JP2009083361A - Polyolefin based multilayered shrink film and packaging process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin based multilayered shrink film preferably used as a packaging film using an electrostatic seal, which keeps dust or waste material undeposited because an antistatic property is not suppressed, and is excellent in electrostatic sealability, and also to provide a packaging process having an electrostatic sealing part using the film. <P>SOLUTION: The polyolefin based multilayered shrink film comprises both surface layers composed mainly of a crystalline propylene-α-olefin random copolymer polymerized by a metallocene catalyst, and the film has a melt-peak temperature of 110-135°C measured by DSC and a surface resistibility coefficient of 10<SP>14</SP>Ω or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a heat-shrinkable packaging material, in particular, suitable for a high-speed packaging machine in an automatic packaging machine, has antistatic performance, is free from adhesion of dust and dirt on the package, and shrinks using an electrostatic seal. The present invention relates to a polyolefin-based multilayer shrink film suitable for packaging and a packaging method using the film.

Conventionally, polyvinyl chloride films, polypropylene films, polyethylene films, and the like are known as heat-shrinkable packaging materials. However, polypropylene, polyethylene, etc. are low in terms of cost and ease of disposal after use. Polyolefin shrink films are preferred. These packaging materials are, for example, prepackaged by a bag of a size suitable for the package with an automatic packaging machine, and then sealed by sealing the flow direction (vertical) and width direction (horizontal) of the film, respectively. Is heat-shrinked into a tight package.
As a sealing method for the heat-shrinkable packaging, a fusing seal is generally used. However, when vertical sealing is performed, film scraps called ears are usually generated. Then, the conversion to the electrostatic seal system which does not generate | occur | produce film waste has been examined.

The electrostatic sealing method is a method in which films are bonded together with a Coulomb force (temporary bonding), and then the films are heat-sealed with hot air from a shrink tunnel. There is a problem that the electrostatic seal surface is easily peeled off due to subsequent thermal contraction, or a sufficient seal strength cannot be obtained, resulting in a poor finish.
Therefore, for packaging materials having antistatic properties, in order to obtain electrostatic sealability that can be heat-shrinkable, for example, for heat-shrinkage that is printed on a film having specific surface characteristics or heated before electrostatic sealing. A packaging film (Patent Document 1), a heat-shrinkable film (Patent Document 2) in which a specific adhesive layer is laminated on the film surface, or a resin layer containing a polylactic acid polymer and an aliphatic polyester as a surface layer and a back layer A heat-shrinkable film (Patent Document 3) is proposed. However, these films have the disadvantage that the method is complicated and expensive.

On the other hand, as a polyolefin film, a sealant film using a polypropylene resin polymerized by a metallocene catalyst as a surface layer has also been proposed (Patent Document 4), and it has been reported that heat seal characteristics are improved. However, there is no report that a specific multilayer film using such a polypropylene resin is excellent in electrostatic sealability in shrink wrapping.
JP 2004-59715 A, JP 2004-268993 A JP 2007-106475 A JP-A-2005-35238 JP 2006-103147 A, JP 2007-13072 A

  The present invention provides a polyolefin-based multilayer shrink film that is free of dirt and dust and has excellent electrostatic sealability without impairing the antistatic performance, and a packaging method using the electrostatic seal using the film. The task is to do.

As a result of intensive studies, the present inventors have found that the problem can be solved by using a specific resin for the surface layer, and have reached the present invention.
That is, the present invention
(1) A crystalline propylene-α-olefin random copolymer (A: polymerized by a metallocene catalyst having a melting peak temperature of 110 to 135 ° C. measured by a differential scanning calorimeter (hereinafter referred to as DSC). Hereinafter, a polyolefin-based multilayer shrink film having both surface layers (X) mainly composed of metallocene PP and having a surface resistivity of 10 ¹⁴ or less,
(2) Polypropylene having a melting peak temperature measured by DSC of 135 to 165 ° C. and a melt flow rate (hereinafter referred to as MFR, measuring temperature 230 ° C., load 2.16 kgf) of 1.0 to 10.0 / min. An inner layer (Y) made of a resin based resin (B), and an inner layer (Z) mainly composed of a polyethylene resin (C) having a density at 23 ° C. of 0.900 to 0.940 g / cm ³ , The polyolefin-based multilayer shrink film according to the above (1), which is composed of at least 4 layers, each stretched at least 3 times in the longitudinal and lateral directions,
(3) A packaging method for shrink-wrapping an article to be packaged with the polyolefin-based multilayer shrink film according to any one of (1) to (2) above, comprising an electrostatic seal portion, and the electrostatic seal A method for wrapping an article to be packaged, wherein the part is heat-sealed during shrink-wrapping,
Is to provide.

