional change rate after a thermal cycle test is the value measured by the method as described in the Example mentioned later.
  • Thermoplastic MFR Based on JIS K7210, the amount of resin per 10 minutes flowing from the cylinder at 230 ° C. and a load of 2.16 kgf was determined.
  • the tensile elongation was calculated from the displacement (mm) until the reinforced face material broke and the chuck interval (mm) of the test using the following formula.
  • Tensile elongation (breaking elongation) (%) of reinforced face material Displacement amount until the reinforced face material breaks (mm) ⁇ Chuck interval (mm) x 100
  • the weight (g) of each test piece was measured to the last two digits with an electronic balance, the basis weight was calculated by the following formula, and the average value of each test piece was obtained.
  • Weight per unit area (g / m 2 ) weight (g) / (0.1 (m) ⁇ 0.1 (m))
  • Lightweight face material reinforced foam weight per unit area of the surface material reinforced foam a case of less than 600 g / m 2 " ⁇ ", a case of 600 ⁇ 650g / m 2 " ⁇ ", a 650 ⁇ 700g / m 2 " ⁇ ”, The case of exceeding 700 g / m 2 was evaluated as“ ⁇ ”.
  • moldable development rate and moldability evaluation of face material reinforced foam The face material reinforced foam was cut into a size of 600 mm in length and 600 mm in width to obtain a test piece. After clamping the four edges of the test piece and sufficiently preheating it in a far-infrared heating furnace to soften and melt it, the face material reinforced foam is immediately conveyed into the mold, and the center of the lower surface is 175 mm long The stamping was performed using a mold having a square plane of 175 mm in width, the flat part and the corners of the rising part are all R30 mm, the upper surface of the mold is concave, and the lower surface is convex. .
  • the clearance between the molds is 6.0 mm, and the molding development rate at this time is 130% in both the MD direction and the TD direction.
  • evaluation content of the moldability it was evaluated whether or not the face material reinforced foam was torn in all parts of the obtained molded body. “ ⁇ ” indicates that there is no tear, and “ ⁇ ” indicates a range where there is a portion where the maximum bending load and dimensional stability are reduced by less than 10%, although there is no visual crack. “ ⁇ ” indicates the range where the maximum bending load and the dimensional stability are locally reduced by 10 to 20%, and / or the reinforced face material and / or the foam of the face material reinforced foam is torn. The case was evaluated as “ ⁇ ”.
  • the expansion rate gradually increases from the state where the molding expansion rate is 130%. Molding until the face material reinforced foam is broken by changing the conditions, investigating the development rate that can be molded in each of MD direction (foaming line progression direction) and TD direction (direction perpendicular to the foaming line), strengthening the face material The elongation of the foam was evaluated.
  • ⁇ when the MD development rate exceeds 135%, “ ⁇ ” for 130 to 135%, “ ⁇ ” for 125 to 130%. The case where tearing occurs at a rate of less than 125% was evaluated as “ ⁇ ”.
  • Foam molding compression ratio of the molded body The thickness immediately after the production of the foam was t0, and the thickness of the foamed layer of the molded body was t1, and was calculated from the following formula.
  • Foam molding compression ratio (%) ((t0 ⁇ t1) ⁇ t0) ⁇ 100
  • a unit of dimensional change x 1/1000 it means a deformation amount (mm) in which a molded body having an initial dimension of 1000 mm is deformed after a thermal cycle test, and the same meaning as dimensional change rate x 0.1 (%). is there.
  • Dimensional change after cooling cycle test ( ⁇ 1/1000)
  • the dimensional change of the molded body is less than 0.8 ⁇ 1/1000 is “ ⁇ ”, 0.8 ⁇ 1/1000 to 1.0 ⁇ 1/1000 is “ ⁇ ”, 1.0 ⁇ 1/1000 to 1.5 The case where ⁇ 1/1000 was evaluated as “ ⁇ ” and the case exceeding 1.5 ⁇ 1/1000 was evaluated as “ ⁇ ”.
  • the LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 50 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 67% by mass and a glass fiber content of 33%.
  • the basis weight of the reinforcing face material is 150 g / m 2
  • the tensile strength at normal temperature is 0.54 kgf / mm
  • the tensile elastic modulus in an atmosphere at 180 ° C. is 15 kgf / mm 2
  • the tensile elongation in an atmosphere at 180 ° C. is 262%. Met.
  • an LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 60 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 67% by mass and a glass fiber content of 33%.
