WO2002032984A1 - Antifogging polyolefin sheet, process for producing antifogging polyolefin sheet, molded object obtained from the sheet, sheet for food packaging, and molded object for food packaging - Google Patents
Antifogging polyolefin sheet, process for producing antifogging polyolefin sheet, molded object obtained from the sheet, sheet for food packaging, and molded object for food packaging Download PDFInfo
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- WO2002032984A1 WO2002032984A1 PCT/JP2001/009028 JP0109028W WO0232984A1 WO 2002032984 A1 WO2002032984 A1 WO 2002032984A1 JP 0109028 W JP0109028 W JP 0109028W WO 0232984 A1 WO0232984 A1 WO 0232984A1
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- polyolefin
- resin
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- antifogging
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Definitions
- Anti-fog polyolefin-based sheet method for producing anti-fog polyolefin-based sheet, molded article using the sheet, food packaging sheet, molded product for food packaging
- the present invention relates to an antifogging polyolefin-based sheet, a method for producing the antifogging polyolefin-based sheet, and a molded article, a food packaging sheet, and a food packaging molded article using the sheet.
- polypropylene without polar groups provides anti-fogging properties, an essential property in this field.Coatings with only anti-fog agents have low film strength and maintain their effects even after thermoforming. To do so, it is necessary to apply a large amount of antifogging agent.
- An object of the present invention is to provide an antifogging polyolefin-based sheet which can exhibit a high antifogging effect without using a large amount of an antifogging agent, in which the layer containing the antifogging agent has high coating strength.
- An object of the present invention is to provide a method for producing a olefin-based sheet, and a molded article, a sheet for food packaging, and a molded article for food packaging using the sheet. Disclosure of the invention
- the anti-fog polyolefin sheet according to the present invention is a polyolefin resin sheet. Is characterized by having a coating layer containing a binder resin composed of an antifogging agent and an acrylic adhesive on at least one surface of the substrate.
- polyolefin-based resin constituting the polyolefin-based resin sheet
- homopolymers and copolymers of various olefins, and mixtures thereof can be used.
- ethylene, propylene, 1-butene, isoprene, butadiene and the like can be used as the monomer constituting the homopolymer.
- the copolymer an ethylene-polyolefin copolymer, a propylene-polyolefin copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, or the like can be used. .
- polypropylene it is preferable to use polypropylene in consideration of transparency, strength and the like.
- the polyolefin resin sheet of the present invention may have either a single-layer structure or a multilayer structure.
- the polyolefin-based resin sheet has a multilayer structure, it is ideal to employ polypropylene for at least the surface layer.
- the antifogging agent is not particularly limited, but may be sucrose fatty acid ester, glycerin fatty acid ester, fatty acid tertiary amide, higher alcohol fatty acid ester, propylene glycol fatty acid ester, etc., alone or in combination of two or more. Can be used in combination.
- the acrylic adhesive is not particularly limited, but a copolymer such as polyacrylic ester can be used.
- acrylate constituting the polyacrylate methyl acrylate, ethyl butyl, butyl acrylate, octy / restenol, 2-ethylhexyl, and the like can be used.
- a polymer obtained by copolymerizing these ester acrylates with ester methacrylate, styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like can be used. Further, a polymer obtained by copolymerizing the above acrylate with various functional monomers such as acrylic acid, acrylamide, methylol acrylamide, and hydroxydialkyl methacrylate can also be used.
- the coating layer it is preferable that the polyolefin-based resin sheet to the anti-fogging agent, respectively 4 ⁇ 40 Om gZm 2 applied to your Yopi binder resin as a solid content, is a layer formed by drying.
- the weight per unit area of the binder resin on the sheet surface is less than 4 mg / m 2 , the strength of the coat layer may be reduced. On the other hand, if it exceeds 4 O Omg / m 2 , the antifogging effect may be reduced.
- the weight per unit area of the anti-fogging agent of the sheet surface is less than 4m gZm 2, there is a possibility that no sufficient anti-fogging effect. On the other hand, if it exceeds 40 Omg / m 2 , the strength of the coat layer may decrease and stickiness may occur.
- polyolefin-based resin sheet has an average spherulite radius is 4 / zm or less, the average spherulite number of sheet cross-section is 600 ZMM 2 or less, the solid density is 0. 890 g / cm 3 or less, differential scanning calorimetry ( (DSC) Polypropylene layer with a melting enthalpy of the maximum endothermic peak ⁇ of less than 95 J / g and a heating layer of 1 j / g or more on the low temperature side of the maximum endothermic peak and a thickness of 50 ⁇ or more It is preferred that
- the average spherulite radius is larger than 4 ⁇ , the internal haze may increase (transparency may decrease). More preferably, the average spherulite radius is 3 / im or less. Further, when the average number of spherulites in the cross section of the sheet is more than 600 / mm 2 , the softening point temperature of the sheet may increase. More preferably, the average number of spherulites is 400 or less and Zmm 2 or less.
- the density is greater than 0.890 g / cm 3 , the density is too high, that is, the crystallinity is too high, which may affect the softening point temperature. If the thickness of the sheet is less than 5 ⁇ , a molded article having rigidity after thermoforming (volume May be difficult to build.
- the anti-fog polyolefin-based sheet having a polypropylene layer having such properties has a low heating softening point temperature, can be subjected to low-temperature thermoforming, and has good internal haze (transparency).
- thermoforming such a sheet since the heating softening temperature is low, it is not necessary to use a special molding device, so that manufacturing costs can be reduced. Moreover, by thermoforming such a sheet, it is possible to obtain a thermoformed article having anti-fogging properties and high transparency. Furthermore, the melting enthalpy ⁇ is relatively small, less than 95 jZg, and heat generation of 1 J / g or more is observed at the low temperature side.Therefore, the amount of heat that must be supplied from the outside to soften the sheet is small, and Since the heating temperature during softening is relatively low, low-temperature thermoforming becomes easier.
- the thickness of this layer in case that the t mm, the internal haze is, (330 t 2 - 1 50 t + 20)% or less it is not preferable.
- (330 t 2 - 1 50 t + 20) measures the relationship between the internal haze and the sheet thickness, an equation obtained by the least squares method.
- the transparency of the thermoformed article obtained by thermoforming the antifogging polyolefin-based sheet may deteriorate. That is, by setting the internal haze of the sheet to the above range, the internal haze of the thermoformed body is (330 s 2 — 150 S + 25)% or less (s: the thickness of the thermoformed body (mm) ), And a thermoformed article having excellent transparency can be obtained.
- the tensile modulus of the polyolefin-based resin sheet is preferably 1500 MPa or less.
- the tensile modulus of the polyolefin-based resin sheet is 150 OMPa or more, the degree of crystallinity is high, so that the softening point temperature becomes high, and molding may be difficult.
- the tensile modulus of the polyolefin resin sheet within the above range, crystallization is promoted by heating during thermoforming, and the tensile elastic modulus of the thermoformed body is maintained at 170 OMPa while maintaining transparency.
- the molded body having sufficient strength Can be obtained.
- the tensile modulus in the present invention refers to a value measured in the moving direction (MD direction) at the time of sheet production by a method based on JIS K7113.
- the polyolefin-based resin sheet of the present invention preferably has a surface subjected to a corona treatment.
- the anti-fogging polyolefin-based sheet described above has a high anti-fogging effect and is excellent in transparency, so that it can be suitably used as an OPS alternative field, for example, as a food packaging sheet.
- a molded article obtained by thermoforming the anti-fogging polyolefin-based sheet of the present invention is also excellent in anti-fogging property and transparency, so that it is suitably used for a molded article for food packaging, for example, a food tray. be able to.
- the method for producing an anti-fog polyolefin-based sheet comprises the steps of: introducing a molten polyolefin-based resin between an endless belt wound around a plurality of cooling ports and a mirror-surface cooling roll; A sheet forming step in which the molten polyolefin resin is pressed into contact with a belt and a mirror cooling roll to form a sheet, and quenched to form a polyolefin resin sheet; and a polyolefin resin obtained by the sheet forming step. Coating a mixed aqueous solution of an anti-fogging agent and a binder resin on at least one surface of the resin sheet, and then drying to form a coat layer.
- the temperature at which the sheet is rapidly cooled is not particularly limited. More preferred.
- the endless belt is not particularly limited, and a mirror stainless steel belt, a belt coated with a polyimide resin, a fluorine resin, or the like on the surface of a metal belt, or the like can be used.
- the polyolefin resin sheet, antifogging agent, and binder resin are the same as described above.
- a sheet forming step in which the molten polyolefin resin is brought into pressure contact with the endless belt and the mirror surface cooling port and quenched. did thus, a polyolefin resin sheet having high transparency and low crystallinity can be obtained, and as a result, the transparency and thermoformability of the anti-fog polyolefin resin sheet can be improved.
- FIG. 1 is a partial cross-sectional view showing an antifogging polyolefin-based sheet according to a first embodiment of the present invention.
- FIG. 2 is a schematic diagram showing an apparatus for producing a polyolefin-based resin sheet in the embodiment of FIG. '' Best mode for carrying out the invention
- FIG. 1 shows an antifogging polyolefin-based sheet 1 according to a first embodiment of the present invention.
- the anti-fog polyolefin-based sheet 1 comprises a polypropylene layer 11 as a polyolefin-based luster sheet, and a coat layer 12 formed by coating a mixed aqueous solution containing an anti-fog agent and an acrylic adhesive. It is provided with.
- the polypropylene layer 11 constituting the anti-fog polyolefin-based sheet 1 has an average spherulite radius of 4 ⁇ or less, an average number of spherulites in the sheet cross section of 600 / mm 2 or less, and a solid density of 0.8. 90 g / cm 3 or less, Tensile modulus 150 OMPa or less, Melting enthalpy ⁇ at the maximum endothermic peak of the DSC curve is less than 95 j / g, and 1 J / g or more at the low temperature side of the maximum endothermic peak The exothermic peak has a thickness of 50 ⁇ or more.
- the manufacturing equipment consists of an extruder T die 22, a first cooling roll 23, a second cooling roll 26, a third cooling roll 24 and a fourth cooling roll 25, and a metal endless belt 27. , A cooling water spray nozzle 28, a water tank 29, a water absorbing roll 30, and a peeling roll 31.
- the fourth cooling port rule 25, the second cooling port rule 26, and the third cooling port rule 24 are metal rolls. Cooling means (not shown) is built-in.
- the surface of the first cooling roll 23 is coated with an elastic material 32 made of nitrile-butadiene rubber (NBR).
- the elastic material 32 has a hardness (measured by a method based on JIS K 6301A) of 60 degrees or less and a thickness of 10 mm.
- Rmax l.0 / m
- Rmax is based on JIS B0601 “Definition and Display of Surface Roughness”
- the resulting polypropylene sheet (polypropylene layer) 11 has low gloss. And a polypropylene sheet 11 with low transparency.
- the second cooling roll 26 is disposed so as to sandwich the polypropylene sheet 11 between the first cooling roll 23 and the metal endless belt 27.
- the endless belt 27 is rotatably wound around the first, third, and fourth cooling rolls 23 to 25 described above.
- the cooling water spray nozzle 28 is provided on the lower surface side of the second cooling port ruler 26, As a result, the cooling water is sprayed on the back surface of the endless belt 27. By spraying the cooling water in this manner, the endless belt 27 is rapidly cooled, and the polypropylene 11 immediately after being pressed by the first and second cooling rolls 23 and 26 is also rapidly cooled. I have.
