JPH0138663B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a foamed sheet or film that has heat shrinkability in the lateral direction and has excellent cushioning effects. Conventionally, heat-shrinkable foam sheets and films have been mainly made from polystyrene, and when used for the exterior of containers such as bottles, they have the effect of preventing pin breakage and providing a cushioning effect. It is well known as a useful packaging material. However, the heat-shrinkable foam sheet or film made of polystyrene is sensitive to impact and brittle due to the characteristics of its raw material, so even if it is attached as a label for a bottle, etc., it will be difficult to clean, fill, or process. has the disadvantage that the foamed sheet or film (hereinafter referred to as the film) is damaged during conveyance, and even if the surface of the film is printed, it cannot be printed clearly, and furthermore, the foamed film is layered from the edge. Phenomena such as aging and partial peeling were observed. Furthermore, when stretching polystyrene foam, it is difficult to stretch it in the transverse direction using a tenter or the like due to its brittleness, and the mainstream is longitudinal stretching using roll stretching, which is relatively easy to stretch. When used as an exterior for
It is not applicable to automatic machines (for PVC), and it may be necessary to prepare a new automatic machine for longitudinally stretched film.Also, in terms of use, for example, a cylindrical body that is coated on a bottle and heat-shrinked to tightly fit it to the bottle. There were also problems such as the process of creating the material was inevitably more complicated than that for the laterally stretched material. Based on this technical background, the present inventors have proposed a solution to the above-mentioned problem in Japanese Patent Application No. 110084/1984, and using the material, for example, a cylindrical body similar to the above-mentioned one can be manufactured. It was found that those that were prepared, coated on a bottle, heat-shrinked, and tightly attached to the bottle became loose due to insufficient binding force over time, and on the other hand, the printability was slightly inferior. This invention was made in order to solve the above-mentioned new problem, and is made of an ethylene-propylene copolymer having an ethylene content of 1 to 10 mol% as a foamed film or sheet having heat shrinkability in the transverse direction. , an ethylene-1-butene random copolymer with an ethylene content of 85 to 95 mol% and a crystallinity of 3 to 20%, and a foaming agent were formed into a film, and then subjected to transverse stretching. The gist of the present invention is that it is configured to have heat shrinkability in the lateral direction. The present invention will be explained in detail below. The ethylene-propylene copolymer used in the present invention usually has an ethylene content of 1 to 10 mol%, preferably 2 to 6 mol%, and if the ethylene content exceeds 10 mol%, the produced foam sheet or film will not be produced. It is undesirable because it becomes sticky and tends to cause blocking, and at less than 1 mol %, its properties approach that of polypropylene, so even if it is stretched, the shrinkage rate is small, and it is unsatisfactory as a heat-shrinkable member, and it does not foam. Cells are easily torn and fluffing occurs. Preferably, the copolymer contains ethylene randomly. At this time, the amount of the copolymer to be used may be an appropriate amount that exhibits the effect, but preferably about 50 to 95% by weight based on the total amount of the polymer. Next, the ethylene-1-butene random copolymer used in the present invention is added to impart elasticity to the foam cells of the foam material, and if this copolymer is not added, the internal pressure during foaming will be Since the foamed cells cannot withstand the heat and easily expand, a fine foamed structure cannot be obtained. This copolymer has the property of imparting elasticity to cells during foaming, and more preferably has an ethylene content of 85 to 95 mol%, preferably 87
~93 mol%, density determined from ethylene content 0.85-0.91 g/cm ³ , preferably 0.88-0.90
g/cm ³ and melt index (190℃) is 0.1
~40 is preferably used. Furthermore, the melting point can be determined by the peak position in DSC measurement.