  In the present invention, for example, even for a film containing an antistatic agent, the heat fusion property is improved by using a specific resin as a surface layer. Therefore, heat fusion in a shrink tunnel after electrostatic sealing is performed. At that time, it was completed based on the knowledge that sufficient sealing strength can be obtained without peeling off the electrostatic seal surface. Therefore, the polyolefin-based multilayer shrink film of the present invention has the effects of preventing dust and dust from being attached and having excellent electrostatic sealability since the antistatic property is not impaired.

Hereinafter, the present invention will be described in detail.
In the present invention, the metallocene PP (A) used for both surface layers (X) is a crystalline propylene-α-olefin random copolymer polymerized by a metallocene catalyst, and a comonomer is selectively introduced into the main chain. It is a thing. The polymer polymerized with this catalyst has a narrow molecular weight distribution, a narrow crystallinity distribution, and a uniform comonomer composition distribution. Such a metallocene PP can be produced by a method described in, for example, JP-A Nos. 2001-240711 and 2002-60566. Examples of the α-olefin copolymerized with propylene include ethylene, an α-olefin having 4 to 20 carbon atoms, or a mixture thereof. Preferably, a copolymer with ethylene is used.
Metallocene PP (A) has a melting peak temperature in the range of 110 to 135 ° C., and if it is less than 110 ° C., the heat resistance and slipperiness of the entire multilayer film are lowered, which is not preferable. This is not preferable because heat fusion in the shrink tunnel cannot be obtained and good electrostatic sealability cannot be obtained. A MFR (measurement temperature 230 ° C., load 2.16 kgf) of 0.5 to 10.0 g / 10 min is preferably used. If it is less than 0.5 g / 10 minutes, there is a problem that the motor load at the time of melt extrusion becomes high, and if it exceeds 10.0 g / 10 minutes, the heat resistance of the entire multilayer film is lowered, which is not preferable.
As a specific example of such metallocene PP (A), Nippon Polypro Co., Ltd. Wintech WFX6 can be exemplified.

  The thickness of both surface layers (X) is preferably 10% or more and 45% or less of the whole, and if it is less than 10%, the waist strength and the low-temperature shrinkage cannot be compatible, and if it exceeds 45%, the tear resistance is inferior. There is a case.

  For the surface layer (X), additives such as a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, an antioxidant, and a nucleating agent should be used as appropriate for the purpose of providing each effective action. Can do.

In the present invention, the polypropylene resin (B) used for the inner layer (Y) has a melting peak temperature measured by DSC of 135 to 165 ° C. and an MFR of 1.0 to 10.0 g / 10 min. And at least one selected from the group consisting of a polypropylene homopolymer, a copolymer of propylene and α-olefin, such as propylene-ethylene, propylene-butene copolymer, and propylene-ethylene-butene terpolymer. It consists mainly of heat resistance and waist strength. Among these, a crystalline propylene-α-olefin random copolymer is preferably used in consideration of the balance of heat resistance, waist strength and heat shrinkage characteristics.
When the melting peak temperature of the polypropylene resin (B) is less than 135 ° C., the heat resistance is low, which is not preferable. When the melting temperature exceeds 165 ° C., the low temperature shrinkability is decreased, which is not preferable. Further, if the MFR is less than 1.0 g / 10 min, there is a problem that the motor load at the time of melt extrusion becomes high, and if it exceeds 10.0 g / 10 min, the fusing sealability is lowered, which is not preferable.

