WO1995012490A1 - Film de polyethylene stratifie thermo-retrecissable - Google Patents

Film de polyethylene stratifie thermo-retrecissable Download PDF

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Publication number
WO1995012490A1
WO1995012490A1 PCT/JP1993/001588 JP9301588W WO9512490A1 WO 1995012490 A1 WO1995012490 A1 WO 1995012490A1 JP 9301588 W JP9301588 W JP 9301588W WO 9512490 A1 WO9512490 A1 WO 9512490A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat
film
temperature
density
layer
Prior art date
Application number
PCT/JP1993/001588
Other languages
English (en)
Japanese (ja)
Inventor
Syuuichi Morita
Shigeyoshi Koyabu
Tamio Moriyama
Masaaki Tateiwa
Original Assignee
Kohjin Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kohjin Co., Ltd. filed Critical Kohjin Co., Ltd.
Priority to US08/313,045 priority Critical patent/US5635286A/en
Priority to CA002118002A priority patent/CA2118002C/fr
Priority to PCT/JP1993/001588 priority patent/WO1995012490A1/fr
Publication of WO1995012490A1 publication Critical patent/WO1995012490A1/fr

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Classifications

    • 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

Definitions

  • the present invention relates to a polyethylene-based heat-shrinkable laminated film, and more particularly, to a heat-shrinkable laminated film made of a specific ethylene-based copolymer and having excellent suitability for a packaging machine. Regarding the film.
  • stretched films such as polyvinyl chloride, polypropylene, and polyethylene have been known.
  • polyethylene-based heat-shrinkable films have been used because of their heat-sealing properties and low cost.
  • Low-density copolymer hereinafter simply abbreviated as linear low-density polyethylene
  • Lum is noted for its excellent impact resistance and heat seal strength, and is expected to be used in many fields.
  • the present inventors have previously proposed a heat-shrinkable film mainly comprising a specific ethylene- ⁇ -olefin copolymer (Japanese Patent Application Laid-Open No. 62-201). No. 229 Publication).
  • the thickness of the film is small and the low-temperature shrinkage of the film is better than that of the film obtained by inflation.
  • the use of automatic packaging machines (pillow wrapping machines, half-fold automatic wrapping machines, etc.) as packaging materials in recent years has led to the increase in packaging speed of packaging machines. Since the speed is significantly increased, there is a problem in that a heat seal defect (partially not sealed), which has not occurred in the past, may occur.
  • the inventors of the present invention have conducted further detailed studies in order to eliminate the above-described seal failure, and as a result, have confirmed the following.
  • the film has low stiffness (small tensile elasticity), it becomes easier for the film to enter during film running, so it is necessary to use a fusing seal at the part where the film is to be sealed.
  • the number of folded parts of the film will increase, and the occurrence of binholes will increase.
  • the viscosity of the fusing resin is low, the fusing resin tends to adhere to the blade edge of the heat knife or the heat knife base, and pinholes are generated in the seal portion.
  • the film must not be cut or, in extreme cases, not completely sealed.
  • the present inventors have made intensive studies on the laminated structure of the film and various kinds of raw material resins.
  • the layer has a low melt index, high total heat of fusion, and a high endothermic area ratio above the melting point to increase the cooling and solidification rate during the fusing seal.
  • a resin with a higher melt index than that of the intermediate layer and having the same characteristics as the intermediate layer is used. It has been found that a heat-shrinkable film having good suitability for a packaging machine can be obtained, and the present invention has been achieved.
  • the intermediate layer has a density of 0.910 to 0.930 g / cm 3 and a melt index of 0.1 to 0.88TZ 10.
  • the temperature was lowered to 20'C in 10 minutes, and then the temperature was raised.
  • Total heat of fusion in the melting curve obtained when the temperature is increased in 10 minutes at a rate of 10 min. Is not less than 135 mJ Zmg and an endotherm not less than the main peak temperature (melting point).
  • the index is 0.8 to 5.Og / 10 min, and the total heat of fusion in the melting curve is in the range of 135 to 160 mJ / mgr; Linear low-density poles whose endothermic area above the main peak temperature is 12% or more of the total endothermic area
  • At least one layer of the linear low-density polyethylene (A) used as a main component of the intermediate layer in the present invention has a density of 0.910 to 0.930 s Z cm 3 , Melt index 0 1 to 0 8 S / 10 A material with a characteristic value of 10 minutes is used, and more preferably, the density is 0.9 to 15 to 0.9. 25 g- / cm 3 ⁇ melt index 0.2 to 0.7 sr / 10 min. Density 0. 9 1 0 g / cm 3 non Mitsurude is rather to Do rather preferable because tensile modulus that Do rather low, the density is exceeds the 0. 9 3 0 gZ cm 3 low temperature shrinkability is insufficient Not good because of it.
