WO2018181385A1 - Base material for coating film surface-protecting film, and coating film surface-protecting film using same - Google Patents

Base material for coating film surface-protecting film, and coating film surface-protecting film using same Download PDF

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Publication number
WO2018181385A1
WO2018181385A1 PCT/JP2018/012552 JP2018012552W WO2018181385A1 WO 2018181385 A1 WO2018181385 A1 WO 2018181385A1 JP 2018012552 W JP2018012552 W JP 2018012552W WO 2018181385 A1 WO2018181385 A1 WO 2018181385A1
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Prior art keywords
layer
coating
mass
sensitive adhesive
pressure
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PCT/JP2018/012552
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French (fr)
Japanese (ja)
Inventor
真三 牧野
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住化積水フィルム株式会社
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Priority to JP2019509929A priority Critical patent/JP6995840B2/en
Publication of WO2018181385A1 publication Critical patent/WO2018181385A1/en

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    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material

Definitions

  • the present invention relates to a coating film surface protective film substrate and a coating film surface protection film further having an adhesive layer on one side of the substrate.
  • Metal plates, decorative plates, resin plates, glass plates, etc. or home appliances, automobiles, electronic parts, etc. processed using them are protected on the surface to prevent scratches, dirt, etc. during transportation or storage
  • a film is affixed.
  • a coating surface protective film is generally used to protect the coating film of a vehicle, and since it is assumed that the temperature becomes high during transportation or storage, unstretched PP (polypropylene) ) Film is used.
  • unstretched PP film has low tear strength in the film winding direction (MD direction) in the film forming process, and when the attached protective film is peeled off, the film cannot be peeled off and cannot be peeled off at one time. There is a problem of doing.
  • PP generally used for the base material for coating film surface protective film there are homo PP, random PP or block PP.
  • homo PP the developing force after the adhesive processing (after forming the adhesive layer) is heavy, and it cannot be easily deployed at the time of use and the workability is impaired.
  • random PP or block PP it swells with a solvent used at the time of adhesive processing, the film curls at the time of drying, and the flatness is impaired, which affects the workability at the time of use.
  • the amount of resin elution measured by the cross fractionation method of polypropylene resin is 40 to 70% by weight of the total polypropylene resin at 0 ° C. or less, and 10 to 30% by weight of the total polypropylene resin at 0 to 70 ° C.
  • a coating film surface protective film comprising 50 to 95% by weight of a component and 5 to 50% by weight of an ⁇ -olefin component other than ethylene is disclosed. And the coating-film surface protection film of patent document 1 is supposed that it can perform the sticking operation
  • the coating surface protective film of Patent Document 1 is said to be able to efficiently perform a sticking operation and a peeling operation after use, but has a problem that curling occurs at the time of adhesive processing. In this regard, if there is curl on the coating surface protective film, there is room for improvement because it affects the work efficiency of the pasting operation. Moreover, it is calculated
  • the present invention provides a coating film surface protective film substrate in which the occurrence of curling is suppressed before and after adhesive processing, and a coating film surface protective film excellent in adhesiveness as well as good tear strength.
  • the purpose is to provide.
  • the present inventors have found that the above object can be achieved when using a coating film surface protective film substrate having a specific layer structure of three or more layers.
  • the invention has been completed.
  • this invention relates to the following base material for coating film surface protection films, and a coating film surface protection film using the same.
  • a base material for a coating surface protective film used as a coating film surface protective film after forming a pressure sensitive adhesive layer by applying a pressure sensitive adhesive to the adhesive coating planned layer (1)
  • the base material contains 50% by mass or more of polyethylene resin and consists of three or more layers.
  • the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 10 to 10% of a homopolypropylene resin.
  • the pressure-sensitive adhesive non-coating layer as the other outermost layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. %contains,
  • the said base material is a base material for coating surface protection films of said claim
  • the pressure-sensitive adhesive coating layer and the pressure-sensitive adhesive non-coating layer have the same thickness, the ratio of the random copolymerized polypropylene in the pressure-sensitive adhesive coating layer is A%, and the pressure-sensitive adhesive non-coating layer
  • the base material for coating film surface protective film of the present invention has a specific layer configuration of three or more layers, and curling is suppressed before and after the adhesive processing, and has excellent flatness.
  • Adhesive processing and adhesive processing Excellent pastability. That is, the occurrence of curling is suppressed at any point of time when the base material is formed (before the adhesive processing) and when the adhesive layer is formed (after the adhesive processing).
  • the coating surface protective film also has good tear strength and is more useful than conventional coating surface protection films.
  • Such a coating film surface protective film of the present invention is particularly useful as a coating film surface protection film used for protecting a coating film of an automobile during transportation or storage of the automobile.
  • (A) It is a layer structure schematic diagram of the one aspect
  • (B) It is a layer structure schematic diagram of the one aspect
  • it is a schematic diagram which shows that it pulls at 250 mm / min in a 90 degree direction when measuring the back surface peeling force of the sample of a coating-film surface protection film.
  • it is a schematic diagram which shows the measurement condition of the curl resistance of the base material for coating-film surface protection films, and the sample of a coating-film surface protection film.
  • Base material for coating film surface protective film The base material for coating film surface protection film of the present invention is used for coating as a coating film surface protective film after forming a pressure-sensitive adhesive layer by coating the pressure-sensitive adhesive coating layer.
  • a base material (1) The base material contains 50% by mass or more of polyethylene resin and consists of three or more layers. (2) Of the pair of outermost layers, the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 10 to 10% of a homopolypropylene resin.
  • the pressure-sensitive adhesive non-coating layer as the other outermost layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. % Content.
  • the base material for coating film surface protective film of the present invention having the above-described features has a specific layer configuration of three or more layers, and curling is suppressed before and after pressure-sensitive adhesive processing (adhesive layer application). Excellent flatness and excellent adhesion and stickability after adhesion.
  • the coating surface protective film also has good tear strength and is more useful than conventional coating surface protection films. And it is useful especially as a coating-film surface protection film used in order to protect the coating film of a motor vehicle at the time of transportation or storage of a motor vehicle.
  • the base material for a coating film surface protective film of the present invention (hereinafter also referred to as “base material”) is composed of three or more layers, and contains 50% by mass or more of polyethylene resin as the whole base material. That is, the base material is mainly composed of polyethylene resin in that the polyethylene resin occupies half or more of the mass of the resin component.
  • the content of the polyethylene resin in the whole substrate is preferably 60% by mass or more, more preferably 60 to 70% by mass.
  • one of the pair of outermost layers is a pressure-sensitive adhesive coating layer, and is a layer that provides a pressure-sensitive adhesive layer by pressure-sensitive adhesive processing.
  • the other is an adhesive non-coating layer.
  • the central layer sandwiched between the pressure-sensitive adhesive coating scheduled layer and the pressure-sensitive adhesive non-coating layer can be composed of one layer or two or more layers.
  • FIG. What is necessary is just to comprise.
  • (A) of FIG. 1 is a structure which has the inner layer 2 between the adhesive application plan layer 1 and the adhesive non-coating layer 3.
  • an adhesive layer can be included between the layers as necessary.
  • the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less and 10 to 50% by mass of a homopolypropylene resin. To do.
  • the ethylene content of the random copolymer polypropylene resin may be 5% by mass or less, preferably 3 to 5% by mass, and more preferably 3.5 to 4.5% by mass.
  • the content of the random copolymer polypropylene resin may be 50 to 90% by mass, preferably 60 to 90% by mass, and more preferably 70 to 80% by mass.