60-90℃, crystallinity is <100> as determined by X-ray diffraction measurement
There is a crystal peak at the diffraction position of the surface, and when the peak area is assigned to the overall intensity, it is preferably in the range of 3 to 20%. At this time, if the ethylene content is outside the range of 85 to 95 mol% and the crystallinity is outside the range of 3 to 20%, the foam will not be in a desirable foamed state and will be unsuitable for use. Such a copolymer can be said to be a random copolymer polymerized mainly with a vanadium catalyst, and the present invention can be more effective by using such an ethylene-1-butyne copolymer. Ru. At this time, the amount of ethylene-1-butene copolymer used should be at least the amount that exhibits its effect, but preferably 5 to 5
Approximately 50% by weight is sufficient. The foaming agent used in the present invention may be any known foaming agent. Examples of suitable foaming agents include pentane and butane based volatile ones, and hydrazine based organic ones. , nitroso-based, azo-based, etc., and inorganic ones such as sodium bicarbonate and ammonium carbonate. In this case, more preferable examples include azo dicarbonamide, azobisisobutyronitrile, etc. for the azo blowing agent, carbonates such as sodium bicarbonate and ammonium carbonate, and organic acids such as citric acid and tartaric acid for the inorganic blowing agents. I can give you something consisting of. The amount of blowing agent to be used should be at least the amount that exhibits its effect, but the total amount of ethylene-propylene copolymer with an ethylene content of 1 to 10 mol% and ethylene-1-butene copolymer should be added. (Total polymer amount) 0.2 to 5 parts by weight per 100 parts by weight,
A more preferable example is about 0.5 to 2 parts by weight.
The above blowing agent may be directly blended with the ethylene-propylene copolymer and ethylene-1-butene copolymer according to the present invention, or may be blended with the addition of master pellets containing a high concentration of blowing agent, or may be blended in advance with the An appropriate amount of a blowing agent may be kneaded into the copolymer, and there are no particular restrictions on its usage. In addition, in the present invention, appropriate additives, fillers, etc. may be added in addition to the above three components, and for example, lubricants, antistatic agents, etc. may be added as necessary to improve physical properties. If necessary, desired coloring can be achieved by adding a pigment. In the present invention, a composition containing the above components is formed into a film, and then stretched in the transverse direction. The purpose of stretching in the transverse direction is to impart heat shrinkability in the transverse direction, and "heat shrinking in the transverse direction" means stretching in the width direction perpendicular to the direction in which the foamed sheet or film is manufactured. In order to perform this lateral stretching, it may be carried out after the composition is formed into a film and foamed, or after foaming and film formation (in some cases, foaming may be performed during stretching). However, the most favorable results are obtained if the foamed material in the form of a flat sheet is carried out using a tenter. Note that the stretching means in the lateral direction is not limited to those described above.
Next, the stretching temperature can be selected as appropriate, and is preferably 100 to 130°C, for example. In addition, the stretching ratio can be selected from 3 to 10 times depending on the need, and if stretching is carried out under the above numerical conditions, a foamed sheet or film with favorable lateral heat shrinkability can be obtained. Become. At this time, a slight tension is applied in the vertical direction when forming the foam sheet or film or to prevent sagging during stretching, and as a result, orientation occurs, so it generally has some heat shrinkability in the vertical direction as well. All are included in the present invention. As an example of producing a sheet or film according to the present invention, a method of forming the film using an extruder and laterally stretching it will be described below. First, the conditions of the extrusion molding machine were set to such an extent that a composition containing an ethylene-propylene copolymer with an ethylene content of 1 to 10 mol%, an ethylene-1-butene copolymer, and a foaming material would not foam in the die. and extrude it into a flat sheet from a die.
