WO2009110601A1 - Film for laminating for thermoforming sheet - Google Patents

Film for laminating for thermoforming sheet Download PDF

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Publication number
WO2009110601A1
WO2009110601A1 PCT/JP2009/054315 JP2009054315W WO2009110601A1 WO 2009110601 A1 WO2009110601 A1 WO 2009110601A1 JP 2009054315 W JP2009054315 W JP 2009054315W WO 2009110601 A1 WO2009110601 A1 WO 2009110601A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
gloss
sheet
container
Prior art date
Application number
PCT/JP2009/054315
Other languages
French (fr)
Japanese (ja)
Inventor
直彦 倉本
昌也 石丸
智康 大田
Original Assignee
サン・トックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by サン・トックス株式会社 filed Critical サン・トックス株式会社
Priority to CN200980102582.1A priority Critical patent/CN101909889B/en
Priority to JP2010501979A priority patent/JP5568809B2/en
Priority to KR1020107016519A priority patent/KR101347489B1/en
Publication of WO2009110601A1 publication Critical patent/WO2009110601A1/en

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Classifications

    • 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
    • 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
    • B29C51/02—Combined thermoforming and manufacture of the preform
    • 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
    • B29C51/14—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 using multilayered preforms or sheets
    • 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
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12—Thermoplastic materials
    • 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
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0022—Bright, glossy or shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/007—Narrow strips, e.g. ribbons, tapes, bands

Definitions

  • the present invention relates to a novel film for laminating a thermoformed sheet. More specifically, the present invention is excellent in lamination suitability when laminated on a resin sheet as a base of a thermoformed sheet.
  • the present invention relates to a thermoformed sheet laminating film capable of imparting excellent gloss to a thermoformed product obtained by thermoforming.
  • polyolefin sheets especially resin sheets such as polypropylene sheets and foamed polypropylene sheets that have high heat resistance due to the widespread use of microwave ovens, are used for food packaging containers such as lunch boxes, trays, and bowl containers. Yes.
  • a polypropylene-based film on which printing has been performed is bonded to these resin sheets for the purpose of improving design and giving a high-class feeling.
  • an unstretched polypropylene film hereinafter referred to as CPP film
  • OPP film biaxially stretched polypropylene film
  • the CPP film is excellent in thermoformability, it is possible to handle the production of a thermoformed article such as a deep-drawn container, but when adopting an extrusion laminating method that can be produced at the lowest cost in bonding with a sheet, Since there is a problem that the gloss of the CPP film is lost after laminating and the thermoformed product after thermoforming the laminate sheet is inferior in surface gloss, improvement thereof is desired.
  • thermoforming conditions are limited, and thermoforming when obtaining thermoformed bodies such as some deep drawn containers There is a problem of inferiority.
  • thermoformed bodies are generally manufactured by a thermoforming method such as vacuum forming or pressure forming.
  • This thermoforming method is a method in which a resin sheet is heated with an infrared heater or the like, and then the sheet is brought into close contact with a mold by an external force such as mechanical force, vacuum, or compressed air.
  • the following studies have been made.
  • a method has been proposed in which an unstretched polypropylene resin film in which a crystal nucleating agent is blended with a polypropylene resin is laminated on at least one surface of a polypropylene resin foam sheet (see Patent Document 1).
  • the polypropylene resin of the unstretched polypropylene resin film is a polypropylene homopolymer (homopolypropylene).
  • the gloss after thermoforming is improved to some extent, but there is a feeling of cloudiness on the surface, and there is room for improvement in this respect.
  • a sheet made of a resin composition in which a crystal nucleating agent is blended with two types of polypropylene resins having specific crystal melting points has been proposed as a resin sheet for thermoforming (see Patent Document 2).
  • an ethylene polymer using a metallocene catalyst system in a specific density, MFR propylene polymer, and a nucleating agent are blended in the surface layer, and a specific MFR propylene / ⁇ -olefin random copolymer, a nucleating agent Has been proposed (see Patent Document 3).
  • the above-mentioned technique has a problem in that although the gloss is improved in the obtained thermoformed article, the surface is cloudy.
  • the gloss of a thermoformed article is a glossy container if the gloss value measured by the 60-degree specular method in accordance with JIS K7105 is 65% or more, and 75% If it is above, it can be said that it is a gloss container with higher commercial value. However, even if the container has a high gloss value, if the container surface has a large cloudiness, the container surface appears whitish and turbid.
  • thermoforming a sheet a phenomenon in which the colored color or pattern of the laminated film having a large cloudiness is not clearly captured occurs.
  • the object of the present invention is to obtain a film laminated on a resin sheet as a base of a thermoforming sheet, which is excellent in laminating suitability when laminated on a resin sheet, and is obtained by thermoforming a thermoformed sheet laminated thereon.
  • An object of the present invention is to provide a film for laminating a thermoformed sheet that is excellent in surface gloss and that can give a thermoformed body with low white turbidity.
  • the present inventors have intensively studied to achieve the above object. As a result, a substantially unstretched polypropylene in which a base layer obtained by adding an organic crystal nucleating agent to a specific propylene homopolymer and a glossy layer obtained by adding an organic crystal nucleating agent to a propylene random copolymer are formed with a specific thickness.
  • the present inventors have found that a system film can achieve all of the above problems, and have completed the present invention.
  • the present invention for solving the above problems includes the following matters as a gist.
  • a glossy layer is formed on one side of the base layer, and an adhesive layer made of a propylene random copolymer having a melting point of 130 ° C. or higher is laminated on the side of the base layer opposite to the glossy layer.
  • the film for laminating thermoformed sheets according to (1) is formed on one side of the base layer, and an adhesive layer made of a propylene random copolymer having a melting point of 130 ° C. or higher is laminated on the side of the base layer opposite to the glossy layer.
  • thermoformed sheets according to (1) or (2) wherein the total thickness of the film is 15 to 100 ⁇ m, and the thickness of the base layer is 50 to 90% of the whole.
  • Either one or both of the organic crystal nucleating agent contained in the base layer and the organic crystal nucleating agent contained in the gloss layer is a phosphate metal salt or an amide compound represented by the following general formula (1)
  • R 1 represents a residue obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid.
  • Three or four R 2 s are the same or different from each other and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.
  • k represents an integer of 3 or 4.
  • thermoforming sheet lamination according to any one of (1) to (4), which has a printing layer on the film surface opposite to the glossy layer.
  • thermoforming sheet obtained by laminating the thermoforming sheet laminating film according to any one of (1) to (5) above on at least one surface of a resin sheet with the glossy layer as a surface layer.
  • thermoformed article obtained by thermoforming the thermoforming sheet described in (6) above.
  • the film for laminating a thermoformed sheet of the present invention is excellent in laminating properties when laminated on a resin sheet as a base of a thermoformed sheet, and is a low stretched film or a substantially unstretched film. There are few restrictions on conditions, and it is particularly suitable for the production of thermoformed bodies such as deep drawn containers. Further, by specifying the resin composition and the layer thickness of the base layer and the gloss layer, it is possible to obtain a thermoformed article having excellent glossiness of a thermoformed article obtained by thermoforming and having a surface without white turbidity.
  • thermoformed sheet laminating film is laminated on at least one surface of a resin sheet such as a polypropylene sheet and is integrated with the resin sheet to constitute a thermoformed sheet.
  • resin sheet such as a polypropylene sheet
  • thermoformed sheets are shaped by vacuum forming, pressure forming, etc., and used as various containers.
  • the film for laminating thermoformed sheets of the present invention comprises a base layer mainly composed of a propylene homopolymer and a glossy layer mainly composed of a propylene random copolymer, and the base layer has a melting point of 162 ° C. or higher. 99 to 99.97% by mass of polymer 99 to 99.97% by mass and 0.03 to 1% by mass of organic crystal nucleating agent, having a thickness of 10 ⁇ m or more and a gloss layer of 99 to 99.97% by mass of a propylene random copolymer And a thickness of 1 ⁇ m or more including the organic crystal nucleating agent 0.03 to 1% by mass is extremely important for achieving a predetermined effect.
  • thermoformed sheet Conventionally, a non-stretched film of a propylene homopolymer is generally used as a film for laminating a thermoformed sheet, but when such a film is used to form a thermoformed sheet and thermoformed, the resulting thermoformed body is obtained. Inferior surface gloss and cloudiness. This is presumably because surface roughness occurs due to the growth of spherulites when the film is remelted and crystallized by the heating temperature, and the surface gloss is lowered.
  • a method of adding a crystal nucleating agent is known, but a propylene homopolymer or a blend of a propylene homopolymer and a propylene- ⁇ -olefin random copolymer or a polyolefin such as polyethylene or polybutene.
  • a crystal nucleating agent is added to the propylene homopolymer, the propylene homopolymer has a relatively high crystallization temperature when recrystallized after melting. It is done.
  • a crystal nucleating agent is formed on a base layer having a specific thickness obtained by blending a crystal nucleating agent with a highly crystalline propylene homopolymer, and a propylene random copolymer formed on at least one side thereof.
  • the propylene homopolymer used for the base layer has a melting point measured by a differential scanning calorimeter of 162 ° C. or higher, preferably 163 ° C. or higher, preferably in the range of 163 to 170 ° C. .
  • the melting point of polypropylene used for the base layer is less than 162 ° C., the gloss of the container after thermoforming is inferior.
  • melt mass flow rate (MFR) at 230 ° C. of the propylene homopolymer is 2 to 50 g / 10 minutes, preferably 4 to 20 g / 10 minutes considering the film forming property. More preferably, the range of 6 to 15 g / 10 min is preferable in order to stabilize the thickness at the time of film formation.
  • the thickness of the base layer composed mainly of the propylene homopolymer as described above is 10 ⁇ m or more, preferably 12 ⁇ m or more, and particularly preferably in the range of 12 to 80 ⁇ m.
  • the thickness of the base layer is less than 10 ⁇ m, the gloss of the container after thermoforming is inferior.
  • the propylene random copolymer used for the glossy layer is a random copolymer of propylene and ⁇ -olefin (including ethylene).
  • ⁇ -olefin an ⁇ -olefin having 2 to 10 carbon atoms is preferable, and specifically, ethylene, butene, pentene-1, hexene-1, octene-1, and the like are preferably used.
  • the content of propylene units in the propylene random copolymer is 99.7 to 85% by mass, preferably 99 to 90% by mass.
  • the copolymer composition of the propylene random copolymer can be measured using a nuclear magnetic resonance apparatus described later.
  • the propylene random copolymer is preferably a propylene-ethylene random copolymer or a propylene-ethylene-butene random copolymer, and more preferably a propylene random copolymer having a narrow composition distribution.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography produced by a metallocene catalyst is 4 .5 or less propylene random copolymer can be exemplified.
  • These propylene random copolymers may be used alone or in combination of two or more.
  • the melting point measured by a differential scanning calorimeter is preferably 130 ° C. or higher, more preferably 133 ° C. or higher.
  • the melting point of the propylene random copolymer is particularly preferably in the range of 133 to 157 ° C.
  • the melting point of the propylene-based random copolymer can be adjusted by a known method for appropriately selecting the type and ratio of monomers to be copolymerized in the production process.
  • the MFR at 230 ° C. of the propylene random copolymer is 2 to 50 g / 10 minutes, preferably 4 to 20 g / 10 minutes considering the film forming property. More preferably, the range of 6 to 15 g / 10 min is preferable in order to stabilize the thickness at the time of film formation.
  • the thickness of the gloss layer mainly composed of the propylene-based random copolymer as described above is 1 ⁇ m or more, particularly preferably 2 ⁇ m or more and 2 to 10 ⁇ m.
  • the thickness of the gloss layer is less than 1 ⁇ m, the cloudiness is inferior and the gloss after thermoforming is inferior. In particular, when a deep-drawn container is formed, the gloss is remarkably reduced.
  • an adhesive layer may be provided on the base layer surface opposite to the glossy layer of the laminated film for the purpose of improving the adhesion between the resin sheet and the laminating film.
  • a gloss layer is provided on both surfaces of the base layer, one gloss layer may be used as an adhesive layer, or an adhesive layer may be provided on the surface of one gloss layer.
  • the adhesive layer can be formed, for example, by laminating 1 ⁇ m or more of a propylene random copolymer having a melting point of 130 ° C. or higher.
  • the thickness is 1 ⁇ m or more, preferably 2 ⁇ m or more and 2 to 10 ⁇ m.
  • the thickness of the adhesive layer is less than 1 ⁇ m, sufficient adhesion may not be obtained. Although it does not restrict
  • the total thickness of the film for laminating thermoformed sheets of the present invention including the base layer, the glossy layer and, if necessary, the adhesive layer is not particularly limited as long as the total thickness can secure the thickness of the base layer and the glossy layer. However, it is generally 15 to 100 ⁇ m, preferably 18 to 60 ⁇ m. Further, the thickness of the base layer is preferably 50 to 90% of the total thickness of the laminated film. When the thickness of the base layer is less than 50% of the total thickness, the surface gloss after thermoforming may decrease. On the other hand, if the thickness of the base layer exceeds 90% of the total thickness, the cloudiness may increase and the appearance may deteriorate.
  • An organic crystal nucleating agent is blended in the base layer and the gloss layer constituting the thermoforming sheet laminating film of the present invention.
  • Inorganic crystal nucleating agents do not necessarily improve the gloss of the container after lamination with a resin sheet and after thermoforming.
  • organic crystal nucleating agent examples include sorbitol derivatives such as dibenzylidene sorbitol and dimethyl benzylidene sorbitol, rosin metal chloride, benzoic acid metal salt, phosphate metal, amide compound represented by the general formula (1), and the like.
  • sorbitol derivatives such as dibenzylidene sorbitol and dimethyl benzylidene sorbitol
  • rosin metal chloride benzoic acid metal salt
  • phosphate metal amide compound represented by the general formula (1)
  • amide compound represented by the general formula (1) and the like.
  • phosphoric acid ester aluminum salts are phosphoric acid ester metal salts
  • amide compounds are amide compounds in which R 2 in the general formula (1) is a hydrogen atom or a methyl group, such as 1,2,3-propanetricarboxylic acid.
  • Acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid Tri (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra (2-methylcyclohexylamide), 1,2, 3,4-Butanetetracarboxylic acid tetra (3-methylcyclohexylamide ), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide) and the like are most effective in improving gloss after thermoforming.
  • the addition amount of the organic crystal nucleating agent is 0.03 to 1 with respect to 99 to 99.97% by mass of the polypropylene component (propylene homopolymer in the base layer and propylene-based random copolymer in the glossy layer) in both the base layer and the gloss layer.
  • % By weight, preferably 0.1 to 0.5% by weight, particularly preferably in the range of 0.12 to 0.4% by weight.
  • the addition amount is less than 0.03% by mass, the dimensional stability during printing and lamination with the resin sheet is inferior, and the gloss after thermoforming is inferior.
  • the addition amount of an organic crystal nucleating agent exceeds 1 mass%, the improvement effect of the glossiness after shaping
  • the presence or absence of addition of an organic crystal nucleating agent is not particularly limited.
  • the addition of the nucleating agent exhibits an effect of increasing the tensile elastic modulus of the film in addition to the effect of improving the glossiness of the film for thermoforming sheet lamination. That is, by adding the organic crystal nucleating agent, the tensile elastic modulus in the flow direction of the film (hereinafter referred to as MD direction) exhibits a value exceeding 1000 MPa.
  • MD direction the tensile elastic modulus in the flow direction of the film
  • a fixed-position molded container is a molded container in which the pattern is always matched at a certain position. In order to perform fixed position molding, it is required that there is little pitch deviation when printing on a laminating film and that there is little pitch deviation when laminating a laminating film and a resin sheet.
  • the film for laminating thermoformed sheets of the present invention meets this demand.
  • thermoforming sheet laminating film of the present invention other thermoformable films such as polypropylene, polyethylene, polystyrene, polyamide, polyethylene terephthalate and the like can be applied to known methods such as dry laminating and extrusion laminating as necessary. Can be laminated. In this case, the surface to be laminated needs to be on the base layer side.
  • the raw resin for the film for laminating the thermoformed sheet of the present invention includes an antistatic agent, an antifogging agent, an antiblocking agent, an antioxidant, a light stabilizer, a lubricant, a surfactant, a colorant, and an antibacterial agent as necessary. You may mix
  • the film for laminating thermoformed sheets of the present invention is formed by a non-stretching method.
  • typical methods include an extrusion molding method using a T die and an inflation molding method using an annular die.
  • a co-extrusion method using a T die by a feed block method or a multi-manifold method is preferably used as the film for laminating thermoformed sheets.
  • a roll capable of adjusting the temperature by extruding the resin composition constituting the film for laminating thermoformed sheets by the T dice method in each extruder.