- the water tank 29 is formed in a box shape having an open upper surface, and is provided so as to cover the entire lower surface of the second cooling roll 26.
- the water tank 29 collects the sprayed cooling water and discharges the collected water from an outlet 29 A formed on the lower surface of the water tank 29.
- the water-absorbing roll 30 is installed on the side surface of the second cooling roll 26 on the side of the third cooling roll 24 so as to be in contact with the endless belt 27, and excess cooling adhered to the back surface of the endless belt 27. It acts to remove water.
- the peeling roll 31 is arranged so as to guide the polypropylene sheet 11 to the endless belt 27 and the third cooling roll 24, and the endless belt for the polypropylene sheet 11 after cooling is completed. Separated from 27. ⁇ In this embodiment, the peeling roll 31 does not press the polypropylene sheet 11 against the third cooling roll 24, but may press it. However, it is preferable not to make pressure contact as in the present embodiment.
- the endless belt 27 and the second cooling roll 26 which come into direct contact with the polypropylene sheet 11 and cool it are kept in advance at each cooling port so that the surface temperature is maintained at the dew point or higher and 30 ° C or lower. Control the temperature of rules 24, 25 and 26.
- the surface temperature of the second cooling roll 26 and the endless belt 27 is lower than the dew point, dew condensation may occur on the surface, making it difficult to form a uniform film.
- the surface temperature is higher than 30 ° C., the transparency of the obtained polypropylene sheet 11 will decrease, and the number of crystals will increase, which may make it difficult to heat-mold. Therefore, in the present embodiment, the surface temperature is set to 14 ° C.
- the polypropylene sheet 11 extruded from the T die 22 of the extruder is sandwiched between the endless belt 27 and the second cooling roll 26 on the first cooling roll 23. Put in. In this state, the polypropylene sheet 11 is pressed against the first and second cooling rolls 23 and 26 and rapidly cooled at 14 ° C.
- the elastic material 32 is compressed and elastically deformed by the pressing force between the first cooling roll 23 and the second cooling roll 26.
- the portion where the elastic member 32 is elastically deformed that is, the arc portion corresponding to the central angle 01 of the first cooling roll 23, the polypropylene sheet 11 is surfaced by the cooling rolls 23, 26. It has been pressed.
- the surface pressure at this time is 0. 220 MPa.
- the polypropylene sheet 11 pressed as described above and sandwiched between the second cooling roll 26 and the endless velvet 27 subsequently has an arc portion corresponding to a substantially lower half circumference of the second cooling roll 26, While being pressed between the endless belt 27 and the second cooling roll 26 in planar contact, the cooling water spray nozzle 28 sprays cooling water on the back side of the endless belt 27 to further cool rapidly.
- the surface pressure at this time is 0.1 to 0.5 MPa, and the temperature of the cooling water is 8 ° C.
- the sprayed cooling water is collected in the water tank 29, and the collected water is discharged from the drain 29A.
- the polypropylene sheet 11 in close contact with the endless belt 27 is moved onto the third cooling roll 24 with the rotation of the endless belt 27.
- the polypropylene sheet 11 guided by the peeling roll 31 is again cooled at a temperature of 30 ° C. or less in an arc portion corresponding to a substantially upper half circumference of the third cooling roll 24. .
- the water adhering to the back surface of the endless belt 27 is removed by the water absorbing roll 30 provided on the way from the second cooling roll 26 to the third cooling roll 24.
- the polypropylene sheet 11 cooled on the third cooling roll 24 is peeled off from the endless belt 17 by the peeling roll 31 and wound up at a predetermined speed by a winding roll (not shown).
- the anti-fogging polyolefin-based sheet 1 thus obtained has a high anti-fogging effect and is excellent in transparency, so that it can be suitably used as an OPS substitute field, for example, as a food packaging sheet. .
- a molded article obtained by thermoforming an antifogging polyolefin-based sheet is also excellent in antifogging property and transparency, so that it can be suitably used for a molded article for food packaging, for example, a food tray. .
- the coating film strength can be increased as compared with a coating layer containing only an anti-fogging agent. As well as reducing stickiness on the surface.
- the melting enthalpy ⁇ H is relatively small, less than 95 JZ g, and heat generation of 1 JZ g or more is observed on the low temperature side, it must be supplied from outside to soften the sheet 1. Since the amount of heat required is small and the heating temperature during softening is relatively low, low-temperature thermoforming becomes easier.
- the tensile modulus of the polypropylene layer 11 is 150 OMPa or less, the crystallinity and softening point temperature are low, and thermoforming can be easily performed. Further, the crystallization is promoted by heating during thermoforming, and the tensile elastic modulus of the thermoformed body of the anti-fog polyolefin-based sheet 1 can be set to 170 OMPa or more while maintaining the transparency. Strength can be obtained.
- the internal haze is, (3 3 0 t 2 - 1 5 0 t + 2 0)% because it will antifogging polyolefin based sheet 1 Of the thermoformed article obtained by thermoforming the polymer. That is, by setting the internal haze of the polypropylene layer 11 within the above range, the internal haze of the thermoformed body is not more than (330 s 2 — 150 S + 25)% (s: thickness of the thermoformed body). (Mm)).
- a low-crystalline polypropylene sheet (polypropylene layer) 11 can be obtained, and as a result, the transparency and thermoformability of the anti-fog polyolefin-based sheet 1 can be improved.
- the present invention is not limited to the above embodiment, and modifications and improvements as long as the object of the present invention can be achieved are included in the present invention.
- the polypropylene layer 11 is employed as the polyolefin-based resin sheet.
- the present invention is not limited to this, and a layer made of various polyolefin-based resins, for example, a polyethylene layer or the like may be used.
- the endless belt 27 is a force wound around three rolls.
- the present invention is not limited to this. In short, if the device can rotate and cool the endless belt, the number of cooling rolls around which the endless belt is wound can be set arbitrarily.
- a belt in which a surface of a metal endless belt is coated with a polyimide resin, a fluororesin such as polytetrafluoroethylene, or the like. May be adopted.
- an elastic member made of NBR has been adopted, but it is not limited to this.
- any material may be used as long as it has a predetermined hardness and thickness and is elastically deformed when the polypropylene sheet is pressed.
- an elastic material made of silicone or the like can be used.
- the surface temperature of the second cooling port ruler 26 and the endless belt 27 was set to 14 ° C., but is not limited thereto, and is not less than the dew point and not more than 50 ° C., preferably the dew point. As described above, any temperature of 30 ° C. or less can be adopted.
- the temperature of the water sprayed by the cooling water spray nozzle 28 was set to 8 ° C, but is not limited to this, and may be arbitrarily set to a value lower than the surface temperature of the second cooling roll 26 and the endless belt 27. Can be set.
- specific structures, shapes, and the like when carrying out the present invention are described below with reference to examples and comparative examples, as well as other structures within a range that can achieve the object of the present invention. Will be described.
- T die 22 width 800 mm
- Polypropylene Idemitsu Polypropylene E—304GP (made by Idemitsu Petrochemical Co., Ltd.) Sheet 11 Pick-up speed: 1 OmZmin
- Second cooling roll 26 and endless belt 27 14 ° C
- Cooling water temperature 8 ° C
- Cooling water spray amount 200 liters Zm i n
- Corona treatment is applied to both sides of the polypropylene layer 11 obtained in the above sheet forming process, and the treated antifogging agent is dried on both sides by 7 Omg per unit area, and the acrylic adhesive is dried. This was applied so as to be 50 mg in weight per unit area, and dried to form a coat layer 12, and an antifogging polyolefin sheet 1 was obtained.
- Riquemar A (manufactured by Riken Vitamin Co., Ltd.) was used as the antifogging agent, and Julimer FC-80 (manufactured by Nippon Pure Chemical Co., Ltd.) was used as the acryloline adhesive.
- the thickness of the coating before drying was measured with an infrared moisture meter (manufactured by Kurashiki Spinning Co., Ltd.).
- An antifogging polyolefin sheet was prepared in the same manner as in Example 1, except that the weight of the antifogging agent was 300 mg per unit area after drying and the weight of the ataryl adhesive was 250 mg per unit area after drying. Got one.
- the antifogging polyolefin-based sheet 1 was obtained in the same manner as in Example 1, except that the weight per unit area was 10 mg.
- An antifogging polyolefin sheet 1 was obtained in the same manner as in Example 1 except that a transparent nucleating agent (dibenzylidene sorbitol derivative) was used as a sheet manufacturing method and a general tattyrol molding was employed.
- a transparent nucleating agent dibenzylidene sorbitol derivative
- An antifogging polyolefin was prepared in the same manner as in Example 1, except that the weight of the antifogging agent was 500 mg per unit area after drying and the weight of the ataryl adhesive was 4 OOmg per unit area after drying. System sheet 1 was obtained.
- An antifogging poly was prepared in the same manner as in Example 1 except that the antifogging agent was 2 mg in weight per unit area after drying and the acrylic adhesive was 1 mg in weight per unit area after drying. An olefinic sheet 1 was obtained.
- An antifogging polyolefin sheet was obtained in the same manner as in Example 1 except that no acrylic adhesive was used.
- the anti-fogging polyolefin-based sheets obtained in the above Examples and Comparative Examples were evaluated for the appearance of the sheet after winding and the anti-fogging property (high temperature Z low temperature) of the wound sheet. It was shown to.
- the antifogging property was evaluated by the following method.
- Example 5 since the antifogging agent and the acrylic binder were applied excessively, transfer unevenness occurred in some parts, and peeling of the coating film occurred in some parts due to elongation during thermoforming. It is not enough to be a problem.
- Example 6 it can be seen that the antifogging effect of the sheet and the antifogging effect of the molded article were slightly reduced because the antifogging agent and the acrylyl binder were small.
- Comparative Example 1 which did not contain the acrylic adhesive, it was found that stickiness of the surface and transfer to the opposite surface of the sheet occurred, resulting in uneven transfer.
- Example 4 the transparency of the sheet was high, but the thermoformability at low temperatures was slightly insufficient, and the transparency of the molded product was low. However, it is superior to Comparative Example 1. Industrial applicability
- the present invention relates to an antifogging polyolefin-based sheet, a method for producing the antifogging polyolefin-based sheet, and a molded article, a food packaging sheet, and a food packaging molded article using the sheet, and is used for packaging food and the like. it can.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
An antifogging polyolefin sheet having a coating layer which contains an antifogging agent and has a high film strength. It can have a high antifogging effect even when the amount of the antifogging agent is small. The sheet (1) comprises a polyolefin resin sheet (11) and formed on at least one side thereof a coating layer (12) comprising an antifogging agent and a binder resin comprising an acrylic adhesive.
Description
明 細 書 防曇性ポリオレフイン系シート、 防曇性ポリオレフイン系シートの製造方法、 お ょぴ該シートを用いた成形体、 食品包装用シート、 食品包装用成形体 技術分野 Description Anti-fog polyolefin-based sheet, method for producing anti-fog polyolefin-based sheet, molded article using the sheet, food packaging sheet, molded product for food packaging
本発明は、 防曇性ポリオレフイン系シート、 防曇性ポリオレフイン系シートの 製造方法、 および該シートを用いた成形体、 食品包装用シート、 食品包装用成形 体に関する。 背景技術 The present invention relates to an antifogging polyolefin-based sheet, a method for producing the antifogging polyolefin-based sheet, and a molded article, a food packaging sheet, and a food packaging molded article using the sheet. Background art
近年、 O P S樹脂 (延伸ポリスチレン樹脂) が使用されている分野における代 替樹脂として、 透明ポリプロピレンの開発が盛んに行われている。 In recent years, transparent polypropylene has been actively developed as an alternative resin in the field where OPS resin (stretched polystyrene resin) is used.