At this time, it is preferable to perform foaming simultaneously with extrusion. Thereafter, transverse stretching is performed, and the stretching means is as described above. The foamed sheet or film according to the present invention is most often used as a printed exterior heat-shrinkable foamed label for bottles, etc., and is made into a cylinder so that the stretching direction coincides with the circumferential direction of the bottle, etc. However, it is often used as a packaging material for various containers and various articles, and its application range is wide and there are no particular restrictions. The present invention is as described above, and when the foamed sheet or film according to the present invention is used, for example, as an exterior label for a bottle or the like, it is particularly excellent in bottle breakage prevention effect and cushioning effect. It also has excellent physical properties such as strength,
Because it is not brittle like conventional materials, it can be folded into a cylindrical body, for example, and the creases that occur during folding disappear when heat shrinks. It does not have the disadvantage of being easily peeled off and exhibits remarkable effects such as being strong and strong. In particular, since the foam sheet or film according to the present invention has heat shrinkability in the lateral direction, for example, a conventionally used automatic machine, for example, can coat the outer periphery of the container with a heat shrink label, and When applied to the mechanism of an automatic label insertion machine that attaches by heat shrinking, a long continuous cylindrical body with a center seal is created in advance (it can also be folded flat and stored in this state). ), and when inserting and covering the outer periphery of containers, it is sufficient to cut it to an appropriate length and use it as a cylindrical body.Therefore, the mechanism of conventional machines can be applied, whereas conventional When using a foam material that heat shrinks in the longitudinal direction, it is not possible to create a long continuous cylindrical body in advance using a center seal, and after cutting the long film to the appropriate size, it is necessary to create individual cylinders. The mechanism of conventional machines cannot be applied as is because it is necessary to create a cylindrical body in advance or to create a cylindrical body at the same time when inserting the label into an automatic label insertion machine. In this respect as well, the sheet or film of the present invention has special effects. The above explanation is shown in drawings in FIGS. 1 and 2. FIG. 1 shows a foamed film having heat shrinkability in the lateral direction according to the present invention, where 1 is a long film, 2 is a long cylindrical body, 3 is a center seal,
4 is an individually cut cylindrical body, 5 is a container, 6 is a cylindrical body (label) that is heat-shrinked and tightly attached to the container 5, and the arrow indicates the direction of shrinkage. Fig. 2 shows a conventional foamed film having heat shrinkability in the longitudinal direction, where 1' is a long film, 2' is an individually cut film, and 4' is a cut film 2'. are sealed 3' to form individual cylindrical bodies, 5 and 6 are the same as in Fig. 1, and the arrows also indicate the direction of shrinkage. When forming the body, it can be seen that it is extremely efficient compared to conventional methods. Next, in the present invention, in order to improve the printability of the foamed sheet or film and improve its surface condition, it is also possible to form a laminate layer on the foamed material, and this laminate layer uses an adhesive layer, Alternatively, it may be laminated with a foamed sheet or film without using it. In this case, when printing, the surface condition is good and phenomena such as ink bleeding do not occur. The thermoplastic film used as this laminate layer (also referred to as skin layer) may be exemplified by films made of various commonly used thermoplastic polymers, and is not particularly limited. To give a few examples of these, polyolefin resins include low, medium, and high density polyethylene, polypropylene and its copolymers, polyamide resins, polyester resins, polyvinyl resins, ethylene-vinyl acetate copolymers, and ethylene. -1-butene copolymer, etc. Among these, a particularly preferred example is one made of the same kind of polymer as the foamed sheet or film of the present invention, and has an ethylene content of 1
~10 mol% ethylene-propylene copolymer and ethylene-1-butene copolymer (preferably ethylene content 85-95 mol%, density 0.85-0.91 g/
^cm3 , melt index (190℃) 0.1~40, melting point
A random copolymer with a temperature range of 60-90℃ and a crystallinity of 3-20%. At this time, the melting point and crystallinity are measured in the same manner as described above. ) alone or as a blend thereof, it is extremely convenient as it allows direct lamination with the foam material by thermocompression bonding without the need for an anchor coat layer. On the other hand, if a different type of thermoplastic film is used, it may be difficult to collect and reuse the scraps, but of course it can be used. The thermoplastic film that forms the laminate layer may also contain appropriate additives and fillers, such as lubricants and antistatic agents, as necessary, in order to improve its physical properties. This can be done as appropriate, and if necessary, a desired coloring can be achieved by adding a pigment. Next, as an example of creating a foamed sheet or film having such a laminate layer, a film or sheet is formed using an extruder, and then a thermoplastic