WO2001034383A1 - Film a structure laminee a excellente adaptation a la configuration tridimensionnelle, et utilisation - Google Patents

Film a structure laminee a excellente adaptation a la configuration tridimensionnelle, et utilisation Download PDF

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Publication number
WO2001034383A1
WO2001034383A1 PCT/JP2000/007746 JP0007746W WO0134383A1 WO 2001034383 A1 WO2001034383 A1 WO 2001034383A1 JP 0007746 W JP0007746 W JP 0007746W WO 0134383 A1 WO0134383 A1 WO 0134383A1
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WO
WIPO (PCT)
Prior art keywords
film
laminated structure
layer
film according
weight
Prior art date
Application number
PCT/JP2000/007746
Other languages
English (en)
Japanese (ja)
Inventor
Nobuyoshi Igarashi
Original Assignee
Sumiron Co., Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumiron Co., Ltd filed Critical Sumiron Co., Ltd
Priority to AU10554/01A priority Critical patent/AU1055401A/en
Publication of WO2001034383A1 publication Critical patent/WO2001034383A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin

Definitions

  • the present invention relates to an 3 ⁇ 4s structure film suitable for sticking to a surface of an object having a three-dimensional shape, for example, for protecting the surface of an object having a three-dimensional shape rather than a plane, for example, for protecting a painted surface, and its use. . Background technology
  • a releasable adhesive film obtained by applying an adhesive such as polyisobutylene to a single-layer film made of a blended product of polypropylene and polyethylene has been used.
  • the reason why the removable adhesive film is used is that it is necessary to remove the surface protection film before handing over a new car to the user.
  • Improvements to the film used as the support of the above release adhesive film mainly include enhancement of weather resistance, prevention of deformation of the coating film, improvement of release workability, and prevention of adhesive residue on the vehicle body. Biodegradability in consideration of disposal after use, preventing air bubbles from remaining between the film and the coating film, and preventing separation of overlapping at the film seam.
  • Japanese Patent Application Laid-Open No. Hei 9-254 5 288, Japanese Patent Laid-Open No. 117-15959, Japanese Patent Laid-Open No. 1i-L3106, etc. No surface protection film has been found so far.
  • the surface protection film When a film is applied to an object having a three-dimensional shape, such as a car body or a bumper, the surface protection film needs to have some elasticity in order to make the film conform to the surface unevenness. In other words, three-dimensional shape followability is required. Moreover, three-dimensional shape followability is required. Moreover,
  • an object of the present invention is to provide a laminated structure film having high mechanical strength and excellent conformability to a three-dimensional shape, and its use.
  • the structural film of the present invention which solves the above problems, is a laminated structure film including a core layer and surface layers disposed on both surfaces thereof, wherein the core layer has a hard segment and a soft segment.
  • a layer composed of a resin material containing 20% by weight or more of elastomer is essential, and at least one of the two layers is composed of a resin material containing 80% or more of linear low-density polyethylene. It is characterized by the following.
  • the self-adhesive film of the present invention which is one of the preferable uses of the laminated structure film of the present invention, is one in which an adhesive layer is provided on one surface of the laminated structure film of the present invention.
  • This adhesive film is particularly suitably used as a protective film for a painted surface of an automobile.
  • the laminated structure film according to the present invention may have a laminated structure composed of only a core layer 1 and surface layers 2 and 2 disposed on both surfaces thereof as shown in FIG. It may have a laminated structure in which a layer (not shown) made of another material is further arranged on one side or on the side. Both surface layers 2 and 2 do not need to be the same, and at least one layer may be a layer made of a resin material containing 80% by weight or more of linear low-density polyethylene. At least one of the rain surface layers 2.2 may be an adhesion improving adhesive layer or a black light blocking layer.