O P S樹脂に比べて極性基のないポリプロピレンは、 この分野の必須特性であ る防曇性を付与するに当たり、 防曇剤のみのコーティングでは、 その塗膜強度が 弱く、 熱成形後も効果を持続させるためには、 大量の防曇剤を塗布する必要があ る。 Compared to OPS resins, polypropylene without polar groups provides anti-fogging properties, an essential property in this field.Coatings with only anti-fog agents have low film strength and maintain their effects even after thermoforming. To do so, it is necessary to apply a large amount of antifogging agent.
しかしながら、 大量の防曇剤を使用した場合、 シート表面がベたつくため、 取 扱い性の極めて悪いシートしか得られないという問題がある。 However, when a large amount of antifogging agent is used, there is a problem that only a sheet having extremely poor handling properties can be obtained because the sheet surface is sticky.
また、 このような問題を解決するため、 防曇剤を内添させたシートも開発され ているが、 防曇剤のプリードアウト量がシートの保存環境に影響されて、 防曇効 果が不安定になり易いという問題がある。 In order to solve such problems, sheets containing an antifogging agent have been developed, but the bleed-out amount of the antifogging agent is affected by the storage environment of the sheet, and the antifogging effect is not sufficient There is a problem that it tends to be stable.
本発明の目的は、 防曇剤を含む層の塗膜強度が高く、 かつ、 大量の防曇剤を使 用せずとも高い防曇効果を発揮できる防曇性ポリオレフイン系シート、 防曇性ポ リオレフイン系シートの製造方法、 およぴ該シートを用いた成形体、 食品包装用 シート、 食品包装用成形体を提供することにある。 発明の開示 An object of the present invention is to provide an antifogging polyolefin-based sheet which can exhibit a high antifogging effect without using a large amount of an antifogging agent, in which the layer containing the antifogging agent has high coating strength. An object of the present invention is to provide a method for producing a olefin-based sheet, and a molded article, a sheet for food packaging, and a molded article for food packaging using the sheet. Disclosure of the invention
本発明に係る防曇性ポリオレフイン系シートは、 ポリオレフイン系樹脂シート
の少なくとも片面に、 防曇剤、 およびアクリル系接着剤からなるバインダ樹脂を 含むコート層を有することを特徴とする。 The anti-fog polyolefin sheet according to the present invention is a polyolefin resin sheet. Is characterized by having a coating layer containing a binder resin composed of an antifogging agent and an acrylic adhesive on at least one surface of the substrate.
ここで、 ポリオレフィン系榭脂シートを構成するポリオレフィン系樹脂として は、 種々のォレフインの単独重合体、 共重合体、 およびこれらの混合物を採用す ることができる。 Here, as the polyolefin-based resin constituting the polyolefin-based resin sheet, homopolymers and copolymers of various olefins, and mixtures thereof can be used.
単独重合体を構成するモノマーとしては、 エチレン、 プロピレン、 1—ブテン、 イソプレン、 ブタジエン等を採用することができる。 また、 共重合体としては、 エチレン一痫一ォレフイン共重合体、 プロピレン一痫ーォレフイン共重合体、 ェ チレン—酢酸ビニル共重合体、 エチレンーァクリル酸エステル共重合体等を採用 することができる。 これらの中でも、 透明性、 強度等を考慮するとポリプロピレ ンを採用することが好ましい。 As the monomer constituting the homopolymer, ethylene, propylene, 1-butene, isoprene, butadiene and the like can be used. In addition, as the copolymer, an ethylene-polyolefin copolymer, a propylene-polyolefin copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylate copolymer, or the like can be used. . Among them, it is preferable to use polypropylene in consideration of transparency, strength and the like.
なお、 本発明におけるポリオレフイン系樹脂シートには、 単層構造、 多層構造 のどちらを採用しても構わない。ポリオレフイン系樹脂シートが多層構造の場合、 少なくとも表層には、 ポリプロピレンを採用するのが理想的である。 The polyolefin resin sheet of the present invention may have either a single-layer structure or a multilayer structure. When the polyolefin-based resin sheet has a multilayer structure, it is ideal to employ polypropylene for at least the surface layer.
また、 防曇剤としては、 特に限定はないが、 ショ糖系脂肪酸エステル、 グリセ リン脂肪酸エステル、 脂肪酸 3級アミ ド、 高級アルコール脂肪酸エステル、 プロ ピレンダリコール脂肪酸エステル等を、 単独または 2種以上を混合して使用する ことができる。 The antifogging agent is not particularly limited, but may be sucrose fatty acid ester, glycerin fatty acid ester, fatty acid tertiary amide, higher alcohol fatty acid ester, propylene glycol fatty acid ester, etc., alone or in combination of two or more. Can be used in combination.
一方、 アクリル系接着剤としては、 特に限定はないが、 ポリアクリル酸エステ ル等の共重合体を採用することができる。 On the other hand, the acrylic adhesive is not particularly limited, but a copolymer such as polyacrylic ester can be used.
ここで、 ポリアクリル酸エステルを構成するアクリル酸エステルとしては、 ァ クリル酸のメチルエステル、 ェチルエステル、 ブチルエステル、 ォクチ/レエステ ノレ、 2 _ェチルへキシルエステル等を採用できる。 Here, as the acrylate constituting the polyacrylate, methyl acrylate, ethyl butyl, butyl acrylate, octy / restenol, 2-ethylhexyl, and the like can be used.
これらのアクリル酸エステノレを、 メタクリノレ酸エステノレ、 スチレン、 ァクリロ 二トリル、 塩化ビニル、 酢酸ビニル等と共重合させたポリマーを採用できる。 ま た、 上記アクリル酸エステルを、 アクリル酸、 アクリルアミ ド、 メチロールァク リルアミ ド、 ヒ ドロキシジアルキルメタタリレート等の種々の官能性モノマーと 共重合させたポリマーを採用することもできる。 A polymer obtained by copolymerizing these ester acrylates with ester methacrylate, styrene, acrylonitrile, vinyl chloride, vinyl acetate and the like can be used. Further, a polymer obtained by copolymerizing the above acrylate with various functional monomers such as acrylic acid, acrylamide, methylol acrylamide, and hydroxydialkyl methacrylate can also be used.
本発明によれば、 ポリオレフイン系樹脂シートの少なくとも片面に、 防曇剤お
ょぴパインダ樹脂を含むコート層を有しているから、 防曇剤のみのコート層と比 ベて、 塗膜強度を高めることができるとともに、 コート層表面のベたつきを抑え ることができる。 しかも、 バインダ樹脂としてアクリル系接着剤を用いているか ら、 コート層表面のベたつきをより一層低下させることができるとともに、 当該 防曇性ポリオレフイン系シートを熱成形して得られる成形体においても、 効果的 に防曇性を発揮させることができる。 According to the present invention, an antifogging agent and / or Since it has a coating layer containing a pinda resin, the coating film strength can be increased and the stickiness of the coating layer surface can be suppressed as compared with a coating layer containing only an antifogging agent. . Moreover, since an acrylic adhesive is used as the binder resin, stickiness on the surface of the coat layer can be further reduced, and a molded article obtained by thermoforming the anti-fog polyolefin-based sheet can be obtained. However, the anti-fogging property can be exhibited effectively.
以上において、 コート層は、 前記ポリオレフイン系樹脂シートに前記防曇剤お ょぴバインダ樹脂を固形分量としてそれぞれ 4〜40 Om gZm2塗布、乾燥して 形成された層であることが好ましい。 In the above, the coating layer, it is preferable that the polyolefin-based resin sheet to the anti-fogging agent, respectively 4~40 Om gZm 2 applied to your Yopi binder resin as a solid content, is a layer formed by drying.
ここで、シート表面のバインダ榭脂の単位面積あたり重量が 4 m g/m2未満で あると、 コート層の強度が低下する可能性がある。 一方、 4 O Om g/m2を超え ると、 防曇効果が低下する可能性がある。 Here, if the weight per unit area of the binder resin on the sheet surface is less than 4 mg / m 2 , the strength of the coat layer may be reduced. On the other hand, if it exceeds 4 O Omg / m 2 , the antifogging effect may be reduced.
また、シート表面の防曇剤の単位面積あたり重量が、 4m gZm2未満であると、 十分な防曇効果が得られない可能性がある。 一方、 40 Omg/m2を超えると、 コート層の強度が低下する可能性があるとともに、 ベたつきが発生することがあ る。 The weight per unit area of the anti-fogging agent of the sheet surface is less than 4m gZm 2, there is a possibility that no sufficient anti-fogging effect. On the other hand, if it exceeds 40 Omg / m 2 , the strength of the coat layer may decrease and stickiness may occur.
また、 ポリオレフイン系樹脂シートは、 平均球晶半径が 4 /zm以下、 シート断 面の平均球晶数が 600個 Zmm2以下、 固体密度が 0. 890 g / c m3以下、 示差走査熱分析 (DS C) 曲線の最大吸熱ピークの融解ェンタルピー ΔΗが 95 J/g未満、 かつ、 前記最大吸熱ピークの低温側に 1 j/g以上の発熱ピ クを 有し、 厚さ 50 μπι以上のポリプロピレン層であることが好ましい。 Further, polyolefin-based resin sheet has an average spherulite radius is 4 / zm or less, the average spherulite number of sheet cross-section is 600 ZMM 2 or less, the solid density is 0. 890 g / cm 3 or less, differential scanning calorimetry ( (DSC) Polypropylene layer with a melting enthalpy of the maximum endothermic peak ΔΗ of less than 95 J / g and a heating layer of 1 j / g or more on the low temperature side of the maximum endothermic peak and a thickness of 50 μπι or more It is preferred that
ここで、 平均球晶半径が 4 μπιより大きいと、 内部ヘイズが高くなる (透明性 が低下する) ことがある。 より好ましくは、 平均球晶半径 3 /i m以下である。 また、 シート断面の平均球晶数が 600個/ mm2より多いと、 シートの軟化点 温度が高くなることがある。 より好ましくは、 平均球晶数 400個 Zmm2以下で ある。 Here, if the average spherulite radius is larger than 4 μπι, the internal haze may increase (transparency may decrease). More preferably, the average spherulite radius is 3 / im or less. Further, when the average number of spherulites in the cross section of the sheet is more than 600 / mm 2 , the softening point temperature of the sheet may increase. More preferably, the average number of spherulites is 400 or less and Zmm 2 or less.
さらに、 固体密度が 0. 890 g/cm3より大きいと、 密度が大きすぎる、 す なわち、 結晶化度が高すぎて、 軟化点温度に影響を及ぼすことがある。 そして、 シートの厚さが 5 Ο μπι未満であると、 熱成形した後に剛性を有する成形体 (容
器等) を造ることが困難になることがある。 Further, when the solid density is greater than 0.890 g / cm 3 , the density is too high, that is, the crystallinity is too high, which may affect the softening point temperature. If the thickness of the sheet is less than 5 μμπι, a molded article having rigidity after thermoforming (volume May be difficult to build.
このような特性を有するポリプロピレン層を有する防曇性ポリオレフイン系 シートは、 加熱軟化点温度が低く、 低温熱成形が可能であり、 かつ、 内部ヘイズ (透明性) が良好になる。 The anti-fog polyolefin-based sheet having a polypropylene layer having such properties has a low heating softening point temperature, can be subjected to low-temperature thermoforming, and has good internal haze (transparency).
