WO2014103472A1

WO2014103472A1 - Method for producing film

Info

Publication number: WO2014103472A1
Application number: PCT/JP2013/077658
Authority: WO
Inventors: 達也斉藤; 広宣青島
Original assignee: ポリプラスチックス株式会社
Priority date: 2012-12-27
Filing date: 2013-10-10
Publication date: 2014-07-03
Also published as: JPWO2014103472A1; JP5632564B1; KR101521192B1; KR20150029034A; TWI509005B; CN104884228A; TW201425406A; CN104884228B

Abstract

To provide a method by which a film having easy tearability can be produced. The present invention provides a method for producing a film, which comprises a molding step wherein a resin composition containing more than 0% by mass but 60% by mass or less of a cyclic olefin resin and a noncyclic olefin resin is molded using an extruder. The glass transition temperature of the cyclic olefin resin is 40°C or more; and the value obtained by subtracting the glass transition temperature of the cyclic olefin resin from the cylinder temperature of the extruder during the molding step is 140°C or less.

Description

Film production method

The present invention relates to a method for producing a film.

In recent years, from the viewpoint of barrier-free and the like, a film used as a material such as a packaging material is required to have a property that is easily tearable by hand (hereinafter referred to as “easy tearability”). As such a film, for example, a multilayer film composed of a layer containing a cyclic olefin resin having a specific glass transition temperature has been proposed (Patent Documents 1 and 2, etc.).

JP 2012-224071 A JP 2012-236382 A

However, the present inventors have found that there is a possibility that a film having a desired easy tearability may not be obtained depending on molding conditions for a conventional film.

This invention was made in order to solve the said subject, and it aims at providing the method which can manufacture the film which has easy tear property.

In the method for producing a film in which a resin composition is molded using an extruder, the inventors have determined the difference between the glass transition temperature of the cyclic olefin resin in the resin composition and the cylinder temperature of the extruder to a predetermined value. As a result, it was found that the above-mentioned problems can be solved, and the present invention has been completed. Specifically, the present invention provides the following.

(1) A method for producing a film including a molding step of molding a resin composition containing a cyclic olefin resin of more than 0% by mass and 60% by mass or less and an acyclic olefin resin, using an extruder, The glass transition temperature of cyclic olefin resin is 40 degreeC or more, The manufacturing method of the film whose value which subtracted the glass transition temperature of the said cyclic olefin resin from the cylinder temperature of the said extruder in the said formation process is 140 degrees C or less.

(2) The method for producing a film according to (1), wherein the cyclic olefin resin has a glass transition temperature of 75 ° C. or higher.

(3) The method for producing a film according to (1) or (2), wherein the acyclic olefin resin is at least one selected from the group consisting of low-density polyethylene, linear low-density polyethylene, and polypropylene.

(4) The method for producing a film according to any one of (1) to (3), wherein the cyclic olefin resin is contained in the resin composition in an amount of 20% by mass or less.

According to the present invention, a method capable of producing a film having easy tearability is provided.

FIG. 1 is a diagram showing an example of the shape of a film obtained from the production method of the present invention. FIG. 2 is a view showing a cross section of a film obtained from the production method of the present invention. FIG. 3 is a view showing a cross section of a film obtained from the production method of the present invention. FIG. 4 is a diagram showing an effect of causing easy tearing of a film obtained from the production method of the present invention.

Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

<Resin composition>
The resin composition in the present invention contains a cyclic olefin resin and an acyclic olefin resin. As a result of investigations by the present inventors, in a molding process of a resin composition containing a cyclic olefin resin and an acyclic olefin resin, if the cylinder temperature of the extruder is too high with respect to the glass transition temperature of the cyclic olefin resin (specifically The value obtained by subtracting the glass transition temperature of the cyclic olefin resin from the cylinder temperature of the extruder in the molding process is more than 140 ° C.), the tear strength of the resulting film is increased, and the easy tearability is inferior. It was issued. This is considered to be because the solidification rate of the cyclic olefin resin and the non-cyclic olefin resin contained in the resin composition and the degree of restoration of the shape of each resin are different. In order to examine this point in detail, the present inventors conducted the following examination. Hereinafter, the cyclic olefin resin is also referred to as “COC” and the glass transition temperature is also referred to as “Tg”.

