Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/06—Propene
• • 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
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
• • 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
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14336—Coating a portion of the article, e.g. the edge of the article
• • 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
  • B32B27/08—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 synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
• • 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
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
  • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
  • B29C2045/14319—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles bonding by a fusion bond
• • 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
  • B29K2623/00—Use of polyalkenes or derivatives thereof for preformed parts, e.g. for inserts
  • B29K2623/10—Polymers of propylene
  • B29K2623/12—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
  • B29K2623/00—Use of polyalkenes or derivatives thereof for preformed parts, e.g. for inserts
  • B29K2623/16—EPM, i.e. ethylene-propylene copolymers; EPDM, i.e. ethylene-propylene-diene copolymers; EPT, i.e. ethylene-propylene terpolymers
• • 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
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
• • 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
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0077—Yield strength; Tensile strength
• • 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
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0089—Impact strength or toughness
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/242—All polymers belonging to those covered by group B32B27/32
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
• • 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
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • 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
  • B32B2307/54—Yield strength; Tensile strength
• • 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
  • B32B2307/554—Wear resistance
• • 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
  • B32B2307/558—Impact strength, toughness
• • 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
  • B32B2307/584—Scratch resistance
• • 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
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • B32B2307/738—Thermoformability
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • 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
  • 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
  • C08J2323/14—Copolymers of propene

Definitions

• the present invention relates to a polymer molded article comprising a base portion and a surface layer portion.
• Patent Document 1 discloses an in-mold label that includes a heat-sensitive adhesive layer on the back side of a biaxially stretched film.
• Patent Documents 2 and 3 disclose techniques for attaching a decorative film onto a resin molded body by thermoforming.
• Patent Document 4 discloses a decorative laminate sheet that includes, in this order, a surface layer, a design layer, and an adhesive layer containing a polymer containing 85% by mass or more of propylene units.
• Patent Document 1 uses a heat-sensitive adhesive layer formed on the back side of the biaxially stretched film to adhere the biaxially stretched film to a substrate.
• the heat-sensitive adhesive layer is made of hot melt resin or the like and has low rigidity. Therefore, with this technique, it is difficult to improve the rigidity and scratch resistance of the substrate. Further, when thermal bonding is applied to the biaxially stretched film, partial melting of the biaxially stretched film occurs, causing problems such as a decrease in rigidity.
• the techniques specifically described in Patent Documents 2 and 3 use polypropylene as the base and unstretched polypropylene resin as the decorative film. Therefore, even with this technique, it is difficult to improve the rigidity and scratch resistance of the substrate.
• Patent Document 4 does not specifically disclose a polymer molded article in which a decorative laminated sheet is actually thermally bonded to a base portion.
• an object of the present invention is to provide a polymer molded article having excellent rigidity and scratch resistance.
• a molded article including a base part and a specific surface layer part thermally bonded onto the base part can solve the above problem. Therefore, the above-mentioned problem is solved by the present invention as described below.
• Aspect 1 The base part and A polymer molded article comprising a surface layer portion thermally bonded onto the base portion, Requirements below: 1) Gs>Gb (Gs is the rigidity of the surface layer portion, and Gb is the rigidity of the base portion.) 2) Tms ⁇ Tp (Tms is the melting point of the surface layer portion at the joint with the base portion, and Tp is the molding temperature during the thermal bonding.)
• Gs>Gb Gs is the rigidity of the surface layer portion, and Gb is the rigidity of the base portion.
• Tms is the melting point of the surface layer portion at the joint with the base portion
• Tp is the molding temperature during the thermal bonding.
• Aspect 2 The molded article according to aspect 1, wherein the base portion and the surface layer portion are composed of a polymer having the same repeating unit.
• Aspect 3 The molded article according to aspect 1 or 2, wherein the surface layer portion has a multilayer structure.
• Aspect 4 The surface layer part has a multilayer structure comprising a biaxially stretched sheet layer L having a melting point Tml and a biaxially stretched sheet layer H having a melting point Tmh, Tmh>Tml, The molded article according to aspect 3, wherein the biaxially stretched sheet layer L forms the joint surface.
• the layer H is Polypropylene resin (A), or contains polypropylene resin (A) and plate-shaped inorganic filler (B), and the weight ratio of component (B)/[component (A) + component (B)] is 0% by weight.
• the polypropylene resin (A) includes a polypropylene resin consisting of component (A1) and optional component (A2),
• the component (A1) is 100 to 50% by weight of a propylene (co)polymer containing 0 to 10% by weight of units derived from comonomers selected from C2 to C10- ⁇ olefins (excluding C3- ⁇ olefins);
• Component (A2) is 0 to 50% by weight of an ethylene- ⁇ -olefin copolymer containing 10 to 90% by weight of ethylene-derived units, MFR (230 ° C., load 2.16 kg) of the polypropylene resin (A) is 1 to 15 g/10 minutes,
• Aspect 7 The molded article according to any one of aspects 4 to 6, wherein the surface layer portion includes a top layer other than the biaxially stretched sheet layers L and H on the outermost surface.
• Aspect 8 The molded article according to any one of aspects 4 to 7, wherein the total thickness of the layer L/thickness of the surface layer portion is 1 to 50%.
• Aspect 9 The molded article according to any one of aspects 4 to 8, wherein the surface layer portion has alternating layers in which the layer L and the layer H are alternately laminated.
• Aspect 10 The molded article according to any one of aspects 1 to 9, wherein the thickness of the surface layer portion is 30 ⁇ m or more.
• Aspect 11 The molded article according to any one of aspects 1 to 10, wherein the thickness of the base portion is 5 to 250 times the thickness of the surface layer portion.
• Aspect 12 Step 1 of preparing the surface layer; and Step 2 of thermoforming the raw material for the base to form the base and thermally bonding the surface layer to the surface thereof.
• the step 2 is a step of arranging the surface layer portion in a cavity of a mold, and forming the base portion by injection molding a raw material for the base portion into the cavity, and thermally bonding the surface layer portion to the surface thereof.
• process The manufacturing method according to aspect 12, comprising:
• the present invention can provide a polymer molded article with excellent rigidity and scratch resistance.
• X ⁇ Y includes its end values, ie, X and Y.
• sheet and film are used synonymously, but in particular, a membrane member having a thickness of 150 ⁇ m or more may be referred to as a sheet, and a membrane member having a thickness of less than 150 ⁇ m may be referred to as a film. Further, sheets and films may be collectively referred to as "sheet-like members”.
• the polymer molded body according to this embodiment includes a base portion and a surface layer portion thermally bonded onto the base portion. That is, the base portion and the surface layer portion are fused together.
• the base portion is a portion that forms the base of the polymer molded body.