  • melt extrusion it is not preferable because the motor load at the time increases and the workability deteriorates, and if it exceeds 0.8 s / 10 minutes, it is preferable because the fusing sealability deteriorates. Not good.
  • the linear low-density polyethylene (A) has a total heat of fusion of 135 mJ / m sr or more in the melting curve in the DSC measurement, and a main peak temperature.
  • the above endothermic area must be at least 12% of the total endothermic area. If the condition is not satisfied, the cooling and solidification rate of the blown resin is slow, and good blown sealability cannot be obtained.
  • the thickness of the intermediate layer with respect to all layers must be 60% or more. When the thickness of the intermediate layer is less than 60%, excellent fusing sealability cannot be exhibited.
  • the linear low-density polyethylene (B) used as a main component in the innermost layer and the outermost layer has a melt index of 0.8 to 5. 0 g Z 10 minutes, the total heat of fusion in the melting curve is in the range of 135 to 160 mJ / mg, and the endothermic area above the main peak temperature is Those having 12% or more of the total endothermic area are used.
  • the melt index is less than 0.8 gr 10 min
  • the transparency is lowered due to the roughening of the film surface, which is not preferable. If it exceeds S / 10 minutes, the heat seal strength is reduced and the drawability is adversely affected, which is not preferable. Further, if the total heat of fusion is less than 135 mJZmg, good fusing sealability is not obtained, and if it exceeds 160 mJZmg, the transparency is unfavorably reduced.
  • the above linear low-density polyethylene (A) and (B) are a linear copolymer of ethylene and an ethylene olefin, and are copolymerized with ethylene.
  • the ⁇ -olefin resin to be polymerized is not particularly limited.
  • butene-11, pentene-11, hexene-11, heptene-11, octene1-1,4-methan with 4 to 12 carbon atoms Tilpentene-11, decene-11, pendecene-11, dodecene-11, etc., among which ⁇ -branched olefins having 4 to 8 carbon atoms are more preferable.
  • the resin composition used in each of the above layers may be used alone or in combination of two or more. Further, the resin composition used in the high-pressure polystyrene may be used as long as the object of the present invention is not hindered. Polyolefin resin such as ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, etc. Can be done.
  • the laminated film of the present invention includes the above-mentioned linear low-density polyethylene resin (A) in a range satisfying the above-described thickness conditions of each layer in addition to the intermediate layer, the innermost layer, and the outermost layer.
  • (B) may contain one or two or more intermediate layers made of a polyolefin resin.
  • a linear low-density polyethylene resin (A) and a linear resin other than (B) are used.
  • Polyolefin resins such as high-density polyethylene resins, high-pressure polyethylene resins, and ethylene-propylene copolymers, and the like. One type or two or more types can be appropriately selected and used as long as they do not cause a problem.
  • additives such as lubricants, antiblocking agents, antistatic agents, and antifogging agents can be used as appropriate for the purpose of achieving their effective effects. This is especially effective for the innermost and outermost layers.
  • the production and stretching of the raw film for stretching used in the present invention can be performed by a known method.
  • a case of three-layer laminated tubular film forming and stretching will be described as an example. This will be specifically described.
  • the linear low-density polyethylene (A) of the above-mentioned ethylene and ⁇ -olefin is placed in the middle layer, and the linear low-density polyethylene of the ethylene and ⁇ -yearly refine is formed.
  • the density polyethylene ( ⁇ ) is melt-kneaded by three extruders so as to become inner and outer layers, and is co-extruded into a tube from a three-layer annular die, and is not stretched once. It is quenched and solidified to produce a tube-shaped unstretched film.
  • the obtained tube-shaped unstretched film is supplied to, for example, a tuber stretching apparatus as shown in FIG. 1 to obtain a highly oriented temperature range, for example, below the melting point of the intermediate layer resin.
  • a gas pressure is applied to the inside of the tube at 0'C, preferably below the melting point and at a temperature lower than 15 to cause simultaneous biaxial orientation by expansion and stretching.
