WO2013121853A1 - Surface protection sheet - Google Patents

Surface protection sheet Download PDF

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Publication number
WO2013121853A1
WO2013121853A1 PCT/JP2013/051522 JP2013051522W WO2013121853A1 WO 2013121853 A1 WO2013121853 A1 WO 2013121853A1 JP 2013051522 W JP2013051522 W JP 2013051522W WO 2013121853 A1 WO2013121853 A1 WO 2013121853A1
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WO
WIPO (PCT)
Prior art keywords
layer
weight
polyethylene
base material
material layer
Prior art date
Application number
PCT/JP2013/051522
Other languages
French (fr)
Japanese (ja)
Inventor
公平 武田
生島 伸祐
二郎 山戸
Original Assignee
日東電工株式会社
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Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2013121853A1 publication Critical patent/WO2013121853A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29Laminated material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/402Coloured
    • B32B2307/4026Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00Adhesive articles, e.g. adhesive tapes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/40Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/006Presence of polyolefin in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer

Definitions

  • the present invention relates to a surface protection sheet. Specifically, the present invention relates to a surface protective sheet that is excellent in adhesion workability to a curved surface, weather resistance, peelability after long-term adhesion, and suitable for protecting a coating film of a car body or a part, a coated steel plate, etc. .
  • a coating material with a wax coating material having a thickness of 5 to 20 ⁇ m is known.
  • it is difficult to form a wax-based coating film with a uniform thickness and it is difficult to obtain a uniform coating film. For this reason, there exists a problem that it is easy to get dirty, and it is weak to acid rain.
  • since a great amount of labor is required for applying and removing the wax-based coating film there is a problem that environmental problems such as the use of a solvent and the treatment of waste liquid are easily induced.
  • the problem of the present invention is that it has excellent workability for adhesion to a curved surface, and also has excellent weather resistance, and even when left in a hot outdoor environment for a long period of time, it retains sufficient sheet strength and causes troubles such as breakage.
  • Another object of the present invention is to provide a surface protective sheet that can be easily peeled off.
  • the surface protective sheet of the present invention is A surface protective sheet in which an adhesive layer is formed on one side of the base material layer,
  • the base material layer includes a white layer containing 50 to 95% by weight of polyethylene and 5 to 30% by weight of titanium oxide, and a black layer containing 50 to 99.9% by weight of polyethylene and 0.1 to 5% by weight of carbon black.
  • Including The base material layer has an initial yield strength of 15 to 50 N / 25 mm at a thickness of 150 ⁇ m or less.
  • the base material layer contains an ultraviolet absorber in a proportion of 0.1 to 2% by weight.
  • the yield point strength is 20 to 35 N / 25 mm.
  • the present invention it is excellent in adhesion workability to a curved surface, is extremely excellent in weather resistance, and has a sufficient sheet strength even when left in a hot outdoor environment for a long time in a bonded state. And a surface protective sheet that can be easily peeled off.
  • an adhesive layer is formed on one side of the base material layer.
  • the base material layer includes at least two layers of a specific white layer and a specific black layer. As a result, it has excellent workability for adhesion to curved surfaces and extremely excellent weather resistance. Even when left in a hot outdoor environment for a long period of time, it retains sufficient sheet strength and can be easily used without any trouble such as breakage. A surface protective sheet that can be peeled can be provided.
  • the white layer is a layer showing a white color tone.
  • the whiteness specified by JIS-L-1015 is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, Particularly preferably, it is 85% or more.
  • the white layer contains titanium oxide.
  • the content of titanium oxide in the white layer is 5 to 30% by weight, preferably 6 to 20% by weight, and more preferably 6 to 15% by weight with respect to the components forming the white layer. .
  • the content of titanium oxide in the white layer is less than 5% by weight, the hiding power is poor, and the base material layer and the adhesive layer may be easily deteriorated by ultraviolet rays.
  • the content ratio of titanium oxide in the white layer exceeds 30% by weight, the moldability such as extrudability may be poor.
  • the white layer contains polyethylene.
  • the polyethylene content in the white layer is 50 to 95% by weight, preferably 60 to 95% by weight, more preferably 65 to 95% by weight, based on the components forming the white layer. Particularly preferred is 70 to 95% by weight.
  • the polyethylene content in the white layer is less than 50% by weight, the strength is poor and the peeling workability may be inferior.