Extruded resin composition containing 20% by mass of cyclic olefin copolymer (trade name “TOPAS 8007F-04”, Tg = 78 ° C., manufactured by Topas Advanced Polymer) and 80% by mass of linear low density polyethylene (LLDPE) A film having the shape shown in FIG. 1 was prepared using a machine, and the cross section was observed with a scanning electron microscope (SEM).

In addition, in order to observe clearly the area | region (henceforth a "COC domain") in which the cyclic olefin resin was contained in the produced film, after performing the following two types of processes with respect to the cross section of a film The cross section of the film was observed by SEM.
(Process 1) After the film was embedded in epoxy, it was microtome cut. The SEM observation of the cross section of this film is shown in FIG.
(Process 2) After microtome cutting the film, it was embedded in epoxy, and the cross section of the film was etched with tetrahydrofuran. By etching, the cyclic olefin resin in the film falls off, and the COC domain can be visualized as a void. The SEM observation of the cross section of this film is shown in FIG.

2B, a film obtained from a resin composition containing a cyclic olefin resin and an acyclic olefin resin has a structure in which COC domains are scattered in the matrix of the acyclic olefin resin.

In the treatment 1, since the etching was not performed, the cyclic olefin resin in the film did not fall off, and a large void as seen in FIG. 2 (B) was not observed, but a small crescent-shaped void was observed. Observed (arrow part in FIG. 3). FIG. 3 is an enlarged photograph of FIG.

3 is thought to be caused by the action shown in FIG. That is, at the time of forming the film, the COC domain is stretched by being drawn off from the die of the extruder, and then the formed film is cooled, and the temperature of the film approaches the glass transition temperature of the cyclic olefin resin. Solidify while restoring from the stretched state. On the other hand, solidification of an acyclic olefin resin (such as LLPDE) in the present invention occurs by crystallization, and such solidification is caused by a decrease in temperature (that is, the temperature of the film approaches the glass transition temperature of the cyclic olefin resin). It occurs later in time than the solidification of the COC domain. That is, solidification of the non-cyclic olefin resin (such as LLPDE) and COC domain solidification may be shifted in timing. Therefore, even when the shape of the COC domain is restored or solidified, the acyclic olefin resin matrix continues to be stretched by pulling down. While stretching of the matrix of the acyclic olefin resin continues, peeling of the solidified COC domain and the matrix of the acyclic olefin resin or an interface (observed as a void indicated by an arrow in FIG. 3) may occur. Such peeling or interface is considered to cause a decrease in the tear strength of the film (that is, an improvement in easy tearability).

In the present invention, the difference between the cylinder temperature of the extruder in the molding process and the glass transition temperature of the cyclic olefin resin in the resin composition is set within a predetermined range (that is, from the cylinder temperature of the extruder in the molding process to the cyclic state). The value obtained by subtracting the glass transition temperature of the olefin resin is 140 ° C. or less). As a result, the timing of solidification of the COC domain in the film pulled from the extruder can be made earlier than the solidification of the matrix of the acyclic olefin resin, and the interfacial strength between the COC domain and the matrix of the acyclic olefin resin is reduced. (In some cases, peeling occurs between the COC domain and the matrix of the acyclic olefin resin), which can lead to a reduction in the tear strength of the film.

(Cyclic olefin resin)
The cyclic olefin resin in the present invention is not particularly limited as long as it contains a cyclic olefin component as a copolymerization component and is a polyolefin resin containing a cyclic olefin component in the main chain. For example, examples of the cyclic olefin resin in the present invention include an addition polymer of a cyclic olefin or a hydrogenated product thereof, an addition copolymer of a cyclic olefin and an α-olefin, or a hydrogenated product thereof. These polymers may be obtained by grafting and / or copolymerizing an unsaturated compound having a hydrophilic group. As the cyclic olefin resin in the present invention, a commercially available resin (TOPAS (registered trademark) (manufactured by Topas Advanced Polymers) or the like) can also be used. These cyclic olefin resins may be used alone or in combination.