• the surface layer portion is formed on the base portion and provides functions to the molded article. Such functions include improved rigidity and improved scratch resistance.
• the base part and the surface part satisfy the relationship Gs>Gb.
• Gs is the stiffness of the surface layer
• Gb is the stiffness of the base. Stiffness is measured using known methods.
• the rigidity is preferably a flexural modulus measured by a bending test (JIS K6921-2) or a tensile modulus measured by a tensile test (JIS K7161).
• the surface layer portion may have a single layer structure or a multilayer structure. When the surface layer has a multilayer structure, Gs means the rigidity of all the layers as one. The same applies to the base portion. The properties of the base portion and surface layer portion of the polymer molded body do not change before and after being bonded.
• the rigidities of the surface layer portion and the base portion before being bonded may be set as Gs and Gb, respectively.
• the base portion can be thermally bonded to the surface layer portion by injection molding such as insert molding.
• the rigidity of the base portion that is individually thermoformed without being thermally bonded to the surface layer portion may be set to Gb.
• the polymer molded body has a rigidity of preferably 1400 MPa or more, more preferably 1500 MPa or more, even more preferably 1600 MPa or more, even more preferably 1800 MPa or more, and particularly preferably 2000 MPa or more at 23° C., regardless of direction. Moreover, at 100° C., the polymer molded body preferably has a rigidity of 300 MPa or more, more preferably 500 MPa or more, regardless of direction. The upper limit of the rigidity of the polymer molded body is not limited, but is 5000 MPa or less at 23° C. regardless of the direction, and 2000 MPa or less at 100° C.
• Gs and Gb are set so that this stiffness can be achieved.
• Gs and Gb are the following, regardless of direction:
• the lower limit of Gs is preferably 2000 MPa or more, more preferably 2200 MPa or more, and even more preferably 2500 MPa or more.
• the upper limit of Gs is preferably 7000 MPa or less, more preferably 6000 MPa or less.
• the lower limit of Gs is preferably 500 MPa or more, more preferably 1000 MPa or more, and the upper limit is preferably 3000 MPa or less, more preferably 2000 MPa or less.
• the lower limit of Gb is preferably 1000 MPa or more, more preferably 1500 MPa or more, and the upper limit is preferably 5000 MPa or less, more preferably 3000 MPa or less.
• the lower limit of Gb is preferably 200 MPa or more, more preferably 300 MPa or more, and the upper limit is preferably 2000 MPa or less, more preferably 1500 MPa or less.
• Tms is the melting point of the surface layer at the joint with the base
• Tp is the molding temperature during thermal bonding.
• Tms is the melting point of the layer representing the joint with the base.
• the representative layer refers to a layer having the highest melting point among the plurality of layers or a layer having the highest weight ratio among the plurality of layers. Melting points are determined by known thermal analysis. It is preferable that the melting point is measured using, for example, DSC.
• Tms may be the melting point of the surface layer before being bonded.
• the condition of the surface layer may change before and after thermal bonding.
• the survival rate is used as an indicator of how much the surface layer retains its original state. The survival rate will be explained in detail later.
• Tp is the molding temperature during thermal bonding.
• Tp is the temperature of the base portion during molding.
• Tp is the temperature of the molten polymer for the base portion discharged from the nozzle of the molding machine. Tp can be measured using a thermocouple, infrared rays, or the like.
• the thickness of the surface layer is not limited, but if it is too thin, the rigidity and impact resistance will tend to be insufficient, and if it is too thick, it will be difficult to manufacture. From this viewpoint, the lower limit of the thickness is preferably 30 ⁇ m or more, more preferably 80 ⁇ m or more, and still more preferably 100 ⁇ m or more. The upper limit of the thickness is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and still more preferably 300 ⁇ m or less.
• the thickness of the base portion is adjusted as appropriate depending on the application, but from the viewpoint of ease of manufacture, it is preferably 5 to 250 times, more preferably 10 to 100 times, the thickness of the surface layer portion.
• the thickness of the polymer molded body is preferably 0.1 to 5 mm, more preferably 1 to 4 mm, and even more preferably 1.5 to 3.5 mm. In the present invention, thickness is defined as the average value of the member.
• peeling strength can be used as an index in one embodiment.
• the peeling strength is preferably 7N/15mm, more preferably 10N/15mm, still more preferably 100N/15mm or more. Peeling strength is determined by a 180 degree peel test at 23° C. using a strip-shaped test piece with a width of 15 mm. Although the upper limit of the peeling strength is not limited, it is preferably 200 N/15 mm or less.
• the distance between the grips is 50 mm
• the moving speed of the grips is 300 mm/min
• the tensile length is 100 mm
• the test value is the average value of the test force in a stable zone of 50 mm during material destruction.
• the base portion and surface layer portion may be composed of any polymer. However, in consideration of the affinity between the two, it is preferable that the base portion and the surface layer portion be made of the same type of polymer, and more preferably made of a polymer having the same repeating unit.
• polymers include polyolefins, engineering plastics, and superengineering plastics.
• Polyolefins include polypropylene and polyethylene.
• engineering plastics include polyesters such as PET.
• super engineering plastics include polyether sulfone and polyether ether ketone.
• the surface layer portion is preferably constructed of a stretched sheet-like member.
• the stretching may be uniaxial or multiaxial, preferably biaxial.
• the surface layer portion preferably has a multilayer structure including a biaxially stretched sheet layer L having a melting point Tml and a biaxially stretched sheet layer H having a melting point Tmh. However, Tmh>Tml. It is preferable that the biaxially stretched sheet layer L is in contact with the base portion.
• FIG. 1 is a surface layer part
• 10 is a base part
• 100 is a polymer molded body.
• H is a biaxially stretched sheet layer H
• L is a biaxially stretched sheet layer L.
• the surface layer portion includes alternating layers in which biaxially stretched sheet layers H and biaxially stretched sheet layers L are alternately laminated.
• the layer L becomes a bonding surface with the base portion.
• the layers of the surface layer 1 are fused and integrated. This can be confirmed by cross-sectional observation using a polarizing microscope, as described in International Publication No. 2020/075755.
• Surface layer At least a portion of all the layers of the surface layer portion 1 may be composed of coextruded layers in which biaxially stretched sheet layers H and biaxially stretched sheet layers L obtained by coextrusion are alternately laminated. . The manufacturing method will be described later.
• the total number of layers in the surface layer portion 1 is preferably 2 to 50. When the total number of layers is within this range, excellent moldability is exhibited.
• the thickness of the coextruded layer is preferably 0.04 to 0.50 mm.
• the total number of coextruded layers is preferably 1 to 6, more preferably 1 to 3.