  • the basis weight of the reinforcing face material is 180 g / m 2
  • the tensile strength at room temperature is 0.93 kgf / mm
  • the tensile elastic modulus at 180 ° C. atmosphere is 13 kgf / mm 2
  • the tensile elongation under 180 ° C. atmosphere is 281%. Met.
  • the LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 40 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 67% by mass and a glass fiber content of 33%.
  • the basis weight of the reinforcing face material is 120 g / m 2
  • the tensile strength at normal temperature is 0.42 kgf / mm
  • the tensile elastic modulus at 180 ° C. is 30 kgf / mm 2
  • the tensile elongation at 180 ° C. is 180%. Met.
  • an LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 48 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 61% by mass and a glass fiber content of 39%.
  • the basis weight of the reinforcing face material is 155 g / m 2
  • the tensile strength at room temperature is 1.03 kgf / mm
  • the tensile elastic modulus at 180 ° C. is 46 kgf / mm 2
  • the tensile elongation at 180 ° C. is 143%. Met.
  • the LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 100 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 83% by mass and a glass fiber content of 17%.
  • the basis weight of the reinforcing face material is 240 g / m 2
  • the tensile strength at normal temperature is 0.46 kgf / mm
  • the tensile elastic modulus at 180 ° C. atmosphere is 10 kgf / mm 2
  • the tensile elongation under 180 ° C. atmosphere is 311%. Met.
  • the LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 50 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 67% by mass and a glass fiber content of 33%.
  • the basis weight of the reinforcing face material is 150 g / m 2
  • the tensile strength at room temperature is 0.40 kgf / mm
  • the tensile elastic modulus at 180 ° C. atmosphere is 8 kgf / mm 2
  • the tensile elongation at 180 ° C. atmosphere is 323%. Met.
  • the LLDPE resin was directly applied to the back side of the glass fiber nonwoven fabric with a basis weight of 50 g / m 2 , and the LLDPE resin was completely infiltrated into the glass fiber nonwoven fabric to produce a reinforced face material.
  • the obtained reinforcing face material had an LLDPE resin content of 67% by mass and a glass fiber content of 33%.
  • the basis weight of the reinforcing face material is 150 g / m 2
  • the tensile strength at room temperature is 0.78 kgf / mm
  • the tensile elastic modulus at 180 ° C. in the atmosphere is 51 kgf / mm 2
  • the tensile elongation in the 180 ° C. atmosphere is 126%. Met.
  • Example 1-1 The first stage is a tandem type extruder with a ⁇ 90 mm single screw extruder and the second stage is a ⁇ 120 mm single screw extruder, and linear polypropylene (hereinafter referred to as “linear PP”) (trade name) “E105PW”, MFR: 15 g / min) 100 parts by mass of block polypropylene (hereinafter referred to as “block PP”) (trade name “BJS-MU” manufactured by Prime Polymer Co., Ltd., MFR: 1.6 g / min, tensile After melting and kneading a polypropylene foam resin (MFR: 7.3 g / min) containing 7 parts by mass of an elastic modulus of 1400 MPa at a discharge rate of 75 kg / h at a temperature setting of 230 ° C., a liquefied carbon dioxide gas is blown into a polypropylene foam An amount of 6.1% by mass was injected with respect to
  • Example 1-2 In Example 1-1, the procedure was the same as Example 1-1 except that a polypropylene-based foamed resin (MFR: 7.6 g / min) containing 15 parts by mass of block PP was used with respect to 100 parts by mass of linear PP. Thus, a foam having a width of 1501 mm, an expansion ratio of 29 times, a thickness of 8.5 mm, and a basis weight of 267 g / m 2 was produced. The tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test based on JIS K7115 was 92% in the MD direction and 141% in the TD direction. Moreover, the maximum load by the bending test based on JISK7171 of a foam was 6.2 (N).
  • MFR polypropylene-based foamed resin
  • Example 1-1 the procedure was the same as Example 1-1, except that a polypropylene-based foamed resin (MFR: 4.6 g / min) containing 67 parts by mass of block PP with respect to 100 parts by mass of linear PP was used.
  • MFR polypropylene-based foamed resin
  • a foam having a width of 1450 mm, an expansion ratio of 26 times, a thickness of 8.5 mm, and a basis weight of 298 g / m 2 was produced.
  • the tensile elongation in the 180 degreeC atmosphere by the tensile test based on JISK7115 of the obtained foam was 111% of MD directions, and 166% of TD directions.