  • a method of cooling and winding with a temperature-adjustable water tank, or a method of cooling and winding the melt by an air cooling method or a water cooling method can be exemplified.
  • the resulting laminating film is a low stretch or a substantially unstretched film that is slightly stretched by the tension during winding. Since the laminating film of the present invention is a low-stretched film or a substantially unstretched film, there are few restrictions on thermoforming conditions, and it is particularly suitable for the production of thermoformed bodies such as deep-drawn containers.
  • the film for laminating thermoformed sheets of the present invention can be subjected to surface treatment according to the use and printed.
  • the surface treatment method is not particularly limited, but generally, a corona discharge treatment, a flame treatment, or the like may be performed for the purpose of improving the adhesion with the printing ink.
  • the surface to be surface-treated is not particularly limited, and may be either one side or both sides.
  • the surface-treated film for laminating thermoformed sheets of the present invention has a printing layer on the surface opposite to the glossy layer. Since the laminating film of the present invention is excellent in printing pitch stability, a highly accurate printing film can be obtained.
  • the print layer is formed on the base layer surface.
  • the film is formed by laminating a gloss layer, a base layer, and an adhesive layer in this order, a printing layer is formed on the surface of the adhesive layer.
  • the print layer is formed on the gloss layer surface disposed on the resin sheet side.
  • the tensile tension of the film during printing and laminating is 50 to 100 N / m, and the film temperature at this time is 60 ° C. or higher.
  • the tensile elastic modulus at 23 ° C. in the film flow direction (hereinafter referred to as MD direction) is preferably 1000 MPa or more, and the film width of the thermoformed sheet laminating film is It is preferable that the dimensional change rate at 100 ° C. with a width of 1000 mm and a load of 100 N is 15% or less.
  • the lamination film of the present invention is excellent in printing and lamination suitability because the tensile elastic modulus in the MD direction of the film exceeds 1000 MPa by the addition of the organic crystal nucleating agent. Therefore, a fixed-position molded container excellent in surface gloss can be obtained by laminating a printing film using the laminating film of the present invention with a resin sheet and thermoforming it.
  • thermoforming As the resin sheet used as the base of the thermoformed sheet, a known sheet used for thermoforming can be used without any limitation.
  • a polypropylene resin a homopolymer of propylene and a copolymer with an ⁇ -olefin other than propylene and having propylene as a main constituent unit are generally used.
  • Specific examples include a polypropylene sheet made of a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, and the like.
  • resins include polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, and the like.
  • the form of the polypropylene-based sheet is simply a sheet of the above-mentioned polypropylene-based resin, a sheet-shaped composition obtained by blending a polypropylene-based resin with a filler (filler-containing sheet), or a polypropylene-based resin. Foamed and formed into a sheet shape (foamed sheet).
  • stacked the layer which does not contain a filler In this case, the gloss after molding becomes higher by laminating the laminating film on the surface of the layer not containing the filler of the laminated sheet.
  • the structure of the thermoformed sheet in this case is, for example, filler-containing layer / filler-free layer / thermoformed sheet laminating film of the present invention.
  • the filler-free layer can be formed by a co-extrusion method with a filler-containing layer or an extrusion lamination method to a filler-containing sheet.
  • the thickness of the resin sheet is not particularly limited, but is preferably 0.2 to 3 mm in consideration of thermoformability.
  • thermoforming sheet laminating film a known method that does not significantly change the properties of the thermoforming sheet laminating film can be used without any particular limitation.
  • methods such as an extrusion lamination method, a heat lamination method, and a dry lamination method can be used. More specifically, a method of laminating a resin for forming a resin sheet on the thermoforming sheet laminating film of the present invention set on a chill roll by an extruder is recommended.
  • the surface of the chill roll is preferably a smooth mirror surface roll.
  • thermoformed sheets of the present invention is laminated on a resin sheet such as the polypropylene sheet to produce thermoformed bodies such as lunch containers, trays, food containers such as bowl containers, general containers, and industrial parts containers. Therefore, it can be suitably used as a thermoformed sheet.
  • the present invention also includes a thermoformed product obtained by cooling a thermoformed sheet after forming in a mold such as a mold by vacuum forming, pressure forming, vacuum pressure forming, etc. To do.
  • Table 3 shows the polypropylene-based sheets used as the base resin sheets in the examples and comparative examples.
  • Measurement mode 1 H-complete decoupling Pulse width: 90 degree pulse pulse repetition time: 3 seconds Integration number: 10000 times
  • Solvent Mixed solvent of orthodichlorobenzene / heavy benzene (76/24 vol%) Sample concentration: 120 mg / 2.5 ml solvent Measurement temperature: 120 ° C.
  • the quantification of the copolymer composition is described in M.C. kakugo, Y, Naito, K.K. Mizunuma, T .; According to Miyatake, [Macromolecules, 15, 1150 (1982)].
  • the molded container was heated at a heater temperature of 500 to 530 ° C. with a cosmic molding machine FK-0631-20 manufactured by Asano Laboratories, so that the gloss layer surface of the thermoformed sheet became the inner surface of the container.
  • a container (dish container: 195 mm long, 145 mm wide, 28 mm high, bowl container: 168 mm ⁇ , 50 mm high) was evaluated at 70 mmHg.
  • molding was 175 degreeC.
  • ⁇ Gross 75% or more
  • ⁇ Gloss 65% or more, less than 75%
  • ⁇ Gloss less than 65% (4) Melting point and crystallization temperature measured by differential scanning calorimeter Approximately 5 to 6 mg of sample was weighed into an aluminum pan The sample was sealed, heated with a differential scanning calorimeter (DSC6200R manufactured by Seiko Denshi Kogyo Co., Ltd.) in a nitrogen stream supplied at 20 ml / min, maintained at this temperature for 10 minutes, and then cooled at a rate of 10 Cool to 20 ° C at ° C / min. Next, the peak temperature showing the maximum endotherm in the endothermic curve obtained when the temperature was raised to 230 ° C. at a rate of temperature rise of 10 ° C./min was taken as the melting point. The crystallization temperature was measured by melting the resin once according to JIS K7121 and then cooling to start crystallization.
  • Tensile modulus A sample having a width of 10 mm and a length of 100 mm is cut out from the laminating film in the film flow direction during film formation, and both ends of the sample are subjected to a tensile tester (Autograph: manufactured by Shimadzu Corporation). It was fixed with a chuck. In this case, the chuck gap in the length direction of the sample was adjusted to 20 mm. A tensile test was performed at a tensile speed of 20 mm / min to prepare a tensile stress-strain curve.
  • the tensile elastic modulus was calculated by the following formula using the first linear part of the tensile stress-strain curve.
  • Em ⁇ / ⁇ Em: Tensile modulus ⁇ : Difference in stress due to the original average cross-sectional area of the sample between two points on the straight line ⁇ : Difference in strain between the same two points (6)
  • Dimensional change rate From film for lamination (thickness 25 ⁇ m) A sample with a width of 100 mm and a length of 100 mm was cut out in the direction of film flow during film formation, and a 10N weight was attached, and the sample was placed in an oven heated at 100 ° C. for 10 minutes and left at 23 ° C. for 2 minutes. The subsequent dimensional change rate was measured.
  • Defective rate (%) (number of cracks in molded product / 50) ⁇ 100 (8)
  • White turbidity The Hunter whiteness “W (Lab)” value was measured for the inner surface (glossy layer surface) of the molded product described in (7) above using a color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd. did.
  • the value of the hunter whiteness of the polypropylene sheet before laminating the film and the value of the hunter whiteness of the molded container after laminating each film were compared and evaluated.
  • Adhesive strength 1.0 N / 15 mm or more B: Adhesive strength 0.5 N / 15 mm or more, less than 1.0 N / 15 mm
  • X Adhesive strength less than 0.5 N / 15 mm
  • resin A propylene homopolymer having a melting point of 165 ° C. (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.)
  • nucleating agent I shown in Table 2
  • Nucleating agent I shown in Table 2 in 99.8% by mass of resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro)) 0.2 mass% was blended and extruded at 250 ° C. with a 65 mm ⁇ extruder to form pellets, and the resulting resin was used for a glossy layer.
  • the gloss layer resin is supplied to Extruder A (50 mm ⁇ extruder), the base layer resin is supplied to Extruder B (75 mm ⁇ extruder), heated and melted at 250 ° C., and die lip 1.
  • a polypropylene sheet (black) to which 30% by mass of talc is added on the surface subjected to corona discharge treatment of the film is solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.5 mm at 250 ° C. A sheet was obtained.
  • thermoformed sheet was vacuum-formed at a film surface temperature of 175 ° C., and the gloss, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated.
  • the results are shown in Table 5.
  • the gloss of the molded container is 78% in the dish container and 78% in the bowl container, and the surface gloss is good, and the hunting whiteness of the polypropylene sheet before bonding the film is 12%. It was a container with almost no change and 12-13%.
  • Example 2 Except for adjusting the gloss layer to 2 ⁇ m and the base layer to 23 ⁇ m and adjusting to a total of 25 ⁇ m (Example 2), adjusting the gloss layer to 10 ⁇ m and the base layer to 15 ⁇ m and changing to a total of 25 ⁇ m (Example 3).
  • Example 2 the gloss of the molded container is 77% for the dish container and 76% for the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene-based sheet before film bonding is 12%.
  • the molded container was 12 to 13%, and it was a container with almost no change in white turbidity.
  • Example 3 the gloss of the molded container is 79% in the dish container and 79% in the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is 12%.
  • the molded container was 12% with no change and no cloudiness.
  • Example 4 The gloss layer resin of Example 1 is shown in Table 1.
  • Resin H metalocene catalyst-based propylene-ethylene random copolymer (WFW4 manufactured by Nippon Polypro Co., Ltd.) having an ethylene content of 4.2 mass% and a melting point of 135 ° C.
  • WFW4 metalocene catalyst-based propylene-ethylene random copolymer
  • Table 5 The gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good.
  • the white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, The container was little changed as 12-13% and had no cloudiness.
  • Example 5-6 The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 2 ⁇ m and the base layer was 23 ⁇ m, and adjusted to a total of 25 ⁇ m (Example 5), so that the gloss layer was 10 ⁇ m and the base layer was 15 ⁇ m. Except for changing to 25 ⁇ m (Example 6), film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1. The results are shown in Table 5. In Example 5, the gloss of the molded container is 81% in the dish container and 81% in the bowl container, and the surface gloss is extremely good.
  • the hunter whiteness of the polypropylene sheet before film bonding is 12 %, 13% of the molded container and almost no change and no cloudiness.
  • the gloss of the molded container is 84% for the dish container and 82% for the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is 12% for the cloudiness.
  • the molded container was 12% with no change and no cloudiness.
  • Example 7 Except that the resin for base layer of Example 4 was resin B shown in Table 1 (propylene homopolymer having a melting point of 164 ° C. (PC600A manufactured by Sun Allomer Co., Ltd.)), film formation, lamination, thermoforming, and evaluation were performed in the same manner. went. The results are shown in Table 5. The gloss of the molded container is 82% in the dish container and 82% in the bowl container, and the surface gloss is very good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was little changed as 12-13% and had no cloudiness.
  • Table 1 propylene homopolymer having a melting point of 164 ° C. (PC600A manufactured by Sun Allomer Co., Ltd.)
  • Example 8 Film formation, lamination, thermoforming, and evaluation were performed in the same manner except that the addition amount of the nucleating agent I added to the gloss layer and the base layer in Example 4 was 0.1% by mass. The results are shown in Table 5.
  • the gloss of the molded container is 80% in the dish container and 80% in the bowl container, and the surface gloss is very good.
  • Regarding the cloudiness the hunter whiteness of the polypropylene sheet before film bonding is 12%.
  • the container was little changed as 12-13% and had no cloudiness.
  • Example 9 The gloss layer resin of Example 4 is represented by Resin F (Propylene-ethylene-butene ternary random copolymer having an ethylene content of 3.2% by mass, a butene content of 1.5% by mass, and a melting point of 137 ° C.) (Example 9), and the resin for the gloss layer shown in Table 1 is resin G (ethylene content is 2.2 mass%, butene content is 6.8 mass%, melting point) Film forming, laminating, thermoforming, and evaluation were carried out in the same manner except that (Example 10) was a propylene-ethylene-butene ternary random copolymer (F794NV manufactured by Prime Polymer Co., Ltd.) at 133 ° C. .
  • Resin F Polylene-ethylene-butene ternary random copolymer having an ethylene content of 3.2% by mass, a butene content of 1.5% by mass, and a melting point of 137 ° C.
  • Example 11 The resin A 99.8% by mass shown in Table 1 was blended with 0.2% by mass of the nucleating agent I shown in Table 2 and extruded into pellets at 250 ° C. with a 65 mm ⁇ extruder, and the resulting resin was used for the base layer.
  • the resin H 99.8% by mass shown in Table 1 was blended with 0.2% by mass of the nucleating agent I shown in Table 2 and extruded at 250 ° C. with a 65 mm ⁇ extruder to form pellets. The resulting resin was used for a glossy layer.
  • Resin E simple substance shown in Table 1 was used as the adhesive layer resin.
  • the gloss layer resin is supplied to Extruder A (50 mm ⁇ extruder), the base layer resin is supplied to Extruder B (75 mm ⁇ extruder), and the adhesive layer resin is supplied to Extruder C (50 mm ⁇ extruder).
  • the feed block method is extruded from a T die with a die lip of 1.2 mm by a coextrusion method, and adjusted so that the gloss layer is 5 ⁇ m, the base layer is 15 ⁇ m, and the adhesive layer is 5 ⁇ m while being cooled and solidified on a cooling roll at 60 ° C.
  • Example 12-13 The thickness of the base layer and the adhesive layer of Example 11 was adjusted so that the base layer was 18 ⁇ m and the adhesive layer was 2 ⁇ m, and adjusted to a total of 25 ⁇ m (Example 12), so that the gloss layer was 8 ⁇ m and the base layer was 12 ⁇ m. Except for changing to 25 ⁇ m (Example 13), film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 11. The results are shown in Table 5. In Example 12, the gloss of the molded container is 81% for the dish container and 80% for the bowl container, and the surface gloss is very good. %, 12 to 13% of the container after molding, and there was almost no change and the container was not cloudy.
  • Example 13 the gloss of the molded container is 80% in the dish container and 79% in the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is also 12% for the cloudiness.
  • the container after molding was 12 to 13%, and it was a container with little change and little cloudiness.
  • Example 14 Film forming, laminating, and thermoforming were performed in exactly the same manner as in Example 11 except that the adhesive layer resin of Example 11 was a resin obtained by adding 0.2% by mass of nucleating agent I to 99.8% by mass of the resin H shown in Table 1. And evaluation. The results are shown in Table 5.
  • the gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good.
  • the white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, The container was a 12% container with no change and no cloudiness.
  • Example 15 The thickness of the gloss layer and the base layer of Example 1 was adjusted so that the gloss layer was 10 ⁇ m and the base layer was 40 ⁇ m, and the total thickness was changed to 50 ⁇ m. And evaluation was performed. The results are shown in Table 5. The gloss of the molded container is 85% in the dish container and 83% in the bowl container, and the surface gloss is very good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was a 12% container with no change and no cloudiness.
  • Example 16 As a raw material resin for film, 97.5% by mass of the resin A shown in Table 1 was blended with 2.5% by mass of the nucleating agent II shown in Table 2. The obtained resin was used for the base layer. A resin obtained by blending 97.5% by mass of the resin H shown in Table 1 with 2.5% by mass of the nucleating agent III shown in Table 2 was used for the gloss layer. Next, except that the gloss layer resin was supplied to the extruder A (50 mm ⁇ extruder) and the base layer resin was supplied to the extruder B (75 mm ⁇ extruder), film formation, lamination, thermoforming, and And evaluated. The results are shown in Table 5. The gloss of the molded container is 71% in the dish container and 70% in the bowl container, and the surface gloss is somewhat good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was a 12% container with no change and no cloudiness.
  • Example 17 On the surface of the film of Example 1 subjected to the corona discharge treatment, a polypropylene sheet (Vermilion Red) to which 30% by mass of talc was added was solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.4 mm at 250 ° C. A polypropylene thermoformed sheet was obtained.
  • a polypropylene sheet (Vermilion Red) to which 30% by mass of talc was added was solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.4 mm at 250 ° C.
  • a polypropylene thermoformed sheet was obtained.
  • thermoformed sheet was vacuum-formed, and the glossiness, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated.
  • the results are shown in Table 5.
  • the gloss of the molded container is 78% for the dish container and 78% for the bowl container, and the surface gloss is good, and the hunting whiteness of the polypropylene sheet before film lamination is 22%. It was a container with almost no change and 22-23%.