  • the content of the homopolypropylene resin may be 10 to 50% by mass, preferably 10 to 40% by mass, and more preferably 20 to 30% by mass. When the content of homopolypropylene is within this range, it is possible to suppress the occurrence of swelling due to the solvent contained in the coating liquid and curling during drying during the pressure-sensitive adhesive processing (adhesive layer formation).
  • the pressure-sensitive adhesive non-coating layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. To do.
  • the ethylene content of the random copolymer polypropylene resin may be 5% by mass or less, and the lower limit is not particularly limited as long as it exceeds 0% by mass.
  • the content of the random copolymer polypropylene resin may be 90 to 100% by mass, preferably 92 to 100% by mass, and more preferably 95 to 100% by mass.
  • the content of the homopolypropylene resin may be 0 to 10% by mass, preferably 0 to 8% by mass, and more preferably 0 to 5% by mass.
  • the content of the homopolypropylene resin By reducing the content of the homopolypropylene resin to 10% by mass or less (including 0% by mass), the content of the random copolymer polypropylene is relatively increased, so that after the adhesive processing (application of the adhesive layer) It is possible to ensure good developability (stickability) of the coating film surface protective film.
  • the resin component contained in an inner layer is not limited.
  • polyethylene alone or a mixture of polyethylene and random copolymerized polyethylene can be preferably used.
  • the random copolymer polyethylene the same ones as described above can be used.
  • the polyethylene resin is not particularly limited, and a commercially available polyethylene resin can be appropriately used.
  • polyethylene resin examples include LDPE (low density polyethylene), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE). These polyethylene resins can be used alone or in admixture of two or more. In the present invention, it is preferable to use LLDPE in terms of excellent balance between tensile strength and tear strength.
  • LDPE is a polyethylene resin (homopolyethylene) having a density in the range of 0.910 to 0.930 g / cm 3 , and preferably in the range of 0.920 to 0.930 g / cm 3 .
  • Examples of the method for producing LDPE include those produced by high-pressure radical polymerization using a radical initiator.
  • the density in this specification is the value measured on the conditions of JIS K7112: 1999 underwater substitution method (A method) and 25 degreeC.
  • the melt flow rate (MFR) of LDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. If the MFR is within this range, good moldability by the T-die method can be easily obtained.
  • the MFR in the present specification is a value measured under the conditions of JIS K7210: 1999, Method A, 190 ° C., and load 21.18N unless otherwise specified.
  • LLDPE and MDPE can be obtained by copolymerizing ethylene and ⁇ -olefin using a single-site catalyst such as Ziegler catalyst, metallocene catalyst, and density by adjusting the type and amount of ⁇ -olefin. The range can be controlled.
  • ⁇ -olefin examples include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. These ⁇ -olefins can be used alone or in combination of two or more.
  • a wide range of products with a density of LLDPE of 0.870 to 0.945 g / cm 3 is commercially available, and a range of 0.925 to 0.935 g / cm 3 is preferable.
  • the MFR of LLDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. When the MFR is within this range, it is easy to obtain a good moldability effect by the T-die method.
  • MDPE refers to LLDPE having a density of about 0.930 to 0.945 / cm 3 , and MFR is preferably about 1.0 to 4.0 g / 10 min.
  • HDPE density is preferably 0.940 ⁇ 0.960g / cm 3, more preferably 0.945 ⁇ 0.960g / cm 3.
  • the MFR of HDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. When the MFR is within this range, it is easy to obtain a good moldability effect by the T-die method.
  • the content of polyethylene resin in the entire substrate is 50% by mass or more, depending on the physical properties of the coating film surface protective film of the final product. Adjust the blending ratio as appropriate.
  • each layer constituting the base material of the present invention is not limited, but in the case where it is composed of three layers of a pressure-sensitive adhesive coating scheduled layer, an inner layer and a pressure-sensitive adhesive non-coated layer, 1: 2 to 8 in order.
  • the thickness ratio is preferably within a range of 1: 1, and more preferably within a range of 1: 4 to 6: 1.
  • the thickness of the adhesive coating scheduled layer is preferably 3 to 10 ⁇ m, more preferably 4 to 7 ⁇ m.
  • the thickness of the inner layer is preferably 6 to 80 ⁇ m, more preferably 16 to 42 ⁇ m.
  • the thickness of the adhesive non-coating scheduled layer is preferably 3 to 10 ⁇ m, more preferably 4 to 7 ⁇ m.
  • the substrate of the present invention is effective in securing a pressure-sensitive adhesive coating layer that has the effect of suppressing swelling during pressure-sensitive adhesive processing and curling during drying, and good developability (adhesiveness) after pressure-sensitive adhesive processing.
  • a pressure-sensitive adhesive coating layer that has the effect of suppressing swelling during pressure-sensitive adhesive processing and curling during drying, and good developability (adhesiveness) after pressure-sensitive adhesive processing.
  • the ratio of the predetermined random copolymer polypropylene in the pressure-sensitive adhesive coating layer is A%. If the ratio of the predetermined random copolymer polypropylene in the non-adhesive layer is B% and the absolute value of AB is 50 or less, the occurrence of curling during the formation of the substrate can be easily suppressed.
  • the absolute value of A (%)-B (%) is preferably 50 or less, more preferably 25 or less, and most preferably 0.
  • a conventionally known method such as an inflation method or a T-die is preferably used, but after preparing each layer separately, it may be formed by dry lamination using an adhesive.
  • Coating surface protection film The substrate for coating surface protection film of the present invention forms an adhesive layer by coating and drying a coating liquid for forming an adhesive layer on the adhesive coating scheduled layer. It can be set as a coating surface protection film.
  • the coating liquid for forming the pressure-sensitive adhesive layer can be selected from various known materials.
  • natural rubber styrene butadiene rubber (SBR); polyisoprene; butyl rubber; polyisoprene and other rubber-based polymers are solvents.
  • SBR styrene butadiene rubber
  • polyisoprene butyl rubber
  • polyisoprene and other rubber-based polymers are solvents.
  • the thickness of the pressure-sensitive adhesive layer is not limited and can be appropriately set depending on the type of the coating surface protective film, but is preferably 3 to 30 ⁇ m, more preferably 5 to 20 ⁇ m.
  • Examples 1 to 4 and Comparative Examples 1 to 8 Depending on the conditions such as the raw material composition, the layer thickness ratio, and the thickness of the entire substrate shown in Table 1, the coating film surface protective film substrates of Examples 1 to 4 and Comparative Examples 1 to 8 (adhesive coating layer / A three-layer film consisting of an inner layer / non-adhesive layer: “/” indicates an interlayer). Thereby, the base material for coating-film surface protection films was obtained.
  • Test example 1 About the base material for coating-film surface protection films produced above, the tear strength, the back surface peeling force, the degree of curling of the base material, and the degree of curling after adhesive processing were examined. The method and evaluation criteria for each test are shown below, and the results of each test are shown in Table 1.
  • a release agent was thinly applied to the non-adhesive layer of the base material (mold release treatment), and a polyisobutylene-based adhesive was applied to the adhesive application planned layer to form an adhesive layer.
  • the coating surface protective film on which the pressure-sensitive adhesive layer was formed was wound around a 3-inch paper tube and slit into a tape having a width of 25 mm.
  • the tape sample was set in a tensile tester used in JIS K7127, and the force when pulling in the 90 ° direction at a pulling speed of 250 mm / min as shown in FIG. 2 was measured.