film is melt-extruded and laminated to form a laminate layer. The method for transverse stretching will be described below. First, the conditions of the extruder were set so that a composition containing an ethylene-propylene copolymer with an ethylene content of 1 to 10 mol%, an ethylene-1-butene copolymer, and a foaming material would not foam in the die. and extrude it into a flat sheet from a die. At this time, it is preferable to perform foaming simultaneously with extrusion. On the other hand, simultaneously extruding a thermoplastic resin blend consisting of an ethylene-propylene copolymer and an ethylene-1-butene copolymer containing 1 to 10 mol% of the same ethylene as the foamed sheet or the raw material composition of the sheet, The foamed material (foamed sheet) is melt-extruded and laminated to form a laminate layer of thermoplastic film. At this time, the thermoplastic film is easily laminated and integrated with the foam sheet using a simple nip roll due to the heat generated during extrusion. Next, the foamed sheet and the thermoplastic film are stretched in the transverse direction using a tenter, but this stretching causes the foamed sheet and the thermoplastic film to bond more strongly, and the two become as if they were a single layer, making it extremely difficult to separate them. Next is the stretching temperature, which can be selected as appropriate and is preferably 100 to 130°C. In addition, the stretching ratio should be selected according to need, but it should be 2 times or more, if necessary, about 3 to 10 times.If stretching is carried out under the above numerical conditions, the desired lateral heat shrinkability can be achieved. A foamed sheet or film having a laminate layer having the above-mentioned properties is obtained, but the present invention is of course not limited to this. A composite foam material is produced in this manner, and the thickness of the foam sheet, film, or laminate layer may be appropriately selected depending on the application. Furthermore, in order to improve printability, the surface of the laminate layer may be subjected to surface treatment such as corona discharge treatment. The above is a method of melt-extrusion laminating a thermoplastic film of the same type on a foam material (foamed sheet). At the same time as foaming, the film may be laminated onto a foamed sheet by pressing it with a nip roll or the like. At this time, since the heat from extrusion remains on the foam sheet side, the two can be laminated and integrated extremely easily. In addition, it is preferable to perform foaming at the same time as film formation, but
Of course, it may be applied before film formation, after film formation, or even simultaneously with stretching. Examples of the present invention will be listed below along with comparative examples. Example 1 A 70% by weight ethylene-propylene random copolymer with an ethylene content of 4.5 mol%, an ethylene content of 88 mol%, a density of 0.88 g/cm ³ , a melt index (199°C) of 4.0, a melting point of about 75°C, Ethylene-1 made with a vanadium catalyst with a crystallinity of about 10%
- Blend 100 with 30% by weight of butene random copolymer
1 part by weight of a blowing agent consisting of a mixture of sodium bicarbonate and citric acid was added to each part by weight, and the mixture was extruded into a flat sheet through a die of an extrusion molding machine. At this time, when we set the conditions so that it would foam when extruded from the die, the thickness
A foam sheet of 1000μ was obtained. Thereafter, the film was stretched approximately 5 times in the transverse direction using a tender at a temperature of 110 to 120°C, to obtain a foamed film having a thickness of 200 μm and heat-shrinkable in the transverse direction. At this time, the foaming agent, sodium bicarbonate, decomposed and produced bubbles. Example 2 Sodium bicarbonate and citric acid were used as blowing agents (amount used: 20% by weight), except that 5 parts by weight of master pellets whose main component was polyethylene (the blowing agent component was 1 part by weight) was used. Using the same formulation as in Example 1, a flat foam sheet with a thickness of 1000 μm was obtained by extrusion film formation. Thereafter, the film was stretched by about 5 times in the transverse direction using a tender at a temperature of 110 to 120°C, to obtain a foamed film having a thickness of 200 μm and heat-shrinkable in the transverse direction. Comparative Example 1 A composition containing 100 parts by weight of an ethylene-propylene random copolymer with an ethylene content of 4.5 mol% and 1 part by weight of a blowing agent consisting of sodium bicarbonate and citric acid was treated in the same manner as in Example 1. A foamed film was obtained. This film was a defective product, with poor foaming and cells bursting in places, making the surface look fluffy, and cracking caused by vertical cracks during stretching. Comparative Example 2 The same amount of blowing agent as in Comparative Example 1 was added to polystyrene, a film was formed in the same manner, and roll stretching was performed three times at a temperature of 110°C, resulting in a film with a thickness of 200μ that shrinks in the longitudinal direction A foamed film was obtained. At this time, we attempted an experiment in which a raw sheet formed by extrusion was stretched 3 times in the horizontal direction using a tenter, but the edges of the raw sheet were destroyed by the tenter clips, or the raw sheet was broken in the center. It was not possible to stretch the film. The physical properties of the foamed films obtained in Examples 1 and 2 and Comparative Example 2 are listed in Table 1 below.

