WO2014103472A1 - フィルムの製造方法 - Google Patents

フィルムの製造方法 Download PDF

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Publication number
WO2014103472A1
WO2014103472A1 PCT/JP2013/077658 JP2013077658W WO2014103472A1 WO 2014103472 A1 WO2014103472 A1 WO 2014103472A1 JP 2013077658 W JP2013077658 W JP 2013077658W WO 2014103472 A1 WO2014103472 A1 WO 2014103472A1
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WO
WIPO (PCT)
Prior art keywords
film
olefin resin
cyclic olefin
mass
resin
Prior art date
Application number
PCT/JP2013/077658
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English (en)
French (fr)
Japanese (ja)
Inventor
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 (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.)
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Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to CN201380062709.8A priority Critical patent/CN104884228B/zh
Priority to KR1020157004206A priority patent/KR101521192B1/ko
Priority to JP2014521389A priority patent/JP5632564B1/ja
Publication of WO2014103472A1 publication Critical patent/WO2014103472A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92209—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0625—LLDPE, i.e. linear low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene

Definitions

  • the present invention relates to a method for producing a film.
  • 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”).
  • 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.).
  • 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.
  • the inventors 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.
  • 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.
  • 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.
  • the resin composition in the present invention contains a cyclic olefin resin and an acyclic olefin resin.
  • a resin composition containing a cyclic olefin resin and an acyclic olefin resin contains a cyclic olefin resin and an acyclic olefin resin.
  • the present inventors conducted the following examination.
  • the cyclic olefin resin is also referred to as “COC” and the glass transition temperature is also referred to as “Tg”.
  • 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).
  • 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.
  • FIG. 3 is an enlarged photograph of FIG.
  • solidification of the non-cyclic olefin resin such as LLPDE
  • 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).
  • 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).
  • 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.
  • 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 ⁇ -olefin, or a hydrogenated product thereof.
  • These polymers may be obtained by grafting and / or copolymerizing an unsaturated compound having a hydrophilic group.
  • 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.
  • 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.
  • 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.
  • cyclic olefin resin is contained more than 0 mass% and 60 mass% or less. If it is this range, in the shape
  • 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.
  • 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.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • PP polypropylene
  • These non-cyclic olefin resins are crystalline and solidify at the time of cooling slower than the cyclic olefin resins in the present invention.
  • 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.
  • 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.
  • each component is melt-kneaded and extruded using a melt-kneader such as a single-screw or twin-screw extruder.
  • a melt-kneader such as a single-screw or twin-screw extruder.
  • melt-kneader such as a single-screw or twin-screw extruder.
  • examples thereof include a method of obtaining a resin composition as pellets.
  • the manufacturing method of the film of this invention includes the formation process which shape
  • 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.
  • 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.
  • 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.
  • the cylinder temperature on the discharge side of the extruder is almost the same as the die temperature.
  • 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. .
  • the film may be prepared as a single layer film or a multilayer film.
  • a film formed by extrusion from an extruder can be used as it is.
  • 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.
  • the amount of the cyclic olefin resin contained in the film is appropriately adjusted according to the easy tearability to be obtained.
  • 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.
  • 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.
  • the thickness of the film is not particularly limited, but for example, it can be adjusted to 5 ⁇ m or more and 200 ⁇ m or less for both a single layer film and a multilayer film.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m 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.
  • 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)”.
  • 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.
  • LLDPE linear low density polyethylene
  • Evolue SP2040 manufactured by Prime Polymer Co., Ltd.
  • 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.
  • LDPE low-density polyethylene
  • PP polypropylene
  • 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.
  • LLDPE linear low density polyethylene
  • the trade names “Novatech UF421” and “Novatech UF321” both manufactured by Nippon Polyethylene Co., Ltd.
  • 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.
  • the conditions for forming the inflation film are as follows.
  • Inflation molding machine 3-layer inflation (manufactured by Tommy Machine Industry Co., Ltd.)
  • Cylinder temperature 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.
  • 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.
PCT/JP2013/077658 2012-12-27 2013-10-10 フィルムの製造方法 WO2014103472A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201380062709.8A CN104884228B (zh) 2012-12-27 2013-10-10 薄膜的制造方法
KR1020157004206A KR101521192B1 (ko) 2012-12-27 2013-10-10 필름의 제조방법
JP2014521389A JP5632564B1 (ja) 2012-12-27 2013-10-10 フィルムの製造方法

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Application Number Priority Date Filing Date Title
JP2012285904 2012-12-27
JP2012-285904 2012-12-27

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WO2014103472A1 true WO2014103472A1 (ja) 2014-07-03

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JP (1) JP5632564B1 (zh)
KR (1) KR101521192B1 (zh)
CN (1) CN104884228B (zh)
TW (1) TWI509005B (zh)
WO (1) WO2014103472A1 (zh)

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WO2014181696A1 (ja) * 2013-05-10 2014-11-13 電気化学工業株式会社 合成樹脂系延伸フィルム
JP2016117159A (ja) * 2014-12-18 2016-06-30 大日本印刷株式会社 シーラントフィルム
JP2017061148A (ja) * 2015-09-24 2017-03-30 日本ポリエチレン株式会社 直線易カット性フィルムの製造方法及び直線易カット性フィルム
JP2019156922A (ja) * 2018-03-09 2019-09-19 株式会社プライムポリマー シーラント用樹脂組成物、シーラント用多層フィルムおよび熱融着性積層フィルム
JP2019202788A (ja) * 2018-05-21 2019-11-28 凸版印刷株式会社 液体用紙容器

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CN106346923B (zh) * 2016-08-31 2018-08-17 江阴升辉包装材料有限公司 一种易撕裂多层共挤热成型拉伸底膜
DE102017118202A1 (de) * 2017-05-15 2018-11-15 Epcos Ag Folienkondensator
CN108682707B (zh) * 2018-06-13 2020-06-09 常州回天新材料有限公司 一种用于双面发电的太阳能光伏电池组件透明背板

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JP2007021755A (ja) * 2005-07-12 2007-02-01 Mitsubishi Plastics Ind Ltd ポリオレフィン系樹脂積層シートおよびこれを用いたｐｔｐ包装体
JP2011005805A (ja) * 2009-06-29 2011-01-13 Polyplastics Co ポリオレフィン系樹脂フィルムの製造方法
JP2012236382A (ja) * 2011-05-13 2012-12-06 Dic Corp 易開封性多層フィルム及び該フィルムを用いた包装材

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WO2014181696A1 (ja) * 2013-05-10 2014-11-13 電気化学工業株式会社 合成樹脂系延伸フィルム
JP2016117159A (ja) * 2014-12-18 2016-06-30 大日本印刷株式会社 シーラントフィルム
JP2017061148A (ja) * 2015-09-24 2017-03-30 日本ポリエチレン株式会社 直線易カット性フィルムの製造方法及び直線易カット性フィルム
JP2019156922A (ja) * 2018-03-09 2019-09-19 株式会社プライムポリマー シーラント用樹脂組成物、シーラント用多層フィルムおよび熱融着性積層フィルム
JP7046657B2 (ja) 2018-03-09 2022-04-04 株式会社プライムポリマー シーラント用樹脂組成物、シーラント用多層フィルムおよび熱融着性積層フィルム
JP2019202788A (ja) * 2018-05-21 2019-11-28 凸版印刷株式会社 液体用紙容器

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