  • the stretching ratio does not have to be the same in both the vertical and horizontal directions.However, in order to obtain physical properties such as excellent strength and shrinkage, it should be at least 2 times in both directions, preferably 2.5 times or more. More preferably, it is stretched three times or more.
  • the film removed from the stretching device can be annealed as desired, and this elimination can suppress natural shrinkage during storage. I can do it.
  • FIG. 1 is a cross-sectional view for explaining a tuber biaxial stretching apparatus used in Examples.
  • FIG. 2 is a schematic diagram for explaining a load-deformation curve for calculating a tensile modulus in the example.
  • each layer of the laminate was measured by observing the cross section of the film with a microscope.
  • the ratio of the scattered light transmittance to the parallel light transmittance was indicated by% using an integrating sphere light transmittance measuring device conforming to JIS-K6714.
  • a film cut into a square of 10 cm in both length and width was immersed in a glycerin bath at a predetermined temperature for 10 seconds, and calculated by the following equation.
  • a and B indicate the vertical and horizontal lengths after immersion (unit: cm).
  • test piece Take a test piece with a width of 15 mm and a length of 300 mm each in the MD (vertical direction) and TD (horizontal direction) from the film sample, and measure the thickness.
  • test specimens were gripped on an universal tensile tester manufactured by Orientec Co., Ltd. at an interval of 5 Omm, and the tensile speed was 40 mmZ, the recording paper speed was 50 Omm / min, and the full scale. Measured under the condition of 2 kg and calculated by the following formula.
  • a half-fold film with a width of 40 O mm was supplied to a half-fold automatic packaging machine (model AT—500) manufactured by Kyowa Electric Co., Ltd., which was 23.5 cm long, 15.5 cm wide, and high.
  • a 5.6 cm lunch box (200 g) is packed continuously at a speed of 25 pieces / min and 100 pieces are measured, and the non-defective rate is measured. If the non-defective rate in the seal temperature range of 100% is 100%, it is O, ⁇ is less than 100%, 80% or more is X, and X is less than 80%.
  • a half-fold automatic packaging machine model AT—500 manufactured by Kyowa Electric Co., Ltd., which was 23.5 cm long, 15.5 cm wide, and high.
  • a 5.6 cm lunch box (200 g) is packed continuously at a speed of 25 pieces / min and 100 pieces are measured, and the non-defective rate is measured. If the non-defective rate in the seal temperature range of 100% is 100%, it is O,
  • non-defective products were non-defective products that had no stringiness in the seal after shrink wrapping and had no pinholes of 1 mm or more.
  • the margin of spare packaging is set to 13% both vertically and horizontally.
  • Linear low-density polyethylene which is a copolymer of ethylene having the properties shown in Table 1 and 41-methylpentene-11 as a comonomer
  • Low-density polyethylene which is a copolymer of ethylene and octen-11, also having the properties shown in Table 1 using resin as the intermediate layer
  • the resin was melted and kneaded at 170 ° C to 240 ° C in three extruders (for the middle layer, the innermost layer, and the outermost layer) as the inner and outer layers, respectively, as shown in Table 1.
  • the extrusion amount from each extruder was set assuming the thickness ratio, and co-extrusion was performed downward from a three-layer annular die maintained at 24 O'C.
  • the formed three-layer tube is used to slide the outer surface of the cylindrical cooling mandrel through which the cooling water circulates on the inside, while passing the water tank on the outside.
  • the bow I was removed to obtain an unstretched film with a diameter of about 75 mm and a thickness of 320 m.
  • the thickness of each layer was adjusted by adjusting the screw rotation speed and the take-up speed of the extruder.
  • This tube-shaped unstretched film is guided to the tube biaxial stretching device shown in Fig. 1 and stretched four times in each of the vertical and horizontal directions at 95 to 105 to form a laminated biaxial film. A stretched film was obtained. Next, this stretched film is put into a chip-availing machine for 75. After being treated with hot air of C for 10 seconds, it was cooled to room temperature, folded and wound.
  • the obtained stretched film had a thickness configuration as shown in Table 1, was excellent in transparency and low-temperature shrinkage, and had a high tensile modulus.
  • Table 1 the continuous actual packaging of the lunch box was evaluated using a half-fold automatic packaging machine, it was found that there was no failure in the seal part and that it had good suitability for the packaging machine in a wide temperature range.
  • Example 1 Using the resin composition shown in Table 1, a heat-shrinkable laminated film was produced in the same manner as in Example 1.
  • the obtained stretched film was excellent in transparency and low-temperature shrinkage, and had a high tensile modulus. Also, as in Example 1, it was excellent in suitability for a packaging machine.