[Table] From Table 1 above, the foamed materials of Examples 1 and 2 of the present invention are tough, have excellent tear strength, have excellent impact strength, and have moderate elongation, making them extremely practical heat shrinkable materials. It has been proven that the material On the other hand, the material of Comparative Example 1 was not a satisfactory material, and the conventional product of Comparative Example 2 could not be stretched horizontally, and even the material stretched longitudinally had extremely poor impact strength and other physical properties.
Another problem was that the buffering effect was insufficient. Example 3 70% by weight of an ethylene-propylene random copolymer with an ethylene content of 4.5 mol% and 30% by weight of the same ethylene-1-butene random copolymer as in Example 1
100 parts by weight of a composition containing 100 parts by weight of a foaming agent consisting of a mixture of sodium bicarbonate and citric acid, extruded into a flat sheet through a die of an extrusion molding machine, and foamed to a thickness of 900μ. I created a sheet. On the other hand, ethylene content 4.5
Mol% ethylene-propylene random copolymer
70% by weight, ethylene content 88mol%, density 0.88
g/cm ³ , melt index (190°C) 4.0, melting point approximately 75°C, crystallinity approximately 10%, made of 30% by weight ethylene-1-butene random copolymer made with a vanadium catalyst, 100μ thick. When the thermoplastic film was extruded and directly melt-extruded and laminated onto the foamed sheet, the two were significantly adhered due to residual heat from extrusion of the thermoplastic film. After that, the foam layer was 180μ and the laminate layer was 20μ when horizontally stretched 5 times at a tender temperature of 115℃.
A foamed film was obtained with a laminate layer having a thickness of 200μ. The foam layer and laminate layer of this film were strongly bonded during the stretching process, and the film had a favorable property of being heat-shrinkable in the transverse direction. Example 4 Example 1 except that 5 parts by weight of master pellets whose main component was low-density polyethylene (the blowing agent component was 1 part by weight) using sodium bicarbonate and citric acid as blowing agents (amount used was 20% by weight) Using the same composition as above, a film was formed in the same manner as above to obtain a flat foam sheet with a thickness of 900μ. After that, a laminate layer was formed in the same manner as in Example 1, and the temperature was adjusted using a tenter.
When stretched approximately 5 times in the transverse direction at 110 to 120°C,
A foamed film having a laminate layer that was heat-shrinkable in the transverse direction and had a total thickness of 200μ, consisting of a foam layer of 180μ and a laminate layer of 20μ, was obtained. Comparative Example 3 A blended composition in which 1 part by weight of a blowing agent consisting of sodium bicarbonate and citric acid was added to 100 parts by weight of an ethylene-propylene random copolymer with an ethylene content of 4.5 mol% was prepared in the same manner as in Example 1, and the thickness was 900μ
A foamed film was obtained, and a thermoplastic film having a thickness of 100 μm made of the single copolymer was laminated with a melt extrusion laminate. When the composite foam material (film) was then laterally stretched using a tenter in the same manner as in Example 1, the cells on the surface of the foam layer were ruptured in places and the surface was fluffy.