  • the core layer may be a single layer or a laminated structure. And a single-layer place In the case of a laminated structure, at least one layer is composed of a copolymer having a hard segment and a soft segment.
  • TPO must be a layer made of a resin material containing 20% or more.
  • the core layer may also be configured such that a layer obtained by blending low-density polyethylene (hereinafter referred to as LDPE) with TP0 is superimposed on a layer composed of only PO.
  • LDPE low-density polyethylene
  • TP0 is a thermoplastic refining elastomer having a hard segment such as an ethylene-propylene copolymer and a soft segment such as an ethylene-propylene copolymer rubber.
  • the core layer containing the elastomer as a page component has a melting point of 130 to 165 as measured according to ASTM D3418. While having heat resistance of C, it not only has excellent mechanical properties such as high tensile strength at break and elastic modulus, but also has elongation. Therefore, this core layer can impart stereoscopic shape followability to the laminated structure film.
  • the TP0 is preferably, but not limited to, a reactor type.
  • Reactor type refers to a type in which a monomer is reacted directly in a reactor to directly polymerize a polymer having a hard segment and a soft segment (PO), and two or more types are separately used. Unlike TP 0, which blends different polymers, it has excellent homogeneity in components and performance.
  • the TP 0 is not limited, but the flexural modulus measured according to ASTM D-790 is 150 to 600 kgf / cm in order to sufficiently exhibit the three-dimensional shape followability. Two propylene-ethylene copolymers are preferred. If the flexural modulus is high, the film becomes hard and the three-dimensional shape followability is poor. On the other hand, if the flexural modulus is low, the film becomes soft, and heat resistance, gluing workability, and sticking workability are inferior.
  • the melting point of the laminated structure film measured in accordance with ASTM D 348 is in the range of 130 to 1650 ° C. Is preferred. Outside of this range, heat shrinkage during the gluing operation and heat shrinkage of the practical adhesive product increase.
  • examples of the other resin include ethylene butene 1 copolymer and ethylene-1-hexene 1 Linear low-density polyethylene, such as polymers, ethylene-1-methylpentene-11 copolymer, and ethylene-octene-11 copolymer: ordinary low-density polyethylene: medium, high-density polyethylene: ethylene-butyl acetate copolymer, ethylene Rubbers such as monomethyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, polybutene, ethylene-propylene rubber, styrene-butadiene rubber, butyl rubber, and 4-methylpentene-11 polymer And less than 80% by weight of the whole resin component.
  • Linear low-density polyethylene such as polymers, ethylene-1-methylpentene-11 copolymer, and ethylene-octene-11 copolymer: ordinary low-density polyethylene: medium,
  • the core layer has a laminated structure and includes a layer other than a layer composed of a resin material containing 20% by weight or more of TP0
  • the other layer is generally used as a support for an adhesive film.
  • synthetic films such as polyolefin resins such as polyethylene, polyester resins, polyamide resins, polyimide resins, polyvinyl alcohol resins, and polyvinyl chloride resins.
  • the laminated structure film or the pressure-sensitive adhesive film according to the present invention may be provided with a synthetic resin film, paper, cellophane, cloth, May have layers such as non-woven fabric, gold foil, and vapor deposition layer.
  • At least one surface of the core layer is used to enhance the weather resistance and heat resistance of the film III structure, and for automotive applications, to prevent perforations from occurring when pebbles or sand hits it.
  • a layer made of a resin material containing 80% by weight or more of LDPE is arranged.
  • This LDPE was measured according to J 1 SK — 670 because it is excellent in mechanical strength such as heat resistance, tensile strength at break, rigidity, etc., and thin film processing suitability.
  • a linear LDPE having a density of 0.920 to 0.945 is preferred.
  • Specific examples of such LDPE include ethylene butene-1 copolymer, ethylene-1 hexene-1 copolymer, ethylene-4-1-methylpentene-11 copolymer, and ethylene-1-butene-11 copolymer.