  • Example 18 As a raw material resin for a film, 94% by mass of resin A (propylene homopolymer having a melting point of 165 ° C. (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.)) shown in Table 1 was blended with 6% by mass of the nucleating agent IV shown in Table 2 in a 65 mm ⁇ extruder. Extrusion pelletization was performed at 250 ° C., and the resulting resin was used for a base layer. Resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C.
  • a polypropylene sheet (black) to which 30% by mass of talc is added on the surface subjected to corona discharge treatment of the film is solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.5 mm at 250 ° C. A sheet was obtained.
  • thermoformed sheet was vacuum-formed at a film surface temperature of 175 ° C., and the gloss, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated.
  • the results are shown in Table 5.
  • the gloss of the molded container is 79% for the dish container and 78% for the bowl container, and the surface gloss is good, and the turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, and the container after molding It was a 12% container with no change and no cloudiness.
  • Example 19 The gloss layer resin of Example 18 is the resin H shown in Table 1 (metallocene catalyst-based propylene-ethylene random copolymer (WFW4 manufactured by Nippon Polypro Co., Ltd.) having an ethylene content of 4.2 mass% and a melting point of 135 ° C.)) Except for the above, film formation, lamination, thermoforming, and evaluation were performed in the same manner. The results are shown in Table 5.
  • the gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good.
  • the white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, It was a 12% container with no change and no cloudiness.
  • Comparative Example 1 Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the organic crystal nucleating agent was not added to the raw material resin of each layer of Example 1.
  • the results are shown in Table 5.
  • the gloss of the molded container is inferior to the surface gloss of 16% for the dish container and 15% for the bowl container, and the whiteness of the turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 15 after molding. % And the container was cloudy.
  • Comparative Example 2 Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent added was 0.02 parts by mass in the raw material resin of each layer of Example 1.
  • the results are shown in Table 5.
  • the gloss of the molded container is 16% for the dish container and 17% for the bowl container, and the surface gloss is inferior. Also for the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%, and the molded container 15 % And the container was cloudy.
  • Comparative Example 3 Film formation was carried out in the same manner as in Example 1 except that instead of the resin A used for the base layer of Example 1, resin C shown in Table 1 (a propylene homopolymer having a melting point of 161 ° C. (FLX80G1 manufactured by Sumitomo Chemical Co., Ltd.)) was used. Lamination, thermoforming, and evaluation were performed.
  • resin C shown in Table 1 a propylene homopolymer having a melting point of 161 ° C. (FLX80G1 manufactured by Sumitomo Chemical Co., Ltd.)
  • the results are shown in Table 5.
  • the gloss of the molded container was inferior in surface gloss, 62% for the dish container and 60% for the bowl container.
  • Comparative Example 4 Film formation was carried out in the same manner as in Example 1 except that instead of the resin A used in the base layer of Example 1, resin D shown in Table 1 (propylene homopolymer having a melting point of 157 ° C. (FB3EBT manufactured by Nippon Polypro Co., Ltd.)) was used. Lamination, thermoforming, and evaluation were performed.
  • the results are shown in Table 5.
  • the gloss of the molded container was 60% for the dish container and 60% for the bowl container, and the surface gloss was inferior.
  • Comparative Example 5 Made in the same manner as in Example 1 except that instead of the resin E used in the glossy layer of Example 1, resin A shown in Table 1 (propylene homopolymer having a melting point of 165 ° C. (FLX80F7 manufactured by Sumitomo Chemical Co., Ltd.)) was used. Films, laminates, thermoforming and evaluation were performed.
  • the results are shown in Table 5.
  • the gloss of the molded container is 60% in the dish container and 60% in the bowl container, and the surface gloss is inferior, and the white turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 21 after molding. % And the container was cloudy.
  • Comparative Example 6 The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 0.5 ⁇ m and the base layer was 24.5 ⁇ m, and the total thickness was 25 ⁇ m. Molding and evaluation were performed. The results are shown in Table 5. The gloss of the molded container is 62% in the dish container and 61% in the bowl container, and the surface gloss is inferior. The white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, and the container 19 after molding. % And the container was cloudy.
  • Comparative Example 7 The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 20 ⁇ m and the base layer was 5 ⁇ m, and the total thickness was 25 ⁇ m. Evaluation was performed. The results are shown in Table 5. The gloss of the molded container was inferior in surface gloss, 62% for the dish container and 61% for the bowl container.
  • Comparative Example 8 instead of the resin A used for the base layer of Example 1, the resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro)) Except that was used, film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1.
  • Table 1 propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro)
  • the results are shown in Table 5.
  • the gloss of the molded container was inferior in surface gloss, 62% for the dish container and 61% for the bowl container.
  • Comparative Example 9 instead of the resin E used for the gloss layer of Example 1, the resin C shown in Table 1 was 90% by mass and the resin I (ethylene content was 89.4% by mass, hexene content was 10.6% by mass, melting point was 110 ° C. 10% by mass of a metallocene catalyst-based ethylene random copolymer (FV402 manufactured by Sumitomo Chemical Co., Ltd.), and instead of resin A used for the base layer, resin E (ethylene content is 3.4% by mass, melting point) Film forming, laminating, thermoforming, and evaluation were performed in the same manner as in Example 1 except that propylene-ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd.) at 146 ° C. was used.
  • FV402 metallocene catalyst-based ethylene random copolymer
  • the results are shown in Table 5.
  • the gloss of the molded container is 60% in the dish container and 60% in the bowl container, and the surface gloss is inferior, and the white turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 21 after molding. % And the container was cloudy.
  • Comparative Example 10 On the surface of the film of Comparative Example 5 subjected to the corona discharge treatment, a polypropylene sheet (Vermilion Red) to which 30% by mass of talc was added was solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.4 mm at 250 ° C. A polypropylene thermoformed sheet was obtained.
  • a polypropylene sheet Very Dark
  • thermoformed sheet was vacuum-formed, and the glossiness, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated.
  • the results are shown in Table 5.
  • the gloss of the molded container is 60% in the dish container and 60% in the bowl container, which is inferior in surface gloss.
  • the hunter whiteness of the polypropylene sheet before film bonding is 22%, and the container 30 after molding. It was a container with a cloudiness of ⁇ 32%.
  • Comparative Example 11 Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent was 0.01 parts by mass in the raw material resin of each layer of Example 18.
  • the results are shown in Table 5.
  • the gloss of the molded container is inferior to the surface gloss of 16% for the dish container and 15% for the bowl container, and the whiteness of the turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 15 after molding. % And the container was cloudy.
  • Table 4 summarizes the layer configurations of the thermoformed sheet laminating films obtained in the above Examples and Comparative Examples. The results of these examples and comparative examples are summarized in Table 5.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

A film for laminating for thermoforming sheets is provided which is for use as a film to be laminated to a resin sheet serving as a base of a sheet for thermoforming. The film has excellent suitability for laminating to the resin sheet. When thermoformed, a thermoforming sheet obtained by laminating the film can give a thermoformed article excellent in surface gloss and reduced in blushing. The film for laminating for thermoforming sheets comprises: a base layer which comprises 99-99.97 mass% propylene homopolymer having a melting point of 162°C or higher and 0.03-1 mass% organic crystal nucleator and has a thickness of 10 µm or larger; and a gloss layer which is formed on at least one side of the base layer, comprises 99-99.97 mass% propylene random copolymer and 0.03-1 mass% organic crystal nucleator, and has a thickness of 1 µm or larger. The film is an unstretched or lowly stretched film.

Description

熱成形シート積層用フィルムFilm for thermoforming sheet lamination
本発明は、新規な熱成形シート積層用フィルムに関し、さらに詳しくは、熱成形用シートのベースとなる樹脂シートに積層する際のラミネート適性に優れ、樹脂シートとラミネート後、得られる熱成形シートを熱成形して得られる熱成形体に、優れた光沢性を付与することが可能な熱成形シート積層用フィルムに関する。 The present invention relates to a novel film for laminating a thermoformed sheet. More specifically, the present invention is excellent in lamination suitability when laminated on a resin sheet as a base of a thermoformed sheet. The present invention relates to a thermoformed sheet laminating film capable of imparting excellent gloss to a thermoformed product obtained by thermoforming.
　現在、弁当容器、トレー、丼容器等の食品包装容器、及び一般包装容器には、ポリオレフィンシート、特に、電子レンジの普及から耐熱性の高いポリプロピレンシートや発泡ポリプロピレンシートなどの樹脂シートが用いられている。これらの樹脂シートには、多くの場合、意匠性の向上、高級感を与える目的で、印刷を施したポリプロピレン系フィルムが貼り合されている。樹脂シートに貼り合わされるポリプロピレン系フィルムは無延伸ポリプロピレンフィルム（以下、ＣＰＰフィルムと記す）、二軸延伸ポリプロピレンフィルム（以下、ＯＰＰフィルムと記す）が用いられている。 At present, polyolefin sheets, especially resin sheets such as polypropylene sheets and foamed polypropylene sheets that have high heat resistance due to the widespread use of microwave ovens, are used for food packaging containers such as lunch boxes, trays, and bowl containers. Yes. In many cases, a polypropylene-based film on which printing has been performed is bonded to these resin sheets for the purpose of improving design and giving a high-class feeling. As the polypropylene film to be bonded to the resin sheet, an unstretched polypropylene film (hereinafter referred to as CPP film) and a biaxially stretched polypropylene film (hereinafter referred to as OPP film) are used.
　上記ＣＰＰフィルムは熱成形性に優れることから深絞り容器のような熱成形体の製造への対応も可能であるが、シートとの貼り合せにおいて最も安価に製造可能な押出しラミネート法を採用すると、ラミネート後にＣＰＰフィルムの光沢が失われラミネートシートを熱成形した後の熱成形体において表面光沢に劣るという問題を有するため、その改善が望まれている。 Since the CPP film is excellent in thermoformability, it is possible to handle the production of a thermoformed article such as a deep-drawn container, but when adopting an extrusion laminating method that can be produced at the lowest cost in bonding with a sheet, Since there is a problem that the gloss of the CPP film is lost after laminating and the thermoformed product after thermoforming the laminate sheet is inferior in surface gloss, improvement thereof is desired.
　一方、ＯＰＰフィルムはＣＰＰフィルムに比べラミネート後および熱成形後の光沢は大幅に向上するものの、熱成形条件に制約があり、一部の深絞り容器のような熱成形体を得る場合の熱成形性に劣るという問題がある。 On the other hand, although the OPP film has significantly improved gloss after lamination and thermoforming compared to the CPP film, the thermoforming conditions are limited, and thermoforming when obtaining thermoformed bodies such as some deep drawn containers There is a problem of inferiority.
　これらの熱成形体（容器）は、一般的に、真空成形、圧空成形等の熱成形法により製造されている。この熱成形方法とは、樹脂シートを赤外線ヒーター等によって加熱した後、機械力、真空、圧空等の外力により、該シートを金型に密着させて成形するという方法である。 These thermoformed bodies (containers) are generally manufactured by a thermoforming method such as vacuum forming or pressure forming. This thermoforming method is a method in which a resin sheet is heated with an infrared heater or the like, and then the sheet is brought into close contact with a mold by an external force such as mechanical force, vacuum, or compressed air.
　ＣＰＰフィルムを樹脂シートに貼り合わせ、ラミネート後の光沢およびラミネートシートを熱成形した後の容器光沢を改善するために以下の検討がなされている。例えば、ポリプロピレン系樹脂発泡シートの少なくとも片面に、ポリプロピレン系樹脂に結晶核剤を配合した無延伸ポリプロピレン系樹脂フィルムを積層する方法が提案されている（特許文献１参照）。この無延伸ポリプロピレン系樹脂フィルムのポリプロピレン系樹脂は、特許文献１の実施例によればポリプロピレン単独重合体（ホモポリプロピレン）である。ポリプロピレン単独重合体に結晶核剤を添加し樹脂シートに積層することで、ある程度熱成形後の光沢は向上するものの表面の白濁感があり、かかる点において改善の余地があった。 In order to improve the gloss after laminating a CPP film to a resin sheet and thermoforming the laminate sheet, the following studies have been made. For example, a method has been proposed in which an unstretched polypropylene resin film in which a crystal nucleating agent is blended with a polypropylene resin is laminated on at least one surface of a polypropylene resin foam sheet (see Patent Document 1). According to the example of Patent Document 1, the polypropylene resin of the unstretched polypropylene resin film is a polypropylene homopolymer (homopolypropylene). By adding a crystal nucleating agent to a polypropylene homopolymer and laminating it on a resin sheet, the gloss after thermoforming is improved to some extent, but there is a feeling of cloudiness on the surface, and there is room for improvement in this respect.
また、同様に熱成形用の樹脂シートとして、特定の結晶融点を持った２種のポリプロピレン系樹脂に結晶核剤を配合した樹脂組成物からなるシートが提案されている（特許文献２参照）。さらに、特定の密度、ＭＦＲのプロピレン重合体にメタロセン触媒系を用いたエチレン系重合体、核剤を表面層に配合し、また特定のＭＦＲであるプロピレン・α－オレフィンランダム共重合体、核剤を中間層に配合してなる積層シートが提案されている（特許文献３参照）。しかし、上記技術は、得られる熱成形体において光沢は向上するものの表面の白濁感があり問題があった。 Similarly, a sheet made of a resin composition in which a crystal nucleating agent is blended with two types of polypropylene resins having specific crystal melting points has been proposed as a resin sheet for thermoforming (see Patent Document 2). Further, an ethylene polymer using a metallocene catalyst system in a specific density, MFR propylene polymer, and a nucleating agent are blended in the surface layer, and a specific MFR propylene / α-olefin random copolymer, a nucleating agent Has been proposed (see Patent Document 3). However, the above-mentioned technique has a problem in that although the gloss is improved in the obtained thermoformed article, the surface is cloudy.
一般に、熱成形体、例えば熱成形後の容器の光沢については、ＪＩＳ　Ｋ７１０５に準拠して６０度鏡面法で測定したグロス値において、６５％以上であれば光沢感のある容器であり、７５％以上であれば更に商品価値の高い光沢容器であると言える。しかし、グロス値が高い容器でも容器表面の白濁感が大きいものは、容器表面が白っぽく写り見た目に濁った状態となる。 In general, the gloss of a thermoformed article, for example, a container after thermoforming, is a glossy container if the gloss value measured by the 60-degree specular method in accordance with JIS K7105 is 65% or more, and 75% If it is above, it can be said that it is a gloss container with higher commercial value. However, even if the container has a high gloss value, if the container surface has a large cloudiness, the container surface appears whitish and turbid.
特に、黒色、赤色その他の色に着色したポリプロピレン系シートにＣＰＰフィルムを貼り合わせた熱成形用シートを熱成形にする場合、あるいは、ポリプロピレン系シートに、印刷したＣＰＰフィルムを貼り合わせた熱成形用シートを熱成形する場合には、前記積層されるフィルムの白濁が大きいものは、その着色した色あるいは柄が鮮明に写らないという現象が発生する。
特開２００２－１０３５４１号公報 特開２００２－３４８４２１号公報 特許第３４１６４３３号公報 In particular, when thermoforming a thermoforming sheet in which a CPP film is bonded to a polypropylene sheet colored in black, red or other colors, or for thermoforming in which a printed CPP film is bonded to a polypropylene sheet. In the case of thermoforming a sheet, a phenomenon in which the colored color or pattern of the laminated film having a large cloudiness is not clearly captured occurs.
JP 2002-103541 A JP 2002-348421 A Japanese Patent No. 3416433
　本発明の目的は、熱成形用シートのベースとなる樹脂シートに積層されるフィルムとして、樹脂シートに積層する際のラミネート適性に優れ、しかも、これを積層した熱成形シートを熱成形して得られる熱成形体において、表面光沢に優れ、また、白濁の小さい熱成形体を与えることが可能な熱成形シート積層用フィルムを提供することにある。 The object of the present invention is to obtain a film laminated on a resin sheet as a base of a thermoforming sheet, which is excellent in laminating suitability when laminated on a resin sheet, and is obtained by thermoforming a thermoformed sheet laminated thereon. An object of the present invention is to provide a film for laminating a thermoformed sheet that is excellent in surface gloss and that can give a thermoformed body with low white turbidity.
　本発明者らは、上記目的を達成すべく鋭意研究を重ねてきた。その結果、特定のプロピレン単独重合体に有機結晶核剤を添加した基層およびプロピレン系ランダム共重合体に有機結晶核剤を添加した光沢層が特定の厚みで形成された実質的に無延伸のポリプロピレン系フィルムが、前記課題を全て達成できることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to achieve the above object. As a result, a substantially unstretched polypropylene in which a base layer obtained by adding an organic crystal nucleating agent to a specific propylene homopolymer and a glossy layer obtained by adding an organic crystal nucleating agent to a propylene random copolymer are formed with a specific thickness. The present inventors have found that a system film can achieve all of the above problems, and have completed the present invention.