  In the inner layer (Y) of the present invention, a polypropylene resin or a polyethylene resin can be mixed in addition to the propylene resin (B) as long as the object of the present invention is not impaired. The polypropylene resin and the polyethylene resin that can be mixed are the same as the metallocene PP (A) used for both surface layers (X) and the polyethylene resin (C) used for the inner layer (Z) described later, respectively, for recycling scrap. It can also be used. When these resins are mixed, the mixing ratio of the polypropylene resin (B) is preferably 40% by weight or more based on the total weight of the inner layer (Y). If it is less than 40% by weight, the low-temperature shrinkage, tear resistance and impact resistance are lowered, which is not preferable.

  The thickness of the inner layer (Y) is preferably 1 μm or more, and if it is less than 1 μm, the fusing sealability, heat resistance, and waist strength may be reduced.

  In the inner layer (Y), additives such as a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, an antioxidant, and a nucleating agent may be appropriately used for the purpose of providing each effective action as desired. Can do.

The polyethylene-based resin (C), which is the main component of the inner layer (Z), has a density in the range of 0.900 to 0.940 g / cm ³ at 23 ° C., low-density polyethylene having long chain branches, ethylene and butene -1, pentene-1, hexene-1, 4-methylpentene-1, octene-1 and a linear low density polyethylene, ethylene-acetic acid, which is a copolymer with an α-olefin having 4 to 20 carbon atoms It consists of at least one selected from vinyl copolymers, ethylene-aliphatic unsaturated carboxylic acid copolymers, ethylene-aliphatic unsaturated carboxylic acid ester copolymers, ionomer resins, low temperature shrinkage, tear resistance, It acts to impart impact resistance. Of these, linear low-density polyethylene is preferably used because it can impart excellent low-temperature shrinkage.
When the density of the polyethylene resin (C) is less than 0.900 g / cm ³ , the tensile strength at break is unfavorable, and when it exceeds 0.940 g / cm ³ , the low-temperature shrinkage property is undesirably lowered. Further, MFR (measurement temperature 190 ° C., load 2.16 kgf) of 0.3 to 5.0 g / 10 min is preferably used. If it is less than 0.3 g / 10 minutes, there is a problem that the motor load at the time of extrusion becomes high, and if it exceeds 5.0 g / 10 minutes, the stretching stability is lowered, which is not preferable.

  In the inner layer (Z) of the present invention, a polypropylene resin and a metallocene PP can be mixed in addition to the polyethylene resin as long as the object of the present invention is not hindered. The polypropylene resin and metallocene PP that can be mixed are the same as the polypropylene resin (A) used for both surface layers (X) and the metallocene PP (B) used for the inner layer (Y), respectively, and should be used for scrap recycling. You can also. When these resins are mixed, the mixing ratio of the polyethylene resin (C) is preferably 40% by weight or more based on the total weight of the inner layer (Z). If it is less than 40% by weight, the low-temperature shrinkage, tear resistance and impact resistance are lowered, which is not preferable.

  The thickness of the inner layer (Z) is preferably 10% or more of the whole, and less than 10% is not preferable because the low-temperature shrinkage and tear resistance deteriorate.

  In the inner layer (Z), additives such as a lubricant, an anti-blocking agent, an antistatic agent, an antifogging agent, an antioxidant, and a nucleating agent should be appropriately used for the purpose of providing each effective action as desired. Can do.

The heat-shrinkable film of the present invention needs to have a surface resistivity of 10 ¹⁴ Ω or less. When the surface resistivity exceeds 10 ¹⁴ Ω, dust adhesion is reduced, and dust adheres at the time of display of the package at the storefront, which is not preferable.
A heat-shrinkable film having a surface resistivity of 10 ¹⁴ Ω or less can be easily obtained, for example, by adding an antistatic agent or the like. As the antistatic agent to be used, a known antistatic agent can be used, and examples thereof include fatty acid monoglycerin ester, sorbitan fatty acid ester, alkyldiethanolamine, polyoxyethylene alkyl ether and the like.
The addition amount of the antistatic agent varies depending on the kind of the antistatic agent and the layer to be added, but can be appropriately determined so that the surface resistivity is 10 ¹⁴ Ω or less.