  • the resin material containing LDPE includes a resin other than LDPE
  • examples of the other resin include ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-butene copolymer, and the like.
  • Ethylene Fin copolymers TP0s; rubbers such as PB, EPR, SBR, BR: 4-methylbenzene-11 polymer, etc., if they are less than 20% by weight of the total resin content May be.
  • the laminated structure film of the present invention comprises, but is not limited to, the core layer and both surface layers, because it protects the coating layer by shading and imparts the weather resistance (light deterioration) of the film itself.
  • Amount of T i 0 2 less effect of addition is less than 1 wt%, it exceeds 2 0 wt%, the strength of the film which may cause a problem that the vulnerable.
  • the addition amount of the weathering agent is less than 0.5% by weight, the effect of the addition is small, and if it exceeds 5% by weight, poor adhesion of the adhesive due to the surface bleed-out of the additive and discoloration with time are remarkable. Problems may occur.
  • Examples of the above-mentioned weathering agent include 1,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, 2-hydroxy-14-n-year-old benzobenzophenone, 2,2'4,4 '' Hydroxybenzophenone-based weathering agents such as 1-tetrahydroxybenzofunone; 2,4-di-t-butylphenyl 3,5-di-t-butyl-14-hydroxybenzoate, etc.
  • Hydroxybenzoic acid weathering agents 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydro- ⁇ -xyphenyl) -5-chloro Hydroxybenzotriazole-based weathering agents such as benzotriazole, 2- (3'-t-butyl-12'-hydroxy-1-5'-methylphenyl) -5-chlorobenzenebenzenetriazole; Nickel Bisoctyl Bisulphide, [2,2'-thiobis (4-t one-year-old butylphenol)] n-butylamine nickel, nickel complex-based weathering agent such as nickel dibutyldithiocarbamate; bis (2,2,6 , 6-tetramethyl-4-piberidine) sebagate, a copolymer of hindered amine, poly [ ⁇ 6- (1,3,3-tetramethylbutyl) amino-3,5-triazine-2,4-di
  • colorants include organic or inorganic colorants such as titanium yellow, cobalt blue, and phthalocyanine, and A1 powder and carbon black.
  • Such acid inhibitors include, for example, 2.2'-oxamidobis [ethyl 3- (3,5-di-t-butyl-14-hydroxyphenyl) probionet] methane, tetrakis [methylene 1-3- (3'.5'-g-t-butyl-1-4'-hydroxyfurnyl) propionate] phenolic antioxidants such as methane: 4,4'-bisphenylenediphosphinic acid tetrakis (2,4- Phosphite systems such as di-t-butylphenyl), citralic neo-bentante triylbis (2,4-di-tert-butylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite And antioxidants.
  • 2.2'-oxamidobis ethyl 3- (3,5-di-t-butyl-14-hydroxyphenyl) probionet
  • Such lubricants include, for example, higher grades such as ethylene bis fatty acid (C 1 B to (: 1 B ) amide), high fatty acid (C to C) amide, stearyl erucamide, and oleyl palmitamide.
  • modifiers examples include antistatic agents such as surfactants, and inorganic and organic natural or synthetic fillers.
  • the above-mentioned calculation of the content of TP0 or LDPE means the ratio of only the resin component not containing the various additives described above in the resin material.
  • the laminated structure film according to the present invention preferably has a total thickness of 20 to 150 m, including, but not limited to, a core layer and both surface layers. Of the total thickness, the thickness of both surface layers is preferably 5 to 50 m on one side and 10 to 100 m on both sides. And a layer composed of a resin material containing TP0 at least 20 Sft%. Preferably has a thickness of at least 10 ⁇ m.
  • the laminated structure film according to the present invention suppresses the amount of shrinkage and swelling due to an increase in the ambient temperature during heating at the time of applying the pressure-sensitive adhesive and after actual application to an automobile paint, and
  • the amount of thermal deformation in an atmosphere at 110 ° C is preferably within ⁇ 3% for both MD and TD in the processing direction of the film.
  • the “process direction of the film” means the direction in which the film is formed and wound in the length direction
  • “MD” is an abbreviation of Machine Direction
  • TD is an abbreviation of Transverese Direction, which means the width and width directions.
  • the measurement of the amount of thermal deformation is performed as follows.
  • Heat shrinkage (%) Measure the length of the gauge mark-1 0 0