　すなわち、上記課題を解決する本願発明は、下記の事項を要旨として含む。 That is, the present invention for solving the above problems includes the following matters as a gist.
（１）融点が１６２℃以上であるプロピレン単独重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１０μｍ以上の厚みを有する基層と、
該基層の片面に形成された、プロピレン系ランダム共重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１μｍ以上の厚みを有する光沢層とからなり、無延伸または低延伸フィルムである、熱成形シート積層用フィルム。 (1) a base layer having a thickness of 10 μm or more, comprising 99 to 99.97% by mass of a propylene homopolymer having a melting point of 162 ° C. or higher and 0.03 to 1% by mass of an organic crystal nucleating agent;
A gloss layer having a thickness of 1 μm or more, comprising 99 to 99.97% by mass of a propylene random copolymer and 0.03 to 1% by mass of an organic crystal nucleating agent, formed on one side of the base layer; A film for laminating thermoformed sheets, which is an unstretched or low-stretched film.
（２）基層の片面に光沢層が形成され、該光沢層とは反対側の基層面に、融点が１３０℃以上のプロピレン系ランダム共重合体よりなり１μｍ以上の厚みを有する接着層が積層されてなる（１）に記載の熱成形シート積層用フィルム。 (2) A glossy layer is formed on one side of the base layer, and an adhesive layer made of a propylene random copolymer having a melting point of 130 ° C. or higher is laminated on the side of the base layer opposite to the glossy layer. The film for laminating thermoformed sheets according to (1).
（３）フィルムの総厚みが１５～１００μｍであり、基層の厚みが全体の５０～９０％である、（１）または（２）に記載の熱成形シート積層用フィルム。 (3) The film for laminating thermoformed sheets according to (1) or (2), wherein the total thickness of the film is 15 to 100 μm, and the thickness of the base layer is 50 to 90% of the whole.
　（４）基層に含まれる有機結晶核剤または光沢層に含まれる有機結晶核剤の何れか一方、または両方が、リン酸エステル金属塩または下記一般式（１）で示されるアミド系化合物である、請求項１～３のいずれかに記載の熱成形シート積層用フィルム。
Figure JPOXMLDOC01-appb-C000002
 ［式中、Ｒ１は、１，２，３－プロパントリカルボン酸又は１，２，３，４－ブタンテトラカルボン酸から全てのカルボンキシル基を除いて得られる残基を表す。３個又４個のＲ２は、互いに同一又は異なって、それぞれ水素原子又は炭素数１～１０の直鎖状若しくは分岐鎖状のアルキル基を表す。ｋは、３又は４の整数を表す。］ (4) Either one or both of the organic crystal nucleating agent contained in the base layer and the organic crystal nucleating agent contained in the gloss layer is a phosphate metal salt or an amide compound represented by the following general formula (1) The film for thermoforming sheet lamination according to any one of claims 1 to 3.
Figure JPOXMLDOC01-appb-C000002
 [Wherein R 1 represents a residue obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. Three or four R 2 s are the same or different from each other and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. k represents an integer of 3 or 4. ]
（５）光沢層と反対側のフィルム表面に印刷層を有する（１）～（４）のいずれかに記載の熱成形シート積層用フィルム。 (5) The film for thermoforming sheet lamination according to any one of (1) to (4), which has a printing layer on the film surface opposite to the glossy layer.
（６）上記（１）～（５）のいずれかに記載の熱成形シート積層用フィルムを、前記光沢層を表層として樹脂シートの少なくとも一方の面に積層した、熱成形用シート。 (6) A thermoforming sheet obtained by laminating the thermoforming sheet laminating film according to any one of (1) to (5) above on at least one surface of a resin sheet with the glossy layer as a surface layer.
（７）上記（６）に記載の熱成形用シートを熱成形して得られた熱成形体。 (7) A thermoformed article obtained by thermoforming the thermoforming sheet described in (6) above.
　本発明の熱成形シート積層用フィルムは、熱成形用シートのベースとなる樹脂シートに積層する際のラミネート適性に優れ、また低延伸フィルムまたは実質的に無延伸のフィルムであることから、熱成形条件の制約が少なく、特に深絞り容器のような熱成形体の製造に適している。また、基層と光沢層の樹脂組成、層厚みを特定することで、熱成形により得られる熱成形体の光沢性に優れ、且つ、白濁感のない表面を有する熱成形体を得ることができる。 The film for laminating a thermoformed sheet of the present invention is excellent in laminating properties when laminated on a resin sheet as a base of a thermoformed sheet, and is a low stretched film or a substantially unstretched film. There are few restrictions on conditions, and it is particularly suitable for the production of thermoformed bodies such as deep drawn containers. Further, by specifying the resin composition and the layer thickness of the base layer and the gloss layer, it is possible to obtain a thermoformed article having excellent glossiness of a thermoformed article obtained by thermoforming and having a surface without white turbidity.
　以下、本発明について、その最良の形態を含めてさらに具体的に説明する。 Hereinafter, the present invention will be described more specifically including the best mode.
　熱成形シート積層用フィルムとは、ポリプロピレン系シートなどの樹脂シートの少なくとも片面に積層され、樹脂シートと一体化して熱成形シートを構成する。かかる熱成形シートは、真空成形、圧空成形などにより賦形され、各種の容器として用いられる。 The thermoformed sheet laminating film is laminated on at least one surface of a resin sheet such as a polypropylene sheet and is integrated with the resin sheet to constitute a thermoformed sheet. Such thermoformed sheets are shaped by vacuum forming, pressure forming, etc., and used as various containers.
　本発明の熱成形シート積層用フィルムは、プロピレン単独重合体を主成分とする基層と、プロピレン系ランダム共重合体を主成分とする光沢層とからなり、基層が融点１６２℃以上であるプロピレン単独重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１０μｍ以上の厚みを有し、かつ光沢層がプロピレン系ランダム共重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１μｍ以上の厚みを有することが、所定の効果を達成する上で極めて重要である。 The film for laminating thermoformed sheets of the present invention comprises a base layer mainly composed of a propylene homopolymer and a glossy layer mainly composed of a propylene random copolymer, and the base layer has a melting point of 162 ° C. or higher. 99 to 99.97% by mass of polymer 99 to 99.97% by mass and 0.03 to 1% by mass of organic crystal nucleating agent, having a thickness of 10 μm or more and a gloss layer of 99 to 99.97% by mass of a propylene random copolymer And a thickness of 1 μm or more including the organic crystal nucleating agent 0.03 to 1% by mass is extremely important for achieving a predetermined effect.
　従来、熱成形シート積層用フィルムは、プロピレンの単独重合体の無延伸フィルムが一般に使用されているが、かかるフィルムを使用して熱成形シートを構成し、熱成形した場合、得られる熱成形体の表面光沢および白濁感に劣る。これは、加熱温度によりフィルムが再溶融し結晶化する際に球晶が成長するために表面荒れが発生し表面光沢が低下するものと思われる。この現象を解決するために結晶核剤を添加する方法は公知であるが、プロピレン単独重合体または、プロピレン単独重合体とプロピレン－αオレフィンランダム共重合体またはポリエチレン、ポリブテン等のポリオレフィンとのブレンド物に結晶核剤を添加した場合、溶融後、再結晶化する際にプロピレン単独重合体は比較的に結晶化温度が高いことから球晶の大きさが大きくなり易いため白濁感が生じるものと考えられる。 Conventionally, a non-stretched film of a propylene homopolymer is generally used as a film for laminating a thermoformed sheet, but when such a film is used to form a thermoformed sheet and thermoformed, the resulting thermoformed body is obtained. Inferior surface gloss and cloudiness. This is presumably because surface roughness occurs due to the growth of spherulites when the film is remelted and crystallized by the heating temperature, and the surface gloss is lowered. In order to solve this phenomenon, a method of adding a crystal nucleating agent is known, but a propylene homopolymer or a blend of a propylene homopolymer and a propylene-α-olefin random copolymer or a polyolefin such as polyethylene or polybutene. When a crystal nucleating agent is added to the propylene homopolymer, the propylene homopolymer has a relatively high crystallization temperature when recrystallized after melting. It is done.
また、プロピレン系ランダム共重合体単独に結晶核剤を添加したフィルムを樹脂シートに積層して熱成形を行った場合、白濁感は改善される。しかしながら、フィルムが比較的柔らかいため、熱成形時に樹脂シート表面の凹凸の影響を受けやすくなることから光沢性において改善の余地があった。 Further, when a film obtained by adding a crystal nucleating agent to a propylene random copolymer alone is laminated on a resin sheet and thermoformed, the cloudiness is improved. However, since the film is relatively soft, it tends to be affected by unevenness on the surface of the resin sheet during thermoforming, so there is room for improvement in glossiness.
これに対して、本発明においては、結晶性の高いプロピレン単独重合体に結晶核剤を配合した特定の厚みを有する基層と、その少なくとも片面に形成されたプロピレン系ランダム共重合体に結晶核剤を配合した特定の厚みを有する光沢層とからなる積層用フィルムを用いて、樹脂シートとの積層面に積層用フィルムの基層を配置することで、熱成形後の成形体において白濁感が少なく、しかも光沢性に極めて優れる成形体が得られる。 On the other hand, in the present invention, a crystal nucleating agent is formed on a base layer having a specific thickness obtained by blending a crystal nucleating agent with a highly crystalline propylene homopolymer, and a propylene random copolymer formed on at least one side thereof. By using a film for lamination consisting of a gloss layer having a specific thickness blended with a base layer of the film for lamination on the lamination surface with the resin sheet, there is little cloudiness in the molded body after thermoforming, In addition, a molded article having extremely excellent gloss can be obtained.
本発明の熱成形シート積層用フィルムにおいて、基層に用いるプロピレン単独重合体は、示差走査熱量計によって測定される融点が１６２℃以上、好ましくは１６３℃以上であり、１６３～１７０℃の範囲が好ましい。基層に用いるポリプロピレンの融点が１６２℃未満の場合、熱成形後の容器の光沢に劣る。 In the film for laminating thermoformed sheets of the present invention, the propylene homopolymer used for the base layer has a melting point measured by a differential scanning calorimeter of 162 ° C. or higher, preferably 163 ° C. or higher, preferably in the range of 163 to 170 ° C. . When the melting point of polypropylene used for the base layer is less than 162 ° C., the gloss of the container after thermoforming is inferior.
また、上記プロピレン単独重合体の２３０℃におけるメルトマスフローレート（ＭＦＲ）は、製膜性を勘案すると２～５０ｇ／１０分、好ましくは、４～２０ｇ／１０分の範囲が好適である。さらに好ましくは、６～１５ｇ／１０分の範囲が製膜時の厚薄を安定させるために好ましい。 Also, the melt mass flow rate (MFR) at 230 ° C. of the propylene homopolymer is 2 to 50 g / 10 minutes, preferably 4 to 20 g / 10 minutes considering the film forming property. More preferably, the range of 6 to 15 g / 10 min is preferable in order to stabilize the thickness at the time of film formation.
上記のようなプロピレン単独重合体を主成分としてなる基層の厚みは、１０μｍ以上、好ましくは１２μｍ以上であり、１２～８０μｍの範囲が特に好ましい。基層の厚みが１０μｍ未満の場合、熱成形後の容器の光沢に劣る。 The thickness of the base layer composed mainly of the propylene homopolymer as described above is 10 μm or more, preferably 12 μm or more, and particularly preferably in the range of 12 to 80 μm. When the thickness of the base layer is less than 10 μm, the gloss of the container after thermoforming is inferior.
光沢層に用いるプロピレン系ランダム共重合体とは、プロピレンとα－オレフィン（エチレンを含む）とのランダム共重合体である。α－オレフィンとしては、炭素数２～１０のα－オレフィンが好ましく、具体的には、エチレン、ブテン、ペンテン－１、ヘキセン－１、オクテン－１等が好ましく用いられる。プロピレン系ランダム共重合体におけるプロピレン単位の含有割合は、９９．７～８５質量％、好ましくは９９～９０質量％である。尚、前記プロピレン系ランダム共重合体の共重合組成は、後記の核磁気共鳴装置を用いて測定することができる。 The propylene random copolymer used for the glossy layer is a random copolymer of propylene and α-olefin (including ethylene). As the α-olefin, an α-olefin having 2 to 10 carbon atoms is preferable, and specifically, ethylene, butene, pentene-1, hexene-1, octene-1, and the like are preferably used. The content of propylene units in the propylene random copolymer is 99.7 to 85% by mass, preferably 99 to 90% by mass. The copolymer composition of the propylene random copolymer can be measured using a nuclear magnetic resonance apparatus described later.
これらの中でもプロピレン系ランダム共重合体としては、プロピレン－エチレンランダム共重合体、プロピレン－エチレン－ブテンランダム共重合体が好ましく、組成分布が狭いプロピレン系ランダム共重合体が更に好ましい。特に好ましいプロピレン系ランダム共重合体としては、メタロセン触媒により製造された、ゲルパーミエーションクロマトグラフィーで測定される重量平均分子量（Ｍｗ）と数平均分量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が４．５以下のプロピレン系ランダム共重合体が例示できる。これらプロピレン系ランダム共重合体は、それぞれ単独で使用しても、２種類以上使用してもよい。 Among these, the propylene random copolymer is preferably a propylene-ethylene random copolymer or a propylene-ethylene-butene random copolymer, and more preferably a propylene random copolymer having a narrow composition distribution. As a particularly preferred propylene-based random copolymer, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography produced by a metallocene catalyst is 4 .5 or less propylene random copolymer can be exemplified. These propylene random copolymers may be used alone or in combination of two or more.
プロピレン系ランダム共重合体について、示差走査熱量計によって測定される融点は１３０℃以上が好ましく、１３３℃以上が更に好ましい。１３０℃未満の場合、成形後の容器において電子レンジ等による加熱後の耐熱性に劣る。したがって、プロピレン系ランダム共重合体の融点は、１３３～１５７℃の範囲にあることが特に好ましい。上記プロピレン系ランダム共重合体の融点は、その製造工程における共重合させるモノマーの種類、割合を適宜選択する公知の方法によって調整することができる。 For the propylene random copolymer, the melting point measured by a differential scanning calorimeter is preferably 130 ° C. or higher, more preferably 133 ° C. or higher. When the temperature is lower than 130 ° C., the molded container is inferior in heat resistance after heating with a microwave oven or the like. Therefore, the melting point of the propylene random copolymer is particularly preferably in the range of 133 to 157 ° C. The melting point of the propylene-based random copolymer can be adjusted by a known method for appropriately selecting the type and ratio of monomers to be copolymerized in the production process.
また、上記プロピレン系ランダム共重合体の２３０℃におけるＭＦＲは、製膜性を勘案すると２～５０ｇ／１０分、好ましくは、４～２０ｇ／１０分の範囲が好適である。さらに好ましくは、６～１５ｇ／１０分の範囲が製膜時の厚薄を安定させるために好ましい。 The MFR at 230 ° C. of the propylene random copolymer is 2 to 50 g / 10 minutes, preferably 4 to 20 g / 10 minutes considering the film forming property. More preferably, the range of 6 to 15 g / 10 min is preferable in order to stabilize the thickness at the time of film formation.
上記のようなプロピレン系ランダム共重合体を主成分としてなる光沢層の厚みは１μｍ以上であり、好ましくは２μｍ以上、２～１０μｍの範囲が特に好ましい。光沢層の厚みが１μｍ未満の場合、白濁感に劣り、また熱成形後の光沢に劣る。特に深絞り容器を成形した場合光沢の低下が著しい。 The thickness of the gloss layer mainly composed of the propylene-based random copolymer as described above is 1 μm or more, particularly preferably 2 μm or more and 2 to 10 μm. When the thickness of the gloss layer is less than 1 μm, the cloudiness is inferior and the gloss after thermoforming is inferior. In particular, when a deep-drawn container is formed, the gloss is remarkably reduced.