  • the maximum load by the bending test based on JISK7171 of a foam was 6.3 (N).
  • Example 1-4 A foam with a width of 1425 mm, a thickness of 10 mm, and a basis weight of 433 g / m 2 was produced in the same manner as in Example 1-2, except that the foaming ratio in Example 1-2 was 21 times.
  • the tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test based on JIS K7115 was 92% in the MD direction and 141% in the TD direction.
  • the maximum load by the bending test based on JISK7171 of a foam was 9.3 (N).
  • Example 1-5 A foam with a width of 1504 mm, a thickness of 8.5 mm, and a basis weight of 258 g / m 2 was produced in the same manner as in Example 1-2, except that the foaming ratio in Example 1-2 was 30 times.
  • the tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test based on JIS K7115 was 92% in the MD direction and 141% in the TD direction.
  • the maximum load by the bending test based on JISK7171 of a foam was 6.1 (N).
  • Example 1-1 In Example 1-1, except that only linear PP was used as the polypropylene-based foamed resin, the width was 1501 mm, the foaming ratio was 29 times, the thickness was 8.5 mm, and the basis weight was 267 g / m 2 in the same manner as in Example 1-1.
  • a foam was produced.
  • the tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test based on JIS K7115 was 60% in the MD direction and 108% in the TD direction.
  • the maximum load by the bending test based on JISK7171 of a foam was 7.3 (N). This foam was inferior in extensibility and inferior in moldability in both the MD direction and the TD direction as compared with Example 1-1.
  • Example 1-1 In Example 1-1, except for using a polypropylene-based foamed resin containing 100 parts by mass of block PP with respect to 100 parts by mass of linear PP, the width was 1430 mm and the expansion ratio was 15 times, as in Example 1-1. A foam with a thickness of 6.7 mm and a basis weight of 406 g / m 2 was produced. The tensile elongation in the 180 degreeC atmosphere by the tensile test based on JISK7115 of the obtained foam was 121% of MD direction, and 188% of TD directions. Moreover, the maximum load by the bending test based on JISK7171 of a foam was 11 (N). This foam had a large maximum load in a bending test and was inferior in rigidity.
  • Example 1-1 a width 1490 mm was obtained in the same manner as in Example 1-1 except that a polypropylene-based foamed resin containing 15 parts by mass of an ethylene-propylene copolymer was used with respect to 100 parts by mass of linear PP.
  • the tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test based on JIS K7115 was 83% in the MD direction and 126% in the TD direction.
  • the maximum load by the bending test based on JISK7171 of a foam was 4.8 (N). This foam had high rigidity and poor moldability.
  • Example 1-1 In Example 1-1, except that a polypropylene-based foamed resin containing 15 parts by mass of polyethylene was used with respect to 100 parts by mass of linear PP, the width was 1471 mm, the expansion ratio was 25 times, A foam having a thickness of 8.5 mm and a basis weight of 309 g / m 2 was produced.
  • the tensile elongation of the obtained foam in a 180 ° C. atmosphere by a tensile test according to JIS K7115 was 66% in the MD direction and 113% in the TD direction.
  • the maximum load by the bending test based on JISK7171 of a foam was 4.5 (N). This foam had high rigidity and poor moldability.
  • Example 2-1 The reinforcing face material of Production Example 1 was laminated on both surfaces of the foam of Example 1-1. A hot air of 280 ° C. is blown between the reinforced face material and the foam of this laminate, promptly pressed with a PTFE roll, and the reinforced face material is bonded to both surfaces of the foam to produce a face material reinforced foam. did.
  • the basis weight of the obtained face material reinforced foam was 567 g / m 2 , thickness 7.5 mm, and the glass fiber content contained in the face material reinforced foam was 18% by mass.
  • This face material reinforced foam is retained for 90 seconds in a far-infrared heating furnace having a set temperature of 280 ° C., and heated so that the surface temperature of the face material reinforced foam becomes 175 ° C.
  • press molding was performed under the conditions that the mold clearance setting was 6.0 mm, and the molding development rate in the MD direction (extending direction of the extrusion foaming line) and the TD direction (line width direction) were both 130%.
  • the molded product obtained as described above was a beautiful molded product having a surface appearance without tearing in all corner portions and inclined surface portions. Further, the molding development rate was further increased until the molded body was torn, and the limit value of the development rate at which molding was possible was investigated.