  In the present invention, the inner layer does not necessarily have to be two layers, and can be formed into two or more layers as necessary, and a layer configuration of four or more layers as a whole can be adopted. For example, X / Y / Z / X 4 layer configuration, X / Y / Z / Y / X, X / Z / Y / Z / X 5 layer configuration, X / Y / Z / Y / Z / X 6 Examples of the layer configuration include a layer configuration, and a symmetrical configuration is preferable from the viewpoint of preventing the curling phenomenon of the film.

Next, the manufacturing method of the film of this invention is shown. The method for producing the stretched film of the present invention using the above-mentioned resin can be performed by a known method, and will be specifically described below by taking the case of 5-layer laminated annular film-forming stretch as an example.
First, the metallocene PP (A) is both surface layers, the resin composition mainly composed of the polyethylene resin (B) is an intermediate layer, and the resin composition mainly composed of the polyethylene resin (C) is the core layer. It is melt-kneaded by five extruders, co-extruded in a circular form from a five-layer annular die, and then rapidly cooled and solidified without stretching to produce a tubular unstretched film.
The obtained tubular unstretched film is supplied to a tubular stretching apparatus, and is in a highly orientable temperature range, for example, at a temperature lower than 10 ° C below the melting point of the core layer resin, preferably lower than 15 ° C below the melting point. Simultaneous biaxial orientation is caused by expansion and stretching by applying gas pressure inside the tube at temperature. The stretching ratios are not necessarily the same in the longitudinal and lateral directions, but in order to obtain excellent physical properties such as strength and shrinkage, it is preferable to stretch at least 3 times in both the longitudinal and lateral directions.
The film taken out from the stretching apparatus can be annealed as desired, and the natural shrinkage during storage can be suppressed by this annealing.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
In addition, each physical property measurement shown in a present Example was based on the following method.
1. Film thickness: measured according to JIS-Z1709.
2. Thickness ratio: Measured by observing the cross section of the film with a microscope.
3. Surface specific resistivity: measured according to JIS-K6911.
The sample was cut into 110 mm × 110 mm, adjusted to humidity at 20 ° C. and 65 RH% for 2 hours, and then set in a surface resistor (HIOK REGAINST METER 4329A manufactured by YOKOGAWA HEWLETT-PACKARD). The measurement guideline after 1-minute measurement charge was read to the first decimal place and calculated by Equation 1.

4). Electrostatic sealability: electrostatically sealed using a half-fold wrapping machine (HP-20) manufactured by Hanagata Co., Ltd., and passed through a shrink tunnel (L-1500FC) manufactured by Kyowa Denki Co., Ltd. The electrostatic seal packaging suitability was measured according to the following criteria.
<Criteria>
○: The electrostatic seal part is completely adhered.
X: There is a portion that is not in close contact with the electrostatic seal portion, or no contact at all.
5). Dust adhesion test: 1.8L liquor pack was wrapped with Hanagata's half-fold packaging machine (HP-20), passed through Kyowa Denki's shrink tunnel (L-1500FC), and heat shrink packaging obtained The body was allowed to stand for 1 month in a normal environment (in a general office), and the adhesion of dust and dirt on the package was observed, and dust adhesion was measured according to the following criteria.
<Criteria>
○: There is almost no dust adhesion.
Δ: There is a little dust adhesion.
X: Dust adhesion is very large.

Example 1
As shown in Table 1, metallocene PP (A1) having the characteristics of adding 3500 ppm of an antistatic agent to each layer, melting peak temperature of 125 ° C., and MFR of 2.0 g / 10 min is applied to both surface layers (X). A propylene-ethylene random copolymer having a melting peak temperature of 145 ° C. and an MFR of 2.3 g / 10 min as an inner layer (Y), a density of 0.920 g / cm ³ , and an MI of 1.0 g / 10 min. Linear low density polyethylene having the characteristics of 10 minutes as the inner layer (Z), melt-kneaded at 130-240 ° C. with 5 extruders, respectively, and the thickness ratio is X / Y / Z / Y / X The extrusion amount of each extruder was set so as to be 1/1/4/1/1, and coextrusion was performed downward with a five-layer annular die maintained at 240 ° C. The formed five-layer tube is cooled by passing through the water tank while sliding the outer surface of the cylindrical cooling mandrel in which the cooling water circulates on the inner side, and has a diameter of 75 mm and a thickness of 210 μm. An unstretched film was obtained.
This tubular unstretched film was guided to a tubular biaxial stretching apparatus, and stretched at 90 to 110 ° C. four times in length and breadth to obtain a laminated biaxially stretched film.
Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and a non-uniform stretching state such as necking was not observed.
As shown in Table 1, the stretched film obtained had a very good electrostatic sealability and a package with very little dust and dirt adhered.