また、 加熱軟化温度が低いため、 特殊な成形装置を使用する必要もないから、 製造コストの低減も図ることができる。 しかも、 このようなシートを熱成形する ことで、 防曇性を有するとともに、 透明性の高い熱成形体を得ることができる。 さらに、 融解ェンタルピー ΔΗが 95 jZg未満と比較的小さく、 かつ、 低温 側で 1 J/g以上の発熱が見られるから、 シートを軟化させるのに外部から供給 しなければならない熱量が少なく、 かつ、 軟化時の加熱温度が比較的低いので、 低温熱成形が一層容易になる。 In addition, since the heating softening temperature is low, it is not necessary to use a special molding device, so that manufacturing costs can be reduced. Moreover, by thermoforming such a sheet, it is possible to obtain a thermoformed article having anti-fogging properties and high transparency. Furthermore, the melting enthalpy ΔΗ is relatively small, less than 95 jZg, and heat generation of 1 J / g or more is observed at the low temperature side.Therefore, the amount of heat that must be supplied from the outside to soften the sheet is small, and Since the heating temperature during softening is relatively low, low-temperature thermoforming becomes easier.
また、 ポリオレフイン系樹脂シートとしては、 この層の厚さを t mmとした場 合に、 内部ヘイズが、 (330 t2— 1 50 t + 20) %以下であることが好まし い。 As the polyolefin-based resin sheet, the thickness of this layer in case that the t mm, the internal haze is, (330 t 2 - 1 50 t + 20)% or less it is not preferable.
ここで、 (330 t2— 1 50 t + 20) は、 内部ヘイズとシート厚さとの関係 を測定し、 最小二乗法により求められた式である。 Here, (330 t 2 - 1 50 t + 20) measures the relationship between the internal haze and the sheet thickness, an equation obtained by the least squares method.
内部ヘイズカ s、上記関係式より得られる値よりも大きいと、防曇性ポリオレフィ ン系シートを熱成形して得られる熱成形体の透明性が悪くなることがある。 すな わち、シートの内部ヘイズを上記範囲にすることで、熱成形体の内部ヘイズを(3 30 s2— 1 50 S + 25) %以下 ( s :熱成形体の厚さ (mm) ) とすることが でき、 透明性に優れた熱成形体を得ることができる。 If the internal haze value is larger than the value obtained from the above relational expression, the transparency of the thermoformed article obtained by thermoforming the antifogging polyolefin-based sheet may deteriorate. That is, by setting the internal haze of the sheet to the above range, the internal haze of the thermoformed body is (330 s 2 — 150 S + 25)% or less (s: the thickness of the thermoformed body (mm) ), And a thermoformed article having excellent transparency can be obtained.
さらに、 ポリオレフイン系樹脂シートの引張弾性率は、 1 500MP a以下で あることが好ましい。 Further, the tensile modulus of the polyolefin-based resin sheet is preferably 1500 MPa or less.
ここで、 ポリオレフイン系樹脂シートの引張弾性率が 1 50 OMP a以上であ ると、 結晶化度が高いため、 軟化点温度が高くなり、 成形しにくくなることがあ る。 Here, if the tensile modulus of the polyolefin-based resin sheet is 150 OMPa or more, the degree of crystallinity is high, so that the softening point temperature becomes high, and molding may be difficult.
また、 ポリオレフイン系榭脂シートの引張弾性率を上記範囲とすることで、 熱 成形時の加熱により結晶化が促進され、 透明性を維持したまま熱成形体の引張弾 性率を 1 70 OMP a以上とすることができるので、 十分な強度を有する成形体
を得ることができる。 Further, by setting the tensile modulus of the polyolefin resin sheet within the above range, crystallization is promoted by heating during thermoforming, and the tensile elastic modulus of the thermoformed body is maintained at 170 OMPa while maintaining transparency. The molded body having sufficient strength Can be obtained.
なお、 本発明における引張弾性率は、 J I S K 7 1 1 3に準拠した方法によ り、 シート製造時の移動方向 (MD方向) について測定した値をいう。 In addition, the tensile modulus in the present invention refers to a value measured in the moving direction (MD direction) at the time of sheet production by a method based on JIS K7113.
また、 本発明におけるポリオレフイン系樹脂シートとしては、 その表面にコロ ナ処理を施したものであることが好ましい。 The polyolefin-based resin sheet of the present invention preferably has a surface subjected to a corona treatment.
以上で説明した防曇性ポリオレフイン系シートは、 防曇効果が高く、 かつ透明 性に優れていることから、 O P S代替分野、 例えば、 食品包装用シートとして好 適に利用することができる。 The anti-fogging polyolefin-based sheet described above has a high anti-fogging effect and is excellent in transparency, so that it can be suitably used as an OPS alternative field, for example, as a food packaging sheet.
また、本発明の防曇性ポリオレフイン系シートを熱成形して得られる成形体も、 防曇性、 透明性に優れているため、 食品包装用成形体、 例えば食品用トレイ等に 好適に利用することができる。 Further, a molded article obtained by thermoforming the anti-fogging polyolefin-based sheet of the present invention is also excellent in anti-fogging property and transparency, so that it is suitably used for a molded article for food packaging, for example, a food tray. be able to.
本発明に係る防曇性ポリオレフイン系シートの製造方法は、 複数の冷却口ール に卷装されたェンドレスベルトと鏡面冷却ロールとの間に溶融ポリオレフイン系 樹脂を導入後、 前記ェンドレスベルトおょぴ鏡面冷却ロールで前記溶融ポリオレ フィン系樹脂を圧接してシート状に成形するとともに、 急冷してポリオレフイン 系樹脂シートを成形するシート成形工程と、 このシート成形工程により得られた ポリオレフイン系樹脂シートの少なくとも一方の表面に、 防曇剤とバインダ樹脂 との混合水溶液を塗布した後、 乾燥させてコート層を形成するコート層形成工程 と、 を備えることを特徴とする。 The method for producing an anti-fog polyolefin-based sheet according to the present invention comprises the steps of: introducing a molten polyolefin-based resin between an endless belt wound around a plurality of cooling ports and a mirror-surface cooling roll; A sheet forming step in which the molten polyolefin resin is pressed into contact with a belt and a mirror cooling roll to form a sheet, and quenched to form a polyolefin resin sheet; and a polyolefin resin obtained by the sheet forming step. Coating a mixed aqueous solution of an anti-fogging agent and a binder resin on at least one surface of the resin sheet, and then drying to form a coat layer.
ここで、 シートを急冷する際の温度としては、 特に限定はないが、 例えば、 露 点以上、 5 0 °C以下で急冷することが好ましく、 露点以上 3 0 °C以下で急冷する ことがより一層好ましい。 Here, the temperature at which the sheet is rapidly cooled is not particularly limited. More preferred.
また、 エンドレスベルトとしては、 特に限定はなく、 鏡面ステンレスベルト、 金属製ベルト表面にポリイミ ド榭脂、 フッ素樹脂等をコーティングしたベルト等 を採用することができる。 The endless belt is not particularly limited, and a mirror stainless steel belt, a belt coated with a polyimide resin, a fluorine resin, or the like on the surface of a metal belt, or the like can be used.
なお、 ポリオレフイン系榭脂シート、 防曇剤、 バインダ樹脂については、 前述 と同様である。 The polyolefin resin sheet, antifogging agent, and binder resin are the same as described above.
本発明によれば、 エンドレスベルトと鏡面冷却口ールとにより溶融ポリオレ フィン系樹脂を圧接するとともに、 急冷するシート成形工程を備えている。 した
がって、 透明性が高く、 低結晶性のポリオレフイン系樹脂シートを得ることがで き、 結果として防曇性ポリオレフイン系シートの透明性、 熱成形性を向上させる ことができる。 According to the present invention, there is provided a sheet forming step in which the molten polyolefin resin is brought into pressure contact with the endless belt and the mirror surface cooling port and quenched. did Thus, a polyolefin resin sheet having high transparency and low crystallinity can be obtained, and as a result, the transparency and thermoformability of the anti-fog polyolefin resin sheet can be improved.
また、 防曇剤とバインダ樹脂との混合水溶液をコーテイングするコート層形成 工程を備えているから、 コート層の塗膜強度を高くできるとともに、 その表面の ベたつきを抑えることができる。 図面の簡単な説明 In addition, since a coating layer forming step of coating a mixed aqueous solution of an antifogging agent and a binder resin is provided, the coating strength of the coating layer can be increased and the stickiness of the surface can be suppressed. BRIEF DESCRIPTION OF THE FIGURES
図 1は本発明の第 1実施形態に係る防曇性ポリオレフイン系シートを示す部分 断面図である。 FIG. 1 is a partial cross-sectional view showing an antifogging polyolefin-based sheet according to a first embodiment of the present invention.
図 2は図 1の実施形態におけるポリオレフイン系樹脂シートの製造装置を示す 概略図である。 ' 発明を実施するための最良の形態 FIG. 2 is a schematic diagram showing an apparatus for producing a polyolefin-based resin sheet in the embodiment of FIG. '' Best mode for carrying out the invention
以下、 本発明の実施の形態を図面に基づいて説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[1]防曇 1"生ポリオレフイン系シート [1] Anti-fog 1 "raw polyolefin sheet
図 1には、 本発明の第 1実施形態に係る防曇性ポリオレフイン系シート 1が示 されている。 FIG. 1 shows an antifogging polyolefin-based sheet 1 according to a first embodiment of the present invention.
防曇性ポリオレフイン系シート 1は、 ポリオレフイン系榭月旨シートとしてのポ リプロピレン層 1 1と、 防曇剤およびアクリル系接着剤を含む混合水溶液をコー ティングして形成されたコート層 1 2とを備えて構成されている。 The anti-fog polyolefin-based sheet 1 comprises a polypropylene layer 11 as a polyolefin-based luster sheet, and a coat layer 12 formed by coating a mixed aqueous solution containing an anti-fog agent and an acrylic adhesive. It is provided with.
ここで、防曇性ポリオレフイン系シート 1を構成するポリプロピレン層 1 1は、 平均球晶半径が 4 μπι以下、 シート断面の平均球晶数が 600個/ mm2以下、 固 体密度が 0. 8 90 g/cm3以下、 引張弾性率が 1 50 OMP a以下、 DS C曲 線の最大吸熱ピークの融解ェンタルピー ΔΗが 95 j/g未満、 かつ、 最大吸熱 ピークの低温側に 1 J/g以上の発熱ピークを有し、 厚さ 50 μπι以上のもので ある。 Here, the polypropylene layer 11 constituting the anti-fog polyolefin-based sheet 1 has an average spherulite radius of 4 μπι or less, an average number of spherulites in the sheet cross section of 600 / mm 2 or less, and a solid density of 0.8. 90 g / cm 3 or less, Tensile modulus 150 OMPa or less, Melting enthalpy ΔΗ at the maximum endothermic peak of the DSC curve is less than 95 j / g, and 1 J / g or more at the low temperature side of the maximum endothermic peak The exothermic peak has a thickness of 50 μπι or more.