• the total thickness (total thickness) of the biaxially stretched sheet layer L in the thickness of the surface layer 1 is not particularly limited, but from the viewpoint of ease of manufacture and cost, it is preferably 2 to 120 ⁇ m, more preferably 5 ⁇ m. -60 ⁇ m, more preferably 10-30 ⁇ m.
• the thickness of each layer may be the same or different. If the ratio of the total thickness of the layer L to the thickness of the surface layer portion (total thickness of layer L/thickness of the surface layer portion) is too small, the fusion properties between the layers of the multilayer sheet will be insufficient, and the value If is too large, the rigidity of the multilayer sheet will be insufficient.
• the total thickness of the layer L/thickness of the surface layer is preferably 1 to 50%.
• the thickness of each layer is then adjusted as appropriate to achieve the above ratio.
• the thickness of each biaxially stretched sheet layer H is preferably 20 to 300 ⁇ m.
• the thickness of each biaxially stretched sheet layer L is preferably 2 to 40 ⁇ m.
• the surface layer 1 is formed by preparing a plurality of multilayer sheets including biaxially stretched sheet layers L, arranging them so that the biaxially stretched sheet layers L are in contact with each other, and heat-sealing them. may be formed. In this case, the thickness of each biaxially stretched sheet layer L in the surface layer portion 1 is 4 to 80 ⁇ m.
• Tmh-Tml is not limited, it is preferably 1°C or higher, more preferably 10°C or higher, and even more preferably 25°C or higher. Further, Tmh-Tml is preferably 60°C or less. If the melting points of Tmh and Tml are too low, the rigidity and heat resistance of the surface layer 1 will be insufficient. From this viewpoint, Tmh is preferably 160°C or higher, more preferably 165°C or higher, and Tml is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. These melting points are obtained by measuring using DSC at a heating rate of 10°C/min from 30°C to 230°C.
• a functional group can be added to the layer constituting the surface layer portion 1. It is preferable to add a functional group to the outermost layer constituting the surface layer portion 1.
• the functional group is preferably an oxygen-containing functional group.
• the oxygen-containing functional group include a carboxyl group, a carboxylate group, an acid anhydride group, a hydroxyl group, an aldehyde group, and an epoxy group. These functional groups improve the adhesion between the surface layer portion 1 and other materials.
• the surface layer portion 1 may include a top layer other than the biaxially stretched sheet layers L and H on the outermost surface. This aspect is shown in FIG. In the figure, T is the top layer.
• the top layer is provided, for example, to impart design properties.
• the top layer is a coating used in car body painting. Examples of such coating films include epoxy coatings, urethane coatings, and polyester coatings. If necessary, a lower coating film (primer coating film), an intermediate coating film, or an upper coating film (clear coating film) may be provided.
• the surface to be coated has a functional group.
• the biaxially stretched sheet layer H is preferably composed of polypropylene resin (A).
• the polypropylene resin (A) consists of 100 to 50% by weight of component (A1) and 0 to 50% by weight of optional component (A2).
• component (A2) is more than 0% by weight
• component (A) is a so-called heterophase copolymer obtained by polymerizing component (A1) and polymerizing component (A2) in the presence of the component. (HECO), or a blend of component (A1) and component (A2) prepared by separate polymerization.
• component (A) is preferably HECO since component (A) can be obtained with fewer manufacturing steps.
• Component (A1) is a propylene (co)polymer containing 0 to 10% by weight of units derived from comonomers selected from C2 to C10 ⁇ -olefins (excluding C3 ⁇ -olefins). Comonomers selected from C2 to C10- ⁇ olefins are naturally free of C3- ⁇ olefins. When a comonomer is included, ethylene is preferred from the economic point of view. If the amount of the units derived from the comonomer exceeds the upper limit, the rigidity of the surface layer portion may decrease.
• component (A1) does not contain any comonomer-derived units, that is, it is a propylene homopolymer.
• component (A1) contains a unit derived from a comonomer, the amount thereof is preferably more than 0% by weight and not more than 1% by weight.
• the content of component (A1) in the polypropylene resin is 50 to 100% by weight. If the content of component (A1) is low, it may become difficult to produce a polypropylene resin, or the rigidity of the surface layer may decrease. Therefore, the content of component (A1) is preferably 60 to 100% by weight, more preferably 70 to 100% by weight.
• the MFR (230° C., load 2.16 kg) of the polypropylene resin (A) is 1 to 15 g/10 minutes. If the MFR exceeds the upper limit, it will be difficult to prepare a biaxially oriented polypropylene sheet-like member that is a raw material for the surface layer, and if it is less than the lower limit, the productivity of the polypropylene resin (A) will decrease. From this point of view, the lower limit of the MFR is preferably 2 g/10 minutes or more, more preferably 3 g/10 minutes or more, and the upper limit thereof is preferably 10 g/10 minutes or less, more preferably It is 8g/10 minutes or less.
• the optional component (A2) is an ethylene- ⁇ -olefin copolymer containing 10 to 90% by weight of ethylene-derived units. If the ethylene-derived unit is less than the lower limit or exceeds the upper limit, cold impact resistance will decrease. From this point of view, the content of ethylene-derived units is preferably 15 to 85% by weight, more preferably 20 to 80% by weight.
• the ⁇ -olefin is not limited as long as it is other than ethylene, but is preferably propylene, 1-butene, 1-hexene, or 1-octene, more preferably propylene or 1-butene, and even more preferably propylene. .
• the content of component (A2) in the polypropylene resin (A) is 0 to 50% by weight. If the content of component (A2) is too high, the productivity of the polypropylene resin (A) will decrease. Therefore, the content of component (A2) is preferably 0 to 40% by weight, more preferably 0 to 30% by weight.
• the polypropylene resin (A) may be a propylene random copolymer (RACO) containing 0 to 5% by weight of units derived from comonomers selected from C2 to C10 ⁇ -olefins (excluding C3 ⁇ -olefins). .
• RAO propylene random copolymer
• the biaxially stretched sheet layer H may be composed of a resin composition containing a nucleating agent.
• a nucleating agent is an additive (transparent nucleating agent) used to control the size of crystalline components in a resin to a small size and increase transparency. Therefore, the transparency of the biaxially stretched sheet layer H is improved by including the nucleating agent.
• the amount of the nucleating agent is preferably 0.5 parts by weight or less, more preferably 0.2 parts by weight or less, and more preferably 0.2 parts by weight or less, based on 100 parts by weight of the polymer forming the biaxially oriented sheet layer H. Preferably it is 0.1 part by weight or less.
• Nucleating agents are not particularly limited, and those commonly used in the field may be used, including nonitol-based nucleating agents, sorbitol-based nucleating agents, phosphate ester-based nucleating agents, triaminobenzene derivative nucleating agents, carboxylic acid metals, etc. It is preferably selected from salt nucleating agents and xylitol-based nucleating agents.