The glass transition temperature of the cyclic olefin resin in the present invention (hereinafter also referred to as “Tg”) is 40 ° C. or higher, and the difference from the cylinder temperature of the extruder in the film forming step is 140 ° C. or lower. Adjusted. The Tg of the cyclic olefin resin is specified by measuring under a temperature increase rate of 10 ° C./min according to JIS K7121. When two or more kinds of cyclic olefin resins are used, the Tg of the cyclic olefin resin is specified as a weighted average of each cyclic olefin resin.

Since the Tg of the cyclic olefin resin is easy to adjust the difference from the cylinder temperature of the extruder within a predetermined range, 40 ° C. or more is sufficient. When the Tg of the cyclic olefin resin is 75 ° C. or higher, preferably 75 ° C. or higher and 150 ° C. or lower, more preferably 75 ° C. or higher and 120 ° C. or lower, the difference from the cylinder temperature of the extruder becomes small, and the molded film Further, peeling and an interface between the COC domain and the matrix of the non-cyclic olefin resin are likely to occur, which is preferable because good easy tearability can be given to the film.

In the resin composition, cyclic olefin resin is contained more than 0 mass% and 60 mass% or less. If it is this range, in the shape | molded film, a COC domain can be formed in the matrix of a non-cyclic olefin resin. Moreover, it is preferable that it is 60 mass% or less also in the meaning of ensuring film toughness from a viewpoint of bag breaking prevention. The cyclic olefin resin may be contained in the resin composition in an amount of 50% by mass or less, preferably 3% by mass to 45% by mass, and more preferably 10% by mass to 40% by mass. Furthermore, even if the content of the cyclic olefin resin in the resin composition is 20% by mass or less, a sufficient effect can be exhibited.

(Acyclic olefin resin)
The acyclic olefin resin in the present invention functions as a matrix resin in the molded film. The non-cyclic olefin resin in the present invention may be those usually used as a film matrix resin, for example, polyethylene, polyester, epoxy, polyamide, polypropylene, polyvinyl alcohol, ethylene vinyl alcohol, polystyrene, vinyl chloride, Examples of the resin include polycarbonate, acrylic, ethylene vinyl acetate copolymer, polyphenylene sulfide, and polymethylpentene.

The non-cyclic olefin resin in the present invention is preferably a polyethylene resin because peeling and an interface with the COC domain are likely to occur, and among the polyethylene resins, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), And at least one selected from the group consisting of polypropylene (PP) is particularly preferred. These non-cyclic olefin resins are crystalline and solidify at the time of cooling slower than the cyclic olefin resins in the present invention. In addition, it is preferable that polypropylene is included as the acyclic olefin resin in that the film is easily tearable.

The melting point of the acyclic olefin resin in the present invention may be, for example, 60 ° C. or higher and 230 ° C. or lower. Further, the viscosity at the molding temperature (for example, 220 ° C.) of the acyclic olefin resin in the present invention may be 300 Pa · s or more and 5000 Pa · s or less at a shear rate (shear rate) of 60 sec ⁻¹ . Such an acyclic olefin resin is preferable in that it can be easily formed as a film.

The resin composition in the present invention contains an acyclic olefin resin of 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more and 97% by mass or less, and further preferably 60% by mass or more and 90% by mass or less. It may be. The content of the acyclic olefin resin in the resin composition is appropriately adjusted according to the content of components other than the acyclic olefin resin.

(Other ingredients)
In the resin composition in the present invention, in addition to the cyclic olefin resin and the non-cyclic olefin resin, components usually used as components of the film may be appropriately contained. Such components include antioxidants, secondary antioxidants, colorants, neutralizers, dispersants, light stabilizers, UV absorbers, lubricants, antistatic agents, antifogging agents, nucleating agents, pigments, Coloring agents, flame retardants, anti-blocking agents, and other various organic / inorganic compounds are exemplified. The content of these components in the resin composition is appropriately adjusted according to the effect to be obtained.