また、ポリプロピレン層 1 1の厚さを tmmとした場合に、内部ヘイズが、 (3 30 t2- 1 50 t + 20) %以下のものである。
[2]防曇性ポリォレフィン系シートを構成するポリオレフィン系樹脂シート(ポリ ォレフィン系シート) の製造装置および製造方法 When the thickness of the polypropylene layer 11 is tmm, the internal haze is (330 t2-150 t + 20)% or less. [2] Apparatus and method for producing polyolefin resin sheet (polyolefin sheet) constituting antifogging polyolefin sheet
まず、 図 2を参照して、 本発明の防曇性ポリオレフイン系シート 1を構成する ポリプロピレンシート (ポリプロピレン層) 1 1の製造に用いられる製造装置に ついて説明する。 First, with reference to FIG. 2, a production apparatus used for producing a polypropylene sheet (polypropylene layer) 11 constituting the anti-fog polyolefin sheet 1 of the present invention will be described.
製造装置は、 押出機の Tダイ 2 2と、 第 1冷却ロール 2 3、 第 2冷却ロール 2 6、 第 3冷却ロール 2 4およぴ第 4冷却ロール 2 5と、 金属製エンドレスベルト 2 7と、冷却水吹き付けノズル 2 8と、水槽 2 9と、吸水ロール 3 0と、剥離ロー ル 3 1とを備えて構成されている。 The manufacturing equipment consists of an extruder T die 22, a first cooling roll 23, a second cooling roll 26, a third cooling roll 24 and a fourth cooling roll 25, and a metal endless belt 27. , A cooling water spray nozzle 28, a water tank 29, a water absorbing roll 30, and a peeling roll 31.
第 4冷却口ール 2 5、 第 2冷却口ール 2 6および第 3冷却口ール 2 4は、 金属 製ロールであり、 その内部には表面温度調節を可能にするために水冷式等の冷却 手段 (図示省略) が内蔵されている。 The fourth cooling port rule 25, the second cooling port rule 26, and the third cooling port rule 24 are metal rolls. Cooling means (not shown) is built-in.
ここで、 第 1冷却ロール 2 3の表面には、 二トリル一ブタジエンゴム (N B R ) 製の弹性材 3 2が被覆されている。 この弾性材 3 2は、 その硬度 (JIS K 6301A に準拠した方法で測定) が 6 0度以下、 厚さが 1 0 mmのものである。 Here, the surface of the first cooling roll 23 is coated with an elastic material 32 made of nitrile-butadiene rubber (NBR). The elastic material 32 has a hardness (measured by a method based on JIS K 6301A) of 60 degrees or less and a thickness of 10 mm.
なお、 第 1、 第 4、 第 3冷却ロール 2 3、 2 5、 2 4の少なくとも一つは、 そ の回転軸が回転駆動手段 (図示省略) と連結されている。 ' 第 2冷却ロール 2 6は、 Rmax= 1 . 0 mの鏡面を有する金属製ロール(鏡面 冷却ロール) であり、 その內部には表面の温度調節を可能にするための水冷式等 の冷却手段 (図示省略) が内蔵されている。 ここで、 Rmax= l . 0 / m ( Rmax は JIS B 0601 「表面粗さ一定義及ぴ表示」 に基づく) より大きいと、 得られるポ リプロピレンシート (ポリプロピレン層) 1 1の光沢度が低くなり、 透明性の低 いポリプロピレンシ一ト 1 1となる。 In addition, at least one of the first, fourth, and third cooling rolls 23, 25, and 24 has its rotating shaft connected to a rotation drive unit (not shown). '' The second cooling roll 26 is a metal roll (mirror cooling roll) having a mirror surface of Rmax = 1.0 m, and a cooling means such as a water-cooling type to enable surface temperature control (Not shown) is built-in. Here, if Rmax = l.0 / m (Rmax is based on JIS B0601 “Definition and Display of Surface Roughness”), the resulting polypropylene sheet (polypropylene layer) 11 has low gloss. And a polypropylene sheet 11 with low transparency.
この第 2冷却ロール 2 6は、 ポリプロピレンシ一ト 1 1を金属製ェンドレスべ ルト 2 7を介して第 1冷却ロール 2 3との間に挟むように配置されている。 The second cooling roll 26 is disposed so as to sandwich the polypropylene sheet 11 between the first cooling roll 23 and the metal endless belt 27.
ェンドレスベルト 2 7は、 ステンレス等からなり、 Rmax= 1 . 0 μ m以下の鏡 面を有するものである。 このエンドレスベルト 2 7は、 上述の第 1、 第 3、 第 4 冷却ロール 2 3〜2 5に回動自在に卷装されている。 The endless belt 27 is made of stainless steel or the like, and has a mirror surface of Rmax = 1.0 μm or less. The endless belt 27 is rotatably wound around the first, third, and fourth cooling rolls 23 to 25 described above.
冷却水吹き付けノズル 2 8は、第 2冷却口ール 2 6の下面側に設けられており、
これによつて、 エンドレスベルト 2 7の裏面に冷却水が吹き付けられることとな る。 このように冷却水を吹き付けることで、 エンドレスベルト 2 7を急冷すると ともに、 第 1、 第 2冷却ロール 2 3、 2 6により面状圧接された直後のポリプロ ピレンシ一ト 1 1をも急冷している。 The cooling water spray nozzle 28 is provided on the lower surface side of the second cooling port ruler 26, As a result, the cooling water is sprayed on the back surface of the endless belt 27. By spraying the cooling water in this manner, the endless belt 27 is rapidly cooled, and the polypropylene 11 immediately after being pressed by the first and second cooling rolls 23 and 26 is also rapidly cooled. I have.
また、 水槽 2 9は、 上面が開口した箱状に形成され、 第 2冷却ロール 2 6の下 面全体を覆うように設けられている。 この水槽 2 9により、 吹き付けられた冷却 水を回収するとともに、 回収した水を水槽 2 9の下面に形成された排出口 2 9 A より排出する。 Further, the water tank 29 is formed in a box shape having an open upper surface, and is provided so as to cover the entire lower surface of the second cooling roll 26. The water tank 29 collects the sprayed cooling water and discharges the collected water from an outlet 29 A formed on the lower surface of the water tank 29.
吸水ロール 3 0は、 第 2冷却ロール 2 6における第 3冷却ロール 2 4側の側面 部に、 エンドレスベルト 2 7に接するように設置されており、 エンドレスベルト 2 7の裏面に付着した余分な冷却水を除去する作用をする。 The water-absorbing roll 30 is installed on the side surface of the second cooling roll 26 on the side of the third cooling roll 24 so as to be in contact with the endless belt 27, and excess cooling adhered to the back surface of the endless belt 27. It acts to remove water.
剥離ロール 3 1は、 ポリプロピレンシ一ト 1 1をエンドレスベルト 2 7および 第 3冷却ロール 2 4にガイドするように配置されるとともに、 冷却終了後のポリ プロピレンシ一ト 1 1をェンドレスベルト 2 7から剥離するものである。 · なお、 本実施形態では、 剥離ロール 3 1は、 ポリプロピレンシ一ト 1 1を第 3 冷却ロール 2 4側に圧接していないが、圧接するようにしても構わない。ただし、 本実施形態のように圧接しない方が好ましい。 The peeling roll 31 is arranged so as to guide the polypropylene sheet 11 to the endless belt 27 and the third cooling roll 24, and the endless belt for the polypropylene sheet 11 after cooling is completed. Separated from 27. · In this embodiment, the peeling roll 31 does not press the polypropylene sheet 11 against the third cooling roll 24, but may press it. However, it is preferable not to make pressure contact as in the present embodiment.
以上のように構成された製造装置を用いたポリプロピレンシート 1 1の製造方 法について説明する (シート成形工程) 。 A method of manufacturing the polypropylene sheet 11 using the manufacturing apparatus configured as described above will be described (sheet forming step).
まず、 ポリプロピレンシート 1 1と直接接触し、 これを冷却するエンドレスべ ルト 2 7および第 2冷却ロール 2 6の表面温度が露点以上、 3 0 °C以下に保たれ るように、 予め各冷却口ール 2 4、 2 5、 2 6の温度制御を行う。 First, the endless belt 27 and the second cooling roll 26 which come into direct contact with the polypropylene sheet 11 and cool it are kept in advance at each cooling port so that the surface temperature is maintained at the dew point or higher and 30 ° C or lower. Control the temperature of rules 24, 25 and 26.
ここで、 第 2冷却ロール 2 6およびエンドレスベルト 2 7の表面温度が露点以 下では、 表面に結露が生じ均一な製膜が困難になる可能性がある。 一方、 表面温 度が 3 0 °Cより高いと、 得られるポリプロピレンシート 1 1の透明性が低くなる とともに、 ひ晶が多くなり、 熱成形しにくいものとなる可能性がある。 したがつ て、 本実施形態では表面温度を 1 4 °Cとしている。 Here, if the surface temperature of the second cooling roll 26 and the endless belt 27 is lower than the dew point, dew condensation may occur on the surface, making it difficult to form a uniform film. On the other hand, if the surface temperature is higher than 30 ° C., the transparency of the obtained polypropylene sheet 11 will decrease, and the number of crystals will increase, which may make it difficult to heat-mold. Therefore, in the present embodiment, the surface temperature is set to 14 ° C.
次に、 押出機の Tダイ 2 2より押し出されたポリプロピレンシ一ト 1 1を、 第 1冷却ロール 2 3上でエンドレスベルト 2 7と第 2冷却ロール 2 6との間に挟み
込む。 この状態で、 ポリプロピレンシート 1 1を第 1、 第 2冷却ロール 2 3、 2 6で圧接するとともに、 1 4 °Cで急冷する。 Next, the polypropylene sheet 11 extruded from the T die 22 of the extruder is sandwiched between the endless belt 27 and the second cooling roll 26 on the first cooling roll 23. Put in. In this state, the polypropylene sheet 11 is pressed against the first and second cooling rolls 23 and 26 and rapidly cooled at 14 ° C.
この際、 第 1冷却ロール 2 3および第 2冷却ロール 2 6間の押圧力で弾性材 3 2が圧縮されて弾性変形することとなる。 この弾性材 3 2が弾性変形している部 分、 すなわち、 第 1冷却ロール 2 3の中心角度 0 1に対応する円弧部分で、 ポリ プロピレンシート 1 1は各冷却ロール 2 3、 2 6により面状圧接されている。 こ の際の面圧は、 0 . :!〜 2 0 M P aである。 At this time, the elastic material 32 is compressed and elastically deformed by the pressing force between the first cooling roll 23 and the second cooling roll 26. The portion where the elastic member 32 is elastically deformed, that is, the arc portion corresponding to the central angle 01 of the first cooling roll 23, the polypropylene sheet 11 is surfaced by the cooling rolls 23, 26. It has been pressed. The surface pressure at this time is 0. 220 MPa.
上述のように圧接され、 第 2冷却ロール 2 6およびエンドレスべノレト 2 7間に 挟まれたポリプロピレンシート 1 1は、 続いて、 第 2冷却ロール 2 6の略下半周 に対応する円弧部分で、 エンドレスベルト 2 7と第 2冷却ロール 2 6とに挟まれ て面状圧接されるとともに、 冷却水吹き付けノズル 2 8によるェンドレスベルト 2 7の裏面側への冷却水の吹き付けにより、 さらに急冷される。 この際の面圧は、 0 . 0 1〜0 . 5 M P aであり、 また、 冷却水の温度は 8 °Cである。 The polypropylene sheet 11 pressed as described above and sandwiched between the second cooling roll 26 and the endless velvet 27 subsequently has an arc portion corresponding to a substantially lower half circumference of the second cooling roll 26, While being pressed between the endless belt 27 and the second cooling roll 26 in planar contact, the cooling water spray nozzle 28 sprays cooling water on the back side of the endless belt 27 to further cool rapidly. You. The surface pressure at this time is 0.1 to 0.5 MPa, and the temperature of the cooling water is 8 ° C.