  • the gap between the sample 7 and the glass plate 6 was measured and evaluated as follows. ⁇ : The gap is less than 5 mm ⁇ : The gap is 5 mm or more
  • a release agent is thinly applied to the non-adhesive layer of the base material (release treatment), and then a polyisobutylene-based adhesive is applied to the planned adhesive coating layer at a rate of 10 g / m 2. A layer was formed. Then, it cut into 25 mm long x 100 mm wide to make a sample.
  • the glass plate 6 was set vertically on the horizontal floor surface 5, and the sample 7 was fixed using a sample fixing tape so that the glass plate 6 and the release treatment surface were in contact with each other.
  • the gap between the sample 7 and the glass plate 6 was measured and evaluated as follows. ⁇ : The gap is less than 5 mm ⁇ : The gap is 5 mm or more
  • Example 1 the coating film surface protective film substrate and the coating film surface protective film of Examples 1 to 4 having a specific layer structure of three or more predetermined layers according to the present invention (collectively referred to as “sample”)
  • the curling is suppressed before and after the adhesive processing, and it has excellent tearability as well as good tear strength.
  • the samples of Comparative Examples 1 to 8 that do not have a specific layer structure of three or more predetermined layers according to the present invention were carried out in any of the occurrence of curl, tear strength, or adhesiveness before and after the adhesive processing. Performance is inferior to the example sample.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention is a base material for a coating film surface-protecting film, which is used as a coating film surface-protecting film after forming a pressure-sensitive adhesive layer on a layer to be coated with a pressure-sensitive adhesive, wherein: (1) the base material contains 50 mass% or more of a polyethylene resin and comprises three or more layers; (2) of the pair of outermost layers, the layer to be coated with a pressure-sensitive adhesive contains 50-90 mass% of a random polypropylene copolymer resin having an ethylene content of 5 mass% or less and 10-50 mass% of a homopolypropylene resin; and (3) a pressure-sensitive adhesive-uncoated layer, which is the other outermost layer, contains 90-100 mass% of a random polypropylene copolymer resin having an ethylene content of 5 mass% or less and 0-10 mass% of a homopolypropylene resin.

Description

塗膜表面保護フィルム用基材及びそれを用いた塗膜表面保護フィルムBase material for coating surface protection film and coating surface protection film using the same
　本発明は、塗膜表面保護フィルム用基材、及び当該基材の片面に更に粘着材層を有する塗膜表面保護フィルムに関する。 The present invention relates to a coating film surface protective film substrate and a coating film surface protection film further having an adhesive layer on one side of the substrate.
　金属板、化粧板、樹脂板、ガラス板等又はそれらを用いて加工される家電製品、自動車、電子部品等には、輸送時又は保管時に傷、汚れ等の発生を防止するために表面に保護フィルムが貼付される。 Metal plates, decorative plates, resin plates, glass plates, etc. or home appliances, automobiles, electronic parts, etc. processed using them are protected on the surface to prevent scratches, dirt, etc. during transportation or storage A film is affixed.
　特に、自動車の輸送時又は保管時には、一般に自動車の塗膜を保護するために塗膜表面保護フィルムが用いられ、輸送時や保管時に高温になることも想定されるために、無延伸ＰＰ（ポリプロピレン）フィルムが用いられている。しかしながら、無延伸ＰＰフィルムは製膜過程におけるフィルム巻取り方向（ＭＤ方向）の引裂強度が弱く、貼付した保護フィルムを剥がす際にフィルムが裂けて一回で剥がすことができず、作業効率が低下するという問題がある。 In particular, when a vehicle is transported or stored, a coating surface protective film is generally used to protect the coating film of a vehicle, and since it is assumed that the temperature becomes high during transportation or storage, unstretched PP (polypropylene) ) Film is used. However, unstretched PP film has low tear strength in the film winding direction (MD direction) in the film forming process, and when the attached protective film is peeled off, the film cannot be peeled off and cannot be peeled off at one time. There is a problem of doing.
　他方、塗膜表面保護フィルム用基材（粘着剤層を設ける前の基材）に一般に使用されるＰＰとしてはホモＰＰ、ランダムＰＰ又はブロックＰＰがあるが、これらのＰＰには次のような課題がある。つまり、ホモＰＰを用いた場合には、粘着加工後（粘着剤層を形成後）の展開力が重く、使用時に簡単に展開できずに作業性を損ねる。また、ランダムＰＰ又はブロックＰＰを用いた場合には、粘着加工時に使用される溶剤により膨潤し、乾燥時にフィルムがカールして平面性が損なわれて使用時の作業性に影響がある。 On the other hand, as PP generally used for the base material for coating film surface protective film (base material before providing an adhesive layer), there are homo PP, random PP or block PP. There are challenges. That is, when homo PP is used, the developing force after the adhesive processing (after forming the adhesive layer) is heavy, and it cannot be easily deployed at the time of use and the workability is impaired. In addition, when random PP or block PP is used, it swells with a solvent used at the time of adhesive processing, the film curls at the time of drying, and the flatness is impaired, which affects the workability at the time of use.
　公知の塗膜表面保護フィルムとしては、例えば、特許文献１に「ポリオレフィン系樹脂の三層積層フィルムよりなる塗膜表面保護フィルムであって、三層積層フィルムの両外層が、メルトフローレートが０．１～３ｇ／１０分で密度が０．９３０～０．９４５ｇ／ｃｍ３のポリエチレン系樹脂からなり、中間層が、メルトフローレート０．１～３ｇ／１０分のポリプロピレン系樹脂からなり、該ポリプロピレン系樹脂のクロス分別法によって測定される樹脂溶出量が、０℃以下で全ポリプロピレン系樹脂量の４０～７０重量％、０℃超７０℃以下で全ポリプロピレン系樹脂量の１０～３０重量％、７０℃超で全ポリプロピレン系樹脂量の２０～４０重量％であり、かつ前記ポリエチレン樹脂及びポリプロピレン系樹脂の合計成分が、エチレン成分５０～９５重量％及びエチレン以外のα－オレフィン成分５～５０重量％よりなることを特徴とする塗膜表面保護フィルム。」が開示されている。そして、特許文献１の塗膜表面保護フィルムは、耐熱性等必要な品質を維持しつつ、貼付作業及び用済み後の引き剥がし作業を効率よく行うことができるとされている。 As a known coating surface protective film, for example, in Patent Document 1, “a coating surface protecting film made of a polyolefin resin three-layer laminated film, in which both outer layers of the three-layer laminated film have a melt flow rate of 0. A polyethylene resin having a density of 0.930 to 0.945 g / cm 3 at 1 to 3 g / 10 minutes, and an intermediate layer made of a polypropylene resin having a melt flow rate of 0.1 to 3 g / 10 minutes, The amount of resin elution measured by the cross fractionation method of polypropylene resin is 40 to 70% by weight of the total polypropylene resin at 0 ° C. or less, and 10 to 30% by weight of the total polypropylene resin at 0 to 70 ° C. or less. , More than 70 ° C. and 20 to 40% by weight of the total amount of polypropylene resin, and the total component of the polyethylene resin and polypropylene resin is ethylene A coating film surface protective film comprising 50 to 95% by weight of a component and 5 to 50% by weight of an α-olefin component other than ethylene is disclosed. And the coating-film surface protection film of patent document 1 is supposed that it can perform the sticking operation | work and the peeling work after used efficiently, maintaining required quality, such as heat resistance.