In addition, some of the products were defective, with directional characteristics appearing in the vertical direction and cracks appearing in some places. Comparative Example 4 The same amount of the same foaming agent as in Comparative Example 1 was added to polystyrene, and a film was formed in the same manner to obtain a foamed sheet with a thickness of 510 μm. On the other hand, a 90μ thick film made only of polystyrene was extruded, laminated on the foamed sheet by melt extrusion lamination, and then rolled three times at a temperature of 110°C, resulting in a film with a thickness of 200μ. A composite film that was heat-shrinkable in the longitudinal direction was obtained. In this article, an attempt was made to stretch an unstretched composite sheet laminated in the same way in the transverse direction three times using a tenter, but the edges of the unstretched sheet were destroyed by the tenter clips, and even if the edges were gripped, the central portion Due to vertical tearing, sufficient stretching could not be achieved. The physical properties of the composite foamed films obtained in Examples 3 and 4 and Comparative Example 4 are listed in Table 2 below.

【table】

[Table] From Table 2 above, the foamed films having the respective laminate layers of Examples 3 and 4 of the present invention are tough, have excellent tear strength, outstanding impact strength, and have moderate elongation, making them extremely practical. It has been proven to be a heat-shrinkable material. On the other hand, the material of Comparative Example 3 was not a satisfactory material, and the conventional product of Comparative Example 4 could not be stretched horizontally, and even the material stretched longitudinally had extremely poor impact strength and other physical properties, and the cushioning effect was poor. In addition to being insufficient, for example, phenomena such as the laminate layer peeling off during handling or washing were also observed, and phenomena such as both layers peeling off were also observed. Example 5 In order to coat bottles with the foamed films obtained in Examples 1, 2, 3, and 4 as heat-shrinkable labels, the surface was printed, then slit into long strips with a width of 22.5 cm, and the center stickers were made. A long cylindrical body with a fold diameter of 11 cm was obtained. This was cut to a length of 11 cm to form a cylindrical body, which was fitted onto a bottle and heat-shrinked to make it adhere tightly to the bottle surface. At this time, the direction of heat shrinkage was in the circumferential direction of the bottle, and there was also some shrinkage in the axial direction of the bottle. Comparative Example 5 In order to coat the foamed films obtained in Comparative Examples 2 and 4 as heat-shrinkable labels on the same bottles as in Example 4, they were printed, then slit into long strips with a width of 11 cm, and then the length of the film was perpendicular to the ulnar direction
A rectangular film with a length of 22.5 cm and a width of 11 cm was created by cutting it into 22.5 cm pieces. This rectangular film was center-sealed to create a cylindrical body with a fold diameter of 11 cm and a length of 11 cm, and was brought into close contact with the bottle surface in the same manner as in Example 4. As can be seen from the above Example 5 and Comparative Example 5, in Example 5, it is extremely efficient to create a cylindrical body, and the cylindrical body can be folded in two, making it possible to create a cylindrical body using conventional automatic labels. While it is possible to continuously attach the cylindrical body to the bottle by using the mechanism of the insertion machine, in Comparative Example 5, the creation of the cylindrical body is extremely complicated and inefficient, and the cylindrical body is When folded in half, there was a risk of the folds tearing, and a special automatic label insertion machine could not be created to make them fit together.

[Brief explanation of drawings]

FIGS. 1 and 2 are explanatory diagrams of a process in which a cylindrical body is heat-shrinked and attached to a bottle using the polyolefin foam film according to the present invention and a conventional foam film. 1... Foamed film having heat shrinkability in the lateral direction according to the present invention, 2... Long cylindrical body, 5... Container,
6...A cylindrical body that is heat-shrinked and tightly attached to the container, 1'
...A conventional foamed film that has heat shrinkability in the vertical direction.

Claims (1)

[Claims] 1 Ethylene with an ethylene content of 1 to 10 mol%
Propylene copolymer and ethylene content 85-95
A composition containing an ethylene-1-butene random copolymer having a crystallinity of 3 to 20% by mole and a blowing agent is formed into a film, and then subjected to transverse stretching to heat the composition in the transverse direction. A polyolefin foam sheet or film characterized by having shrinkability.