  • the moldable development rate of the face material reinforced foam obtained as described above is 134% in the MD direction (that is, 135% forming causes tearing), and 224% in the TD direction (breaking at 225%). It was confirmed that the molding having a development rate of 130% has sufficient elongation characteristics. Moreover, the bending maximum load of a molded object is 25N, It has confirmed that it was a molded object with moderate rigidity. Further, when the dimensional change of the molded body before and after the test was examined by a thermal cycle test, the dimensional change was 0.90 ⁇ 1/1000 (0.090%), and it was confirmed that the molded product was excellent in dimensional stability. did it.
  • Example 2-2 In Example 2-1, the basis weight was 567 g / m 2 , the thickness was the same as in Example 2-1, except that the reinforcing face material of Production Example 1 was laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 18% by mass was produced.
  • Example 2-3 In Example 2-1, except that the reinforcing face material of Production Example 1 was laminated on both surfaces of the foam of Example 1-3, the basis weight was 595 g / m 2 and the thickness was 7 A face material-reinforced foam having a glass fiber content of 0.5 mm and a mass of 17% by mass was produced.
  • Example 2-4 In Example 2-1, the basis weight of 642 g / m 2 , thickness was obtained in the same manner as in Example 2-1, except that the reinforcing face material of Production Example 2 was laminated on both surfaces of the foam of Example 1-2. A face material reinforced foam having a diameter of 7.5 mm and a glass fiber content of 19% by mass was produced.
  • Example 2-5 In Example 2-1, the basis weight of 673 g / m 2 , thickness was obtained in the same manner as in Example 2-1, except that the reinforcing face material of Production Example 3 was laminated on both surfaces of the foam of Example 1-4. A face material-reinforced foam having a thickness of 7.5 mm and a glass fiber content of 12% by mass was produced.
  • Example 2-6 In Example 2-1, the basis weight is 562 g / m 2 , the thickness is the same as Example 2-1, except that the reinforcing face material of Production Example 8 is laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 18% by mass was produced.
  • Example 2--7 In Example 2-1, the basis weight is 562 g / m 2 , the thickness is the same as in Example 2-1, except that the reinforcing face material of Production Example 9 is laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 18% by mass was produced.
  • Example 2-8 In Example 2-1, the basis weight is 562 g / m 2 , the thickness is the same as in Example 2-1, except that the reinforcing face material of Production Example 10 is laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 18% by mass was produced.
  • Example 2-1 (Comparative Example 2-1)
  • the basis weight was 567 g / m 2
  • the thickness was the same as in Example 2-1, except that the reinforcing face material of Production Example 1 was laminated on both surfaces of the foam of Comparative Example 1-1.
  • Example 2-1 the basis weight is 693 g / m 2 , the thickness is the same as Example 2-1, except that the reinforcing face material of Production Example 1 is laminated on both surfaces of the foam of Comparative Example 1-2.
  • Example 2-3 (Comparative Example 2-3)
  • the basis weight was 577 g / m 2 and the thickness was the same as Example 2-1, except that the reinforcing face material of Production Example 1 was laminated on both surfaces of the foam of Comparative Example 1-3.
  • Example 2-1 the basis weight is 605 g / m 2 , the thickness is the same as in Example 2-1, except that the reinforcing face material of Production Example 1 is laminated on both surfaces of the foam of Comparative Example 1-4.
  • Example 2-5 In Example 2-1, the basis weight is 530 g / m 2 , the thickness is the same as in Example 2-1, except that the reinforcing face material of Production Example 4 is laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 23% by mass was produced.
  • Example 2-6 In Example 2-1, the basis weight is 857 g / m 2 and the thickness is the same as in Example 2-1, except that the reinforcing face material of Production Example 5 is laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a thickness of 7.5 mm and a glass fiber content of 9% by mass was produced.
  • Example 2-7 In Example 2-1, the basis weight was 567 g / m 2 , the thickness was the same as in Example 2-1, except that the reinforcing face material of Production Example 6 was laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 18% by mass was produced.
  • Example 2-8 In Example 2-1, the basis weight was 567 g / m 2 , the thickness was the same as in Example 2-1, except that the reinforcing face material of Production Example 7 was laminated on both surfaces of the foam of Example 1-2. A face material-reinforced foam having a diameter of 7.5 mm and a glass fiber content of 21% by mass was produced.