また、樹脂シートとの積層の際、樹脂シートと積層用フィルムとの接着性を向上する目的で、積層フィルムの光沢層と反対の基層面に接着層を設けても良い。また基層の両面に光沢層を設けた場合には、一方の光沢層を接着層として使用してもよく、また一方の光沢層の表面に接着層を設けても良い。接着層は、たとえば、融点が１３０℃以上のプロピレン系ランダム共重合体を１μｍ以上積層することで形成できる。接着層を設ける場合、その厚みは１μｍ以上であり、好ましくは２μｍ以上、２～１０μｍの範囲が特に好ましい。接着層の厚みが１μｍ未満の場合、十分な接着性が得られないおそれがある。接着層を構成するプロピレン系ランダム共重合体については特に制限するものではないが、前記光沢層に用いるプロピレン系ランダム共重合体が好適に使用できる。 Moreover, when laminating with the resin sheet, an adhesive layer may be provided on the base layer surface opposite to the glossy layer of the laminated film for the purpose of improving the adhesion between the resin sheet and the laminating film. When a gloss layer is provided on both surfaces of the base layer, one gloss layer may be used as an adhesive layer, or an adhesive layer may be provided on the surface of one gloss layer. The adhesive layer can be formed, for example, by laminating 1 μm or more of a propylene random copolymer having a melting point of 130 ° C. or higher. When the adhesive layer is provided, the thickness is 1 μm or more, preferably 2 μm or more and 2 to 10 μm. When the thickness of the adhesive layer is less than 1 μm, sufficient adhesion may not be obtained. Although it does not restrict | limit especially about the propylene random copolymer which comprises an contact bonding layer, The propylene random copolymer used for the said glossy layer can be used conveniently.
これら基層、光沢層および必要に応じ接着層を含む本発明の熱成形シート積層用フィルムの総厚みは、前記基層および光沢層の厚みを確保できる総厚みであれば、特に制限されるものでは無いが、一般に、１５～１００μｍ、好ましくは、１８～６０μｍである。また、基層の厚みが積層フィルムの総厚の５０～９０％であることが好ましい。基層の厚みが総厚の５０％未満の場合、熱成形後の表面光沢が低下するおそれがある。また、基層の厚みが総厚の９０％を超えると白濁感が増し、外観が劣化するおそれがある。 The total thickness of the film for laminating thermoformed sheets of the present invention including the base layer, the glossy layer and, if necessary, the adhesive layer is not particularly limited as long as the total thickness can secure the thickness of the base layer and the glossy layer. However, it is generally 15 to 100 μm, preferably 18 to 60 μm. Further, the thickness of the base layer is preferably 50 to 90% of the total thickness of the laminated film. When the thickness of the base layer is less than 50% of the total thickness, the surface gloss after thermoforming may decrease. On the other hand, if the thickness of the base layer exceeds 90% of the total thickness, the cloudiness may increase and the appearance may deteriorate.
本発明の熱成形シート積層用フィルムを構成する基層および光沢層には有機結晶核剤が配合される。無機系結晶核剤では樹脂シートとのラミネート後および熱成形した後の容器の光沢は必ずしも改善されない。 An organic crystal nucleating agent is blended in the base layer and the gloss layer constituting the thermoforming sheet laminating film of the present invention. Inorganic crystal nucleating agents do not necessarily improve the gloss of the container after lamination with a resin sheet and after thermoforming.
　有機結晶核剤としては、ジベンジリデンソルビトール、ジメチルベンジリデンソルビトール等のソルビトール系誘導体、ロジン金属塩化物、安息香酸金属塩、リン酸エステル金属、前記一般式（１）で表されるアミド系化合物等が挙げられる。中でも、リン酸エステル金属塩ではリン酸エステルアルミニウム塩が、アミド系化合物では、前記一般式（１）におけるＲ２が水素原子又はメチル基であるアミド系化合物、例えば１，２，３－プロパントリカルボン酸トリシクロヘキシルアミド、１，２，３－プロパントリカルボン酸トリ（２－メチルシクロヘキシルアミド）、１，２，３－プロパントリカルボン酸トリ（３－メチルシクロヘキシルアミド）、１，２，３－プロパントリカルボン酸トリ（４－メチルシクロヘキシルアミド）、１，２，３，４－ブタンテトラカルボン酸テトラシクロヘキシルアミド、１，２，３，４－ブタンテトラカルボン酸テトラ（２－メチルシクロヘキシルアミド）、１，２，３，４－ブタンテトラカルボン酸テトラ（３－メチルシクロヘキシルアミド）、１，２，３，４－ブタンテトラカルボン酸テトラ（４－メチルシクロヘキシルアミド）などが、熱成形後の光沢向上には最も効果が高い。 Examples of the organic crystal nucleating agent include sorbitol derivatives such as dibenzylidene sorbitol and dimethyl benzylidene sorbitol, rosin metal chloride, benzoic acid metal salt, phosphate metal, amide compound represented by the general formula (1), and the like. Can be mentioned. Among them, phosphoric acid ester aluminum salts are phosphoric acid ester metal salts, and amide compounds are amide compounds in which R 2 in the general formula (1) is a hydrogen atom or a methyl group, such as 1,2,3-propanetricarboxylic acid. Acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid Tri (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra (2-methylcyclohexylamide), 1,2, 3,4-Butanetetracarboxylic acid tetra (3-methylcyclohexylamide ), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide) and the like are most effective in improving gloss after thermoforming.
有機結晶核剤の添加量は、基層および光沢層ともに、ポリプロピレン成分（基層ではプロピレン単独重合体、光沢層ではプロピレン系ランダム共重合体）９９～９９．９７質量％に対して０．０３～１質量％であり、０．１～０．５質量％が好ましく、０．１２～０．４質量％の範囲が特に好ましい。添加量が０．０３質量％未満の場合、印刷時、および樹脂シートとのラミネート時の寸法安定性に劣り、また熱成形後の光沢に劣る。また、有機結晶核剤の添加量が１質量％を超えた場合、成形後の光沢性の向上効果が頭打ちとなり、経済的に不利となる。接着層について、有機結晶核剤の添加の有無は特に限定しない。 The addition amount of the organic crystal nucleating agent is 0.03 to 1 with respect to 99 to 99.97% by mass of the polypropylene component (propylene homopolymer in the base layer and propylene-based random copolymer in the glossy layer) in both the base layer and the gloss layer. % By weight, preferably 0.1 to 0.5% by weight, particularly preferably in the range of 0.12 to 0.4% by weight. When the addition amount is less than 0.03% by mass, the dimensional stability during printing and lamination with the resin sheet is inferior, and the gloss after thermoforming is inferior. Moreover, when the addition amount of an organic crystal nucleating agent exceeds 1 mass%, the improvement effect of the glossiness after shaping | molding will peak, and it becomes economically disadvantageous. With respect to the adhesive layer, the presence or absence of addition of an organic crystal nucleating agent is not particularly limited.
本発明において、上記核剤の添加は熱成形シート積層用フィルムの光沢性等の向上効果以外に、該フィルムの引張弾性率を高くする効果も発揮する。即ち、有機結晶核剤の添加により上記フィルムの流れ方向（以下、ＭＤ方向と記す）の引張弾性率は１０００ＭＰａを超える値を示すようになる。これにより本発明において、熱成形シート積層用フィルムを樹脂シートに積層して熱成形シートを構成する際、積層時のラミネート適性に優れるという効果を発揮する。また、後述するように、印刷層を形成する際にも、ピッチ安定性に優れるため、定位置成形容器を製造する際に有効である。定位置成形容器とは、絵柄を常に一定の位置に合わせた成形容器である。定位置成形をするためには、積層用フィルムに印刷する際、ピッチずれが少なく、また、積層用フィルムと樹脂シートとのラミネート時にもピッチずれが少ないことが要求される。本発明の熱成形シート積層用フィルムはかかる要望に応えるものである。 In the present invention, the addition of the nucleating agent exhibits an effect of increasing the tensile elastic modulus of the film in addition to the effect of improving the glossiness of the film for thermoforming sheet lamination. That is, by adding the organic crystal nucleating agent, the tensile elastic modulus in the flow direction of the film (hereinafter referred to as MD direction) exhibits a value exceeding 1000 MPa. Thereby, in this invention, when laminating | stacking the film for thermoforming sheet | seat lamination | stacking on a resin sheet and comprising a thermoforming sheet | seat, the effect that it is excellent in the lamination suitability at the time of lamination | stacking is exhibited. Further, as will be described later, when forming a printed layer, the pitch stability is excellent, which is effective in producing a fixed-position molded container. A fixed-position molded container is a molded container in which the pattern is always matched at a certain position. In order to perform fixed position molding, it is required that there is little pitch deviation when printing on a laminating film and that there is little pitch deviation when laminating a laminating film and a resin sheet. The film for laminating thermoformed sheets of the present invention meets this demand.
また、本発明の熱成形シート積層用フィルムには、必要に応じてポリプロピレン、ポリエチレン、ポリスチレン、ポリアミド、ポリエチレンテレフタレート等の他の熱成形可能なフィルムをドライラミネート、押出ラミネート法等の公知の方法にてラミネートして使用できる。この場合ラミネートする面は、基層側であることが必要である。 In addition, for the thermoforming sheet laminating film of the present invention, other thermoformable films such as polypropylene, polyethylene, polystyrene, polyamide, polyethylene terephthalate and the like can be applied to known methods such as dry laminating and extrusion laminating as necessary. Can be laminated. In this case, the surface to be laminated needs to be on the base layer side.
本発明の熱成形シート積層用フィルムの原料樹脂には、必要に応じて帯電防止剤、防曇剤、アンチブロッキング剤、酸化防止剤、光安定剤、滑剤、界面活性剤、着色剤、抗菌剤等の公知の添加剤を配合しても良い。 The raw resin for the film for laminating the thermoformed sheet of the present invention includes an antistatic agent, an antifogging agent, an antiblocking agent, an antioxidant, a light stabilizer, a lubricant, a surfactant, a colorant, and an antibacterial agent as necessary. You may mix | blend well-known additives, such as.
本発明の熱成形シート積層用フィルムは無延伸法にて製膜されたものである。代表的な方法を例示すれば、Ｔダイスを使用した押出成形法、環状ダイスを使用したインフレーション成形法が挙げられる。上記成形法において、前記熱成形シート積層用フィルムは、例えば、フィードブロック法やマルチマニホールド法によるＴダイスによる共押出法が好適に用いられる。 The film for laminating thermoformed sheets of the present invention is formed by a non-stretching method. Examples of typical methods include an extrusion molding method using a T die and an inflation molding method using an annular die. In the above molding method, for example, a co-extrusion method using a T die by a feed block method or a multi-manifold method is preferably used as the film for laminating thermoformed sheets.
　上記Ｔダイスを使用した押出成形法について、具体的に示せば、熱成形シート積層用フィルムを構成する樹脂組成物をそれぞれの押出機にてＴダイス法により溶融物を押し出し、温度調整可能なロールまたは温度調整可能な水槽により冷却し巻き取る方法、あるいは、該溶融物を空冷法または水冷法により冷却し巻き取る方法等を挙げることができる。 Regarding the extrusion method using the above-mentioned T dice, specifically, a roll capable of adjusting the temperature by extruding the resin composition constituting the film for laminating thermoformed sheets by the T dice method in each extruder. Alternatively, a method of cooling and winding with a temperature-adjustable water tank, or a method of cooling and winding the melt by an air cooling method or a water cooling method can be exemplified.
　得られる積層用フィルムは、巻き取り時のテンション等によりわずかに延伸される程度の低延伸または実質的に無延伸のフィルムである。本発明の積層用フィルムは、低延伸フィルムまたは実質的に無延伸のフィルムであることから、熱成形条件の制約が少なく、特に深絞り容器のような熱成形体の製造に適している。 The resulting laminating film is a low stretch or a substantially unstretched film that is slightly stretched by the tension during winding. Since the laminating film of the present invention is a low-stretched film or a substantially unstretched film, there are few restrictions on thermoforming conditions, and it is particularly suitable for the production of thermoformed bodies such as deep-drawn containers.
本発明の熱成形シート積層用フィルムには用途に応じて表面処理を施し、印刷することができる。表面処理の方法は特に制限するものではないが一般的に印刷インキとの密着性を向上する目的でコロナ放電処理、火炎処理等を行っても構わない。また、表面処理を施す面も特に制限はなく、片面、両面のいずれでも構わない。 The film for laminating thermoformed sheets of the present invention can be subjected to surface treatment according to the use and printed. The surface treatment method is not particularly limited, but generally, a corona discharge treatment, a flame treatment, or the like may be performed for the purpose of improving the adhesion with the printing ink. Further, the surface to be surface-treated is not particularly limited, and may be either one side or both sides.
このようにして表面処理された本発明の熱成形シート積層用フィルムは、光沢層と反対の面に印刷層が形成される。本発明の積層用フィルムは、印刷ピッチ安定性に優れるため、精度の高い印刷フィルムが得られる。印刷層は、フィルムが光沢層と基層とからなる場合には、基層面に形成する。またフィルムが光沢層と基層と接着層とがこの順に積層されてなる場合には、接着層表面に印刷層を形成する。また、基層の両面に光沢層を形成した場合には、樹脂シート側に配置される光沢層面に印刷層を形成する。 The surface-treated film for laminating thermoformed sheets of the present invention has a printing layer on the surface opposite to the glossy layer. Since the laminating film of the present invention is excellent in printing pitch stability, a highly accurate printing film can be obtained. When the film is composed of a gloss layer and a base layer, the print layer is formed on the base layer surface. Further, when the film is formed by laminating a gloss layer, a base layer, and an adhesive layer in this order, a printing layer is formed on the surface of the adhesive layer. In addition, when the gloss layer is formed on both surfaces of the base layer, the print layer is formed on the gloss layer surface disposed on the resin sheet side.
通常、印刷、ラミネート時におけるフィルムの引張張力は５０～１００Ｎ／ｍであり、この際のフィルム温度は６０℃以上となる。印刷時のピッチを安定させるためには、フィルムの流れ方向（以下、ＭＤ方向と記す）の２３℃での引張弾性率が１０００ＭＰａ以上であることが好ましく、熱成形シート積層用フィルムのフィルム幅が１０００ｍｍ幅で１００Ｎ加重時の１００℃における寸法変化率が１５％以下であることが好ましい。本発明の積層用フィルムは、有機結晶核剤の添加により上記フィルムのＭＤ方向の引張弾性率が１０００ＭＰａを超える値を示すようになるため、印刷およびラミネート適性に優れる。したがって、本発明の積層用フィルムを用いた印刷フィルムを樹脂シートと貼り合せ、熱成形することで、表面光沢に優れた定位置成形容器を得ることができる。 Usually, the tensile tension of the film during printing and laminating is 50 to 100 N / m, and the film temperature at this time is 60 ° C. or higher. In order to stabilize the pitch during printing, the tensile elastic modulus at 23 ° C. in the film flow direction (hereinafter referred to as MD direction) is preferably 1000 MPa or more, and the film width of the thermoformed sheet laminating film is It is preferable that the dimensional change rate at 100 ° C. with a width of 1000 mm and a load of 100 N is 15% or less. The lamination film of the present invention is excellent in printing and lamination suitability because the tensile elastic modulus in the MD direction of the film exceeds 1000 MPa by the addition of the organic crystal nucleating agent. Therefore, a fixed-position molded container excellent in surface gloss can be obtained by laminating a printing film using the laminating film of the present invention with a resin sheet and thermoforming it.
　上記熱成形シートのベースとして用いられる樹脂シートは、熱成形に使用される公知のものが何ら制限なく使用される。例えば、ポリプロピレン系樹脂としては、プロピレンの単独重合体、プロピレンを主構成単位とした、プロピレン以外のα－オレフィンとの共重合体が一般に使用される。具体的には、プロピレン単独重合体、プロピレン系ランダム共重合体、プロピレン系ブロック共重合体等からなるポリプロピレン系シートが挙げられる。 As the resin sheet used as the base of the thermoformed sheet, a known sheet used for thermoforming can be used without any limitation. For example, as a polypropylene resin, a homopolymer of propylene and a copolymer with an α-olefin other than propylene and having propylene as a main constituent unit are generally used. Specific examples include a polypropylene sheet made of a propylene homopolymer, a propylene random copolymer, a propylene block copolymer, and the like.
　また、他の樹脂としては、ポリエチレン、ポリスチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。 Also, other resins include polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, and the like.
　また、前記ポリプロピレン系シートの形態としては、上記ポリプロピレン系樹脂を単にシート状に成形したもの、ポリプロピレン系樹脂にフィラーを配合した組成物をシート状に成形したもの（フィラー含有シート）、ポリプロピレン系樹脂を発泡せしめてシート状に成形したもの（発泡シート）などである。 In addition, the form of the polypropylene-based sheet is simply a sheet of the above-mentioned polypropylene-based resin, a sheet-shaped composition obtained by blending a polypropylene-based resin with a filler (filler-containing sheet), or a polypropylene-based resin. Foamed and formed into a sheet shape (foamed sheet).