Example 2
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that 2000 ppm of the antistatic agent was added to all layers. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and a non-uniform stretching state such as necking was not observed.
As shown in Table 1, the stretched film obtained had a very good electrostatic sealability and a package with very little dust and dirt adhered.

Example 3
In Example 1, five layers were formed in the same manner as in Example 1, except that metallocene PP (A2) having a melting peak temperature of 125 ° C. and MFR of 7.0 g / 10 min was used as both surface layers (X). A biaxially stretched film was obtained. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and a non-uniform stretching state such as necking was not observed.
As shown in Table 1, the stretched film obtained had a very good electrostatic sealability and a package with very little dust and dirt adhered.

Comparative Example 1
In Example 1, a propylene-ethylene random copolymer having a melting peak temperature of 145 ° C. and an MFR of 2.3 g / 10 min was used as both surface layers (X), a melting peak temperature of 125 ° C., and an MFR of 2 A 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that the metallocene PP (A1) having the characteristics of 0.0 g / 10 min was used as the inner layer (Y). Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and a non-uniform stretching state such as necking was not observed.
As shown in Table 2, the obtained stretched film was able to obtain a package without dust and dust, but the surface layer had a high melting point and heat fusion was weak, so the electrostatic seal part was completely It was not in close contact, and good electrostatic sealability could not be obtained.

Comparative Example 2
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that 1000 ppm of the antistatic agent for all layers was added. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The drawability was good, there was no up-and-down movement of the drawing point, no fluctuation of the drawing tube, and non-uniform drawing conditions such as necking were not observed.
As shown in Table 2, the obtained stretched film had very good electrostatic sealing properties, but did not have antistatic properties, and dust and dust adhesion were remarkably observed.

Comparative Example 3
In Example 1, a 5-layer biaxially stretched film was obtained in the same manner as in Example 1 except that no antistatic agent was added. Next, the stretched film was relaxed by 10% in the longitudinal and lateral directions with hot air at 75 ° C. in a tube annealing apparatus, cooled to room temperature, trimmed at both ends of the film, and wound up two separately. The final film thickness was 15 μm.
The stretchability was good, there was no up-and-down movement of the stretching point, the swinging of the stretching tube, and a non-uniform stretching state such as necking was not observed.
As shown in Table 2, the obtained stretched film had very good electrostatic sealing properties, but did not have antistatic properties, and dust and dust adhesion were remarkably observed.

  Since the polyolefin-based multilayer shrink film of the present invention does not impair the antistatic property, there is no adhesion of dust and dust, and there is an effect that the electrostatic sealability is excellent. It can be suitably used as a packaging film.

Claims (3)

A crystalline propylene-α-olefin random copolymer (A: hereinafter referred to as metallocene) having a melting peak temperature of 110 to 135 ° C. measured by a differential scanning calorimeter (hereinafter referred to as DSC) and polymerized by a metallocene catalyst. A polyolefin-based multilayer shrink film having both surface layers (X) mainly composed of PP) and having a surface resistivity of 10 ¹⁴ or less. Polypropylene resin having a melting peak temperature measured by DSC of 135 to 165 ° C. and a melt flow rate (hereinafter referred to as MFR, measuring temperature 230 ° C., load 2.16 kgf) of 1.0 to 10.0 / min. B) and an inner layer (Z) mainly composed of polyethylene resin (C) having a density of 0.900 to 0.940 g / cm ³ at 23 ° C. The polyolefin-based multilayer shrink film according to claim 1, comprising at least four layers stretched twice or more.   A packaging method for shrink-wrapping an article to be packaged with the polyolefin-based multilayer shrink film according to claim 1, comprising an electrostatic seal portion, and the electrostatic seal portion is heat-sealed during shrink-wrapping. A packaging method for an article to be packaged.