  • the content ratio of polyethylene in the white layer exceeds 95% by weight, the strength is excessive and the flexibility is poor, and the curved surface adhesion may be poor.
  • any appropriate polyethylene can be adopted as the polyethylene contained in the white layer.
  • specific examples of such polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • Such polyethylene may use only 1 type and may use 2 or more types.
  • the high density polyethylene preferably has a density of 0.94 g / cm 3 or more.
  • the low density polyethylene such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) has a density of preferably 0.88 to 0.93 g / cm 3 , more preferably 0.895 to 0.920 g / cm 3 . cm 3 .
  • the white layer may contain any appropriate other resin other than polyethylene.
  • Such other resin is preferably a polyolefin resin other than polyethylene, and more preferably polypropylene.
  • any appropriate thickness can be adopted as the thickness of the white layer depending on the purpose.
  • Such a thickness is preferably 1 to 50 ⁇ m, more preferably 3 to 40 ⁇ m, still more preferably 5 to 30 ⁇ m, and particularly preferably 10 to 30 ⁇ m.
  • the black layer is a layer showing a black color tone.
  • the black layer includes carbon black.
  • the content ratio of carbon black in the black layer is 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.1% to the component forming the black layer. ⁇ 1% by weight.
  • the content ratio of carbon black in the black layer is less than 0.1% by weight, sufficient weather resistance may not be imparted to the resulting surface protective sheet. If the carbon black content in the black layer exceeds 5% by weight, moldability such as extrudability may be poor.
  • the black layer contains polyethylene.
  • the polyethylene content in the black layer is 50 to 99.9% by weight, preferably 60 to 99% by weight, more preferably 70 to 99% by weight, based on the components forming the black layer. It is particularly preferably 80 to 99% by weight. If the polyethylene content in the black layer is less than 50% by weight, the strength is poor and the peeling workability may be poor. If the polyethylene content in the black layer exceeds 99.9% by weight, the strength becomes excessive, the flexibility is poor, and the curved surface adhesion may be poor.
  • any appropriate polyethylene can be adopted as the polyethylene contained in the black layer.
  • specific examples of such polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • Such polyethylene may use only 1 type and may use 2 or more types.
  • the black layer may contain any appropriate other resin other than polyethylene.
  • Such other resin is preferably a polyolefin resin other than polyethylene, and more preferably polypropylene.
  • any appropriate thickness can be adopted as the thickness of the black layer according to the purpose.
  • Such a thickness is preferably 1 to 100 ⁇ m, more preferably 5 to 70 ⁇ m, still more preferably 10 to 60 ⁇ m, and particularly preferably 20 to 50 ⁇ m.
  • the base material layer preferably contains an ultraviolet absorber.
  • the content ratio of the ultraviolet absorber in the base material layer is preferably 0.1 to 2% by weight, more preferably 0.2 to 1.5% by weight, and still more preferably based on the components forming the base material layer. 0.3 to 1.0% by weight. If the content ratio of the ultraviolet absorber in the base material layer is less than 0.1% by weight, the base material layer or the pressure-sensitive adhesive layer may be easily deteriorated by ultraviolet rays, and the content ratio of the ultraviolet absorber in the base material layer If it exceeds 2% by weight, the ultraviolet absorber tends to bleed on the surface of the base material layer, which may cause a dusting phenomenon.
  • any appropriate UV absorber such as a benzotriazole UV absorber, a hindered amine UV absorber, or a benzoate UV absorber can be adopted.
  • an ultraviolet absorber include, for example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t- Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ ( 2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ], dimethyl succinate 1- (2-hydroxy Ethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 2,4-
  • the base material layer may contain any appropriate additive for the purpose of preventing deterioration.
  • additives include antioxidants; light stabilizers such as hindered amine light stabilizers; antistatic agents; fillers such as calcium oxide, magnesium oxide, silica, and zinc oxide; pigments; A lubricant, an anti-blocking agent, a foaming agent, polyethyleneimine, and the like.
  • the thickness of the base material layer is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and still more preferably 30 to 50 ⁇ m.
  • the back surface side of the base material layer may be subjected to uneven processing for the purpose of imparting slip resistance and handy cut property. Furthermore, you may form various functional layers, such as a printing layer, in the back side of a base material layer.