• the biaxially oriented sheet layer L is preferably made of propylene random copolymer (RACO) or It is formed from a resin composition containing the RACO. If the comonomer content of RACO is too low, the adhesiveness with the base part or the adhesiveness with other layers when the surface layer part is formed of multiple layers may not be sufficient. The rigidity of the multilayer sheet may decrease. From this point of view, the comonomer content is preferably more than 0% by weight and not more than 4.5% by weight. Ethylene (C2- ⁇ olefin) is preferred as the comonomer.
• RACO propylene random copolymer
• the MFR (230°C, load 2.16 kg) of the polymer or resin composition constituting the biaxially stretched sheet layer L is not limited, but is preferably 1 to 15 g/10 minutes, more preferably 2 to 10 g/10 minutes, More preferably, it is 3 to 8 g/10 minutes.
• the biaxially stretched sheet layer L may be composed of a resin composition containing a nucleating agent, or may be composed of a resin composition or a polymer that does not contain a nucleating agent.
• the amount of the nucleating agent is preferably 1 part by weight or less based on 100 parts by weight of the polymer forming the biaxially stretched sheet layer L from an economical viewpoint.
• the resin composition constituting the layer includes an antioxidant, a chlorine absorber, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an internal lubricant, an external lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, and a flame retardant. It may also contain conventional additives commonly used in polyolefins, such as dispersants, copper inhibitors, neutralizers, plasticizers, crosslinkers, peroxides, oil extenders and other organic and inorganic pigments. The amount of each additive added may be a known amount.
• synthetic resins or synthetic rubbers other than polypropylene may be contained within a range that does not impair the effects of the present invention.
• the synthetic resin or synthetic rubber may be one type or two or more types.
• Base part is composed of the above-mentioned polymer, but is preferably composed of the same type of polymer as the surface layer part, more preferably composed of a polymer having the same repeating unit, and is composed of polypropylene resin. It is more preferable that
• the biaxially stretched sheet layer H contains a polypropylene resin (A) and a plate-shaped inorganic filler (B), component (B)/[component (A) + It is composed of a resin composition in which the weight ratio of component (B) is more than 0% by weight and not more than 60% by weight.
• the surface layer portion in this embodiment preferably has a multilayer structure in which biaxially stretched sheet layers H and biaxially stretched sheet layers L are alternately laminated.
• the biaxially stretched sheet layer H is also referred to as "filler layer F”
• the biaxially stretched sheet layer L is also referred to as "neat layer N”. Since the layers are fused together, the surface layer is integrated.
• FIG. 1 is a surface layer part
• 10 is a base part
• F and N are a filler layer F and a neat layer N, which correspond to the biaxially oriented sheet layer H and the biaxially oriented sheet layer L, respectively, in the above-mentioned first embodiment. Equivalent to.
• the filler layer F in the surface layer portion is derived from a biaxially stretched polypropylene sheet member for the layer, and the neat layer N is derived from the biaxially stretched polypropylene sheet member for the layer.
• Each layer may be composed of independent sheet-like members. Details of the surface layer portion are shown in FIG. 3A.
• 1' is a precursor described later. The layers of the precursor 1' are fused to form the surface layer 1.
• At least a portion of all the layers may be composed of coextruded layers in which filler layers F and neat layers N obtained by coextrusion are alternately laminated.
• C indicates a coextrusion layer, and for example, C[N/F] is a coextrusion layer having two layers, a neat layer N and a filler layer F.
• the surface layer portion 1 is formed from a precursor 1' in which three sheets of C[N/F/N] exist between C[F/N] and C[N/F].
• the thickness of each C may be the same or different. Furthermore, the thicknesses of the layers constituting each C may be the same or different.
• the total number of layers in the surface layer ranges from 2 to 50. When the total number of layers is within this range, excellent moldability is exhibited. In the embodiment of FIG. 3B, the total number of layers in the surface layer portion is eleven. Further, in embodiments including a coextruded layer, the thickness of the coextruded layer is preferably 0.04 to 0.50 mm. The total number of coextruded layers is preferably 2 to 6, more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 to 3. The thickness of the coextruded layer refers to the overall thickness of C (represented by t in FIG. 3B). In the case of FIG. 3B, the total number of coextruded layers is five.
• the ratio is preferably 1 to 30, more preferably 1 to 25, and even more preferably 4 to 15.
• the thickness of each layer may be the same or different. The thickness of each layer is adjusted as appropriate so that the ratio falls within the range.
• the thickness of each filler layer F is preferably 50 ⁇ m to 200 ⁇ m.
• the thickness of each neat layer N is preferably 5 ⁇ m to 40 ⁇ m.
• TmF of the filler layer F and the melting point TmN of the neat layer N satisfy the relationship TmF>TmN. That is, Tmh in the first aspect corresponds to TmF, and Tml corresponds to TmN.
• TmF-TmN is not limited, the temperature is preferably 1°C or higher, more preferably 10°C or higher, and even more preferably 25°C or higher. Furthermore, the temperature of TmF-TmN is preferably 60°C or lower. If their melting points are too low, the multilayer sheet will have insufficient rigidity and heat resistance.
• TmF is preferably 160°C or higher, more preferably 165°C or higher
• TmN is preferably 100°C or higher, more preferably 120°C or higher, and still more preferably 130°C or higher.
• Filler layer F is formed from a resin composition containing component polypropylene resin (A) and inorganic filler (B).
• the polypropylene resin (A) is as described above.
• the inorganic filler (B) is added mainly for the purpose of improving the rigidity of the material.
• examples of inorganic fillers include the following from the viewpoint of substances. Natural silicic acid or silicates such as talc, kaolinite, clay, birophyllite, selinite, wollastonite, and mica; Synthetic silicic acid or silicates such as hydrated calcium silicate, hydrated aluminum silicate, hydrated silicic acid, and anhydrous silicic acid; Precipitated carbonic acid Carbonates such as calcium, heavy calcium carbonate and magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; oxides such as zinc oxide and magnesium oxide.
• examples of the inorganic filler include the following. Powdered fillers such as synthetic silicic acids or silicates such as hydrated calcium silicate, hydrated aluminum silicate, hydrated silicic acid, and anhydrous silicic acid; Platy fillers such as talc, kaolinite, clay, and mica; Basic magnesium sulfate whiskers, titanic acid Whisker-like fillers such as calcium whiskers, aluminum borate whiskers, sepiolite, PMF (Processed Mineral Filler), xonotlite, potassium titanate, and elastadite; Ball-like fillers such as glass balloons and fly ash balloons; Fibrous fillers such as glass fibers Filling material.