特開２００１－１２１６６２号公報Japanese Patent Laid-Open No. 2001-121661
　特許文献１の塗膜表面保護フィルムは、貼付作業及び用済み後の引き剥がし作業を効率よく行うことができるとされているが、粘着加工時にカールが発生するという課題がある。この点、塗膜表面保護フィルムにカールがあると、貼付作業の作業効率に影響があるため改善の余地がある。また、粘着加工時の作業効率を高める点では、粘着加工前の塗膜表面保護フィルム基材が良好な平面性を有することも求められる。 The coating surface protective film of Patent Document 1 is said to be able to efficiently perform a sticking operation and a peeling operation after use, but has a problem that curling occurs at the time of adhesive processing. In this regard, if there is curl on the coating surface protective film, there is room for improvement because it affects the work efficiency of the pasting operation. Moreover, it is calculated | required that the coating-film surface protection film base material before adhesion processing has favorable planarity at the point which improves the working efficiency at the time of adhesion processing.
　本発明は、従来技術の問題に鑑み、粘着加工の前後においてカールの発生が抑制されている塗膜表面保護フィルム基材、並びに、良好な引裂き強度とともに貼付性に優れた塗膜表面保護フィルムを提供することを目的とする。 In view of the problems of the prior art, the present invention provides a coating film surface protective film substrate in which the occurrence of curling is suppressed before and after adhesive processing, and a coating film surface protective film excellent in adhesiveness as well as good tear strength. The purpose is to provide.
　本発明者らは上記目的を達成すべく鋭意研究を重ねた結果、三層以上の特定の層構成からなる塗膜表面保護フィルム用基材を用いる場合には上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved when using a coating film surface protective film substrate having a specific layer structure of three or more layers. The invention has been completed.
　即ち、本発明は下記の塗膜表面保護フィルム用基材及びそれを用いた塗膜表面保護フィルムに関する。
１．粘着剤塗工予定層に粘着剤を塗工して粘着剤層を形成後に塗膜表面保護フィルムとして用いる塗膜表面保護フィルム用基材であって、
（１）前記基材は、ポリエチレン樹脂を５０質量％以上含有し、三層以上からなり、
（２）一対の最外層のうち、前記粘着剤塗工予定層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を５０～９０質量％含有し、且つ、ホモポリプロピレン樹脂を１０～５０質量％含有し、
（３）他方の最外層である粘着剤非塗工層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を９０～１００質量％含有し、且つ、ホモポリプロピレン樹脂を０～１０質量％含有する、
ことを特徴とする塗膜表面保護フィルム用基材。
２．前記基材は、前記粘着剤塗工予定層、内層及び前記粘着剤非塗工層の三層からなる、上記項１に記載の塗装表面保護フィルム用基材。
３．前記粘着剤塗工予定層及び前記粘着剤非塗工層の厚さが同じであり、前記粘着剤塗工予定層中の前記ランダム共重合ポリプロピレンの比率をＡ％とし、前記粘着剤非塗工層中の前記ランダム共重合ポリプロピレンの比率をＢ％とし、Ａ－Ｂの絶対値が５０以下である、請求項１又は２に記載の塗装表面保護フィルム用基材。
４．上記項１～３のいずれかに記載の塗膜表面保護フィルム用基材の前記粘着剤塗工予定層に接して粘着剤層を有する塗膜表面保護フィルム。 That is, this invention relates to the following base material for coating film surface protection films, and a coating film surface protection film using the same.
1. A base material for a coating surface protective film used as a coating film surface protective film after forming a pressure sensitive adhesive layer by applying a pressure sensitive adhesive to the adhesive coating planned layer,
(1) The base material contains 50% by mass or more of polyethylene resin and consists of three or more layers.
(2) Of the pair of outermost layers, the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 10 to 10% of a homopolypropylene resin. Containing 50% by weight,
(3) The pressure-sensitive adhesive non-coating layer as the other outermost layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. %contains,
The base material for coating-film surface protection films characterized by this.
2. The said base material is a base material for coating surface protection films of said claim | item 1 which consists of three layers of the said adhesive coating plan layer, an inner layer, and the said adhesive non-coating layer.
3. The pressure-sensitive adhesive coating layer and the pressure-sensitive adhesive non-coating layer have the same thickness, the ratio of the random copolymerized polypropylene in the pressure-sensitive adhesive coating layer is A%, and the pressure-sensitive adhesive non-coating layer The coated surface protective film substrate according to claim 1 or 2, wherein the ratio of the random copolymerized polypropylene in the layer is B%, and the absolute value of AB is 50 or less.
4). 4. A coating film surface protective film having a pressure-sensitive adhesive layer in contact with the pressure-sensitive adhesive coating scheduled layer of the substrate for a coating film surface protective film according to any one of items 1 to 3.
　本発明の塗膜表面保護フィルム用基材は、三層以上の特定の層構成を有することにより、粘着加工前後においてカールの発生が抑制されていて平面性に優れており、粘着加工及び粘着加工後の貼付性に優れている。つまり、基材形成時（粘着加工前）及び粘着剤層の形成時（粘着加工後）のいずれの時点でもカールの発生が抑制されている。また、塗膜表面保護フィルムは、良好な引裂き強度も有しており、従来品の塗膜表面保護フィルムに比して有用性が高い。このような本発明の塗膜表面保護フィルムは、特に自動車の輸送時又は保管時に自動車の塗膜を保護するために用いる塗膜表面保護フィルムとして有用である。 The base material for coating film surface protective film of the present invention has a specific layer configuration of three or more layers, and curling is suppressed before and after the adhesive processing, and has excellent flatness. Adhesive processing and adhesive processing Excellent pastability. That is, the occurrence of curling is suppressed at any point of time when the base material is formed (before the adhesive processing) and when the adhesive layer is formed (after the adhesive processing). The coating surface protective film also has good tear strength and is more useful than conventional coating surface protection films. Such a coating film surface protective film of the present invention is particularly useful as a coating film surface protection film used for protecting a coating film of an automobile during transportation or storage of the automobile.
（ａ）本発明の塗膜表面保護フィルム用基材の一態様の層構成模式図である。（ｂ）本発明の塗膜表面保護フィルムの一態様の層構成模式図である。(A) It is a layer structure schematic diagram of the one aspect | mode of the base material for coating-film surface protection films of this invention. (B) It is a layer structure schematic diagram of the one aspect | mode of the coating-film surface protection film of this invention. 試験例１において、塗膜表面保護フィルムのサンプルの背面剥離力を測定する際に９０°方向に２５０ｍｍ／ｍｉｎで引っ張ることを示す模式図である。In Experiment 1, it is a schematic diagram which shows that it pulls at 250 mm / min in a 90 degree direction when measuring the back surface peeling force of the sample of a coating-film surface protection film. 試験例１において、塗膜表面保護フィルム用基材、及び塗膜表面保護フィルムのサンプルの耐カール性の測定状況を示す模式図である。In Experiment 1, it is a schematic diagram which shows the measurement condition of the curl resistance of the base material for coating-film surface protection films, and the sample of a coating-film surface protection film.
　塗膜表面保護フィルム用基材
　本発明の塗膜表面保護フィルム用基材は、粘着剤塗工予定層に粘着剤を塗工して粘着剤層を形成後に塗膜表面保護フィルムとして用いるための基材であって、
（１）前記基材は、ポリエチレン樹脂を５０質量％以上含有し、三層以上からなり、
（２）一対の最外層のうち、前記粘着剤塗工予定層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を５０～９０質量％含有し、且つ、ホモポリプロピレン樹脂を１０～５０質量％含有し、
（３）他方の最外層である粘着剤非塗工層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を９０～１００質量％含有し、且つ、ホモポリプロピレン樹脂を０～１０質量％含有する、ことを特徴とする。 Base material for coating film surface protective film The base material for coating film surface protection film of the present invention is used for coating as a coating film surface protective film after forming a pressure-sensitive adhesive layer by coating the pressure-sensitive adhesive coating layer. A base material,
(1) The base material contains 50% by mass or more of polyethylene resin and consists of three or more layers.