ポリプロピレン系樹脂にフィラーを配合した組成物をシート状に成形したもの（フィラー含有シート）を使用する場合には、フィラーを含有しない層を積層した積層シートを用いることが好ましい。この場合、積層シートのフィラーが含有されていない層の面に、積層用フィルムを積層することで、成形後の光沢がより高くなる。この場合の熱成形シートの構成は、例えば、フィラー含有層／フィラー不含有層／本発明の熱成形シート積層用フィルムである。フィラー不含有層は、フィラー含有層との共押出法あるいはフィラー含有シートへの押出ラミネート法にて形成することができる。 When using what formed the composition which mix | blended the filler with the polypropylene resin in the sheet form (filler containing sheet), it is preferable to use the lamination sheet which laminated | stacked the layer which does not contain a filler. In this case, the gloss after molding becomes higher by laminating the laminating film on the surface of the layer not containing the filler of the laminated sheet. The structure of the thermoformed sheet in this case is, for example, filler-containing layer / filler-free layer / thermoformed sheet laminating film of the present invention. The filler-free layer can be formed by a co-extrusion method with a filler-containing layer or an extrusion lamination method to a filler-containing sheet.
　前記樹脂シートの厚みも特に制限されないが、熱成形性を勘案すると、０．２～３ｍｍが好ましい。 The thickness of the resin sheet is not particularly limited, but is preferably 0.2 to 3 mm in consideration of thermoformability.
　また、上記積層方法は、熱成形シート積層用フィルムの特性を著しく変化させない公知の方法が特に制限なく用いることができる。例えば、押出ラミネート法、熱ラミネート法、ドライラミネート法などの方法が使用できる。より具体的には、チルロール上にセットされた本発明の熱成形シート積層用フィルムに、樹脂シートを形成する樹脂を押出機よりラミネートする方法が推奨される。この場合、チルロールの表面は平滑な鏡面ロールであることが好ましい。 In addition, as the laminating method, a known method that does not significantly change the properties of the thermoforming sheet laminating film can be used without any particular limitation. For example, methods such as an extrusion lamination method, a heat lamination method, and a dry lamination method can be used. More specifically, a method of laminating a resin for forming a resin sheet on the thermoforming sheet laminating film of the present invention set on a chill roll by an extruder is recommended. In this case, the surface of the chill roll is preferably a smooth mirror surface roll.
　本発明の熱成形シート積層用フィルムは、前記ポリプロピレン系シート等の樹脂シートに積層して、弁当容器、トレー、丼容器等の食品容器、一般容器、工業部品容器等の熱成形体を製造するための熱成形シートとして好適に使用できる。 The film for laminating thermoformed sheets of the present invention is laminated on a resin sheet such as the polypropylene sheet to produce thermoformed bodies such as lunch containers, trays, food containers such as bowl containers, general containers, and industrial parts containers. Therefore, it can be suitably used as a thermoformed sheet.
　さらに、本発明は、熱成形シートを加熱後、真空成形、圧空成形、真空圧空成形等により、金型等の型枠内にて賦形した後冷却して得られた熱成形体をも包含する。 Furthermore, the present invention also includes a thermoformed product obtained by cooling a thermoformed sheet after forming in a mold such as a mold by vacuum forming, pressure forming, vacuum pressure forming, etc. To do.
　以下、本発明を実施例及び比較例を掲げて説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例、及び、比較例において使用したフィルムの原料樹脂を表１に、使用した結晶核剤を表２に示す。
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
 Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the raw material resin of the film used in the following Examples and Comparative Examples is shown in Table 1, and the crystal nucleating agent used is shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
　また、実施例及び比較例においてベースとなる樹脂シートとして使用した、ポリプロピレン系シートを表３に示す。
Figure JPOXMLDOC01-appb-T000005
 Table 3 shows the polypropylene-based sheets used as the base resin sheets in the examples and comparative examples.
Figure JPOXMLDOC01-appb-T000005
　実施例及び比較例における樹脂及びフィルム物性等の測定については以下の方法により行った。 The measurement of resin and film properties in Examples and Comparative Examples was performed by the following method.
（１） 共重合組成
　核磁気共鳴分光装置（日本電子（株）製ＪＮＭ－ＧＳＸ－２７０（13Ｃ－核共鳴周波数６７．８ＭＨｚ）を用いて、次の条件で測定した。 (1) Copolymerization composition Using a nuclear magnetic resonance spectrometer (JNM-GSX-270 ( 13 C-nuclear resonance frequency 67.8 MHz) manufactured by JEOL Ltd.), measurement was performed under the following conditions.
　測定モード：１Ｈ－完全デカップリング
　パルス幅：９０度パルス
パルス繰返し時間：３秒
　積算回数：１００００回
　溶媒：オルトジクロルベンゼン／重ベンゼンの混合溶媒（７６／２４容量％）
　試料濃度：１２０ｍｇ／２．５ｍｌ溶媒
　測定温度：１２０℃
　共重合組成の定量はＭ．ｋａｋｕｇｏ，Ｙ，Ｎａｉｔｏ，Ｋ．Ｍｉｚｕｎｕｍａ，Ｔ．Ｍｉｙａｔａｋｅ，［Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１５，１１５０（１９８２）］に従って行った。 Measurement mode: 1 H-complete decoupling Pulse width: 90 degree pulse pulse repetition time: 3 seconds Integration number: 10000 times Solvent: Mixed solvent of orthodichlorobenzene / heavy benzene (76/24 vol%)
Sample concentration: 120 mg / 2.5 ml solvent Measurement temperature: 120 ° C.
The quantification of the copolymer composition is described in M.C. kakugo, Y, Naito, K.K. Mizunuma, T .; According to Miyatake, [Macromolecules, 15, 1150 (1982)].
（２）メルトマスフローレイト（ＭＦＲ）
　ＪＩＳ　Ｋ７２１０に準拠して、２３０℃でのＭＦＲを測定した。 (2) Melt mass flow rate (MFR)
MFR at 230 ° C. was measured according to JIS K7210.
（３）光沢（グロス）
　ＪＩＳ　Ｋ７１０５に準拠して、６０度鏡面法で測定した。 (3) Gloss (Gloss)
Based on JIS K7105, it measured by the 60-degree specular method.
　尚、積層用フィルム、熱成形シートについては、光沢層面を測定した。 In addition, about the film for lamination | stacking and the thermoforming sheet | seat, the glossy layer surface was measured.
　また、成形容器は、熱成形シートの光沢層面が容器の内面となるように、（株）浅野研究所製コスミック成形機ＦＫ－０６３１－２０型にて、加熱ヒーター温度５００～５３０℃、真空度７０ｍｍＨｇで、容器（皿容器：縦１９５ｍｍ、横１４５ｍｍ、高さ２８ｍｍ、丼容器：１６８ｍｍφ、高さ５０ｍｍ）を真空成形したもので評価した。尚、成形時のフィルム表面温度は、１７５℃であった。 Further, the molded container was heated at a heater temperature of 500 to 530 ° C. with a cosmic molding machine FK-0631-20 manufactured by Asano Laboratories, so that the gloss layer surface of the thermoformed sheet became the inner surface of the container. A container (dish container: 195 mm long, 145 mm wide, 28 mm high, bowl container: 168 mmφ, 50 mm high) was evaluated at 70 mmHg. In addition, the film surface temperature at the time of shaping | molding was 175 degreeC.
　また、成形容器の光沢性について以下の３段階で評価した。 Also, the glossiness of the molded container was evaluated in the following three stages.
　○：グロス７５％以上
　△：グロス６５％以上、７５％未満
　×：グロス６５％未満
（４）示差走査熱量計によって測定される融点および結晶化温度
　約５～６ｍｇの試料を秤量後アルミパンに封入し、示差走査熱量計（セイコー電子工業（株）製ＤＳＣ６２００Ｒ）にて、２０ｍｌ／分で供給される窒素気流中で２３０℃まで昇温し、この温度で１０分間保持し、次いで降温速度１０℃／分で２０℃まで冷却する。次いで、昇温速度１０℃／分で２３０℃まで昇温する際に得られる吸熱曲線において最大吸熱を示すピーク温度を融点とした。また、結晶化温度は、ＪＩＳ　Ｋ７１２１に準じて樹脂を一旦融解した後、冷却し結晶化が開始した際の温度を測定した。 ○: Gross 75% or more Δ: Gloss 65% or more, less than 75% ×: Gloss less than 65% (4) Melting point and crystallization temperature measured by differential scanning calorimeter Approximately 5 to 6 mg of sample was weighed into an aluminum pan The sample was sealed, heated with a differential scanning calorimeter (DSC6200R manufactured by Seiko Denshi Kogyo Co., Ltd.) in a nitrogen stream supplied at 20 ml / min, maintained at this temperature for 10 minutes, and then cooled at a rate of 10 Cool to 20 ° C at ° C / min. Next, the peak temperature showing the maximum endotherm in the endothermic curve obtained when the temperature was raised to 230 ° C. at a rate of temperature rise of 10 ° C./min was taken as the melting point. The crystallization temperature was measured by melting the resin once according to JIS K7121 and then cooling to start crystallization.
（５）引張弾性率
　積層用フィルムから幅１０ｍｍ、長さ１００ｍｍのサンプルを、製膜加工時のフィルムの流れ方向に切り出し、サンプルの両端を引張試験機（オートグラフ：（株）島津製作所製）のチャックで固定した。この場合、サンプルの長さ方向のチャック間隙が２０ｍｍになるように調整した。引張速度２０ｍｍ／ｍｉｎで引張試験を行い、引張応力－歪み曲線を作成した。 (5) Tensile modulus A sample having a width of 10 mm and a length of 100 mm is cut out from the laminating film in the film flow direction during film formation, and both ends of the sample are subjected to a tensile tester (Autograph: manufactured by Shimadzu Corporation). It was fixed with a chuck. In this case, the chuck gap in the length direction of the sample was adjusted to 20 mm. A tensile test was performed at a tensile speed of 20 mm / min to prepare a tensile stress-strain curve.
　引張弾性率は、引張応力－歪み曲線の初めの直線部を用いて次の式によって計算した。 The tensile elastic modulus was calculated by the following formula using the first linear part of the tensile stress-strain curve.
　　　Ｅｍ＝Δδ／Δε
　　　　　Ｅｍ：引張弾性率
　　　　　Δδ：直線上の２点間の、サンプルの元の平均断面積による応力の差
　　　　　Δε：同じ２点間の歪みの差
（６）寸法変化率
　積層用フィルム（厚み２５μｍ）から幅１００ｍｍ、長さ１００ｍｍのサンプルを、製膜加工時のフィルムの流れ方向に切り出し、１０Ｎの重りを取り付け１００℃の雰囲気に加熱されたオーブンに１０分入れ、２３℃の雰囲気で２分放置した後の寸法変化率を測定した。 Em = Δδ / Δε
Em: Tensile modulus Δδ: Difference in stress due to the original average cross-sectional area of the sample between two points on the straight line Δε: Difference in strain between the same two points (6) Dimensional change rate From film for lamination (thickness 25 μm) A sample with a width of 100 mm and a length of 100 mm was cut out in the direction of film flow during film formation, and a 10N weight was attached, and the sample was placed in an oven heated at 100 ° C. for 10 minutes and left at 23 ° C. for 2 minutes. The subsequent dimensional change rate was measured.
（７）成形性
　前記光沢の評価と同様にして容器成型を５０回行い、成形品の割れ（フィルム割れ）を目視により判定し、不良率を計算した。 (7) Formability The container was molded 50 times in the same manner as in the evaluation of the gloss, and the crack (film crack) of the molded product was judged visually, and the defect rate was calculated.
　不良率（％）＝（成形品割れ個数／５０）×１００
（８）白濁感
　上記（７）に記した成形品の容器内面（光沢層面）についてスガ試験機（株）製カラーコンピューター型式ＳＭ－３を用いてハンター白色度「Ｗ（Ｌaｂ）」値を測定した。 Defective rate (%) = (number of cracks in molded product / 50) × 100
(8) White turbidity The Hunter whiteness “W (Lab)” value was measured for the inner surface (glossy layer surface) of the molded product described in (7) above using a color computer model SM-3 manufactured by Suga Test Instruments Co., Ltd. did.
フィルムを積層する前のポリプロピレン系シートのハンター白色度の値と各フィルム積層後の成形容器のハンター白色度の値を比較し評価した。 The value of the hunter whiteness of the polypropylene sheet before laminating the film and the value of the hunter whiteness of the molded container after laminating each film were compared and evaluated.
フィルムを積層する前のポリプロピレン系シートのハンター白色度に比べ各フィルム積層後の成形容器のハンター白色度の値が大きいほど白濁感が増すことを意味し以下の３段階で評価した。 The larger the Hunter Whiteness value of the molded container after each film was laminated, the greater the cloudiness, compared to the Hunter Whiteness of the polypropylene sheet before the film was laminated.
　○：（フィルム積層後の成形容器のハンター白色度）－（フィルムを積層する前のポリプロピレン系シートのハンター白色度）＝２％未満
　△：（フィルム積層後の成形容器のハンター白色度）－（フィルムを積層する前のポリプロピレン系シートのハンター白色度）＝２％以上、５％未満
　×：（フィルム積層後の成形容器のハンター白色度）－（フィルムを積層する前のポリプロピレン系シートのハンター白色度）＝５％以上
（９）シートとの接着性
　上記（３）に記した成形機および金型を用いた成形品にて、樹脂シートと積層用フィルムとの接着強度を引張試験機（オートグラフ：（株）島津製作所製）にて幅１５ｍｍで引張速度３００ｍｍ／ｍｉｎで１８０°剥離引張試験を行い、以下の３段階で評価した。 ○: (Hunter whiteness of molded container after film lamination) − (Hunter whiteness of polypropylene sheet before film lamination) = less than 2% Δ: (Hunter whiteness of molded container after film lamination) − ( Hunter whiteness of polypropylene sheet before film lamination) = 2% or more and less than 5% ×: (hunter whiteness of molded container after film lamination) − (hunter whiteness of polypropylene sheet before film lamination) Degree) = 5% or more (9) Adhesiveness to sheet In the molded article using the molding machine and mold described in (3) above, the tensile strength of the adhesive strength between the resin sheet and the laminating film is measured (auto Graph: manufactured by Shimadzu Corporation) was subjected to a 180 ° peel tensile test at a width of 15 mm and a tensile speed of 300 mm / min, and was evaluated in the following three stages.
　◎ ：接着強度１．０Ｎ／１５ｍｍ以上
　○　：接着強度０．５Ｎ／１５ｍｍ以上、１．０Ｎ／１５ｍｍ未満
　×　：接着強度０．５Ｎ／１５ｍｍ未満
実施例１
　フィルム用原料樹脂として表１に示す樹脂Ａ（融点１６５℃のプロピレン単独重合体（住友化学社製ＦＬＸ８０Ｇ７））９９．８質量％に表２に示す核剤Ｉを０．２質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を基層用とした。表１に示す樹脂Ｅ（エチレン含有量が３．４質量％、融点が１４６℃のプロピレン－エチレンランダム共重合体（日本ポリプロ社製ＦＷ３ＧＴ））９９．８質量％に表２に示す核剤Ｉを０．２質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を光沢層用とした。次に光沢層用樹脂を押出機Ａ（５０ｍｍφ押出機）に、基層用樹脂を押出機Ｂ（７５ｍｍφ押出機）に供給し２５０℃で加熱溶融しフィードブロック方式で共押出法にてダイリップ１．２ｍｍのＴダイスより押出し、４０℃の冷却ロール上で冷却固化しながら光沢層が５μｍ、基層が２０μｍになる様調整し、計２５μｍのフィルムとし、基層側表面に表面張力が４２ｍＮ／ｍになるようにコロナ放電処理を施した後、巻取り機にて巻取り、熱成形シート積層用フィルムを得た。 A: Adhesive strength 1.0 N / 15 mm or more B: Adhesive strength 0.5 N / 15 mm or more, less than 1.0 N / 15 mm X: Adhesive strength less than 0.5 N / 15 mm Example 1
As a raw material resin for film, 99.8% by mass of resin A (propylene homopolymer having a melting point of 165 ° C. (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.)) shown in Table 1 was blended with 0.2% by mass of nucleating agent I shown in Table 2 to obtain 65 mmφ. Extrusion pelletization was performed at 250 ° C. with an extruder, and the obtained resin was used for a base layer. Nucleating agent I shown in Table 2 in 99.8% by mass of resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro)) 0.2 mass% was blended and extruded at 250 ° C. with a 65 mmφ extruder to form pellets, and the resulting resin was used for a glossy layer. Next, the gloss layer resin is supplied to Extruder A (50 mmφ extruder), the base layer resin is supplied to Extruder B (75 mmφ extruder), heated and melted at 250 ° C., and die lip 1. Extruded from a 2mm T-die and cooled and solidified on a 40 ° C cooling roll, adjusted so that the gloss layer is 5μm and the base layer is 20μm, making a total 25μm film, and the surface tension on the base layer side surface is 42mN / m After performing the corona discharge treatment as described above, the film was wound by a winder to obtain a film for thermoforming sheet lamination.