  • the substrate layer has an initial yield strength of 15 to 50 N / 25 mm, preferably 20 to 35 N / 25 mm, at a thickness of 150 ⁇ m or less. If the yield point strength is less than 15 N / 25 mm, the strength is poor, the waist (self-supporting property) is weak, wrinkles easily occur during the bonding work, and the peeling workability may be inferior. When the yield point strength exceeds 50 N / 25 mm, the flexibility is poor and the workability of bonding to a curved surface may be inferior. In the present invention, the initial yield strength of the base material layer is measured based on the method described later.
  • Any appropriate method can be adopted as a method for forming the base material layer.
  • a formation method include film formation methods such as a T-die method and an inflation method.
  • Arbitrary appropriate adhesive can be employ
  • adhesives include known rubber adhesives, acrylic adhesives, polyester adhesives, polyurethane adhesives, polyisobutylene adhesives, styrene adhesives, olefin adhesives, and the like. It is done.
  • the adhesive layer for the purpose of controlling adhesive properties, etc., for example, a softening agent, an olefin resin, a silicone polymer, a liquid acrylic copolymer, a phosphate ester compound, a tackifier , Antioxidants, hindered amine light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (eg calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide) An agent can be added as appropriate.
  • corona discharge treatment ultraviolet irradiation treatment, flame treatment, plasma treatment, sputter etching treatment, and other surface treatments for the purpose of adhesion control and pasting workability are performed on the adhesive layer surface as necessary. You can also.
  • Blending of tackifier is effective for improving adhesive strength.
  • the blending amount of the tackifier is appropriately determined according to the adherend to which the surface protective sheet is applied in order to avoid the occurrence of the adhesive residue problem due to the decrease in cohesive force.
  • the blending amount of the tackifier is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer.
  • the adherend to which the surface protective sheet is applied is a metal plate, it is preferable not to add a tackifier when forming the adhesive layer.
  • tackifier examples include petroleum-based resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymer systems and alicyclic copolymers, and coumarone-indene resins.
  • what is marketed as a blend with an olefin resin can also be used for a tackifier.
  • Softener blending is effective in improving adhesive strength.
  • the softening agent include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and derivatives thereof.
  • such derivatives include those having an OH group or a COOH group at one or both ends.
  • examples thereof include polyisoprene monool.
  • hydrogenated products of diene polymers such as hydrogenated polybutadiene and hydrogenated polyisoprene, olefinic softeners, and the like are preferable for the purpose of suppressing the improvement in adhesiveness to the adherend.
  • a softening agent specifically, trade name “Kuraprene LIR-200” manufactured by Kuraray Co., Ltd. is available. These softeners may be used alone or in combination of two or more.
  • the blending amount of the softening agent is preferably 40% by weight or less, more preferably 20% by weight or less, and further preferably 10% by weight or less with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer. When the blending amount of the softening agent is 40% by weight or more with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer, there is a possibility that the adhesive residue at the time of high temperature or outdoor exposure becomes remarkable.
  • the molecular weight of the softening agent can be appropriately set to any appropriate amount, but if the molecular weight is small, there is a risk of causing material transfer or heavy peeling from the adhesive layer to the adherend, while the molecular weight is large. Therefore, the softening agent has a number average molecular weight of preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
  • the thickness of the adhesive layer may be appropriately set to any appropriate thickness according to the required adhesive strength.
  • the thickness of the adhesive layer is preferably 1 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 20 ⁇ m.
  • the surface protective sheet of the present invention can be produced by any appropriate method.
  • the surface protective sheet of the present invention is preferably obtained by forming the base material layer and the adhesive layer by coextrusion using the forming material for forming the base material layer and the forming material for forming the adhesive layer. It is done.
  • the surface protective sheet of the present invention can also be obtained by applying a solution-type or emulsion-type adhesive on one side of the base material layer or transferring the adhesive layer formed on the separator to one side of the base material layer. Can be manufactured.
  • the structure of the surface protective sheet of the present invention is not particularly limited, and any structure of “white layer / black layer / adhesive layer” and “black layer / white layer / adhesive layer” can be adopted. .
  • a base material layer it can also be set as the layer structure of 3 or more layers which formed layers other than a black-type layer and a white-type layer.