(2) Of the pair of outermost layers, the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 10 to 10% of a homopolypropylene resin. Containing 50% by weight,
(3) The pressure-sensitive adhesive non-coating layer as the other outermost layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. % Content.
　上記特徴を有する本発明の塗膜表面保護フィルム用基材は、三層以上の特定の層構成を有することにより、粘着加工（粘着剤層の付与）の前後においてカールの発生が抑制されていて平面性に優れており、粘着加工及び粘着加工後の貼付性に優れている。また、塗膜表面保護フィルムは、良好な引裂き強度も有しており、従来品の塗膜表面保護フィルムに比して有用性が高い。そして、特に自動車の輸送時又は保管時に自動車の塗膜を保護するために用いる塗膜表面保護フィルムとして有用である。 The base material for coating film surface protective film of the present invention having the above-described features has a specific layer configuration of three or more layers, and curling is suppressed before and after pressure-sensitive adhesive processing (adhesive layer application). Excellent flatness and excellent adhesion and stickability after adhesion. The coating surface protective film also has good tear strength and is more useful than conventional coating surface protection films. And it is useful especially as a coating-film surface protection film used in order to protect the coating film of a motor vehicle at the time of transportation or storage of a motor vehicle.
　本発明の塗膜表面保護フィルム用基材（以下「基材」ともいう）は、三層以上からなり、基材全体としてポリエチレン樹脂を５０質量％以上含有する。つまり、ポリエチレン樹脂が樹脂成分の質量の半分以上を占める点で、基材はポリエチレン樹脂を主成分とする。基材全体におけるポリエチレン樹脂の含有量は６０質量％以上が好ましく、６０～７０質量％がより好ましい。基材全体としてポリエチレン樹脂を５０質量％以上含有することにより、良好な引裂き強度を有する塗膜表面保護フィルムとすることができる。 The base material for a coating film surface protective film of the present invention (hereinafter also referred to as “base material”) is composed of three or more layers, and contains 50% by mass or more of polyethylene resin as the whole base material. That is, the base material is mainly composed of polyethylene resin in that the polyethylene resin occupies half or more of the mass of the resin component. The content of the polyethylene resin in the whole substrate is preferably 60% by mass or more, more preferably 60 to 70% by mass. By containing 50% by mass or more of the polyethylene resin as the whole base material, it is possible to obtain a coating film surface protective film having good tear strength.
　本発明の基材は、一対の最外層のうち一方が粘着剤塗工予定層であり、粘着加工により粘着剤層を付与する層である。また、他方は粘着剤非塗工層である。粘着剤塗工予定層と粘着剤非塗工層とに挟まれた中心層は、一層又は二層以上で構成できるが、通常は図１の（ａ）に例示されるように一層の内層により構成すればよい。図１の（ａ）は、粘着剤塗工予定層１と粘着剤非塗工層３との間に内層２を有する構成である。なお、各層の間に必要に応じて接着剤層を含めることができる。 In the base material of the present invention, one of the pair of outermost layers is a pressure-sensitive adhesive coating layer, and is a layer that provides a pressure-sensitive adhesive layer by pressure-sensitive adhesive processing. The other is an adhesive non-coating layer. The central layer sandwiched between the pressure-sensitive adhesive coating scheduled layer and the pressure-sensitive adhesive non-coating layer can be composed of one layer or two or more layers. Usually, as shown in FIG. What is necessary is just to comprise. (A) of FIG. 1 is a structure which has the inner layer 2 between the adhesive application plan layer 1 and the adhesive non-coating layer 3. FIG. In addition, an adhesive layer can be included between the layers as necessary.
　本発明の基材は、粘着剤塗工予定層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を５０～９０質量％含有し、且つ、ホモポリプロピレン樹脂を１０～５０質量％含有する。 In the base material of the present invention, the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less and 10 to 50% by mass of a homopolypropylene resin. To do.
　ランダム共重合ポリプロピレン樹脂のエチレン含有量は５質量％以下であればよいが、３～５質量％が好ましく、３．５～４．５質量％がより好ましい。ランダム共重合ポリプロピレン樹脂の含有量は５０～９０質量％であればよいが、６０～９０質量％が好ましく、７０～８０質量％がより好ましい。また、ホモポリプロピレン樹脂の含有量は１０～５０質量％であればよいが、１０～４０質量％が好ましく、２０～３０質量％がより好ましい。ホモポリプロピレンの含有量がかかる範囲内であることにより、粘着加工（粘着剤層の形成）の際に塗工液に含まれる溶剤による膨潤及び乾燥時のカールの発生を抑制することができる。 The ethylene content of the random copolymer polypropylene resin may be 5% by mass or less, preferably 3 to 5% by mass, and more preferably 3.5 to 4.5% by mass. The content of the random copolymer polypropylene resin may be 50 to 90% by mass, preferably 60 to 90% by mass, and more preferably 70 to 80% by mass. Further, the content of the homopolypropylene resin may be 10 to 50% by mass, preferably 10 to 40% by mass, and more preferably 20 to 30% by mass. When the content of homopolypropylene is within this range, it is possible to suppress the occurrence of swelling due to the solvent contained in the coating liquid and curling during drying during the pressure-sensitive adhesive processing (adhesive layer formation).
　本発明の基材は、粘着剤非塗工層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を９０～１００質量％含有し、且つ、ホモポリプロピレン樹脂を０～１０質量％含有する。 In the base material of the present invention, the pressure-sensitive adhesive non-coating layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. To do.
　ランダム共重合ポリプロピレン樹脂のエチレン含有量は５質量％以下であればよく、下限値は０質量％超過であれば特に限定されない。ランダム共重合ポリプロピレン樹脂の含有量は９０～１００質量％であればよいが、９２～１００質量％が好ましく、９５～１００質量％がより好ましい。また、ホモポリプロピレン樹脂の含有量は０～１０質量％であればよいが、０～８質量％が好ましく、０～５質量％がより好ましい。ホモポリプロピレン樹脂の含有量を１０質量％以下（０質量％を含む）に低減することにより、相対的にランダム共重合ポリプロピレンの含有量が多くなることにより、粘着加工（粘着剤層の付与）後の塗膜表面保護フィルムの良好な展開性（貼付性）を確保することができる。 The ethylene content of the random copolymer polypropylene resin may be 5% by mass or less, and the lower limit is not particularly limited as long as it exceeds 0% by mass. The content of the random copolymer polypropylene resin may be 90 to 100% by mass, preferably 92 to 100% by mass, and more preferably 95 to 100% by mass. The content of the homopolypropylene resin may be 0 to 10% by mass, preferably 0 to 8% by mass, and more preferably 0 to 5% by mass. By reducing the content of the homopolypropylene resin to 10% by mass or less (including 0% by mass), the content of the random copolymer polypropylene is relatively increased, so that after the adhesive processing (application of the adhesive layer) It is possible to ensure good developability (stickability) of the coating film surface protective film.
　前記中心層については、図１（ａ）の通り内層を一層有する場合について説明すると、基材全体としてポリエチレン樹脂を５０質量％以上含有する条件を満たす限り、内層に含まれる樹脂成分は限定的ではないが、ポリエチレン単独又はポリエチレンとランダム共重合ポリエチレンとの混合物を好適に用いることができる。ここで、ランダム共重合ポリエチレンとしては、前述したものと同じものが使用できる。 About the said center layer, when explaining the case where it has one inner layer as Fig.1 (a), as long as the conditions which contain the polyethylene resin 50 mass% or more as a whole base material are satisfy | filled, the resin component contained in an inner layer is not limited. However, polyethylene alone or a mixture of polyethylene and random copolymerized polyethylene can be preferably used. Here, as the random copolymer polyethylene, the same ones as described above can be used.