  • a heat-shrinkable laminated film was produced in the same manner as in Example 1. 500,000 ppm of monoglyceride stearate was added to the inner and outer layers as an anti-fog agent, but it has excellent transparency, low-temperature shrinkage, high tensile modulus, and packaging. It was a film with excellent adaptability.
  • linear low-density polyethylene with a melt index of 2.0 g / 10 min was used for the intermediate layer, and the inner and outer layers of Example 1 were used.
  • extruded under the same conditions as in Example 1 cooled, pulled off, and had a diameter of about 75 mm
  • a raw material of a laminated unstretched film having a thickness of 320 wm was obtained. The thickness of each layer was adjusted by adjusting the screw rotation speed and take-off speed of the extruder.
  • This tube-shaped unstretched film was guided to the tuber biaxial stretching device shown in Fig. 1 in the same manner as in Example 1, and it was quadrupled vertically and horizontally at 95 to 105'C.
  • the film was stretched to obtain a laminated biaxially stretched film.
  • this stretched film was treated with 75 pieces of hot air for 10 seconds in a tube-one-ring apparatus, cooled to room temperature, folded and wound up.
  • the intermediate layer of Comparative Example 2 has a total heat of fusion of 132.0 mJZ mg in the melting curve, and uses a linear low-density polyethylene that is not more than 135 mJ / msr.
  • the intermediate layer of Comparative Example 3 has an endothermic area ratio equal to or higher than the melting point in the melting curve of 11.0%, and uses a linear low-density polyethylene which is not higher than 12%.
  • the same linear low-density polyethylene was used as in Example 1, and a heat-shrinkable laminated film was obtained in the same manner as in Example 1.
  • the heat-shrinkable films obtained were both excellent in transparency and low-temperature heat shrinkage in Comparative Examples 2 and 3, but had low tensile modulus. In the actual packaging test using the packaging machine, pinholes were liable to occur in the seals of both, and the sealability was insufficient.
  • the middle layer uses the same linear low-density polyethylene as in Example 1, and the inner and outer layers have a melt index of 0.68T / 10 minutes and 1.0.
  • a heat-shrinkable laminated film was obtained in the same manner as in Example 1 by using a linear low-density polyethylene not in the range of 5.0 S / 10 minutes.
  • the resulting film has excellent low-temperature shrinkage and a large tensile modulus, and exhibits good fusing sealability even in actual packaging tests using a packaging machine. There was, however, less transparency.
  • the intermediate layer uses the same linear low-density polyethylene as in Example 2, and the inner and outer layers have a total heat of fusion of 121 mJZ mg in the melting curve, and 135 to 16
  • a heat-shrinkable laminated film was obtained in the same manner as in Example 1 using a linear low-density polyethylene that was not in the range of 0 mJZ mg.
  • the resulting film was excellent in transparency and low-temperature shrinkage.
  • the tensile elasticity was slightly inferior, and resin adhesion to the heat knife and adhesion of the film to the heat knife tray were observed, and the length of the seal was about 3 mm. There was a hole in the hole, and the sealability was very unstable.
  • the intermediate layer uses the same linear low-density polyethylene as in Example 1, and the inner and outer layers have a total heat of fusion of 162.4 mJZ mg in the melting curve, and 16 OmJ /
  • a heat-shrinkable laminated film was obtained in the same manner as in Example 1 by using a linear low-density polyethylene of msr or more.
  • the film obtained has poor stability in the stretching process, and the obtained film is inferior in transparency and low-temperature shrinkage.In actual packaging tests using a packaging machine, the seal may be easily sealed. Some pinholes were observed.
  • Example 2 The same linear low-density polyethylene as in Example 1 was used for both the intermediate layer and the inner and outer layers, except that the thickness of the intermediate layer was set to 50% of the total thickness.
  • a heat-shrinkable laminated film was obtained in the same manner as in Example 1. The resulting film was excellent in transparency and low-temperature shrinkage, but had some pinholes in the seal part and was insufficiently sealable. .
  • the polyethylene-based heat-shrinkable laminated film of the present invention is made of a material that satisfies specific conditions as a raw material for each layer, and therefore has excellent transparency and low-temperature shrinkage.
  • it provides a shrink film excellent in suitability for packaging machines because it uses a raw material that has a high rate of cooling and solidification of the blown resin at the time of fusing sealing and that can obtain a high tensile modulus. It is. Table 11