  • a configuration such as “transparent resin layer / white color layer / black color layer / adhesive layer” may be employed.
  • the thickness of the white layer and the black layer may be the same, and the thickness may be different (a white layer is thinner than the black layer, and a white layer is thicker than the black layer). May be.
  • the co-extrusion method it can be carried out according to the inflation method, T-die method and the like generally used for film production.
  • the substrate layer and the pressure-sensitive adhesive layer can be subjected to the surface treatment as necessary.
  • the adhesive layer can be protected by temporarily attaching a separator or the like until it is put to practical use.
  • a mold release treatment by adding fatty acid amide or polyethyleneimine to the base material layer for the purpose of forming a wound body that can be easily rewound.
  • a coat layer made of an appropriate release agent such as silicone, long chain alkyl, or fluorine.
  • Example 1 20% by weight of MFR5 low density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA), white pigment (Daiichi Seika Co., Ltd., HCM2035W (titanium oxide concentration) 65 wt%)) 15 wt% (titanium oxide 9.75 wt%) and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 0.3 wt% 20% by weight of MFR5 low-density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA), carbon black (Mitsubishi) compared to the added base material white layer forming material and MFR0.07 high-density polyethylene (Tosoh, Nipolon Hard 6900) Chemical, carbon black “# 45”) 2% by weight, and A base black layer forming material to which 0.3% by weight of 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole was
  • a 20 wt% toluene solution of a polyisobutylene pressure-sensitive adhesive is applied to the corona treatment surface.
  • the obtained surface protective sheet had a base material layer thickness of 30 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • Example 2 MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4) 10% by weight, white pigment (Daiichi Seika Co., Ltd., HCM2035W (titanium oxide concentration 65) 15 wt% (titanium oxide 9.75 wt%) and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 0.3 wt% added 10% by weight of MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4), carbon black (Mitsubishi Chemical) , Carbon black “# 45”) 2% by weight, and 2- ( -T-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and a base black layer forming material added thereto, and the same procedure as in Example 1 was carried out.
  • the obtained surface protective sheet had a base material layer thickness of 30 ⁇ m and an adhesive layer thickness
  • Example 3 20% by weight of MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4) and MFR5 low density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA) with respect to MFR0.05 high density polyethylene (Tosoh, Nipolon Hard 7300A) 10% by weight, white pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W (titanium oxide concentration 65% by weight)) 15% by weight (titanium oxide 9.75% by weight), and 2- (3-t-butyl-5-methyl -2-Hydroxyphenyl) -5-chlorobenzotriazole 0.3% by weight of base material white layer forming material and MFR0.05 high density polyethylene (Tosoh Nipolon Hard 7300A), MFR5 homopolypropylene ( Nippon Polypropylene, Novatec PP-FY4) 0 wt%, MFR5 low density polyethylene (Nippon Polyethylene, Nova
  • the acrylic pressure-sensitive adhesive was obtained by polymerizing 40 parts by weight of 2-ethylhexyl acrylate / 50 parts by weight of ethyl acrylate / 9 parts by weight of styrene / 1 part by weight of acrylic acid in an ethyl acetate by a conventional method to obtain a weight average molecular weight of 60 This was prepared by preparing 5 million polymers and adding 5 parts by weight of a trifunctional isocyanate to the solution.
  • the obtained surface protective sheet had a base material layer thickness of 25 ⁇ m and an adhesive layer thickness of 5 ⁇ m.
  • the surface protection sheets obtained in Examples and Comparative Examples were cut into strips having a width of 20 mm to prepare evaluation samples. This sample was pressed against a SUS430BA plate by reciprocating a 2 kg roller, and then put into a sunshine carbon weather meter (product of Suga Test Instruments Co., Ltd.) for 1000 hours, and then from one end of the sample to a length of 100 mm Was peeled in the 180 ° direction at a tensile speed of 0.3 m / min. The above results were evaluated according to the following criteria. The results are shown in Table 1. ⁇ : The sample was not broken and could be peeled off very well. X: The sample was broken in the middle due to deterioration of the substrate, or the adhesive remained on the adherend and was contaminated.
  • the surface protective sheet of the present invention has excellent workability for adhesion to curved surfaces and extremely excellent weather resistance, and retains sufficient sheet strength even when left in a hot outdoor environment for a long time. Thus, it can be easily peeled off without any trouble such as breakage.
  • the surface protective sheet of the present invention is, for example, a member such as a metal plate, a painted metal plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate, etc. It can be used for purposes such as attaching to the surface to protect.