(Production method of resin composition)
As a method for producing a resin composition in the present invention, a conventionally known method for producing a resin composition can be used. For example, each component is melt-kneaded and extruded using a melt-kneader such as a single-screw or twin-screw extruder. Examples thereof include a method of obtaining a resin composition as pellets. As another method, you may throw into a film extruder as a mixture, such as a resin pellet and powder, mix | blended in the ratio of each component of the resin composition in this invention.

<The manufacturing method of the film of this invention>
The manufacturing method of the film of this invention includes the formation process which shape | molds the resin composition mentioned above into a film using an extruder. In this molding process, according to normal extrusion molding, after the resin composition described above is melted in the cylinder of the extruder, it is drawn down from the die of the extruder and cooled in the air or in water, etc. Molded. Although it does not specifically limit as an extruder used in a shaping | molding process, A single screw extruder, a twin screw extruder, a screw extruder (types, such as a full flight and a double flight), etc. can be used.

In the present invention, since the value obtained by subtracting the glass transition temperature of the cyclic olefin resin from the cylinder temperature of the extruder in the molding process is 140 ° C. or less, the COC domain is formed in the matrix of the non-cyclic olefin resin, and the above-described action The film can be given good easy tearability. The value obtained by subtracting the glass transition temperature of the cyclic olefin resin from the cylinder temperature of the extruder in the molding step is preferably 130 ° C. or lower, more preferably 50 ° C. or higher and 130 ° C. or lower. Normally, the cylinder temperature on the discharge side of the extruder is almost the same as the die temperature. Accordingly, the “cylinder temperature of the extruder” in the present invention refers to the temperature of the cylinder and die on the discharge side of the extruder, which is substantially the same value as the temperature of the resin discharged from the extruder. .

In the film production method of the present invention, the film may be prepared as a single layer film or a multilayer film. When preparing a film as a single layer film, a film formed by extrusion from an extruder can be used as it is. In such a case, the amount of the cyclic olefin resin contained in the film may be more than 0 mass% and 60 mass% or less, for example, 3 mass% or more and 45 mass% or less.

When preparing a film as a multilayer film, use a known laminating method such as an extrusion coating method, a hot lamination method, or a dry lamination method to prepare a multilayer film with the film obtained from the production method of the present invention as a sealant layer. it can. In such a case, the amount of the cyclic olefin resin contained in the film is appropriately adjusted according to the easy tearability to be obtained. Specifically, in the case of a multilayer film, the amount of the cyclic olefin resin contained in the composition of the entire film may be more than 0% by mass and 60% by mass or less, and 50% by mass or less, preferably 3% by mass. % To 45% by mass, more preferably 10% to 40% by mass. Furthermore, even if the amount of the cyclic olefin resin in the configuration of the entire multilayer film is 20% by mass or less, a sufficient effect can be exhibited.

In the method for producing a film of the present invention, the thickness of the film is not particularly limited, but for example, it can be adjusted to 5 μm or more and 200 μm or less for both a single layer film and a multilayer film.

<Film obtained from the production method of the present invention>
The film obtained from the production method of the present invention is excellent in easy tearability. The easy tearability of the film obtained from the production method of the present invention is specified by an Elmendorf tear test according to JIS K7128 and JIS P8116. The lower the obtained value, the lower the tear strength and the better the easy tearability. For example, the film obtained from the production method of the present invention has a strength of 5 to 350 g / 16 sheets when it is torn in the longitudinal direction in the Elmendorf tear test. In addition, the film obtained from the production method of the present invention has a strength of 10 to 400 g / 16 sheets when it is laterally split in the Elmendorf tear test.

The film obtained from the production method of the present invention can be preferably used as various packaging materials, container lids, labels and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

<Example 1 and Comparative Example 1>
Low density polyethylene (“LDPE” in Table 1, trade name “Novatech LD LF640MA”, manufactured by Nippon Polyethylene Co., Ltd.) and cyclic olefin copolymers (hereinafter “Tg” in the table) having different glass transition temperatures (in Table 1) “COC”) was mixed at a ratio shown in Table 1 to obtain a resin composition. The obtained resin composition was molded into a cast film (single layer) having a thickness of 30 μm using an extruder (this process corresponds to a “molding process”). The cylinder and die temperatures of the extruder in the molding process are as shown in Table 1.