なお、 吹き付けられた冷却水は、 水槽 2 9に回収されるとともに、 回収された 水は排水口 2 9 Aより排出される。 The sprayed cooling water is collected in the water tank 29, and the collected water is discharged from the drain 29A.
このように第 2冷却ロール 2 6で面状圧接および冷却された後、 エンドレスべ ルト 2 7に密着したポリプロピレンシ一ト 1 1は、 エンドレスベルト 2 7の回動 とともに第 3冷却ロール 2 4上に移動される。 ここで、 剥離ロール 3 1によりガ ィドされたポリプロピレンシ一ト 1 1は、 第 3冷却ロール 2 4の略上半周に対応 する円弧部分で、 再び 3 0 °C以下の温度で冷却される。 After being pressed and cooled by the second cooling roll 26 in this manner, the polypropylene sheet 11 in close contact with the endless belt 27 is moved onto the third cooling roll 24 with the rotation of the endless belt 27. Moved to Here, the polypropylene sheet 11 guided by the peeling roll 31 is again cooled at a temperature of 30 ° C. or less in an arc portion corresponding to a substantially upper half circumference of the third cooling roll 24. .
なお、 エンドレスベルト 2 7の裏面に付着した水は、 第 2冷却ロール 2 6から 第 3冷却ロール 2 4への移動途中に設けられている吸水ロール 3 0により除去さ れる。 The water adhering to the back surface of the endless belt 27 is removed by the water absorbing roll 30 provided on the way from the second cooling roll 26 to the third cooling roll 24.
第 3冷却ロール 2 4上で冷却されたポリプロピレンシート 1 1は、 剥離ロール 3 1によりエンドレスベルト 1 7から剥離され、 卷取りロール (図示省略) によ り、 所定の速度で卷き取られる。 The polypropylene sheet 11 cooled on the third cooling roll 24 is peeled off from the endless belt 17 by the peeling roll 31 and wound up at a predetermined speed by a winding roll (not shown).
[3]防曇性ポリオレフイン系シートの製造方法 (コート層形成工程) [3] Method for producing anti-fog polyolefin-based sheet (coat layer forming step)
次に、上記 [2]で説明した方法により得られたポリプロピレン層(ポリプロピレ ンシート) 1 1の両面にコート層 1 2を形成する方法について説明する。
まず、 ポリプロピレン層 1 1の両面にコロナ処理を施す。 コロナ処理を施した ポリプロピレン層 1 1の表面に防曇剤おょぴバインダ樹脂としてのァクリル系接 着剤を混合した水溶液をグラビアコータにて固形分量としてそれぞれ 4〜 4 0 0 m gノ m2になるように塗布した後、 乾燥させコート層 1 2を形成し、 防曇性ポリ ォレフィン系シ一ト 1を得る。 Next, a method of forming the coat layers 12 on both surfaces of the polypropylene layer (polypropylene sheet) 11 obtained by the method described in the above [2] will be described. First, a corona treatment is applied to both sides of the polypropylene layer 11. Polypropylene layer 1 1 of the surface was subjected to corona treatment of an aqueous solution of a mixture of Akuriru system adhesives as anti-fogging agent Contact Yopi binder resin, respectively. 4 to 4 0 0 mg Roh m 2 as solid content by gravure coater Then, the coated layer is dried to form a coat layer 12, and an anti-fogging polyolefin sheet 1 is obtained.
このようにして得られた防曇性ポリオレフイン系シート 1は、防曇効果が高く、 かつ透明性に優れていることから、 O P S代替分野、 例えば、 食品包装用シート として好適に利用することができる。 The anti-fogging polyolefin-based sheet 1 thus obtained has a high anti-fogging effect and is excellent in transparency, so that it can be suitably used as an OPS substitute field, for example, as a food packaging sheet. .
また、 防曇性ポリオレフイン系シート を熱成形して得られる成形体も、 防曇 性、 透明性に優れているため、 食品包装用成形体、 例えば食品用トレイ等に好適 に利用することができる。 Further, a molded article obtained by thermoforming an antifogging polyolefin-based sheet is also excellent in antifogging property and transparency, so that it can be suitably used for a molded article for food packaging, for example, a food tray. .
これらの点については、 以下の第 2実施形態においても同様である。 These points are the same in the following second embodiment.
上述のような本実施形態によれば、 次のような効果がある。 According to the above-described embodiment, the following effects can be obtained.
(1)ポリプロピレン層 1 1の表面に、防曇剤おょぴパインダ樹脂を含むコート層 1 2を有しているから、 防曇剤のみのコート層と比べて、 塗膜強度を高めることが できるとともに、 表面のベたつきを抑えることができる。 (1) Since the surface of the polypropylene layer 11 has a coating layer 12 containing an anti-fogging agent and a pinda resin, the coating film strength can be increased as compared with a coating layer containing only an anti-fogging agent. As well as reducing stickiness on the surface.
(2)バインダ樹脂としてァクリル系接着剤を用いているから、コート層 1 2表面の ベたつきをより一層低下させることができるとともに、 当該防曇性ポリオレフィ ン系シ一ト 1を熱成形して得られる成形体においても効果的に防曇性を発揮させ ることができる。 (2) Since an acryl-based adhesive is used as the binder resin, the tackiness of the surface of the coating layer 12 can be further reduced, and the anti-fog polyolefin-based sheet 1 is thermoformed. The anti-fogging property can be effectively exhibited also in the molded article obtained by the above method.
(3)平均球晶半径が 4 μ πι以下、 平均球晶数 6 0 0個 Zmm2以下、 固体密度が 0 . 8 9 5 g Z c m3以下という特性を有するポリプロピレン層 1 1を有する防曇性 ポリオレフイン系シート 1である。 したがって、 加熱軟化点温度が低く、 低温熱 成形可能、 かつ、 内部ヘイズ (透明性) の良好なシート 1を得ることができる。 また、 加熱軟化温度が低いため特殊な成形装置を使用する必要もないから、 製造 コストの低減も図ることができる。 しかも、 このようなシート 1を熱成形するこ とで、 防曇性を有するとともに透明性の高い熱成形体を得ることができる。 (3) Anti-fog having a polypropylene layer 11 having a characteristic that the average spherulite radius is 4 μπι or less, the average number of spherulites is 600 Zmm 2 or less, and the solid density is 0.895 g Zcm 3 or less. Polyolefin-based sheet 1. Therefore, it is possible to obtain the sheet 1 having a low heating softening point temperature, capable of performing low-temperature thermoforming, and having good internal haze (transparency). In addition, since the heating softening temperature is low, it is not necessary to use a special molding device, so that manufacturing costs can be reduced. Moreover, by thermoforming such a sheet 1, a thermoformed product having anti-fogging properties and high transparency can be obtained.
(4)融解ェンタルピー Δ Hが 9 5 J Z g未満と比較的小さく、かつ、低温側で 1 J Z g以上の発熱が見られるから、 シート 1を軟化させるのに外部から供給しなけ
ればならない熱量が少なく、 かつ、 軟化時の加熱温度が比較的低いので、 低温熱 成形が一層容易になる。 (4) Since the melting enthalpy ΔH is relatively small, less than 95 JZ g, and heat generation of 1 JZ g or more is observed on the low temperature side, it must be supplied from outside to soften the sheet 1. Since the amount of heat required is small and the heating temperature during softening is relatively low, low-temperature thermoforming becomes easier.
(5)ポリプロピレン層 1 1の引張弾性率が 1 5 0 O M P a以下であるから、結晶化 度および軟化点温度が低く、 熱成形を容易に行うことができる。 また、 熱成形時 の加熱により結晶化が促進され、 透明性を維持したまま防曇性ポリオレフイン系 シート 1の熱成形体の引張弾性率を 1 7 0 O M P a以上とすることができ、 十分 な強度を得ることができる。 (5) Since the tensile modulus of the polypropylene layer 11 is 150 OMPa or less, the crystallinity and softening point temperature are low, and thermoforming can be easily performed. Further, the crystallization is promoted by heating during thermoforming, and the tensile elastic modulus of the thermoformed body of the anti-fog polyolefin-based sheet 1 can be set to 170 OMPa or more while maintaining the transparency. Strength can be obtained.
(6)ポリプロピレン層 1 1の厚さを t mmとした場合に、内部ヘイズが、 (3 3 0 t 2- 1 5 0 t + 2 0 ) %以下であるから、 防曇性ポリオレフイン系シート 1を熱 成形して得られる熱成形体の透明性を高めることができる。 すなわち、 ポリプロ ピレン層 1 1の内部ヘイズを上記範囲にすることで、熱成形体の内部ヘイズを(3 3 0 s 2— 1 5 0 S + 2 5 ) %以下 (s :熱成形体の厚さ (mm) ) とすることが できる。 (6) the thickness of the polypropylene layer 1 1 in case of a t mm, the internal haze is, (3 3 0 t 2 - 1 5 0 t + 2 0)% because it will antifogging polyolefin based sheet 1 Of the thermoformed article obtained by thermoforming the polymer. That is, by setting the internal haze of the polypropylene layer 11 within the above range, the internal haze of the thermoformed body is not more than (330 s 2 — 150 S + 25)% (s: thickness of the thermoformed body). (Mm)).
(7)ェンドレスベルト 2 7と鏡面冷却ロールである第 2冷却ロール 2 6とにより 溶融状態のポリプロピレンシート 1 1を圧接するとともに、 急冷するシート成形 工程を備えているから、 透明性が高く、 低結晶性のポリプロピレンシート (ポリ プロピレン層) 1 1を得ることができ、 結果として防曇性ポリオレフイン系シー ト 1の透明性、 熱成形性を向上させることができる。 (7) The endless belt 27 and the second cooling roll 26, which is a mirror-surface cooling roll, press the molten polypropylene sheet 11 in contact with the sheet, and have a sheet forming process for rapid cooling. Thus, a low-crystalline polypropylene sheet (polypropylene layer) 11 can be obtained, and as a result, the transparency and thermoformability of the anti-fog polyolefin-based sheet 1 can be improved.
(8)防曇剤とバインダ樹脂との混合水溶液をコーティングするコート層形成工程 を備えているから、 コート層 1 2の塗膜強度を高くできるとともに、 その表面の ベたつきを抑えることができる。 (8) Since a coating layer forming step of coating a mixed aqueous solution of an anti-fogging agent and a binder resin is provided, the coating strength of the coating layer 12 can be increased and the stickiness of the surface can be suppressed. .
(9)弾性材 3 2の弾性変形を伴ってポリプロピレンシ一ト 1 1を面状に圧接して 冷却しているから、 鏡面転写効率および冷却効率が高まり、 透明性の高いポリプ 口ピレンシ一ト 1 1を高速で製造することができる。 (9) Since the polypropylene sheet 11 is cooled while being pressed against the surface of the polypropylene sheet 11 with the elastic deformation of the elastic material 32, the mirror transfer efficiency and cooling efficiency are increased, and the transparent polyester sheet is highly transparent. 1 1 can be manufactured at high speed.
(10)第 2冷却ロール 2 6およぴェンドレスベルト 2 7の Rmax= 1 . 0 ^ m以下と しているから、 表面光沢度おょぴ透明性の高いポリプロピレンシート 1 1を得る ことができる。 (10) Since the Rmax of the second cooling roll 26 and the endless belt 27 are not more than 1.0 ^ m, it is necessary to obtain a highly transparent polypropylene sheet 11 with a high surface gloss. Can be.
