WO2009110601A1 - Film for laminating for thermoforming sheet - Google Patents
Film for laminating for thermoforming sheet Download PDFInfo
- 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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- WIPO (PCT)
- Prior art keywords
- film
- layer
- gloss
- sheet
- container
- Prior art date
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
Description
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.
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.
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)].
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.
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.
△: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.
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.
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.
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.
(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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Claims (7)
- 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. - 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.
- 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.
- 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。
- 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.
- 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.
- 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.
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JP2010501979A JP5568809B2 (en) | 2008-03-06 | 2009-03-06 | Film for thermoforming sheet lamination |
CN200980102582.1A CN101909889B (en) | 2008-03-06 | 2009-03-06 | Film for laminating for thermoforming sheet |
KR1020107016519A KR101347489B1 (en) | 2008-03-06 | 2009-03-06 | Film for laminating for thermoforming sheet |
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JP (1) | JP5568809B2 (en) |
KR (1) | KR101347489B1 (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011079152A (en) * | 2009-10-05 | 2011-04-21 | Japan Polypropylene Corp | Thermoformed multilayer container |
JP2011237583A (en) * | 2010-05-10 | 2011-11-24 | Dainippon Printing Co Ltd | Retardation film, and polarizer and display device using the same |
KR101258728B1 (en) | 2008-08-01 | 2013-04-26 | 산·톡스 가부시키가이샤 | Packaging material |
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 |
Families Citing this family (1)
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KR101226455B1 (en) * | 2012-08-20 | 2013-01-28 | (주)한도기공 | Perpendicular to the discharge dies for forming a sheet |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10138419A (en) * | 1996-11-08 | 1998-05-26 | Tokuyama Corp | Laminated polypropylene film |
JP2000280420A (en) * | 1999-03-30 | 2000-10-10 | Denki Kagaku Kogyo Kk | Polypropylene multi-layer sheet and container |
JP2000334899A (en) * | 1999-05-26 | 2000-12-05 | Chisso Corp | Polypropylene-based multilayered sheet and molded object |
JP2002292813A (en) * | 2001-04-03 | 2002-10-09 | Chisso Corp | Thermoformed object comprising multilayered sheet |
JP3416433B2 (en) * | 1996-12-25 | 2003-06-16 | 日本ポリケム株式会社 | Propylene polymer laminated sheet |
JP2003236833A (en) * | 2002-02-15 | 2003-08-26 | Chisso Corp | Polypropylene sheet for heat-molding and molded product thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10180909A (en) * | 1996-12-25 | 1998-07-07 | Nippon Porikemu Kk | Propylene polymer laminated container |
JP3335114B2 (en) * | 1997-10-24 | 2002-10-15 | 株式会社トクヤマ | Laminated sheet |
JP2000094603A (en) * | 1998-09-18 | 2000-04-04 | Sekisui Chem Co Ltd | Manufacture of laminated film |
JP4978466B2 (en) * | 2005-04-07 | 2012-07-18 | 新日本理化株式会社 | Process for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide) |
JP2008062524A (en) * | 2006-09-07 | 2008-03-21 | Tokuyama Corp | Film for laminating thermoforming sheet |
-
2009
- 2009-03-06 JP JP2010501979A patent/JP5568809B2/en not_active Expired - Fee Related
- 2009-03-06 TW TW098107245A patent/TWI451971B/en not_active IP Right Cessation
- 2009-03-06 CN CN200980102582.1A patent/CN101909889B/en not_active Expired - Fee Related
- 2009-03-06 KR KR1020107016519A patent/KR101347489B1/en not_active IP Right Cessation
- 2009-03-06 WO PCT/JP2009/054315 patent/WO2009110601A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10138419A (en) * | 1996-11-08 | 1998-05-26 | Tokuyama Corp | Laminated polypropylene film |
JP3416433B2 (en) * | 1996-12-25 | 2003-06-16 | 日本ポリケム株式会社 | Propylene polymer laminated sheet |
JP2000280420A (en) * | 1999-03-30 | 2000-10-10 | Denki Kagaku Kogyo Kk | Polypropylene multi-layer sheet and container |
JP2000334899A (en) * | 1999-05-26 | 2000-12-05 | Chisso Corp | Polypropylene-based multilayered sheet and molded object |
JP2002292813A (en) * | 2001-04-03 | 2002-10-09 | Chisso Corp | Thermoformed object comprising multilayered sheet |
JP2003236833A (en) * | 2002-02-15 | 2003-08-26 | Chisso Corp | Polypropylene sheet for heat-molding and molded product thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101258728B1 (en) | 2008-08-01 | 2013-04-26 | 산·톡스 가부시키가이샤 | Packaging material |
JP2011079152A (en) * | 2009-10-05 | 2011-04-21 | Japan Polypropylene Corp | Thermoformed multilayer container |
JP2011237583A (en) * | 2010-05-10 | 2011-11-24 | Dainippon Printing Co Ltd | Retardation film, and polarizer and display device using the same |
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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CN101909889A (en) | 2010-12-08 |
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KR20100129722A (en) | 2010-12-09 |
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