　該フィルムのコロナ放電処理を施した面の上に、タルクが３０質量％添加されたポリプロピレン系シート（黒）厚み０．５ｍｍを２５０℃で押出しながら４０℃の冷却ロールで固化しポリプロピレン系熱成形シートを得た。 A polypropylene sheet (black) to which 30% by mass of talc is added on the surface subjected to corona discharge treatment of the film is solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.5 mm at 250 ° C. A sheet was obtained.
　得られた熱成形シートをフィルムの表面温度１７５℃にて真空成形し容器の光沢、白濁度（ハンター白色度）、シートとフィルムの接着性について評価しその結果を表５に示した。成形容器のグロスは皿容器で７８％、丼容器で７８％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化なく白濁感のない容器であった。 The obtained thermoformed sheet was vacuum-formed at a film surface temperature of 175 ° C., and the gloss, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated. The results are shown in Table 5. The gloss of the molded container is 78% in the dish container and 78% in the bowl container, and the surface gloss is good, and the hunting whiteness of the polypropylene sheet before bonding the film is 12%. It was a container with almost no change and 12-13%.
　実施例２～３
　光沢層が２μｍ、基層が２３μｍになる様調整し、計２５μｍ（実施例２）へ、光沢層が１０μｍ、基層が１５μｍになる様調整し、計２５μｍ（実施例３）に変更すること以外は、実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。実施例２では、成形容器のグロスは皿容器で７７％、丼容器で７６％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化なく白濁感のない容器であった。実施例３では、成形容器のグロスは皿容器で７９％、丼容器で７９％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく全く白濁感のない容器であった。 Examples 2 to 3
Except for adjusting the gloss layer to 2 μm and the base layer to 23 μm and adjusting to a total of 25 μm (Example 2), adjusting the gloss layer to 10 μm and the base layer to 15 μm and changing to a total of 25 μm (Example 3). In the same manner as in Example 1, film formation, lamination, thermoforming, and evaluation were performed. The results are shown in Table 5. In Example 2, the gloss of the molded container is 77% for the dish container and 76% for the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene-based sheet before film bonding is 12%. The molded container was 12 to 13%, and it was a container with almost no change in white turbidity. In Example 3, the gloss of the molded container is 79% in the dish container and 79% in the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is 12%. The molded container was 12% with no change and no cloudiness.
　実施例４
　実施例１の光沢層用樹脂を表１に示す樹脂Ｈ（エチレン含有量が４．２質量％、融点が１３５℃のメタロセン触媒系プロピレン－エチレンランダム共重合体（日本ポリプロ社製ＷＦＷ４））とした以外は、全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８２％、丼容器で８１％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Example 4
The gloss layer resin of Example 1 is shown in Table 1. Resin H (metallocene catalyst-based propylene-ethylene random copolymer (WFW4 manufactured by Nippon Polypro Co., Ltd.) having an ethylene content of 4.2 mass% and a melting point of 135 ° C.) and Except for the above, film formation, lamination, thermoforming, and evaluation were performed in the same manner. The results are shown in Table 5. The gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good. The white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, The container was little changed as 12-13% and had no cloudiness.
　実施例５～６
　実施例４の光沢層と基層の厚みを、光沢層が２μｍ、基層が２３μｍになる様調整し、計２５μｍ（実施例５）へ、光沢層が１０μｍ、基層が１５μｍになる様調整し、計２５μｍ（実施例６）に変更すること以外は、実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。実施例５では、成形容器のグロスは皿容器で８１％、丼容器で８１％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１３％とほとんど変化なく白濁感のない容器であった。実施例６では、成形容器のグロスは皿容器で８４％、丼容器で８２％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく全く白濁感のない容器であった。 Examples 5-6
The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 2 μm and the base layer was 23 μm, and adjusted to a total of 25 μm (Example 5), so that the gloss layer was 10 μm and the base layer was 15 μm. Except for changing to 25 μm (Example 6), film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1. The results are shown in Table 5. In Example 5, the gloss of the molded container is 81% in the dish container and 81% in the bowl container, and the surface gloss is extremely good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12 %, 13% of the molded container and almost no change and no cloudiness. In Example 6, the gloss of the molded container is 84% for the dish container and 82% for the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is 12% for the cloudiness. The molded container was 12% with no change and no cloudiness.
　実施例７
　実施例４の基層用樹脂を表１に示す樹脂Ｂ（融点１６４℃のプロピレン単独重合体（サンアロマー社製ＰＣ６００Ａ））とした以外は、全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８２％、丼容器で８２％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Example 7
Except that the resin for base layer of Example 4 was resin B shown in Table 1 (propylene homopolymer having a melting point of 164 ° C. (PC600A manufactured by Sun Allomer Co., Ltd.)), film formation, lamination, thermoforming, and evaluation were performed in the same manner. went. The results are shown in Table 5. The gloss of the molded container is 82% in the dish container and 82% in the bowl container, and the surface gloss is very good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was little changed as 12-13% and had no cloudiness.
　実施例８
　実施例４の光沢層および基層に添加する核剤Ｉの添加量を０．１質量％とした以外は、全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８０％、丼容器で８０％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Example 8
Film formation, lamination, thermoforming, and evaluation were performed in the same manner except that the addition amount of the nucleating agent I added to the gloss layer and the base layer in Example 4 was 0.1% by mass. The results are shown in Table 5. The gloss of the molded container is 80% in the dish container and 80% in the bowl container, and the surface gloss is very good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was little changed as 12-13% and had no cloudiness.
　実施例９～１０
　実施例４の光沢層用樹脂を表１に示す樹脂Ｆ（エチレン含有量が３．２質量％、ブテン含有量が１．５質量％、融点が１３７℃のプロピレン－エチレン－ブテン三元ランダム共重合体（日本ポリプロ社製ＦＷ４ＢＴ））とし（実施例９）、光沢層用樹脂を表１に示す樹脂Ｇ（エチレン含有量が２．２質量％、ブテン含有量が６．８質量％、融点が１３３℃のプロピレン－エチレン－ブテン三元ランダム共重合体（プライムポリマ社製Ｆ７９４ＮＶ））とした（実施例１０）以外は、全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。実施例９、１０ともに、成形容器のグロスは皿容器で７８％、丼容器で７８％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Examples 9-10
The gloss layer resin of Example 4 is represented by Resin F (Propylene-ethylene-butene ternary random copolymer having an ethylene content of 3.2% by mass, a butene content of 1.5% by mass, and a melting point of 137 ° C.) (Example 9), and the resin for the gloss layer shown in Table 1 is resin G (ethylene content is 2.2 mass%, butene content is 6.8 mass%, melting point) Film forming, laminating, thermoforming, and evaluation were carried out in the same manner except that (Example 10) was a propylene-ethylene-butene ternary random copolymer (F794NV manufactured by Prime Polymer Co., Ltd.) at 133 ° C. . The results are shown in Table 5. In both Examples 9 and 10, the gloss of the molded container is 78% in the dish container and 78% in the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene-based sheet before film lamination is also about the cloudiness. It was a container with almost no change and no cloudiness, with 12% and 12-13% after molding.
　実施例１１
　表１に示す樹脂Ａ９９．８質量％に表２に示す核剤Ｉを０．２質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を基層用とした。表１に示す樹脂Ｈ９９．８質量％に表２に示す核剤Ｉを０．２質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を光沢層用とした。接着層樹脂として表１に示す樹脂Ｅ単体を使用した。光沢層用樹脂を押出機Ａ（５０ｍｍφ押出機）に、基層用樹脂を押出機Ｂ（７５ｍｍφ押出機）に、接着層用樹脂を押出機Ｃ（５０ｍｍφ押出機）に供給し２５０℃で加熱溶融しフィードブロック方式で共押出法にてダイリップ１．２ｍｍのＴダイスより押出し、６０℃の冷却ロール上で冷却固化しながら光沢層が５μｍ、基層が１５μｍ、接着層が５μｍになる様調整し、計２５μｍのフィルムとし、接着層側表面に表面張力が４２ｍＮ／ｍになるようにコロナ放電処理を施した以外は実施例４と全く同様にラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８１％、丼容器で８０％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Example 11
The resin A 99.8% by mass shown in Table 1 was blended with 0.2% by mass of the nucleating agent I shown in Table 2 and extruded into pellets at 250 ° C. with a 65 mmφ extruder, and the resulting resin was used for the base layer. The resin H 99.8% by mass shown in Table 1 was blended with 0.2% by mass of the nucleating agent I shown in Table 2 and extruded at 250 ° C. with a 65 mmφ extruder to form pellets. The resulting resin was used for a glossy layer. Resin E simple substance shown in Table 1 was used as the adhesive layer resin. The gloss layer resin is supplied to Extruder A (50 mmφ extruder), the base layer resin is supplied to Extruder B (75 mmφ extruder), and the adhesive layer resin is supplied to Extruder C (50 mmφ extruder). The feed block method is extruded from a T die with a die lip of 1.2 mm by a coextrusion method, and adjusted so that the gloss layer is 5 μm, the base layer is 15 μm, and the adhesive layer is 5 μm while being cooled and solidified on a cooling roll at 60 ° C. Lamination, thermoforming, and evaluation were performed in exactly the same manner as in Example 4 except that a film with a total thickness of 25 μm was used, and the surface of the adhesive layer was subjected to corona discharge treatment so that the surface tension was 42 mN / m. The results are shown in Table 5. The gloss of the molded container is 81% in the dish container and 80% in the bowl container, and the surface gloss is very good. The white turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, The container was little changed as 12-13% and had no cloudiness.
　実施例１２～１３
　実施例１１の基層と接着層の厚みを、基層が１８μｍ、接着層が２μｍになる様調整し、計２５μｍ（実施例１２）へ、光沢層が８μｍ、基層が１２μｍになる様調整し、計２５μｍ（実施例１３）に変更すること以外は、実施例１１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。実施例１２では、成形容器のグロスは皿容器で８１％、丼容器で８０％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化なく白濁感のない容器であった。実施例１３では、成形容器のグロスは皿容器で８０％、丼容器で７９％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２～１３％とほとんど変化が少なく白濁感のない容器であった。 Examples 12-13
The thickness of the base layer and the adhesive layer of Example 11 was adjusted so that the base layer was 18 μm and the adhesive layer was 2 μm, and adjusted to a total of 25 μm (Example 12), so that the gloss layer was 8 μm and the base layer was 12 μm. Except for changing to 25 μm (Example 13), film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 11. The results are shown in Table 5. In Example 12, the gloss of the molded container is 81% for the dish container and 80% for the bowl container, and the surface gloss is very good. %, 12 to 13% of the container after molding, and there was almost no change and the container was not cloudy. In Example 13, the gloss of the molded container is 80% in the dish container and 79% in the bowl container, and the surface gloss is good, and the hunter whiteness of the polypropylene sheet before film bonding is also 12% for the cloudiness. The container after molding was 12 to 13%, and it was a container with little change and little cloudiness.
　実施例１４
　実施例１１の接着層樹脂を、表１に示す樹脂Ｈ９９．８質量％に核剤Ｉを０．２質量％添加した樹脂とした以外は実施例１１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８２％、丼容器で８１％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく全く白濁感のない容器であった。 Example 14
Film forming, laminating, and thermoforming were performed in exactly the same manner as in Example 11 except that the adhesive layer resin of Example 11 was a resin obtained by adding 0.2% by mass of nucleating agent I to 99.8% by mass of the resin H shown in Table 1. And evaluation. The results are shown in Table 5. The gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good. The white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, The container was a 12% container with no change and no cloudiness.
　実施例１５
　実施例１の光沢層と基層の厚みを、光沢層が１０μｍ、基層が４０μｍになる様調整し、計５０μｍに変更すること以外は、実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８５％、丼容器で８３％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく全く白濁感のない容器であった。 Example 15
The thickness of the gloss layer and the base layer of Example 1 was adjusted so that the gloss layer was 10 μm and the base layer was 40 μm, and the total thickness was changed to 50 μm. And evaluation was performed. The results are shown in Table 5. The gloss of the molded container is 85% in the dish container and 83% in the bowl container, and the surface gloss is very good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was a 12% container with no change and no cloudiness.
　実施例１６
フィルム用原料樹脂として表１に示す樹脂Ａ９７．５質量％に表２に示す核剤IIを２．５質量％ブレンドし、得られた樹脂を基層用とした。表１に示す樹脂Ｈ９７．５質量％に表２に示す核剤IIIを２．５質量％ブレンドし得られた樹脂を光沢層用とした。次に光沢層用樹脂を押出機Ａ（５０ｍｍφ押出機）に、基層用樹脂を押出機Ｂ（７５ｍｍφ押出機）に供給した以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で７１％、丼容器で７０％と表面光沢はやや良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく全く白濁感のない容器であった。 Example 16
As a raw material resin for film, 97.5% by mass of the resin A shown in Table 1 was blended with 2.5% by mass of the nucleating agent II shown in Table 2. The obtained resin was used for the base layer. A resin obtained by blending 97.5% by mass of the resin H shown in Table 1 with 2.5% by mass of the nucleating agent III shown in Table 2 was used for the gloss layer. Next, except that the gloss layer resin was supplied to the extruder A (50 mmφ extruder) and the base layer resin was supplied to the extruder B (75 mmφ extruder), film formation, lamination, thermoforming, and And evaluated. The results are shown in Table 5. The gloss of the molded container is 71% in the dish container and 70% in the bowl container, and the surface gloss is somewhat good. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%. The container was a 12% container with no change and no cloudiness.
　実施例１７
　実施例１のフィルムのコロナ放電処理を施した面の上に、タルクが３０質量％添加されたポリプロピレン系シート（朱赤）厚み０．４ｍｍを２５０℃で押出しながら４０℃の冷却ロールで固化しポリプロピレン系熱成形シートを得た。 Example 17
On the surface of the film of Example 1 subjected to the corona discharge treatment, a polypropylene sheet (Vermilion Red) to which 30% by mass of talc was added was solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.4 mm at 250 ° C. A polypropylene thermoformed sheet was obtained.
　得られた熱成形シートを真空成形し容器の光沢、白濁度（ハンター白色度）、シートとフィルムの接着性について評価しその結果を表５に示した。成形容器のグロスは皿容器で７８％、丼容器で７８％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が２２％、成形後の容器２２～２３％とほとんど変化なく白濁感のない容器であった。 The obtained thermoformed sheet was vacuum-formed, and the glossiness, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated. The results are shown in Table 5. The gloss of the molded container is 78% for the dish container and 78% for the bowl container, and the surface gloss is good, and the hunting whiteness of the polypropylene sheet before film lamination is 22%. It was a container with almost no change and 22-23%.
　実施例１８
　フィルム用原料樹脂として表１に示す樹脂Ａ（融点１６５℃のプロピレン単独重合体（住友化学社製ＦＬＸ８０Ｇ７））９４質量％に表２に示す核剤IVを６質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を基層用とした。表１に示す樹脂Ｅ（エチレン含有量が３．４質量％、融点が１４６℃のプロピレン－エチレンランダム共重合体（日本ポリプロ社製ＦＷ３ＧＴ））９４質量％に表２に示す核剤IVを６質量％ブレンドし６５ｍｍφ押出機にて２５０℃で押出しペレット化し、得られた樹脂を光沢層用とした。次に光沢層用樹脂を押出機Ａ（５０ｍｍφ押出機）に、基層用樹脂を押出機Ｂ（７５ｍｍφ押出機）に供給し２５０℃で加熱溶融しフィードブロック方式で共押出法にてダイリップ１．２ｍｍのＴダイスより押出し、４０℃の冷却ロール上で冷却固化しながら光沢層が５μｍ、基層が２０μｍになる様調整し、計２５μｍのフィルムとし、基層側表面に表面張力が４２ｍＮ／ｍになるようにコロナ放電処理を施した後、巻取り機にて巻取り、熱成形シート積層用フィルムを得た。 Example 18
As a raw material resin for a film, 94% by mass of resin A (propylene homopolymer having a melting point of 165 ° C. (FLX80G7 manufactured by Sumitomo Chemical Co., Ltd.)) shown in Table 1 was blended with 6% by mass of the nucleating agent IV shown in Table 2 in a 65 mmφ extruder. Extrusion pelletization was performed at 250 ° C., and the resulting resin was used for a base layer. Resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro Co., Ltd.)) is 94% by mass with 6 nucleating agents IV shown in Table 2. The resulting resin was blended by mass% and extruded into pellets at 250 ° C. with a 65 mmφ extruder, and the resulting resin was used for a glossy layer. Next, the gloss layer resin is supplied to Extruder A (50 mmφ extruder), the base layer resin is supplied to Extruder B (75 mmφ extruder), heated and melted at 250 ° C., and die lip 1. Extruded from a 2mm T-die and cooled and solidified on a 40 ° C cooling roll, adjusted so that the gloss layer is 5μm and the base layer is 20μm, making a total 25μm film, and the surface tension on the base layer side surface is 42mN / m After performing the corona discharge treatment as described above, the film was wound by a winder to obtain a film for thermoforming sheet lamination.