In the following, the unit of the numerical values of the prescriptions in the table is “mass%”. “T (C + D)” refers to the temperature of the cylinder and die of the extruder in the molding process. “T (C + D) −Tg” refers to a value obtained by subtracting the Tg of COC from “T (C + D)”.

The COC used is as follows.
Trade name “TOPAS 7010F-600”, Tg = 110 ° C., manufactured by Topas advanced Polymer, trade name “TOPAS 8007F-500”, Tg = 78 ° C., manufactured by Topas advanced Polymer, trade name “TOPAS 9903D-10”, Tg = 33 ° C, manufactured by Topas advanced Polymer

The molding conditions for the cast film are as follows.
[Film forming equipment]
φ32mm analysis extrusion equipment (Plastic Engineering Laboratory Co., Ltd.)
A 300-width coat hanger die was used.
The screw used was L / D = 30, compression ratio 3.0, and tip end unimelt.
[Molding condition]
Die lip clearance: 1.0mm
Film thickness: 30 μm
Reduction ratio (thickness ratio): 33.3
Air gap: about 40mm
Roll temperature: 50 ° C
Screw rotation speed: 50rpm
Discharge rate: 5.5kg / h
Take-off speed: 11.5m / min
Film thickness: 30 μm

<Example 2 and Comparative Example 2>
Cast in the same manner as in Example 1 and Comparative Example 1 except that linear low density polyethylene ("LLDPE" in Table 2, trade name "Evolue SP2040", manufactured by Prime Polymer Co., Ltd.) is used instead of low density polyethylene. A film was obtained.

<Example 3 and Comparative Example 3>
A cast film was obtained in the same manner as in Example 1 and Comparative Example 1 except that polypropylene ("PP" in Table 3, trade name "NOVATEC PP FL02A", manufactured by Nippon Polyethylene Co., Ltd.) was used instead of low-density polyethylene. .

<Example 4 and Comparative Example 4>
Instead of low-density polyethylene, low-density polyethylene (“LDPE” in Table 4; trade name “Novatech LD LF640MA”, manufactured by Nippon Polyethylene Co., Ltd.) and polypropylene (“PP” in Table 4; trade name “Novatech PP FL02A”) A cast film was obtained in the same manner as in Example 1 and Comparative Example 1 except that “made by Nippon Polyethylene Co., Ltd.” was used.

<Tear strength>
About the cast film prepared by the said Example and comparative example, the Elmendorf tear test was done according to JISK7128 and JISP8116, and tear strength of each cast film was measured. The results are shown in Tables 1 to 4. In the table, “vertical” indicates the strength when the cast film is torn in the vertical direction (MD direction). Further, “lateral” indicates strength when the cast film is torn in the lateral direction (TD direction).

As shown in Tables 1 to 4, from the resin composition containing no cyclic olefin resin, only a film having high tear strength was obtained, and a film excellent in easy tearability was not obtained (Comparative Example 1-1, Comparative Example 1). Example 2-1 and comparative example 3-1).

Further, even in the case of a resin composition containing a cyclic olefin resin, unless the condition that the Tg of the cyclic olefin resin is 40 ° C. or higher and “T (C + D) −Tg” is 140 ° C. or lower is satisfied, Although easy tearability is better than when a resin composition not containing a cyclic olefin resin is used, sufficient easy tearability is difficult to obtain (Comparative Examples 1-2 to 4, Comparative Examples 2-2 and 3, Comparative Example 3-2, Comparative Examples 4-2 and 3).

On the other hand, if a resin composition containing a cyclic olefin resin is molded under the conditions that the Tg of the cyclic olefin resin is 40 ° C. or higher and “T (C + D) −Tg” is 140 ° C. or lower, easy tearing occurs. It turns out that the film which is excellent in a property is obtained (each Example). In particular, when a cyclic olefin resin having a Tg of 110 ° C. was used, the easy tearability was excellent (Example 1-1, Example 2-1, Example 3-1, Examples 4-1 to 3). ). In addition, when polypropylene was included as the acyclic olefin resin contained in the resin composition, the easy tearability was particularly good (Example 3-1 and Examples 4-1 to 3).