• Powdered fillers such as synthetic silicic acids or silicates such as hydrated calcium silicate, hydrated aluminum silicate, hydrated silicic acid, and anhydrous silicic acid
• Platy fillers such as talc, kaolinite, clay, and mica
• the inorganic filler may be surface-treated as necessary.
• the inorganic filler used in the present invention is not limited, a plate-shaped inorganic filler is preferable from the viewpoint of increasing rigidity and impact resistance by promoting orientation of polypropylene crystals in the filler layer F in the direction along the sheet surface.
• Known materials such as talc, kaolinite, clay, and mica can be used as the plate-shaped inorganic filler, but talc is preferable in consideration of its affinity with polypropylene resin, ease of procurement as a raw material, and economic efficiency. , mica, and more preferably talc.
• the volume average particle diameter of the plate-shaped inorganic filler is preferably 1 to 10 ⁇ m, more preferably 2 to 7 ⁇ m.
• the volume average particle diameter is less than the lower limit, the rigidity of the filler layer F may become low.
• the volume average particle diameter exceeds the above upper limit, breakage is likely to occur during stretching, making it difficult to prepare a biaxially stretched sheet-like member that is a raw material for a multilayer sheet.
• the volume average particle diameter can be measured as a 50% diameter in a volume-based integrated fraction by a laser diffraction method (based on JIS R1629).
• the neat layer N is formed from a resin composition containing a polypropylene resin as component (A) and optionally the component (B).
• Component (A) here is selected so as to satisfy the above relationship between TmF and TmN, and is preferably a propylene homopolymer (HOMO) or a C2 to C10- ⁇ olefin (however, a C3- ⁇ olefin) of 5% by weight or less.
• HOMO propylene homopolymer
• REO propylene random copolymer
• the amount of comonomer-derived units is preferably more than 0% by weight and not more than 10% by weight.
• Ethylene (C2- ⁇ olefin) is preferred as the comonomer.
• the MFR (230°C, load 2.16 kg) of the polymer or resin composition constituting the neat layer N is preferably 1 to 15 g/10 minutes, more preferably 2 to 10 g/10 minutes, and even more preferably 3 to 8 g/10 minutes. It's 10 minutes. If the MFR is too small, the productivity of the polypropylene resin as a raw material will decrease, and if it is too large, breakage will occur during biaxial stretching, making it impossible to stably produce a multilayer sheet as a raw material for the surface layer.
• the weight ratio is preferably 8% by weight or less.
• the weight ratio is more preferably 5% by weight or less, further preferably 1% by weight or less, particularly preferably 0.5% by weight or less, and most preferably 0.5% by weight or less. is 0% by weight.
• the weight ratio in the neat layer N is smaller than the weight ratio in the filler layer F.
• the filler layer F and the neat layer N may contain the above-mentioned nucleating agent or additive.
• the residual rate is an index of how much the surface layer retains its original state before and after thermal bonding.
• the residual rate is measured by a known analytical method such as DSC, X-ray diffraction, or density method.
• DSC X-ray diffraction
• density method For example, when using DSC, it can be expressed by the area ratio of each melting component in a DSC chart obtained from a portion in contact with the base portion and a portion not in contact with the surface.
• the survival rate R regarding higher-order structure is defined as ⁇ Hin/ ⁇ Hout.
• ⁇ Hout is the amount of heat determined by DSC analysis of the near-surface portion of the surface layer portion of the polymer molded body.
• ⁇ Hout is an index of the state of the higher-order structure before thermal bonding. Specifically, ⁇ Hout is measured by the following means. 1) A 10 to 50% thick portion is sampled from the surface of the surface layer on the opposite side from the base portion. 2) The collected sample is subjected to DSC analysis under elevated temperature conditions to determine the amount of heat (J/g) in the range of ⁇ 5° C. of the melting point in the melting profile, which is defined as ⁇ Hout.
• the amount of heat (J/g) in the range of Tmh ⁇ 5° C. is representatively expressed as ⁇ Hout.
• Melting point is the peak top temperature in the melting profile.
• ⁇ Hin is the amount of heat determined by DSC analysis of the surface portion of the polymer molded article near the interface.
• ⁇ Hin is an index of the state of the higher-order structure after thermal bonding. Specifically, ⁇ Hin is measured by the following means. 1) Take a 10 to 50% thick portion of the surface layer from the interface with the base portion. 2) The collected sample is subjected to DSC analysis under elevated temperature conditions to determine the amount of heat (J/g) in the range of ⁇ 5° C. of the melting point in the melting profile, which is defined as ⁇ Hin.
• the amount of heat (J/g) in the range of Tmh ⁇ 5° C. is representatively expressed as ⁇ Hin.
• R ⁇ Hin/ ⁇ Hout
• the value of the residual rate is not limited, it is preferably 60 to 100%, and the lower limit thereof is more preferably 70% or more, 80% or more, 90% or more, or 95% or more.
• the value of ⁇ Hin is not limited, but is preferably 5 to 8 J/g.
• the polymer molded article comprises a step 1 of preparing the surface layer portion, and a step 2 of thermoforming a raw material for the base portion to form the base portion and thermally bonding the surface layer portion to the surface thereof.
• a manufacturing method Preferably, it is manufactured by a manufacturing method.
• Process 1 This step will be explained using the above-mentioned second preferred embodiment as an example.
• the manufacturing method and multilayer sheet are disclosed in PCT/JP2021/041525. The contents of this document are incorporated herein by reference.
• the multilayer sheet includes a step i of preparing a precursor in which a filler layer F and a neat layer N are laminated so that the filler layers F are not adjacent to each other, and a heating body is brought into contact with the outermost layer of the precursor. It is preferable that the sheet be manufactured by a method including step ii of heating and fusing the layers of the sheet.
• the melting point TmF of the filler layer F and the melting point TmN of the neat layer N satisfy the relationship TmF>TmN, and preferably satisfy the relationship TmF ⁇ TmN ⁇ 1 (° C.).
• f and n are resin compositions that will ultimately constitute layer F and layer N.
• F" and N" are unstretched sheets (original sheets) that will eventually constitute layer F and layer N.
• F' and N' are biaxially stretched sheet-like members that ultimately constitute layer F and layer N.
• 1' is a precursor, 1 is a multilayer sheet, F is a filler layer, and N is a neat layer.
• 2 is an unstretched sheet preparation process
• 3 is a stretching process
• 4 is a lamination process
• 5 is an interlayer fusion process.
• the melting points Tmf and Tmn of the resin composition, the melting points TmF'' and TmN'' of the unstretched sheet, the melting points TmF' and TmN' of the biaxially stretched sheet member, and the melting points TmF and TmN of the layer have the following relationships.