  • Example 2-2 to Comparative Example 2-8 were molded in the same manner as in Example 2-1, and the expansion rate, dimensional change after the thermal cycle test, maximum bending load, formability, and extensibility. Light weight, dimensional stability, and rigidity were evaluated. The results are summarized in Tables 3 and 4.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne une mousse et une mousse renforcée par un matériau en surface qui présentent une excellente moulabilité et comprennent une résine sans réticulation capable de donner un article moulé présentant une bonne rigidité et une stabilité dimensionnelle et un article moulé présentant une bonne rigidité et une stabilité dimensionnelle. La mousse renforcée par un matériau en surface est formée par stratification, comme couche de matériau de surface, d'une feuille de résine thermoplastique contenant des fibres de verre contenant 20 %-40 % en masse de fibres de verre et présentant un module d'élasticité à la traction de 10-45 kgf/mm2 dans une atmosphère à 180 °C sur une surface de la mousse comprenant une résine sans réticulation obtenu par moussage d'une composition de matériau de départ de mousse comprenant une résine de mousse de polypropylène contenant 5-70 parties en masse de polypropylène séquencé pour 100 parties en masse de polypropylène linéaire. Le corps moulé est formé par moulage de la mousse renforcée par un matériau en surface.
PCT/JP2011/079584 2010-12-28 2011-12-21 Mousse, mousse renforcée par un matériau en surface et corps moulé WO2012090802A1 (fr)

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JP2014069444A (ja) * 2012-09-28 2014-04-21 Asahi Fiber Glass Co Ltd 自動車内装材用成形材料
WO2018017536A1 (fr) * 2016-07-20 2018-01-25 Sabic Global Technologies B.V. Procédés de fabrication d'articles en polypropylène chargés de fibres de verre
KR102171526B1 (ko) * 2020-07-29 2020-10-30 이응기 재활용이 용이한 자동차용 헤드라이너 기재 및 그 제조방법
KR20210094180A (ko) * 2020-01-20 2021-07-29 김효식 자동차의 러기지 보드용 판넬 및 그 제조 방법

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JP2006181957A (ja) * 2004-12-28 2006-07-13 Kyoraku Co Ltd ポリプロピレン系樹脂発泡成形体
WO2009001959A1 (fr) * 2007-06-28 2008-12-31 Asahi Fiber Glass Company, Limited Procédé de fabrication d'une mousse de résine de polyoléfine non réticulée
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JPH04363227A (ja) * 1991-03-26 1992-12-16 Jsp Corp プロピレン系樹脂押出発泡体、成形体及びその製造方法
JP2001001384A (ja) * 1999-04-23 2001-01-09 Kanegafuchi Chem Ind Co Ltd ポリプロピレン系樹脂押出発泡細条集束体の製造方法
WO2005026255A1 (fr) * 2003-09-12 2005-03-24 Kaneka Corporation Composition de resine a base de polypropylene, moulages expanses comprenant ladite composition et procede de production associe
JP2006181957A (ja) * 2004-12-28 2006-07-13 Kyoraku Co Ltd ポリプロピレン系樹脂発泡成形体
WO2009001959A1 (fr) * 2007-06-28 2008-12-31 Asahi Fiber Glass Company, Limited Procédé de fabrication d'une mousse de résine de polyoléfine non réticulée
WO2009035111A1 (fr) * 2007-09-14 2009-03-19 Asahi Fiber Glass Company, Limited Mousse de résine de polypropylène extrudé et son processus de production

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014069444A (ja) * 2012-09-28 2014-04-21 Asahi Fiber Glass Co Ltd 自動車内装材用成形材料
WO2018017536A1 (fr) * 2016-07-20 2018-01-25 Sabic Global Technologies B.V. Procédés de fabrication d'articles en polypropylène chargés de fibres de verre
CN109562559A (zh) * 2016-07-20 2019-04-02 沙特基础工业全球技术公司 制备玻璃填充的聚丙烯制品的方法
KR20210094180A (ko) * 2020-01-20 2021-07-29 김효식 자동차의 러기지 보드용 판넬 및 그 제조 방법
WO2021149976A1 (fr) * 2020-01-20 2021-07-29 김효식 Panneau à bagages pour automobile et son procédé de fabrication
KR102387971B1 (ko) * 2020-01-20 2022-04-18 김효식 자동차의 러기지 보드용 판넬 및 그 제조 방법
KR102171526B1 (ko) * 2020-07-29 2020-10-30 이응기 재활용이 용이한 자동차용 헤드라이너 기재 및 그 제조방법

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