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Abstract

Un film de polyéthylène stratifié thermo-rétrécissable, parfaitemnt adapté à l'emballage des machines, se compose d'une couche intermédiaire comprenant une composition à base d'un polyéthylène (A) linéaire présentant une faible densité de 0,91 à 0,93 g/cm3, un indice de fusion de 0,1 à 0,8 g/10 min, une quantité totale de chaleur de fusion de 135 mJ/mg ou plus, la zone endothermique située au-dessus du point de fusion représentant au moins 12 % de la zone endothermique totale. Ses couches internes et externes comprennent chacune une composition à base de polyéthylène (B) présentant une faible densité faible de 0,91 à 0,93 g/cm3, un indice de fusion de 0,8 à 5 g/10 min, et une quantité totale de chaleur de fusion de 135 à 160 mJ/mg, la zone endothermique située au-dessus du point de fusion représentant au moins 12 % de la zone endothermique totale.
PCT/JP1993/001588 1991-11-12 1993-11-02 Film de polyethylene stratifie thermo-retrecissable WO1995012490A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US08/313,045 US5635286A (en) 1991-11-12 1993-11-02 Heat shrinkable polyethylene laminate film
CA002118002A CA2118002C (fr) 1993-11-02 1993-11-02 Film de polyethylene stratifie thermo-retrecissable
PCT/JP1993/001588 WO1995012490A1 (fr) 1993-11-02 1993-11-02 Film de polyethylene stratifie thermo-retrecissable

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1993/001588 WO1995012490A1 (fr) 1993-11-02 1993-11-02 Film de polyethylene stratifie thermo-retrecissable

Publications (1)

Publication Number Publication Date
WO1995012490A1 true WO1995012490A1 (fr) 1995-05-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT5038B (lt) 2000-06-14 2003-07-25 CHEMOSVIT, a. s., , Dviejų ašių kryptimi orientuotojo polipropileno nuo karščio susitraukianti plėvelė tabakui

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63264349A (ja) * 1987-04-10 1988-11-01 ダブリユー・アール・グレイス・アンド・カンパニー―コネチカット 柔軟性伸縮フイルム
JPS6422548A (en) * 1987-07-17 1989-01-25 Okura Industrial Co Ltd Heat-shrinkable film
JPH01301251A (ja) * 1988-05-31 1989-12-05 Kohjin Co Ltd ポリエチレン系熱収縮性多層フィルム
JPH03215034A (ja) * 1989-10-09 1991-09-20 Kohjin Co Ltd 多層ポリエチレン系ストレッチシュリンクフイルム及びその製造方法
JPH0418347A (ja) * 1990-05-11 1992-01-22 Kohjin Co Ltd ポリエチレン系熱収縮性積層フイルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63264349A (ja) * 1987-04-10 1988-11-01 ダブリユー・アール・グレイス・アンド・カンパニー―コネチカット 柔軟性伸縮フイルム
JPS6422548A (en) * 1987-07-17 1989-01-25 Okura Industrial Co Ltd Heat-shrinkable film
JPH01301251A (ja) * 1988-05-31 1989-12-05 Kohjin Co Ltd ポリエチレン系熱収縮性多層フィルム
JPH03215034A (ja) * 1989-10-09 1991-09-20 Kohjin Co Ltd 多層ポリエチレン系ストレッチシュリンクフイルム及びその製造方法
JPH0418347A (ja) * 1990-05-11 1992-01-22 Kohjin Co Ltd ポリエチレン系熱収縮性積層フイルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT5038B (lt) 2000-06-14 2003-07-25 CHEMOSVIT, a. s., , Dviejų ašių kryptimi orientuotojo polipropileno nuo karščio susitraukianti plėvelė tabakui

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CA2118002A1 (fr) 1995-05-03
CA2118002C (fr) 2004-01-20

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