(11)第 2冷却ロール 2 6およびエンドレスベルト 2 7の表面温度を露点以上、 3 0 °C以下に保っているから、 均一に製膜されたポリプロピレンシ一ト 1 1を得る
ことができる。 (11) Since the surface temperature of the second cooling roll 26 and the endless belt 27 is maintained at the dew point or higher and 30 ° C or lower, a polypropylene sheet 11 uniformly formed is obtained. be able to.
(12)冷却水吹き付けノズル 2 8により冷却水を吹き付けてさらに冷却しているか ら、 ポリプロピレンシート 1 1の急冷効果を一層向上でき、 ポリプロピレンシー ト 1 1の結晶化を抑制することができる。 なお、 本発明は前記実施形態に限定されるものではなく、 本発明の目的を達成 できる範囲での変形、 改良は、 本発明に含まれるものである。 例えば、 前記実施 形態では、 ポリオレフイン系樹脂シートとしてポリプロピレン層 1 1を採用して いたが、 これに限られず、 種々のポリオレフイン系樹脂からなる層、 例えば、 ポ リエチレン層等を用いてもよい。 (12) Since the cooling water is sprayed by the cooling water spray nozzle 28 for further cooling, the quenching effect of the polypropylene sheet 11 can be further improved, and the crystallization of the polypropylene sheet 11 can be suppressed. It should be noted that the present invention is not limited to the above embodiment, and modifications and improvements as long as the object of the present invention can be achieved are included in the present invention. For example, in the above-described embodiment, the polypropylene layer 11 is employed as the polyolefin-based resin sheet. However, the present invention is not limited to this, and a layer made of various polyolefin-based resins, for example, a polyethylene layer or the like may be used.
前記実施形態では、 エンドレスベルト 2 7は、 3個のロールに卷装されていた 力 これに限られない。 要するにエンドレスベルトを回動、 冷却できる装置であ れば、 ェンドレスベルトが卷装される冷却ロールの数は任意に設定することがで さる。 In the above-described embodiment, the endless belt 27 is a force wound around three rolls. The present invention is not limited to this. In short, if the device can rotate and cool the endless belt, the number of cooling rolls around which the endless belt is wound can be set arbitrarily.
前記実施形態では、 ェンドレスベルト 2 7として鏡面ステンレスベルトを採用 していたが、 これに限られない。 すなわち、 Rmax= 1 . O /z m以下のエンドレス ベルトであれば特に限定はなく、 例えば、 金属製エンドレスベルトの表面にポリ イミ ド樹脂、 ポリテトラフルォロエチレン等のフッ素樹脂等をコーティングした ベルトを採用してもよい。 In the above embodiment, the mirrorless stainless steel belt is used as the endless belt 27, but the present invention is not limited to this. That is, there is no particular limitation as long as the endless belt is Rmax = 1.O / zm or less.For example, a belt in which a surface of a metal endless belt is coated with a polyimide resin, a fluororesin such as polytetrafluoroethylene, or the like. May be adopted.
また、 弾性材 3 2として、 N B R製の弾性材を採用していたが、 これに限られ ない。 要するに、 所定の硬度および厚さを持ち、 ポリプロピレンシートの圧接時 に弾性変形する材質のものであればよい。 例えば、 シリコーン製の弾性材等を採 用することもできる。 Further, as the elastic member 32, an elastic member made of NBR has been adopted, but it is not limited to this. In short, any material may be used as long as it has a predetermined hardness and thickness and is elastically deformed when the polypropylene sheet is pressed. For example, an elastic material made of silicone or the like can be used.
前記実施形態では、 第 2冷却口ール 2 6およびエンドレスベルト 2 7の表面温 度を 1 4 °Cとしていたが、 これに限定されず、 露点以上 5 0 °C以下、 好ま'しくは 露点以上、 3 0 °C以下の任意の温度を採用することができる。 In the above embodiment, the surface temperature of the second cooling port ruler 26 and the endless belt 27 was set to 14 ° C., but is not limited thereto, and is not less than the dew point and not more than 50 ° C., preferably the dew point. As described above, any temperature of 30 ° C. or less can be adopted.
また、 冷却水吹き付けノズル 2 8により吹き付けられる水の温度は 8 °Cに設定 されていたが、 これに限られず、 第 2冷却ロール 2 6およびエンドレスベルト 2 7の表面温度より低い値で任意に設定することができる。
その他、 本発明を実施する際の具体的な構造および形状等は、 本発明の目的を 達成できる範囲内で他の構造等と 以下、 実施例および比較例を挙げて、 本発明をより具体的に説明する。 In addition, the temperature of the water sprayed by the cooling water spray nozzle 28 was set to 8 ° C, but is not limited to this, and may be arbitrarily set to a value lower than the surface temperature of the second cooling roll 26 and the endless belt 27. Can be set. In addition, specific structures, shapes, and the like when carrying out the present invention are described below with reference to examples and comparative examples, as well as other structures within a range that can achieve the object of the present invention. Will be described.
[実施例 1 ] [Example 1]
[1]ポリオレフイン系樹脂シートの製造 (シート成形工程) [1] Manufacture of polyolefin resin sheet (sheet forming process)
前述の実施形態において、 製造装置および製造方法の具体的条件を以下のよう に設定し、 ポリプロピレン層 1 1を得た。 In the above embodiment, the specific conditions of the production apparatus and the production method were set as follows, and the polypropylene layer 11 was obtained.
押出機の直径: 9 Omm Extruder diameter: 9 Omm
Tダイ 22の幅: 800 mm T die 22 width: 800 mm
ポリプロピレン:出光ポリプロ E— 304GP (出光石油化学 (株) 製) シート 1 1の引き取り速度: 1 OmZm i n Polypropylene: Idemitsu Polypropylene E—304GP (made by Idemitsu Petrochemical Co., Ltd.) Sheet 11 Pick-up speed: 1 OmZmin
第 2冷却ロール 26およびェンドレスベルト 27の表面温度: 14°C 冷却水温度: 8 °C Surface temperature of second cooling roll 26 and endless belt 27: 14 ° C Cooling water temperature: 8 ° C
冷却水吹き付け量: 200リツトル Zm i n Cooling water spray amount: 200 liters Zm i n
[2]コート層の形成 (コート層形成工程) [2] Formation of coat layer (coat layer formation step)
上記シート成形工程にて得られたポリプロピレン層 1 1の両面にコロナ処理を 施し、 処理した両面に、 防曇剤が乾燥後の単位面積あたり重量で 7 Omg、 ァク リル系接着剤が乾燥後の単位面積あたり重量で 50mgとなるように塗布して乾 燥させ、 コート層 12を形成し、 防曇性ポリオレフイン系シート 1を得た。 Corona treatment is applied to both sides of the polypropylene layer 11 obtained in the above sheet forming process, and the treated antifogging agent is dried on both sides by 7 Omg per unit area, and the acrylic adhesive is dried. This was applied so as to be 50 mg in weight per unit area, and dried to form a coat layer 12, and an antifogging polyolefin sheet 1 was obtained.
なお、 防曇剤としては、 リケマール A (理研ビタミン (株) 製) を、 ァクリノレ 系接着剤としては、 ジュリマー FC— 80 (日本純薬 (株) 製) を使用した。 また、 乾燥前の塗膜厚みは、 赤外線水分計 (倉敷紡績 (株) 製) で測定した。 Riquemar A (manufactured by Riken Vitamin Co., Ltd.) was used as the antifogging agent, and Julimer FC-80 (manufactured by Nippon Pure Chemical Co., Ltd.) was used as the acryloline adhesive. The thickness of the coating before drying was measured with an infrared moisture meter (manufactured by Kurashiki Spinning Co., Ltd.).
[実施例 2] [Example 2]
防曇剤が乾燥後の単位面積あたり重量で 300mg、 アタリル系接着剤が乾燥 後の単位面積あたり重量で 250mgとなるようにした以外は、 実施例 1と同様 にして、 防曇性ポリオレフイン系シート 1を得た。 An antifogging polyolefin sheet was prepared in the same manner as in Example 1, except that the weight of the antifogging agent was 300 mg per unit area after drying and the weight of the ataryl adhesive was 250 mg per unit area after drying. Got one.
[実施例 3] [Example 3]
防曇剤が乾燥後の単位面積あたり重量で 10 m g、 アタリル系接着剤が乾燥後
の単位面積あたり重量で 10mgとなるようにした以外は、 実施例 1と同様にし て、 防曇性ポリオレフイン系シート 1を得た。 10 mg by weight per unit area after drying of antifogging agent, after drying of ataryl adhesive The antifogging polyolefin-based sheet 1 was obtained in the same manner as in Example 1, except that the weight per unit area was 10 mg.
[実施例 4] [Example 4]
シートの製法として、 透明化核剤 (ジベンジリデンソルビトール誘導体) を用 い、 一般のタツチロール成形を採用した以外は実施例 1と同様にして、 防曇性ポ リォレフィン系シート 1を得た。 An antifogging polyolefin sheet 1 was obtained in the same manner as in Example 1 except that a transparent nucleating agent (dibenzylidene sorbitol derivative) was used as a sheet manufacturing method and a general tattyrol molding was employed.
[実施例 5 ] [Example 5]
防曇剤が乾燥後の単位面積あたり重量で 500mg、 アタリル系接着剤が乾燥 後の単位面積あたり重量で 4 O Omgとなるようにした以外は、 実施例 1と同様 にして、 防曇性ポリオレフイン系シート 1を得た。 An antifogging polyolefin was prepared in the same manner as in Example 1, except that the weight of the antifogging agent was 500 mg per unit area after drying and the weight of the ataryl adhesive was 4 OOmg per unit area after drying. System sheet 1 was obtained.
[実施例 6 ] [Example 6]
防曇剤が乾燥後の単位面積あたり重量で 2m g、 アクリル系接着剤が乾燥後の 単位面積あたり重量で lmgとなるようにした以外は、 実施例 1と同様にして、 防曇性ポリ.ォレフィン系シート 1を得た。 An antifogging poly was prepared in the same manner as in Example 1 except that the antifogging agent was 2 mg in weight per unit area after drying and the acrylic adhesive was 1 mg in weight per unit area after drying. An olefinic sheet 1 was obtained.
[比較例 1 ] [Comparative Example 1]
アクリル系接着剤を用いない以外は、 実施例 1と同様にして防曇性ポリオレ フィン系シ一トを得た。 An antifogging polyolefin sheet was obtained in the same manner as in Example 1 except that no acrylic adhesive was used.
上記各実施例および比較例で得られた防曇性ポリオレフイン系シートについ て、 巻取り後のシート外観、 卷取り後のシートの防曇性 (高温 Z低温) について 評価を行い、 結果を表 1に示した。 The anti-fogging polyolefin-based sheets obtained in the above Examples and Comparative Examples were evaluated for the appearance of the sheet after winding and the anti-fogging property (high temperature Z low temperature) of the wound sheet. It was shown to.