　ポリエチレン樹脂としては、特に限定されず、市販されているポリエチレン樹脂を適宜用いることができる。 The polyethylene resin is not particularly limited, and a commercially available polyethylene resin can be appropriately used.
　ポリエチレン樹脂としては、例えば、ＬＤＰＥ（低密度ポリエチレン）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等を用いることができる。これらのポリエチレン樹脂は、単独又は２種以上を混合して用いることができるが、本発明では引張強度と引裂強度のバランスに優れている点でＬＬＤＰＥを用いることが好ましい。 Examples of the polyethylene resin include LDPE (low density polyethylene), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE). These polyethylene resins can be used alone or in admixture of two or more. In the present invention, it is preferable to use LLDPE in terms of excellent balance between tensile strength and tear strength.
　ＬＤＰＥは、密度が０．９１０～０．９３０ｇ／ｃｍ３の範囲のポリエチレン系樹脂（ホモポリエチレン）であり、その中でも０．９２０～０．９３０ｇ／ｃｍ３の範囲が好ましい。ＬＤＰＥの製造方法としては例えば、ラジカル開始剤を用いて高圧ラジカル重合により製造されるものが挙げられる。なお、本明細書における密度は、ＪＩＳ　Ｋ７１１２：１９９９　水中置換法（Ａ法），２５℃の条件で測定した値である。 LDPE is a polyethylene resin (homopolyethylene) having a density in the range of 0.910 to 0.930 g / cm 3 , and preferably in the range of 0.920 to 0.930 g / cm 3 . Examples of the method for producing LDPE include those produced by high-pressure radical polymerization using a radical initiator. In addition, the density in this specification is the value measured on the conditions of JIS K7112: 1999 underwater substitution method (A method) and 25 degreeC.
　ＬＤＰＥのメルトフローレート（ＭＦＲ）は、０．５～６．０ｇ／１０分が好ましく、１．０～４．０ｇ／１０分がより好ましい。ＭＦＲがこの範囲内であれば、Ｔダイ法での良好な成形性が得られ易い。なお、本明細書におけるＭＦＲは、別途測定条件を規定しない限り、ＪＩＳ　Ｋ７２１０：１９９９，Ａ法，１９０℃，荷重２１．１８Ｎの条件で測定した値である。 The melt flow rate (MFR) of LDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. If the MFR is within this range, good moldability by the T-die method can be easily obtained. The MFR in the present specification is a value measured under the conditions of JIS K7210: 1999, Method A, 190 ° C., and load 21.18N unless otherwise specified.
　ＬＬＤＰＥ及びＭＤＰＥには明確な区別はないが、密度によって便宜上区別することがある。ＬＬＤＰＥ及びＭＤＰＥは、Ｚｉｅｇｌｅｒ触媒、メタロセン触媒等のシングルサイト系触媒を用いて、エチレンとα－オレフィンとを共重合することにより得ることができ、α－オレフィンの種類や量を調整することによって密度範囲を制御することができる。 Ｌ There is no clear distinction between LLDPE and MDPE, but there are cases where it is distinguished for convenience depending on density. LLDPE and MDPE can be obtained by copolymerizing ethylene and α-olefin using a single-site catalyst such as Ziegler catalyst, metallocene catalyst, and density by adjusting the type and amount of α-olefin. The range can be controlled.
　上記α－オレフィンとしては、例えば、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテン、１－ヘプテン、１－オクテン等が挙げられる。これらのα－オレフィンは、単独又は２種以上を併用することができる。 Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like. These α-olefins can be used alone or in combination of two or more.
　ＬＬＤＰＥの密度は、０．８７０～０．９４５ｇ／ｃｍ３という広範囲の製品が市販されており、その中でも０．９２５～０．９３５ｇ／ｃｍ３の範囲が好ましい。ＬＬＤＰＥのＭＦＲは、０．５～６．０ｇ／１０分が好ましく、１．０～４．０ｇ／１０分がより好ましい。ＭＦＲがこの範囲内であれば、Ｔダイ法での良好な成形性の効果が得られ易い。 A wide range of products with a density of LLDPE of 0.870 to 0.945 g / cm 3 is commercially available, and a range of 0.925 to 0.935 g / cm 3 is preferable. The MFR of LLDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. When the MFR is within this range, it is easy to obtain a good moldability effect by the T-die method.
　ＭＤＰＥは、ＬＬＤＰＥの中で特に密度が０．９３０～０．９４５／ｃｍ３程度のものを指し、ＭＦＲとしては１．０～４．０ｇ／１０分程度が好ましい。 MDPE refers to LLDPE having a density of about 0.930 to 0.945 / cm 3 , and MFR is preferably about 1.0 to 4.0 g / 10 min.
　ＨＤＰＥとしては特に限定されないが、密度は０．９４０～０．９６０ｇ／ｃｍ３が好ましく、０．９４５～０．９６０ｇ／ｃｍ３がより好ましい。また、ＨＤＰＥのＭＦＲは、０．５～６．０ｇ／１０分が好ましく、１．０～４．０ｇ／１０分がより好ましい。ＭＦＲがこの範囲内であれば、Ｔダイ法での良好な成形性の効果が得られ易い。 Is not particularly limited as HDPE, density is preferably 0.940 ~ 0.960g / cm 3, more preferably 0.945 ~ 0.960g / cm 3. The MFR of HDPE is preferably 0.5 to 6.0 g / 10 minutes, and more preferably 1.0 to 4.0 g / 10 minutes. When the MFR is within this range, it is easy to obtain a good moldability effect by the T-die method.
　ポリエチレンとランダム共重合ポリエチレンとの混合物を用いる場合には、基材全体中のポリエチレン樹脂の含有量を５０質量％以上とすることを前提とし、最終製品の塗膜表面保護フィルムの物性等に応じて適宜配合割合を調整する。 When using a mixture of polyethylene and random copolymerized polyethylene, it is assumed that the content of polyethylene resin in the entire substrate is 50% by mass or more, depending on the physical properties of the coating film surface protective film of the final product. Adjust the blending ratio as appropriate.
　本発明の基材を構成する各層の厚みは限定的ではないが、粘着剤塗工予定層、内層及び粘着剤非塗工層の三層から構成される場合には、順に１：２～８：１の厚み比の範囲内であることが好ましく、１：４～６：１の厚み比の範囲がより好ましい。 The thickness of each layer constituting the base material of the present invention is not limited, but in the case where it is composed of three layers of a pressure-sensitive adhesive coating scheduled layer, an inner layer and a pressure-sensitive adhesive non-coated layer, 1: 2 to 8 in order. The thickness ratio is preferably within a range of 1: 1, and more preferably within a range of 1: 4 to 6: 1.
　具体的には、粘着剤塗工予定層の厚みは、３～１０μｍが好ましく、４～７μｍがより好ましい。内層の厚みは、６～８０μｍが好ましく、１６～４２μｍがより好ましい。粘着剤非塗工予定層の厚みは、３～１０μｍが好ましく、４～７μｍがより好ましい。 Specifically, the thickness of the adhesive coating scheduled layer is preferably 3 to 10 μm, more preferably 4 to 7 μm. The thickness of the inner layer is preferably 6 to 80 μm, more preferably 16 to 42 μm. The thickness of the adhesive non-coating scheduled layer is preferably 3 to 10 μm, more preferably 4 to 7 μm.