<Example 5 and Comparative Example 5>
A three-layer film was formed by inflation molding, and the easy tearability of the film was evaluated in the same manner as in Examples 1 to 4 and Comparative Examples 1 to 4 described above.

Specifically, as the linear low density polyethylene (LLDPE), the trade names “Novatech UF421” and “Novatech UF321” (both manufactured by Nippon Polyethylene Co., Ltd.) are used, and the glass transition temperature (hereinafter referred to as “ Using a cyclic olefin copolymer ("COC" in Table 5) having different Tg "), inflation molding was performed so as to have a layer configuration of 3 layers (A layer to C layer) according to the formulation shown in Table 5 (this The process corresponds to a “molding process”). LLDPE and COC were blended by a pellet blend method. The cylinder and die temperatures of the extruder in the molding process are as shown in Table 5.

In the following, the numerical unit of the prescription in Table 5 and the notation of “T (C + D)” and “T (C + D) −Tg” are the same as those in Tables 1 to 4. The COC used is the same as that used in Example 1.

The conditions for forming the inflation film are as follows.
[Film forming equipment]
Inflation molding machine: 3-layer inflation (manufactured by Tommy Machine Industry Co., Ltd.)
[Molding condition]
Cylinder temperature:
(Inner and outer layers) 180 ° C. (C1) → 190 ° C. (C2) → 190 ° C. (H) → 190 ° C. (JC)
(Intermediate layer) 210 ° C. (C1) → 210 ° C. (C2) → 190 ° C. (H) → 190 ° C. (JC)
Die temperature: 190 ° C (D1) → 190 ° C (D2) → 190 ° C (D3)
Blow-up ratio: 2.0
Take-off speed: 12.5m / min
Layer thickness ratio of three layers: outer (A) layer: intermediate (B) layer: inner (C) layer = 1: 1: 1
Film thickness: 50 μm

Since the layer thickness ratio of the three layers is 1: 1: 1, the cyclic polyolefin content in the entire multilayer film is 3.3% by mass in Examples 5-1 and 5-2. In 5-3 and 5-4, it is 6.7% by mass, and in Examples 5-5 and 5-6, it is approximately 17% by mass.

As shown in Table 5, even in the formation of an inflation film mainly composed of LLDPE, only a film having high tear strength can be obtained from a resin composition not containing a cyclic olefin resin, and a film excellent in easy tearability can be obtained. (Comparative Example 5).

Further, when a resin composition containing a cyclic olefin resin in the intermediate layer is molded under the conditions that the Tg of the cyclic olefin resin is 40 ° C. or higher and “T (C + D) −Tg” is 140 ° C. or lower. A film excellent in easy tearability was obtained (each example of Example 5). In particular, the higher the content of the cyclic olefin resin, the more easily the tearing tendency tends to be obtained. When the content of the cyclic olefin resin is the same, the cyclic olefin resin having a Tg of 110 ° C. is used. This was superior in easy tearability (Example 5-1, Example 5-3, Example 5-5).

Claims

A method for producing a film including a molding step of molding a resin composition containing a cyclic olefin resin of greater than 0% by mass and equal to or less than 60% by mass and an acyclic olefin resin using an extruder,
The glass transition temperature of the cyclic olefin resin is 40 ° C. or higher,
The manufacturing method of the film whose value which reduced the glass transition temperature of the said cyclic olefin resin from the cylinder temperature of the said extruder in the said formation process is 140 degrees C or less.
The method for producing a film according to claim 1, wherein the cyclic olefin resin has a glass transition temperature of 75 ° C or higher.
The method for producing a film according to claim 1 or 2, wherein the acyclic olefin resin is at least one selected from the group consisting of low density polyethylene, linear low density polyethylene, and polypropylene.
The method for producing a film according to any one of claims 1 to 3, wherein the cyclic olefin resin is contained in the resin composition in an amount of 20% by mass or less.