  • the laminated structure film according to the present invention can be obtained by using an inflation film forming machine or a T-die film forming machine having three or more dies having a core layer and a surface layer. With multiple extruders set at a temperature of 10 ° C to 130 ° C for the melting point of each LDPE and TPO to be used, multi-layer processing in the same temperature range as your own is possible. It is obtained by passing through a die having a structure, pulling it down into a single film, slitting it into a desired width while continuously cooling, and winding it. After cooling, it is possible to perform corona treatment on one or both sides ⁇ or one part during the process up to winding, if desired.
  • the pressure-sensitive adhesive film using the laminated structure film according to the present invention as a support comprises an acrylic pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, and an ethylene-vinyl acetate copolymer-based pressure-sensitive adhesive on the surface of the support.
  • An adhesive layer is provided by applying a silicone adhesive, for example, in a thickness of 3 to 3.
  • a silicone adhesive for example, in a thickness of 3 to 3.
  • an adhesive containing polyisobutylene, butyl rubber, polybutene, or the like as a main component is preferable.
  • a surface treatment such as edge treatment or plasma treatment, or a primer is applied.
  • FIG. 1 is a partial cross-sectional view showing one embodiment of the laminated structure film according to the present invention.
  • i core layer, 2 ... surface layer.
  • a laminated structure film was produced as follows.
  • One side of the three-layer film was coated with a 15% by weight of a polyisobutylene-based adhesive and dried at 80 for 3 minutes to form an adhesive layer having a thickness of 10 Aim.
  • a structural sheet was obtained.
  • Table 1 shows the results of measuring the mechanical properties and the three-dimensional shape following of the laminated structure film.
  • Characteristics that are difficult to break and are difficult to elongate are required, and characteristics that are difficult to break are quantified by bow I tearing, and characteristics that are difficult to elongate are quantified by bow I tension yield strength.
  • the tear strength was measured by the C method of JIS K 7 12.8 method.
  • the bow I tension yield strength was measured by cutting the laminated structure films obtained in the examples and comparative examples into a width of 15 mm, and measuring the tensile strength at a tensile speed of 30 Omm / min (MD direction) and a chuck interval of 50 mm. The yield point was determined from the chart.
  • Comparative Example 1 A single-layer polyethylene / polypropylene blend type film was prepared in the same manner as in Example 1 except that the resin composition was as shown in Table 1 using a single-layer structure die, and the mechanical properties and three-dimensional shape The followability was measured and the results are shown in Table 1.
  • TP ⁇ 1 Propylene-ethylene copolymer TP 0 with a temperature of 1338 ° C and a flexural modulus of 5100 kgf / cm 2
  • TP 02 propylene-ethylene copolymer with a melting point of i 60 ° C and a flexural modulus of 3500 kgf / cm 2
  • HALS poly [(6- (1,1,3,3-tetramethylbutyl) amino_1,3,5-triazine-1,4-diyl ⁇ ⁇ (2.2.6.6-tetra Methyl-1-4-pyridyl) imino) hexamethylene ⁇ (2,2,6,6-tetramethyl-1-pyridyl) imino)]
  • the laminated structure film according to the present invention has a high mechanical strength because the core layer must have a layer composed of a resin material containing at least 10% by weight of a thermoplastic olefin elastomer having hard segments and soft segments. It has a three-dimensional shape followability.
  • both surface layers are low density polyethylene. It is a layer composed of a resin material containing 80% by weight or more, and has excellent weather resistance and heat resistance. In addition, perforations are less likely to occur in automotive applications.
  • the pressure-sensitive adhesive film according to the present invention has high mechanical strength and conformability to a three-dimensional shape because the laminated structure film is used as a support. Therefore, the pressure-sensitive adhesive film according to the present invention is excellent in perforation resistance, and thus is suitably used as a release-type surface protective film for automobiles.