また、 上記各実施例おょぴ比較例で得られた防曇性ポリオレフィン系シ一トを 一般的な真空圧空成形機で Φ 100、 深さ 1 Ommの容器を成形し、 得られた容 器についても同様の評価を行い、 併せて表 1に示した。
表 1 Further, the anti-fogging polyolefin-based sheet obtained in each of the above Examples and Comparative Examples was molded into a container having a diameter of 100 mm and a depth of 1 Omm using a general vacuum pressure air molding machine. The same evaluation was performed for, and also shown in Table 1. table 1
ここで、 卷取り後のシート外観および成形体の外観は、 目視で評価した。 また、 防曇性は、 以下のような手法で評価した。 Here, the appearance of the sheet after winding and the appearance of the molded body were visually evaluated. The antifogging property was evaluated by the following method.
[1]高温防曇性 [1] High temperature anti-fog properties
一定容量の容器に 9 0 °Cの熱水を一定量注ぎ、 成形蓋で密閉する。 室温で放置
後の経時変化を目視して評価した (評価 5 :良好、 評価 1 :不良) 。 Pour a certain amount of hot water at 90 ° C into a container of fixed volume and seal with a molding lid. Leave at room temperature The subsequent change over time was visually evaluated (evaluation 5: good, evaluation 1: bad).
[2]低温防曇性 [2] Low temperature anti-fog properties
—定容量の容器に 2 3 °Cの水を一定量注ぎ、 成形蓋で密閉する。 5 °Cの冷蔵庫 で放置後の経時変化を目視して評価した (評価 5 :良好、 評価 1 :不良) 。 表 1に示されるように、 実施例 1〜 3で得られた防曇性ポリオレフイン系シー トについては、 シートの外観、 防曇性、 および成形体の外観、 防曇性が極めて良 好であることがわかる。 — Pour a certain amount of water at 23 ° C into a container of constant volume and seal with a molding lid. Changes over time after standing in a refrigerator at 5 ° C were visually evaluated (evaluation 5: good, evaluation 1: bad). As shown in Table 1, the anti-fogging polyolefin-based sheets obtained in Examples 1 to 3 have extremely good sheet appearance, anti-fogging property, appearance of molded article, and anti-fogging property. You can see that.
実施例 5では、 防曇剤おょぴアクリルバインダを過剰に塗布しているため、 一 部に転写ムラが生じるとともに、 熱成形時の伸びにより一部に塗膜剥離が生じて いるが、 実用上問題となるほどではない。 In Example 5, since the antifogging agent and the acrylic binder were applied excessively, transfer unevenness occurred in some parts, and peeling of the coating film occurred in some parts due to elongation during thermoforming. It is not enough to be a problem.
実施例 6では、 防曇剤およびァクリルバインダが少ないため、 シートの防曇効 果およぴ成形体の防曇効果が若干低下していることがわかる。 In Example 6, it can be seen that the antifogging effect of the sheet and the antifogging effect of the molded article were slightly reduced because the antifogging agent and the acrylyl binder were small.
これに対して、 アクリル系接着剤を含有していない比較例 1では、 表面のベた つきおよぴシート反対面への転写が発生して、 転写ムラが生じていることがわか る。 On the other hand, in Comparative Example 1, which did not contain the acrylic adhesive, it was found that stickiness of the surface and transfer to the opposite surface of the sheet occurred, resulting in uneven transfer.
実施例 4では、 シートの透明性は高いが、 低温での熱成形性がやや不足し成型 品の透明性は低くなつている。 但し、 比較例 1に対しては優れたものとなってい る。 産業上の利用可能性 In Example 4, the transparency of the sheet was high, but the thermoformability at low temperatures was slightly insufficient, and the transparency of the molded product was low. However, it is superior to Comparative Example 1. Industrial applicability
本発明は、 防曇性ポリオレフイン系シート、 防曇性ポリオレフイン系シートの 製造方法、 およぴ該シートを用いた成形体、 食品包装用シート、 食品包装用成形 体に関し、 食品等の包装に利用できる。
The present invention relates to an antifogging polyolefin-based sheet, a method for producing the antifogging polyolefin-based sheet, and a molded article, a food packaging sheet, and a food packaging molded article using the sheet, and is used for packaging food and the like. it can.
Claims
1. ポリオレフイン系樹脂シートの少なくとも片面に、 防曇剤、 およびアタリ ル系接着剤からなるバインダ樹脂を含むコート層を有することを特徴とする防曇 性ポリオレフイン系シート。 1. An anti-fogging polyolefin sheet comprising at least one surface of a polyolefin resin sheet having a coating layer containing a binder resin comprising an anti-fogging agent and an atalylic adhesive.
2. 請求項 1に記載の防曇性ポリオレフイン系シートにおいて、 2. The anti-fog polyolefin sheet according to claim 1,
前記コート層は、 前記ポリオレフイン系樹脂シートに前記防曇剤およびバイン ダ樹脂を固形分量としてそれぞれ 4〜 40 Omg/m2塗布して形成された層で あることを特徴とする防曇性ポリオレフイン系シート。 The coating layer, antifogging polyolefin system, characterized in that said anti-fogging agent and Vine da resin to the polyolefin-based resin sheet is a layer formed by 4~ 40 Omg / m 2 respectively coated solid basis Sheet.
3. 請求項 1または請求項 2に記載の防曇性ポリオレフイン系シートにおいて、 前記ポリオレフイン系樹脂シートの少なくとも表層が、 ポリプロピレン層であ ることを特徴とする防曇性ポリオレフイン系シート。 3. The anti-fog polyolefin-based sheet according to claim 1, wherein at least a surface layer of the polyolefin-based resin sheet is a polypropylene layer.
4. 請求項 1から請求項 3のいずれかに記載の防曇性ポリオレフイン系シート において、 4. The antifogging polyolefin sheet according to any one of claims 1 to 3,
前記ポリオレフイン系樹脂シートは、 平均球晶半径が 4 μπι以下、 シート断面 の平均球晶数が 600個 Zmm2以下、 固体密度が 0. 890 g/cm3以下、 示 差走査熱分析 (DSC) 曲線の最大吸熱ピークの融解ェンタルピー ΔΗが 95 J /g未満、 かつ、 前記最大吸熱ピークの低温側に 1 J /g以上の発熱ピークを有 し、 厚さ 50 μπι以上のポリプロピレン層であることを特徴とする防曇性ポリオ レフイン系シート。 The polyolefin-based resin sheet has an average spherulite radius of 4 μπι or less, an average number of spherulites in the sheet cross section of 600 or less Zmm 2 , a solid density of 0.890 g / cm 3 or less, and differential scanning calorimetry (DSC). The melting enthalpy ΔΗ of the maximum endothermic peak of the curve is less than 95 J / g, and the polypropylene layer has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak and has a thickness of 50 μπι or more. Characteristic anti-fog polyolefin sheet.
5. 請求項 1から請求項 4のいずれかに記載の防曇性ポリオレフイン系シート において、 5. The anti-fog polyolefin sheet according to any one of claims 1 to 4,
前記ポリオレフィン系樹脂シートは、このシートの厚さを t mmとした場合に、 内部ヘイズが、 (330 t2_ 150 t + 20) %以下であることを特徴とする防 曇性ポリオレフイン系シート。 The anti-fog polyolefin-based sheet, wherein the polyolefin-based resin sheet has an internal haze of (330 t 2 _ 150 t + 20)% or less when the thickness of the sheet is t mm.
6. 請求項 1から請求項 5のいずれかに記載の防曇性ポリオレフイン系シート にお ヽて、 6. In the anti-fog polyolefin sheet according to any one of claims 1 to 5,
前記ポリオレフイン系樹脂シートの引張弾性率は、 1500MP a以下である ことを特徴とする防曇性ポリオレフイン系シート。
The anti-fog polyolefin-based sheet, wherein the tensile modulus of the polyolefin-based resin sheet is 1500 MPa or less.
7 . 複数の冷却口一ルに卷装されたェンドレスベルトと鏡面冷却口ールとの間 に溶融ポリオレフィン系榭脂を導入後、 前記ェンドレスベルトおよび鏡面冷却 ロールで前記溶融ポリすレフイン系榭脂を圧接してシート状に成形するととも に、 急冷してポリオレフィン系樹脂シートを成形するシート成形工程と、 このシート成形工程により得られたポリオレフイン系樹脂シートの少なくとも 一方の表面に、 防曇剤とパインダ樹脂との混合水溶液を塗布した後、 乾燥させて コート層を形成するコート層形成工程と、 を備えることを特徴とする防曇性ポリ ォレフィン系シートの製造方法。 7. After the molten polyolefin resin is introduced between the endless belt wound around the plurality of cooling openings and the mirror cooling opening, the molten polymer is introduced by the endless belt and the mirror cooling roll. A sheet forming step of forming a polyolefin resin sheet by quenching and forming a olefin resin sheet by pressing the refin resin into a sheet shape, and forming at least one surface of the polyolefin resin sheet obtained by the sheet forming step. A method for producing an anti-fogging polyolefin sheet, comprising: applying a mixed aqueous solution of an anti-fogging agent and a pinda resin, followed by drying to form a coat layer.
8 . 請求項 1から請求項 6のいずれかに記載の防曇性ポリオレフイン系シート を熱成形して得られることを特徴とする成形体。 8. A molded article obtained by thermoforming the anti-fog polyolefin sheet according to any one of claims 1 to 6.
9 . 請求項 1から請求項 6のいずれかに記載の防曇性ポリオレフイン系シート を用いたことを特徴とする食品包装用シート。 9. A food packaging sheet using the antifogging polyolefin-based sheet according to any one of claims 1 to 6.
1 0 . 請求項 8に記載の成形体を用いたことを特徴とする食品包装用成形体。
10. A molded article for food packaging, characterized by using the molded article according to claim 8.
Priority Applications (1)
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JP2002536362A JPWO2002032984A1 (en) | 2000-10-16 | 2001-10-15 | Antifogging polyolefin sheet, method for producing antifogging polyolefin sheet, molded article using the sheet, sheet for food packaging, molded article for food packaging |
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JP2000-315356 | 2000-10-16 | ||
JP2000315356 | 2000-10-16 |
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PCT/JP2001/009028 WO2002032984A1 (en) | 2000-10-16 | 2001-10-15 | Antifogging polyolefin sheet, process for producing antifogging polyolefin sheet, molded object obtained from the sheet, sheet for food packaging, and molded object for food packaging |
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JP (2) | JPWO2002032984A1 (en) |
WO (1) | WO2002032984A1 (en) |
Cited By (3)
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JP2007022589A (en) * | 2005-07-15 | 2007-02-01 | Idemitsu Unitech Co Ltd | Package |
JP2015231718A (en) * | 2014-06-10 | 2015-12-24 | 出光ユニテック株式会社 | Antifogging polyolefin base sheet, method for producing the same, molded body thereof, and molded body for food package |
US10948745B2 (en) | 2014-12-05 | 2021-03-16 | 3M Innovative Properties Company | Vision-protecting filter lens having organic polymer multilayer and neutral-density optical filter |
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JP5970769B2 (en) * | 2010-09-30 | 2016-08-17 | 大日本印刷株式会社 | Solar cell module sealing material and method for producing solar cell module using the same |
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JP2015231718A (en) * | 2014-06-10 | 2015-12-24 | 出光ユニテック株式会社 | Antifogging polyolefin base sheet, method for producing the same, molded body thereof, and molded body for food package |
US10948745B2 (en) | 2014-12-05 | 2021-03-16 | 3M Innovative Properties Company | Vision-protecting filter lens having organic polymer multilayer and neutral-density optical filter |
Also Published As
Publication number | Publication date |
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JPWO2002032984A1 (en) | 2004-02-26 |
JP2010180407A (en) | 2010-08-19 |
JP5227986B2 (en) | 2013-07-03 |
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