　本発明の基材は、粘着加工時の膨潤及び乾燥時のカールの発生を抑制する効果がある粘着剤塗工予定層と、粘着加工後の良好な展開性（貼付性）の確保に効果がある粘着剤非塗工層との間に前述の内層が含まれることにより、一対の最外層の熱的性質の違いを緩和し、基材形成中、及び基材に対する粘着加工後のカールの発生を抑制することができる。 The substrate of the present invention is effective in securing a pressure-sensitive adhesive coating layer that has the effect of suppressing swelling during pressure-sensitive adhesive processing and curling during drying, and good developability (adhesiveness) after pressure-sensitive adhesive processing. By including the above-mentioned inner layer between a certain adhesive non-coating layer, the difference in the thermal properties of the pair of outermost layers is alleviated, and curling occurs during base material formation and after adhesive processing to the base material Can be suppressed.
　本発明の基材は、特に粘着剤塗工予定層及び粘着剤非塗工層の厚さが同じである場合、粘着剤塗工予定層中の所定のランダム共重合ポリプロピレンの比率をＡ％とし、粘着剤非塗工層中の所定のランダム共重合ポリプロピレンの比率をＢ％とし、Ａ－Ｂの絶対値が５０以下であれば基材形成中のカールの発生を抑制し易い。Ａ（％）－Ｂ（％）の絶対値は５０以下が好ましいが、２５以下がより好ましく、０が最も好ましい。 In the base material of the present invention, in particular, when the thickness of the pressure-sensitive adhesive coating layer and the pressure-sensitive adhesive non-coating layer are the same, the ratio of the predetermined random copolymer polypropylene in the pressure-sensitive adhesive coating layer is A%. If the ratio of the predetermined random copolymer polypropylene in the non-adhesive layer is B% and the absolute value of AB is 50 or less, the occurrence of curling during the formation of the substrate can be easily suppressed. The absolute value of A (%)-B (%) is preferably 50 or less, more preferably 25 or less, and most preferably 0.
　本発明の基材を形成する際は、インフレーション法、Ｔダイ等の従来公知の方法が好適に用いられるが、各層を別途用意した後、接着剤を用いたドライラミネートにより形成してもよい。 When forming the base material of the present invention, a conventionally known method such as an inflation method or a T-die is preferably used, but after preparing each layer separately, it may be formed by dry lamination using an adhesive.
　塗膜表面保護フィルム
　本発明の塗膜表面保護フィルム用基材は、粘着剤塗工予定層に粘着剤層を形成するための塗工液を塗工及び乾燥させることにより粘着剤層を形成し、塗膜表面保護フィルムとすることができる。 Coating surface protection film The substrate for coating surface protection film of the present invention forms an adhesive layer by coating and drying a coating liquid for forming an adhesive layer on the adhesive coating scheduled layer. It can be set as a coating surface protection film.
　粘着剤層を形成するための塗工液は、公知の各種材料より選択可能であり、例えば、天然ゴム；スチレンブタジエンゴム（ＳＢＲ）；ポリイソプレン；ブチルゴム類；ポリイソプレン等のゴム系ポリマーに溶剤を添加することにより調製できる。 The coating liquid for forming the pressure-sensitive adhesive layer can be selected from various known materials. For example, natural rubber; styrene butadiene rubber (SBR); polyisoprene; butyl rubber; polyisoprene and other rubber-based polymers are solvents. Can be prepared.
　粘着剤層の厚みは限定されず、塗膜表面保護フィルムの種類により適宜設定できるが、３～３０μｍが好ましく、５～２０μｍがより好ましい。 The thickness of the pressure-sensitive adhesive layer is not limited and can be appropriately set depending on the type of the coating surface protective film, but is preferably 3 to 30 μm, more preferably 5 to 20 μm.
　以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
　実施例１～４及び比較例１～８
　表１に記載の原料組成、層厚比、基材全体の厚み等の条件により、実施例１～４及び比較例１～８の塗膜表面保護フィルム用基材（粘着剤塗工予定層／内層／粘着剤非塗工層からなる三層フィルム：「／」は層間を示す）を作製した。これにより、塗膜表面保護フィルム用基材を得た。 Examples 1 to 4 and Comparative Examples 1 to 8
Depending on the conditions such as the raw material composition, the layer thickness ratio, and the thickness of the entire substrate shown in Table 1, the coating film surface protective film substrates of Examples 1 to 4 and Comparative Examples 1 to 8 (adhesive coating layer / A three-layer film consisting of an inner layer / non-adhesive layer: “/” indicates an interlayer). Thereby, the base material for coating-film surface protection films was obtained.
　試験例１
　上記で作製した塗膜表面保護フィルム用基材について、引裂強度、背面剥離力、基材のカールの程度、及び粘着加工後のカールの程度について調べた。各試験の方法及び評価基準を下記に示し、各試験の結果を表１に示す。 Test example 1
About the base material for coating-film surface protection films produced above, the tear strength, the back surface peeling force, the degree of curling of the base material, and the degree of curling after adhesive processing were examined. The method and evaluation criteria for each test are shown below, and the results of each test are shown in Table 1.
≪引裂強度≫
　ＪＩＳ　Ｋ７１２８－２（エルメンドルフ引裂法）に従って各基材のＭＤ方向の引裂強さ（Ｎ）を調べた。 ≪Tear strength≫
The tear strength (N) in the MD direction of each substrate was examined in accordance with JIS K7128-2 (Elmendorf tear method).
≪背面剥離力（Ｎ／２５ｍｍ）≫
　基材の粘着剤非塗工層に離型剤を薄く塗布（離型処理）し、粘着剤塗工予定層にポリイソブチレン系粘着剤を塗工して粘着剤層を形成した。粘着剤層を形成した塗膜表面保護フィルムを３インチ紙管に巻取り２５ｍｍ幅のテープ状にスリットした。 ≪Back peeling force (N / 25mm) ≫
A release agent was thinly applied to the non-adhesive layer of the base material (mold release treatment), and a polyisobutylene-based adhesive was applied to the adhesive application planned layer to form an adhesive layer. The coating surface protective film on which the pressure-sensitive adhesive layer was formed was wound around a 3-inch paper tube and slit into a tape having a width of 25 mm.
　ＪＩＳ　Ｋ７１２７で使用する引張試験機に、上記のテープ試料をセットし、図２に示す通りに引張速度２５０ｍｍ／ｍｉｎで９０°方向に引張る際の力を測定した。 The tape sample was set in a tensile tester used in JIS K7127, and the force when pulling in the 90 ° direction at a pulling speed of 250 mm / min as shown in FIG. 2 was measured.
≪基材のカールの程度≫
　各基材を作製後、縦２５ｍｍ×横１００ｍｍにカットした。図３に示す通りに水平な床面５に垂直にガラス板６をセットし、１００ｍｍの長さが床面に対して垂直となるように試料７を試料固定用テープ８を用いて固定した。 ≪Degree of curling of base material≫
After producing each substrate, it was cut into 25 mm length × 100 mm width. As shown in FIG. 3, the glass plate 6 was set vertically on the horizontal floor surface 5, and the sample 7 was fixed using the sample fixing tape 8 so that the length of 100 mm was perpendicular to the floor surface.
　試料７とガラス板６との隙間を測定し、下記の通りに評価した。
　○：隙間が５ｍｍ未満
　×：隙間が５ｍｍ以上 The gap between the sample 7 and the glass plate 6 was measured and evaluated as follows.