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  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film à structure laminée comprenant une couche noyau (1), sur les deux côtés de laquelle se trouvent des couches de surface (2) et (2). La couche noyau comporte impérativement une couche en matériau à base de résine qui renferme au moins 20 %, en poids, d'élastomère d'oléfine thermoplastique à un ou plusieurs segments durs et un ou plusieurs segments mous. Au moins une couche de surface est en matériau à base de résine comprenant au moins 80 %, en poids, de polyéthylène linéaire à faible densité. L'invention concerne en outre un film adhésif autocollant qui comporte le film à structure laminée considéré en guise de support.
PCT/JP2000/007746 1999-11-08 2000-11-02 Film a structure laminee a excellente adaptation a la configuration tridimensionnelle, et utilisation WO2001034383A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10554/01A AU1055401A (en) 1999-11-08 2000-11-02 Film of laminated structure with excellent conformability to three-dimensional shape and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP31754699 1999-11-08
JP11/317546 1999-11-08

Publications (1)

Publication Number Publication Date
WO2001034383A1 true WO2001034383A1 (fr) 2001-05-17

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PCT/JP2000/007746 WO2001034383A1 (fr) 1999-11-08 2000-11-02 Film a structure laminee a excellente adaptation a la configuration tridimensionnelle, et utilisation

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AU (1) AU1055401A (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003172973A (ja) * 2001-12-06 2003-06-20 Nikon Corp カメラ用ミラー装置
JP2015193753A (ja) * 2014-03-31 2015-11-05 住友化学株式会社 粘着テープ

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993826A (en) * 1974-01-18 1976-11-23 Adhesive Tapes Limited Pressure-sensitive adhesive tape substrate
JPH09314767A (ja) * 1996-05-27 1997-12-09 Fukuvi Chem Ind Co Ltd 耐候性に優れた共押出成形体
JPH10166524A (ja) * 1996-12-16 1998-06-23 Asahi Chem Ind Co Ltd 合成樹脂板用保護フィルム
JPH11106716A (ja) * 1997-09-30 1999-04-20 Mitsui Chem Inc 粘着フィルム
JPH11302605A (ja) * 1998-04-17 1999-11-02 Hitachi Chem Co Ltd 自動車塗膜保護用粘着フィルム
JPH11320780A (ja) * 1998-05-20 1999-11-24 Dainippon Ink & Chem Inc 多層フィルム及びそれを用いた粘着テープ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993826A (en) * 1974-01-18 1976-11-23 Adhesive Tapes Limited Pressure-sensitive adhesive tape substrate
JPH09314767A (ja) * 1996-05-27 1997-12-09 Fukuvi Chem Ind Co Ltd 耐候性に優れた共押出成形体
JPH10166524A (ja) * 1996-12-16 1998-06-23 Asahi Chem Ind Co Ltd 合成樹脂板用保護フィルム
JPH11106716A (ja) * 1997-09-30 1999-04-20 Mitsui Chem Inc 粘着フィルム
JPH11302605A (ja) * 1998-04-17 1999-11-02 Hitachi Chem Co Ltd 自動車塗膜保護用粘着フィルム
JPH11320780A (ja) * 1998-05-20 1999-11-24 Dainippon Ink & Chem Inc 多層フィルム及びそれを用いた粘着テープ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003172973A (ja) * 2001-12-06 2003-06-20 Nikon Corp カメラ用ミラー装置
JP2015193753A (ja) * 2014-03-31 2015-11-05 住友化学株式会社 粘着テープ

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Publication number Publication date
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