• Tmf TmF”
• Tmn TmN”
• the precursor is prepared.
• a part of the layers constituting the precursor may be composed of the above-mentioned coextrusion layer. All layers of the precursor are unfused or some are fused.
• a biaxially oriented polypropylene sheet member F' for the filler layer F and a biaxially oriented polypropylene sheet member N' for the neat layer N are separately prepared and then laminated alternately.
• the precursor 1' can be prepared by laminating N'/F'/N'/.../N'. In this case, it is preferable that all the layers are not fused.
• biaxially oriented polypropylene sheet-like members F' and N' are prepared separately, and the precursor 1' is prepared by laminating them alternately. In this case, it is preferable that all the layers are not fused, but one or some of the layers may be fused. From the viewpoint of improving thermal adhesion with the base portion of the sheet obtained, at least one of the outermost layers is preferably a biaxially stretched polypropylene sheet member N'.
• the biaxially stretched polypropylene sheet-like member N' can be prepared by a known method. For example, it is possible to prepare a raw sheet (unstretched polypropylene sheet-like member N'') from the raw material resin composition n, and then biaxially stretch this using a known method to obtain a biaxially-stretched polypropylene sheet-like member N'.
• the thickness of the raw sheet is preferably more than 0.15 mm, and the upper limit is not limited, but from the viewpoint of ease of handling, it is preferably 6 mm or less.
• the temperature during biaxial stretching is not limited, but ( It is preferably in the range of TmN"-10°C) to TmN".
• the thickness of the raw sheet is preferably more than 0.15 mm, and although the upper limit is not limited, it is preferably 6 mm or less from the viewpoint of ease of handling. Further, the stretching ratio is preferably 4 to 8 times per axis from the viewpoint of rigidity.
• the magnification on one axis and the magnification on the other axis may be the same or different. Both axes are preferably orthogonal.
• step ii can be omitted or simplified.
• FIG. 5 shows a mode of simplification. Specifically, a raw material for layer F and a raw material for layer N are coextruded to prepare a coextruded raw sheet C'' having a plurality of layers, and this is biaxially stretched to form a coextruded biaxially stretched sheet. A member C' is prepared. The temperature V at which the coextruded raw sheet C'' is biaxially stretched is preferably selected so as to satisfy the above relationship.
• a precursor 1' is prepared by laminating the coextruded biaxially oriented sheet members C' or the coextruded biaxially oriented sheet member C' and the above-mentioned biaxially oriented sheet member F' or N'. do.
• the total number of coextruded layers in the precursor 1' is not limited, but is preferably 2 to 6.
• the thickness of the coextruded biaxially stretched sheet member C' is preferably 0.01 to 0.50 mm, more preferably 0.02 to 0.50 mm.
• Each of the single layer biaxially oriented sheet member and the coextruded biaxially oriented sheet member can be placed in any direction. Depending on this placement, the orientation direction within the plane of the multilayer sheet can be adjusted.
• Step ii In this step (5 in FIGS. 4 and 5), a heating element is brought into contact with the outermost layer of the multilayer sheet precursor 1' to thermally fuse each layer.
• the temperature T preferably satisfies the relationship Tmh ⁇ T ⁇ Tml (TmF ⁇ T ⁇ TmN), and more preferably satisfies the relationship Tmh ⁇ T ⁇ Tml+10 (°C) (TmF ⁇ T ⁇ TmN+10 (°C)). . If T exceeds the upper limit, the laminate may melt and its mechanical properties may deteriorate. Furthermore, if T is less than the lower limit, the layers may not be sufficiently fused and the mechanical properties may deteriorate.
• the specific temperature of the heating body is preferably about 120 to 190°C, more preferably 140 to 170°C, and even more preferably 150 to 165°C.
• T can be measured by any method, it is preferably measured using a non-contact thermometer such as a radiation thermometer.
• the melting point is defined as the peak temperature of a melting curve obtained by measuring by DSC from 30°C to 230°C at a heating rate of 10°C/min.
• This step is preferably carried out continuously using a heating roll as a heating body.
• the multilayer sheet precursor is passed between two heated rolls to fuse the layers.
• Two rolls may be made into one set, and a heating roll made by combining two or more sets of rolls may be used as a heating body for fusing.
• the pressure applied at this time is adjusted as appropriate.
• the take-up speed in the roll forming is not limited, but is preferably about 0.05 to 10 m/min.
• Examples of methods other than roll molding include pressure molding and fusion molding. Further, when heat-sealing the sheet-like member, it is preferable to apply pressure to suppress thermal shrinkage and further promote orientation. The pressure at that time is adjusted according to the fusion temperature.
• the manufacturing method of the present invention may further include known steps such as cooling the multilayer sheet obtained in the previous step.
• the cooling method is not limited, but examples include a method of allowing it to cool at room temperature and a method of cold pressing at room temperature or 10 to 20°C.
• the raw material for the base part is thermoformed to form the base part, and the surface layer part is thermally bonded to the surface of the base part.
• Thermoforming includes, but is not limited to, injection molding, press molding, and vacuum forming. Among these, injection molding is preferable, so this process will be described below using injection molding as an example with reference to FIG.
• 90 is an injection molding machine
• 92 is a mold
• 1 is a multilayer sheet
• 10' is a molten polymer forming the base part.
• the multilayer sheet 1 is placed in the cavity of a mold.
• the mold is closed, a molten polymer constituting the base portion is injected into the mold, and the surface layer portion and the base portion are thermally bonded.
• the molding conditions are appropriately adjusted depending on the polymer used, and are appropriately adjusted so that Tms ⁇ Tp and, if necessary, the residual ratio R ( ⁇ Hin/ ⁇ Hout) ⁇ 60% is satisfied.
• the cylinder temperature of the molding machine can be about 180 to 250°C, and the mold temperature can be about 30 to 60°C.
• Tp is the temperature of the molten polymer for the base portion discharged from the nozzle of the molding machine, and can be set at 180 to 250°C. This molding method is also called insert molding.
• the surface layer of the polymer molded product has a high degree of orientation in the in-plane direction and a specific higher-order structure, and the dependence of the degree of orientation in the thickness direction is small, so it has excellent mechanical properties while being lightweight. It has particularly excellent rigidity and scratch resistance. Further, when the surface layer portion includes the filler layer F, the layer has easy peelability. Therefore, when the surface layer portion includes a top layer, the top layer can be easily peeled off from the polymer molded article, and the recyclability is also excellent. Therefore, since the polymer molded body has excellent recyclability, rigidity, and scratch resistance, it can be used as a substitute for steel plates for automobile parts, electric/electronic parts, housing members, and the like.