○: The gap is less than 5 mm ×: The gap is 5 mm or more
≪粘着加工後のカールの程度≫
　基材の粘着剤非塗工層に離型剤を薄く塗布（離型処理）し、次いで粘着剤塗工予定層にポリイソブチレン系粘着剤を１０ｇ／ｍ２の割合で塗工して粘着剤層を形成した。その後、縦２５ｍｍ×横１００ｍｍにカットして試料とした。 ≪Curl degree after adhesive processing≫
A release agent is thinly applied to the non-adhesive layer of the base material (release treatment), and then a polyisobutylene-based adhesive is applied to the planned adhesive coating layer at a rate of 10 g / m 2. A layer was formed. Then, it cut into 25 mm long x 100 mm wide to make a sample.
　図３と同様に、水平な床面５に垂直にガラス板６をセットし、ガラス板６と離型処理面が接するように試料７を試料固定用テープを用いて固定した。 As in FIG. 3, the glass plate 6 was set vertically on the horizontal floor surface 5, and the sample 7 was fixed using a sample fixing tape so that the glass plate 6 and the release treatment surface were in contact with each other.
　試料７とガラス板６との隙間を測定し、下記の通りに評価した。
　○：隙間が５ｍｍ未満
　×：隙間が５ｍｍ以上 The gap between the sample 7 and the glass plate 6 was measured and evaluated as follows.
○: The gap is less than 5 mm ×: The gap is 5 mm or more
（考　察）
　表１の結果から分かる通り、本発明所定の三層以上の特定の層構成を有する実施例１～４の塗膜表面保護フィルム用基材及び塗膜表面保護フィルム（まとめて「試料」という）は粘着加工の前後においてカールの発生が抑制されており、しかも良好な引裂き強度とともに貼付性に優れる。これに対して、本発明所定の三層以上の特定の層構成を有さない比較例１～８の試料は粘着加工の前後いずれかのカールの発生、引裂き強度又は貼付性のいずれかにおいて実施例の試料に対して性能が劣っている。 (Discussion)
As can be seen from the results in Table 1, the coating film surface protective film substrate and the coating film surface protective film of Examples 1 to 4 having a specific layer structure of three or more predetermined layers according to the present invention (collectively referred to as “sample”) The curling is suppressed before and after the adhesive processing, and it has excellent tearability as well as good tear strength. In contrast, the samples of Comparative Examples 1 to 8 that do not have a specific layer structure of three or more predetermined layers according to the present invention were carried out in any of the occurrence of curl, tear strength, or adhesiveness before and after the adhesive processing. Performance is inferior to the example sample.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
ａ．塗膜表面保護フィルム用基材
ｂ．塗膜表面保護フィルム
１．粘着剤塗工予定層
２．内層
３．粘着剤非塗工層
４．粘着剤層
５．床面
６．ガラス板
７．試料
８．試料固定用テープ a. Base material for coating surface protective film b. Coating surface protective film 1. Adhesive layer to be coated Inner layer 3. 3. Adhesive non-coating layer 4. Adhesive layer Floor surface 6. 6. Glass plate Sample 8 Sample fixing tape

Claims (4)

  1. 　粘着剤塗工予定層に粘着剤を塗工して粘着剤層を形成後に塗膜表面保護フィルムとして用いる塗膜表面保護フィルム用基材であって、
    （１）前記基材は、ポリエチレン樹脂を５０質量％以上含有し、三層以上からなり、
    （２）一対の最外層のうち、前記粘着剤塗工予定層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を５０～９０質量％含有し、且つ、ホモポリプロピレン樹脂を１０～５０質量％含有し、
    （３）他方の最外層である粘着剤非塗工層は、エチレン含有量が５質量％以下のランダム共重合ポリプロピレン樹脂を９０～１００質量％含有し、且つ、ホモポリプロピレン樹脂を０～１０質量％含有する、
    ことを特徴とする塗膜表面保護フィルム用基材。     A base material for a coating surface protective film used as a coating film surface protective film after forming a pressure sensitive adhesive layer by applying a pressure sensitive adhesive to the adhesive coating planned layer,
    (1) The base material contains 50% by mass or more of polyethylene resin and consists of three or more layers.
    (2) Of the pair of outermost layers, the pressure-sensitive adhesive coating layer contains 50 to 90% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 10 to 10% of a homopolypropylene resin. Containing 50% by weight,
    (3) The pressure-sensitive adhesive non-coating layer as the other outermost layer contains 90 to 100% by mass of a random copolymer polypropylene resin having an ethylene content of 5% by mass or less, and 0 to 10% by mass of a homopolypropylene resin. %contains,
    The base material for coating-film surface protection films characterized by this.
  2. 　前記基材は、前記粘着剤塗工予定層、内層及び前記粘着剤非塗工層の三層からなる、請求項１に記載の塗装表面保護フィルム用基材。 The said base material is a base material for coating surface protection films of Claim 1 which consists of three layers of the said adhesive coating plan layer, an inner layer, and the said adhesive non-coating layer.
  3. 　前記粘着剤塗工予定層及び前記粘着剤非塗工層の厚さが同じであり、前記粘着剤塗工予定層中の前記ランダム共重合ポリプロピレンの比率をＡ％とし、前記粘着剤非塗工層中の前記ランダム共重合ポリプロピレンの比率をＢ％とし、Ａ－Ｂの絶対値が５０以下である、請求項１又は２に記載の塗装表面保護フィルム用基材。 The pressure-sensitive adhesive coating layer and the pressure-sensitive adhesive non-coating layer have the same thickness, the ratio of the random copolymerized polypropylene in the pressure-sensitive adhesive coating layer is A%, and the pressure-sensitive adhesive non-coating layer The coated surface protective film substrate according to claim 1 or 2, wherein the ratio of the random copolymerized polypropylene in the layer is B%, and the absolute value of AB is 50 or less.
  4. 　請求項１～３のいずれかに記載の塗膜表面保護フィルム用基材の前記粘着剤塗工予定層に接して粘着剤層を有する塗膜表面保護フィルム。 A coated film surface protective film having a pressure sensitive adhesive layer in contact with the pressure sensitive adhesive coating planned layer of the coated film surface protective film substrate according to any one of claims 1 to 3.
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JPH06328640A (en) * 1993-05-18 1994-11-29 Okura Ind Co Ltd Base material film to be used for surface protective film of automobile
JP2000343660A (en) * 1999-04-01 2000-12-12 Japan Polychem Corp Laminate and medical bag formed of the same
JP2003119442A (en) * 2001-10-12 2003-04-23 Idemitsu Unitech Co Ltd Marking film
JP2007246589A (en) * 2006-03-14 2007-09-27 Nitto Denko Corp Adhesive sheet for glass protection and auto glass protection film
JP2010052163A (en) * 2008-08-26 2010-03-11 Dainippon Printing Co Ltd Protective film

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Publication number Priority date Publication date Assignee Title
GB2505958B (en) 2012-09-18 2020-12-30 Intelligent Energy Ltd Excess coolant fluid feed to fuel cell stacks

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06328640A (en) * 1993-05-18 1994-11-29 Okura Ind Co Ltd Base material film to be used for surface protective film of automobile
JP2000343660A (en) * 1999-04-01 2000-12-12 Japan Polychem Corp Laminate and medical bag formed of the same
JP2003119442A (en) * 2001-10-12 2003-04-23 Idemitsu Unitech Co Ltd Marking film
JP2007246589A (en) * 2006-03-14 2007-09-27 Nitto Denko Corp Adhesive sheet for glass protection and auto glass protection film
JP2010052163A (en) * 2008-08-26 2010-03-11 Dainippon Printing Co Ltd Protective film

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