　該フィルムのコロナ放電処理を施した面の上に、タルクが３０質量％添加されたポリプロピレン系シート（黒）厚み０．５ｍｍを２５０℃で押出しながら４０℃の冷却ロールで固化しポリプロピレン系熱成形シートを得た。 A polypropylene sheet (black) to which 30% by mass of talc is added on the surface subjected to corona discharge treatment of the film is solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.5 mm at 250 ° C. A sheet was obtained.
　得られた熱成形シートをフィルムの表面温度１７５℃にて真空成形し容器の光沢、白濁度（ハンター白色度）、シートとフィルムの接着性について評価しその結果を表５に示した。成形容器のグロスは皿容器で７９％、丼容器で７８％と表面光沢が良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく白濁感のない容器であった。 The obtained thermoformed sheet was vacuum-formed at a film surface temperature of 175 ° C., and the gloss, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated. The results are shown in Table 5. The gloss of the molded container is 79% for the dish container and 78% for the bowl container, and the surface gloss is good, and the turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, and the container after molding It was a 12% container with no change and no cloudiness.
　実施例１９
　実施例１８の光沢層用樹脂を表１に示す樹脂Ｈ（エチレン含有量が４．２質量％、融点が１３５℃のメタロセン触媒系プロピレン－エチレンランダム共重合体（日本ポリプロ社製ＷＦＷ４））とした以外は、全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で８２％、丼容器で８１％と表面光沢が極めて良好なものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１２％と変化なく白濁感のない容器であった。 Example 19
The gloss layer resin of Example 18 is the resin H shown in Table 1 (metallocene catalyst-based propylene-ethylene random copolymer (WFW4 manufactured by Nippon Polypro Co., Ltd.) having an ethylene content of 4.2 mass% and a melting point of 135 ° C.)) Except for the above, film formation, lamination, thermoforming, and evaluation were performed in the same manner. The results are shown in Table 5. The gloss of the molded container is 82% in the dish container and 81% in the bowl container, and the surface gloss is very good. The white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, It was a 12% container with no change and no cloudiness.
　比較例１
　実施例１の各層の原料樹脂にて有機結晶核剤を添加しないこと以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 1
Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the organic crystal nucleating agent was not added to the raw material resin of each layer of Example 1.
　結果を表５に示した。成形容器のグロスは皿容器で１６％、丼容器で１５％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１５％と白濁感のある容器であった。 The results are shown in Table 5. The gloss of the molded container is inferior to the surface gloss of 16% for the dish container and 15% for the bowl container, and the whiteness of the turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 15 after molding. % And the container was cloudy.
　比較例２
　実施例１の各層の原料樹脂にて有機結晶核剤の添加量を０．０２質量部とした以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 2
Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent added was 0.02 parts by mass in the raw material resin of each layer of Example 1.
　結果を表５に示した。成形容器のグロスは皿容器で１６％、丼容器で１７％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１５％と白濁感のある容器であった。 The results are shown in Table 5. The gloss of the molded container is 16% for the dish container and 17% for the bowl container, and the surface gloss is inferior. Also for the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 12%, and the molded container 15 % And the container was cloudy.
　比較例３
　実施例１の基層に用いる樹脂Ａの変わりに、表１に示す樹脂Ｃ（融点１６１℃のプロピレン単独重合体（住友化学社製ＦＬＸ８０Ｇ１））を用いた以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 3
Film formation was carried out in the same manner as in Example 1 except that instead of the resin A used for the base layer of Example 1, resin C shown in Table 1 (a propylene homopolymer having a melting point of 161 ° C. (FLX80G1 manufactured by Sumitomo Chemical Co., Ltd.)) was used. Lamination, thermoforming, and evaluation were performed.
　結果を表５に示した。成形容器のグロスは皿容器で６２％、丼容器で６０％と表面光沢に劣るものであった。 The results are shown in Table 5. The gloss of the molded container was inferior in surface gloss, 62% for the dish container and 60% for the bowl container.
　比較例４
　実施例１の基層に用いる樹脂Ａの変わりに、表１に示す樹脂Ｄ（融点１５７℃のプロピレン単独重合体（日本ポリプロ社製ＦＢ３ＥＢＴ））を用いた以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 4
Film formation was carried out in the same manner as in Example 1 except that instead of the resin A used in the base layer of Example 1, resin D shown in Table 1 (propylene homopolymer having a melting point of 157 ° C. (FB3EBT manufactured by Nippon Polypro Co., Ltd.)) was used. Lamination, thermoforming, and evaluation were performed.
　結果を表５に示した。成形容器のグロスは皿容器で６０％、丼容器で６０％と表面光沢に劣るものであった。 The results are shown in Table 5. The gloss of the molded container was 60% for the dish container and 60% for the bowl container, and the surface gloss was inferior.
　比較例５
　実施例１の光沢層に用いる樹脂Ｅの変わりに、表１に示す樹脂Ａ（融点１６５℃のプロピレン単独重合体（住友化学社製ＦＬＸ８０Ｆ７））を用いた以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 5
Made in the same manner as in Example 1 except that instead of the resin E used in the glossy layer of Example 1, resin A shown in Table 1 (propylene homopolymer having a melting point of 165 ° C. (FLX80F7 manufactured by Sumitomo Chemical Co., Ltd.)) was used. Films, laminates, thermoforming and evaluation were performed.
　結果を表５に示した。成形容器のグロスは皿容器で６０％、丼容器で６０％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器２１％と白濁感のある容器であった。 The results are shown in Table 5. The gloss of the molded container is 60% in the dish container and 60% in the bowl container, and the surface gloss is inferior, and the white turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 21 after molding. % And the container was cloudy.
　比較例６
　実施例４の光沢層と基層の厚みを、光沢層が０．５μｍ、基層が２４．５μｍになる様調整し、計２５μｍとした以外は、実施例４と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で６２％、丼容器で６１％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１９％と白濁感のある容器であった。 Comparative Example 6
The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 0.5 μm and the base layer was 24.5 μm, and the total thickness was 25 μm. Molding and evaluation were performed. The results are shown in Table 5. The gloss of the molded container is 62% in the dish container and 61% in the bowl container, and the surface gloss is inferior. The white turbidity is 12% for the Hunter whiteness of the polypropylene sheet before film bonding, and the container 19 after molding. % And the container was cloudy.
　比較例７
　実施例４の光沢層と基層の厚みを、光沢層が２０μｍ、基層が５μｍになる様調整し、計２５μｍとした以外は、実施例４と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。結果を表５に示した。成形容器のグロスは皿容器で６２％、丼容器で６１％と表面光沢に劣るものであった。 Comparative Example 7
The thickness of the gloss layer and the base layer in Example 4 was adjusted so that the gloss layer was 20 μm and the base layer was 5 μm, and the total thickness was 25 μm. Evaluation was performed. The results are shown in Table 5. The gloss of the molded container was inferior in surface gloss, 62% for the dish container and 61% for the bowl container.
　比較例８
　実施例１の基層に用いる樹脂Ａの変わりに、表１に示す樹脂Ｅ（エチレン含有量が３．４質量％、融点が１４６℃のプロピレン－エチレンランダム共重合体（日本ポリプロ社製ＦＷ３ＧＴ））を用いた以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 8
Instead of the resin A used for the base layer of Example 1, the resin E shown in Table 1 (propylene-ethylene random copolymer having an ethylene content of 3.4% by mass and a melting point of 146 ° C. (FW3GT manufactured by Nippon Polypro)) Except that was used, film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1.
　結果を表５に示した。成形容器のグロスは皿容器で６２％、丼容器で６１％と表面光沢に劣るものであった。 The results are shown in Table 5. The gloss of the molded container was inferior in surface gloss, 62% for the dish container and 61% for the bowl container.
　比較例９
　実施例１の光沢層に用いる樹脂Ｅの変わりに、表１に示す樹脂Ｃ９０質量％と樹脂Ｉ（エチレン含有量が８９．４質量％、ヘキセン含有量が１０．６質量％、融点が１１０℃のメタロセン触媒系エチレン系ランダム共重合体（住友化学社製ＦＶ４０２））１０質量％をブレンドしたものとし、基層に用いる樹脂Ａの変わりに、樹脂Ｅ（エチレン含有量が３．４質量％、融点が１４６℃のプロピレン－エチレンランダム共重合体（日本ポリプロ社製ＦＷ３ＧＴ））を用いた以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 9
Instead of the resin E used for the gloss layer of Example 1, the resin C shown in Table 1 was 90% by mass and the resin I (ethylene content was 89.4% by mass, hexene content was 10.6% by mass, melting point was 110 ° C. 10% by mass of a metallocene catalyst-based ethylene random copolymer (FV402 manufactured by Sumitomo Chemical Co., Ltd.), and instead of resin A used for the base layer, resin E (ethylene content is 3.4% by mass, melting point) Film forming, laminating, thermoforming, and evaluation were performed in the same manner as in Example 1 except that propylene-ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd.) at 146 ° C. was used.
　結果を表５に示した。成形容器のグロスは皿容器で６０％、丼容器で６０％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器２１％と白濁感のある容器であった。 The results are shown in Table 5. The gloss of the molded container is 60% in the dish container and 60% in the bowl container, and the surface gloss is inferior, and the white turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 21 after molding. % And the container was cloudy.
　比較例１０
　比較例５のフィルムのコロナ放電処理を施した面の上に、タルクが３０質量％添加されたポリプロピレン系シート（朱赤）厚み０．４ｍｍを２５０℃で押出しながら４０℃の冷却ロールで固化しポリプロピレン系熱成形シートを得た。 Comparative Example 10
On the surface of the film of Comparative Example 5 subjected to the corona discharge treatment, a polypropylene sheet (Vermilion Red) to which 30% by mass of talc was added was solidified with a cooling roll at 40 ° C. while extruding a thickness of 0.4 mm at 250 ° C. A polypropylene thermoformed sheet was obtained.
　得られた熱成形シートを真空成形し容器の光沢、白濁度（ハンター白色度）、シートとフィルムの接着性について評価しその結果を表５に示した。成形容器のグロスは皿容器で６０％、丼容器で６０％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が２２％、成形後の容器３０～３２％と白濁感のある容器であった。 The obtained thermoformed sheet was vacuum-formed, and the glossiness, white turbidity (hunter whiteness) of the container, and the adhesion between the sheet and the film were evaluated. The results are shown in Table 5. The gloss of the molded container is 60% in the dish container and 60% in the bowl container, which is inferior in surface gloss. Regarding the cloudiness, the hunter whiteness of the polypropylene sheet before film bonding is 22%, and the container 30 after molding. It was a container with a cloudiness of ~ 32%.
　比較例１１
　実施例１８の各層の原料樹脂にて有機結晶核剤の添加量を０．０１質量部とした以外は実施例１と全く同様に製膜、ラミネート、熱成形、及び、評価を行った。 Comparative Example 11
Film formation, lamination, thermoforming, and evaluation were performed in the same manner as in Example 1 except that the amount of the organic crystal nucleating agent was 0.01 parts by mass in the raw material resin of each layer of Example 18.
　結果を表５に示した。成形容器のグロスは皿容器で１６％、丼容器で１５％と表面光沢に劣るものであり、白濁感についてもフィルム貼り合わせ前のポリプロピレン系シートのハンター白色度が１２％、成形後の容器１５％と白濁感のある容器であった。 The results are shown in Table 5. The gloss of the molded container is inferior to the surface gloss of 16% for the dish container and 15% for the bowl container, and the whiteness of the turbidity is 12% for the hunter whiteness of the polypropylene sheet before film bonding, and the container 15 after molding. % And the container was cloudy.
　以上の実施例及び比較例において得られた熱成形シート積層用フィルムの層構成を表４にまとめて示す。また、これらの実施例及び比較例の結果を表５にまとめて示す。
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
 Table 4 summarizes the layer configurations of the thermoformed sheet laminating films obtained in the above Examples and Comparative Examples. The results of these examples and comparative examples are summarized in Table 5.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007

Claims (7)

  1. 融点が１６２℃以上であるプロピレン単独重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１０μｍ以上の厚みを有する基層と、
    該基層の少なくとも片面に形成された、プロピレン系ランダム共重合体９９～９９．９７質量％と有機結晶核剤０．０３～１質量％とを含み、１μｍ以上の厚みを有する光沢層とからなり、無延伸または低延伸フィルムである、熱成形シート積層用フィルム。     A base layer having 99 to 99.97% by mass of a propylene homopolymer having a melting point of 162 ° C. or higher and 0.03 to 1% by mass of an organic crystal nucleating agent, and having a thickness of 10 μm or more;
    And a glossy layer having a thickness of 1 μm or more, comprising 99 to 99.97% by mass of a propylene random copolymer and 0.03 to 1% by mass of an organic crystal nucleating agent, formed on at least one side of the base layer. A film for thermoforming sheet lamination, which is an unstretched or low-stretch film.
  2. 基層の片面に光沢層が形成され、該光沢層とは反対側の基層面に、融点が１３０℃以上のプロピレン系ランダム共重合体よりなり１μｍ以上の厚みを有する接着層が積層されてなる請求項１に記載の熱成形シート積層用フィルム。 A gloss layer is formed on one side of the base layer, and an adhesive layer made of a propylene random copolymer having a melting point of 130 ° C. or higher is laminated on the base layer surface opposite to the gloss layer. Item 2. The film for thermoforming sheet lamination according to Item 1.
  3. フィルムの総厚みが１５～１００μｍであり、基層の厚みが全体の５０～９０％である、請求項１または２に記載の熱成形シート積層用フィルム。 The film for laminating thermoformed sheets according to claim 1 or 2, wherein the total thickness of the film is 15 to 100 µm, and the thickness of the base layer is 50 to 90% of the whole.
  4. 　基層に含まれる有機結晶核剤または光沢層に含まれる有機結晶核剤の何れか一方、または両方が、リン酸エステル金属塩または下記一般式（１）で示されるアミド系化合物である、請求項１～３のいずれかに記載の熱成形シート積層用フィルム。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ１は、１，２，３－プロパントリカルボン酸又は１，２，３，４－ブタンテトラカルボン酸から全てのカルボンキシル基を除いて得られる残基を表す。３個又４個のＲ２は、互いに同一又は異なって、それぞれ水素原子又は炭素数１～１０の直鎖状若しくは分岐鎖状のアルキル基を表す。ｋは、３又は４の整数を表す。］     Either or both of the organic crystal nucleating agent contained in the base layer and the organic crystal nucleating agent contained in the gloss layer, or both, are a phosphoric acid ester metal salt or an amide compound represented by the following general formula (1). The film for laminating thermoformed sheets according to any one of 1 to 3.
    Figure JPOXMLDOC01-appb-C000001
     [Wherein R 1 represents a residue obtained by removing all carboxyxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. Three or four R 2 s are the same or different from each other and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. k represents an integer of 3 or 4. ]
  5. 光沢層と反対側のフィルム表面に印刷層を有する請求項１～４のいずれかに記載の熱成形シート積層用フィルム。 The thermoforming sheet laminating film according to any one of claims 1 to 4, further comprising a printing layer on the film surface opposite to the glossy layer.
  6. 請求項１～５のいずれかに記載の熱成形シート積層用フィルムを、前記光沢層を表層として樹脂シートの少なくとも一方の面に積層した、熱成形用シート。 A thermoforming sheet comprising the thermoforming sheet laminating film according to any one of claims 1 to 5 laminated on at least one surface of a resin sheet with the glossy layer as a surface layer.
  7. 請求項６に記載の熱成形用シートを熱成形して得られた熱成形体。 A thermoformed article obtained by thermoforming the thermoforming sheet according to claim 6.
PCT/JP2009/054315 2008-03-06 2009-03-06 Film for laminating for thermoforming sheet WO2009110601A1 (en)

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CN112622388A (en) * 2019-09-24 2021-04-09 上海如夏新材料技术有限公司 Polypropylene sheet material with multilayer co-extrusion structure

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KR101226455B1 (en) * 2012-08-20 2013-01-28 (주)한도기공 Perpendicular to the discharge dies for forming a sheet

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