• polymer molded article is useful as a food packaging material, a container, a lid, etc., which has a thinner wall, reduced weight, and has excellent opening properties.
• polymer molded bodies have high rigidity, they are useful as miscellaneous goods, daily necessities, home appliance parts, toy parts, furniture parts, building material parts, packaging parts, industrial materials, distribution materials, agricultural materials, and the like.
• the polymer molded body has the above-mentioned rigidity.
• the polymer molded body preferably has a surface impact strength of 5 J/mm or more, more preferably 7 J/mm or more, and still more preferably 9 J/mm or more (-30°C, JIS K7211 -2).
• the scratch resistance test a sample is scratched and evaluated based on the width of the scratch.
• the wounding conditions are as follows. Scratching speed: 100 min/m, load: 10 N, tip diameter: 1.0 mm, scratch length: 50 mm.
• a biaxially-stretched sheet-like member was prepared as follows.
• Polymer 1 A solid catalyst used for polymerization was prepared by the method described in Example 1 of European Patent No. 674,991. The solid catalyst has Ti and diisobutyl phthalate as an internal donor supported on MgCl 2 by the method described in the above patent publication.
• the solid catalyst (1), triethylaluminum (TEAL) and dicyclopentyldimethoxysilane (DCPMS) were mixed in amounts such that the weight ratio of TEAL to the solid catalyst was 11 and the weight ratio of TEAL/DCPMS was 10, and -5 The contact was carried out for 5 minutes at °C.
• TEAL triethylaluminum
• DCPMS dicyclopentyldimethoxysilane
• Prepolymerization was carried out by holding the resulting catalyst system in suspension in liquid propylene at 20° C. for 5 minutes. After introducing the obtained prepolymerized product into a polymerization reactor, hydrogen and propylene were fed, the polymerization temperature and hydrogen concentration were set to 75°C and 0.15 mol%, respectively, and the pressure was adjusted to produce a propylene homopolymer. Polymer 1 was obtained.
• [Resin composition (e)] (talc-containing resin composition) 60 parts by weight of Polymer 1, 40 parts by weight of talc (Neotalc UNI05 manufactured by Neolite Kosan Co., Ltd. (volume average particle diameter measured by laser diffraction method: 5 ⁇ m), and 0 parts of antioxidant (B225 manufactured by BASF). .2 parts by weight and 0.05 parts by weight of a neutralizing agent (calcium stearate manufactured by Tannan Kagaku Kogyo Co., Ltd.) were mixed by stirring for 1 minute using a Henschel mixer. NVC ⁇ 50 mm single screw extrusion manufactured by Nakatani Kikai Co., Ltd.
• the mixture was melt-kneaded using a machine at a cylinder temperature of 230°C, and the extruded strands were cooled in water and then cut with a pelletizer to obtain pellet-shaped resin composition (e).
• Resin composition (e) The MFR (temperature 230°C, load 2.16 kg) was 4.6 g/10 minutes.
• Polymer 2-1 was obtained as a propylene-ethylene copolymer.
• Resin composition (b1) For 100 parts by weight of polymer 2-1, 0.2 parts by weight of an antioxidant (B225 manufactured by BASF) and 0.05 parts by weight of a neutralizing agent (calcium stearate manufactured by Tannan Kagaku Kogyo Co., Ltd.) , and 0.25 parts by weight of a nonitol-based nucleating agent (Millad NX8000J manufactured by Milliken) were mixed by stirring for 1 minute using a Henschel mixer.
• an antioxidant B225 manufactured by BASF
• a neutralizing agent calcium stearate manufactured by Tannan Kagaku Kogyo Co., Ltd.
• a nonitol-based nucleating agent Melad NX8000J manufactured by Milliken
• the mixture was melt-kneaded at a cylinder temperature of 230°C using an NVC ⁇ 50mm single-screw extruder manufactured by Nakatani Kikai Co., Ltd., and the extruded strands were cooled in water and then cut with a pelletizer to obtain pellet-shaped resin composition (b1). Obtained.
• the resin composition (b1) contained 1.7% by weight of ethylene-derived units and had an MFR (temperature of 230° C., load of 2.16 kg) of 4.9 g/10 minutes.
• Polymer 2-2 was obtained as a propylene-ethylene copolymer.
• Resin composition (b2) For 100 parts by weight of Polymer 2-2, 0.2 parts by weight of an antioxidant (B225 manufactured by BASF) and 0.05 parts by weight of a neutralizing agent (calcium stearate manufactured by Tannan Kagaku Kogyo Co., Ltd.) The mixture was blended by stirring with a Henschel mixer for 1 minute. The mixture was melt-kneaded at a cylinder temperature of 230°C using an NVC ⁇ 50mm single-screw extruder manufactured by Nakatani Kikai Co., Ltd., and the extruded strands were cooled in water and then cut with a pelletizer to obtain pellet-shaped resin composition (b2). Obtained.
• the resin composition (b2) contained 4.0% by weight of ethylene-derived units, and had an MFR (temperature of 230° C., load of 2.16 kg) of 7.5 g/10 minutes.
• Resin composition (a) For 100 parts by weight of polymer 3, 0.2 parts by weight of B225 manufactured by BASF as an antioxidant, 0.05 parts by weight of calcium stearate manufactured by Tannan Kagaku Kogyo Co., Ltd. as a neutralizing agent, and nonitol-based 0.05 parts by weight of a nucleating agent (Millad NX8000J manufactured by Milliken) was added and mixed by stirring for 1 minute using a Henschel mixer. The strands were melt-kneaded using an NVC extruder manufactured by Nakatani Kikai Co., Ltd.
• pellet-shaped resin composition (a) contained 0.36% by weight of ethylene-derived units and had an MFR (temperature of 230° C., load of 2.16 kg) of 4.4 g/10 minutes.
• Biaxially stretched sheet LHL50 A coextruded biaxially stretched sheet LHL50 having a thickness of 0.05 mm was obtained in the same manner as the biaxially stretched sheet LHL100. However, the magnification of the sequential biaxial stretching was 5 times x 8 times. The thickness ratio was 1/18/1.
• the raw sheet was simultaneously biaxially stretched (3 times x 3 times) at 165°C using a film stretching device (KARO-IV manufactured by Bruckner) to obtain a coextruded biaxially stretched sheet NFN150 with a thickness of 0.15 mm. Obtained.
• the thickness ratio was 1/18/1.
• Example 1 An EC160N II injection molding machine manufactured by Toshiba Machine Co., Ltd. was equipped with a mold having a cavity of 150 mm x 300 mm x 2.5 mm thick and a film gate. The mold temperature was 40° C., and a biaxially stretched sheet LHL100 was placed on one inner surface (150 mm ⁇ 300 mm) of the cavity. Next, polypropylene (manufactured by Sun Allomer Co., Ltd., YC582P) was injected into the cavity to perform insert molding. In this way, a polymer molded article was produced, which included a base portion and a surface layer portion (biaxially stretched sheet LHL100) thermally bonded onto the base portion. The molded article was evaluated as shown in Table 1.
• Tp (resin temperature during thermal bonding) was 210°C.
• the cross section of the molded product was cut after thermal bonding to obtain a section Sin having a thickness of about 30% from the interface between YC582P and the surface layer toward the surface. Further, a section Sout having a thickness of about 30% was obtained from the surface of the surface layer toward the interface. DSC analysis was performed on these sections, and the residual rate R was measured by the method described below. The survival rate R was 95%.
• the molding conditions were as follows. Cylinder temperature: 180-240°C Mold temperature: 40°C Injection time: 15 seconds Cooling time: 25 seconds
• Example 2 The same method as in Example 1 except that biaxially stretched sheet LHL30 was used instead of biaxially stretched sheet LHL100, the thickness of the mold cavity was changed to 3 mm, and the resin temperature was changed as shown in Table 1. Polymer molded bodies were produced and evaluated.
• Example 3 A polymer molded article was produced and evaluated in the same manner as in Example 1, except that biaxially stretched sheet LHL30 was used instead of biaxially stretched sheet LHL100, and the thickness of the mold cavity was changed to 3 mm.
• Example 4 Polymer molded bodies were manufactured and evaluated in the same manner as in Example 3, except that the resin temperature was changed as shown in Table 1.
• Example 5 A polymer molded body was produced and evaluated in the same manner as in Example 3, except that biaxially stretched sheet LHL50 was used instead of biaxially stretched sheet LHL30.
• Example 6, 7 Two precursors were prepared by stacking two and three biaxially stretched sheets LHL50. Using a press molding machine manufactured by Shoji Co., Ltd. heated to 160° C. as a heating element, each layer of each precursor was heat-fused to produce a multilayer sheet as a laminate. During pressing, both sides of the precursor were inserted between an aluminum plate with a thickness of 3 mm and a steel plate with a thickness of 1 mm from the outside, and pressurized at 4 MPa for 2 minutes. Multilayer sheets of 0.1 and 0.15 mm thickness were thus produced and evaluated. Using the multilayer sheet instead of the biaxially stretched sheet LHL30, polymer molded bodies were produced and evaluated in the same manner as in Example 3.
• Example 8 9 Polymer molded bodies were manufactured and evaluated in the same manner as in Examples 5 and 6, except that biaxially stretched sheet LHL200 was used instead of biaxially stretched sheet LHL50.
• Example 10 A polymer molded article was produced and evaluated in the same manner as in Example 3, except that biaxially stretched sheet NFN150 was used instead of biaxially stretched sheet LHL30.
• Example 11 A precursor was prepared by stacking 19 sheets of LHL50 and further stacking NFN150 on the top layer. Using a press molding machine manufactured by Shoji Co., Ltd. heated to 160° C. as a heating element, each layer of the precursor was heat-fused to produce a multilayer sheet as a laminate. During pressing, both sides of the precursor were inserted between an aluminum plate with a thickness of 3 mm and a steel plate with a thickness of 1 mm from the outside, and pressurized at 4 MPa for 2 minutes. In this way, a 1.1 mm thick multilayer sheet was produced. A polymer molded product was produced in the same manner as in Example 3, except that the multilayer sheet obtained as described above was placed in place of the biaxially stretched sheet LHL30 so that the top layer faced the inner surface of the cavity of the mold. was manufactured and evaluated.
• Example 12 Polymer molded bodies were manufactured and evaluated in the same manner as in Example 3, except that the resin temperature was changed as shown in Table 1.
• Example 3 A polymer molded article was produced and evaluated in the same manner as in Example 3, except that the unstretched sheet LHL_U was used.
• a polymer molded body having the thickness shown in Table 1 was processed into a width of 10 mm and a length of 80 mm to obtain a measurement test piece (type B2).
• a precision universal testing machine Autograph AG-X10kN manufactured by Shimadzu Corporation, bending of a type B2 measurement specimen was performed under the conditions of temperature 23°C, relative humidity 50%, distance between supports 48mm, and test speed 2mm/min. The elastic modulus was measured. The measurement was performed by applying an indenter from the surface side.
• the polymer molded body was processed into a square of 70 ⁇ 2 mm to obtain a test piece for measurement.
• a test piece for measurement was placed on a support stand with a hole with an inner diameter of 40 mm ⁇ in a tank adjusted to -30°C.
• the specimen was struck with a striker with a diameter of 20.0 ⁇ 0.2 mm ⁇ and a hemispherical striking surface at an impact speed of 4.4 ⁇ 0.2 m/sec, and various energies ( J) and fracture behavior were determined.
• the average value of the puncture energy of each of the four measurement test pieces was defined as the impact strength.
• Impact fracture behavior_Fracture type was determined as YD/YS/YU/NY according to JIS K7211-2 using test pieces whose impact strength was measured under the above conditions.
• Maximum impact force energy Energy (J) expended to reach the displacement representing the maximum impact force F M that occurs during the test. Puncture energy: Energy expended until the displacement reaches the point where the maximum impact force F M is reduced by half (J)
• Total energy Energy expended from the start of the test until the impact force reaches zero displacement (J)
• Melting point by DSC (Tms, Tmh, Tml) Approximately 5 mg was sampled and weighed using an electronic balance, and then held at 30°C for 5 minutes using a differential thermal analyzer (DSC) (Q-200 manufactured by TA Instruments), and then heated at a heating rate of 10°C/min to 230°C. The melting curve was obtained by heating to °C. The peak temperature of the melting curve was taken as the melting point. When determining the heat of fusion ⁇ H using the above melting curve, it was calculated from the area of the melting peak in a predetermined temperature range on the baseline after complete melting in the baseline corrected melting profile.
• DSC differential thermal analyzer
• Tms Melting point
• Survival rate R ( ⁇ Hin/ ⁇ Hout) 1) A 10 to 50% thick portion was sampled from the surface of the surface layer on the opposite side from the base portion. 2) The sample collected in 1) above was subjected to DSC analysis under elevated temperature conditions, and the amount of heat (J/g) in the range of Tmh ⁇ 5°C was determined as ⁇ Hout. The melting point was defined as the peak top temperature in the melting profile. 3) A 10 to 50% thick portion of the surface layer was sampled from the interface with the base portion. 4) The sample collected in 3) above was subjected to DSC analysis under the above temperature increasing conditions, and the amount of heat (J/g) in the range of Tmh ⁇ 5°C was determined as ⁇ Hin.

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