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

Abstract

Provided is a surface protection sheet: having excellent adhesion workability on curved surfaces, and exceptional weather resistance; and that maintains sufficient sheet strength and can easily be detached without causing trouble, such as damage, even when left in an attached state for a long period outdoors at high temperatures. This surface protection sheet has an adhesive layer formed on one surface of a base layer. The base layer includes: a whitish layer containing 50 to 95 wt% of polyethylene and 5 to 30 wt% of titanium oxide; and a blackish layer containing 50 to 99.9 wt% of polyethylene and 0.1 to 5 wt% of carbon black. The base layer has an initial yield-point strength of 15 to 50 N/25 mm at a thickness of 150 μm or less.

Description

表面保護シートSurface protection sheet
 本発明は表面保護シートに関する。詳細には、本発明は、曲面への接着作業性、耐候性、長期接着後の剥離性に優れており、自動車のボディや部品、塗装鋼板等の塗膜保護などに好適な表面保護シートに関する。 The present invention relates to a surface protection sheet. Specifically, the present invention relates to a surface protective sheet that is excellent in adhesion workability to a curved surface, weather resistance, peelability after long-term adhesion, and suitable for protecting a coating film of a car body or a part, a coated steel plate, etc. .
 塗装を終えた自動車やその部品等をトラックや船に荷積して海外等の遠隔地に移送する際などにおける、塵や埃、雨や石粒等の浮遊物、衝突物などによる塗膜の損傷や艶ボケや変色等を予防する手段が求められている。 When painting finished automobiles and their parts on trucks and ships and transporting them to remote places such as overseas, the coating of dust, dirt, rain and stone particles, etc. There is a need for means for preventing damage, glossy blurring, and discoloration.
 このような予防手段として、ワックス系塗膜材料を5~20μmの厚さで塗布したものが知られている。しかしながら、ワックス系塗膜を均一な厚さに形成することは困難であり、一様な塗膜が得られ難い。このため、汚れやすいという問題や、酸性雨に弱いという問題がある。また、ワックス系塗膜の付与とその除去に多大な労力を要するため、溶剤の使用や廃液の処理等の環境問題を誘発しやすいという問題がある。 As such a preventive measure, a coating material with a wax coating material having a thickness of 5 to 20 μm is known. However, it is difficult to form a wax-based coating film with a uniform thickness, and it is difficult to obtain a uniform coating film. For this reason, there exists a problem that it is easy to get dirty, and it is weak to acid rain. In addition, since a great amount of labor is required for applying and removing the wax-based coating film, there is a problem that environmental problems such as the use of a solvent and the treatment of waste liquid are easily induced.
 一方、ポリエステル等の支持フィルム上に粘着層を設けてなる塗膜用等の種々の表面保護シートが提案されている。このようなシート方式によれば、上記の問題は克服し得る。しかしながら、高温屋外下にて長期間放置される用途においては、シートの柔軟性や強度の低下、粘着層における粘着力の上昇などにより、塗膜から表面保護シートを剥離することが困難になるという問題が生じる。 On the other hand, various surface protection sheets for coating films in which an adhesive layer is provided on a support film such as polyester have been proposed. According to such a sheet system, the above problem can be overcome. However, in applications that are left for a long time outdoors at high temperatures, it is difficult to peel the surface protective sheet from the coating film due to a decrease in flexibility and strength of the sheet, an increase in adhesive strength in the adhesive layer, and the like. Problems arise.
 支持フィルムの強度を上げて、高温屋外下におけるシートの柔軟性や強度の低下の問題を克服することも提案されている(例えば、特許文献1参照)。しかし、その提案においては、支持フィルムの初期強度の上昇に伴って自動車ボディ等の曲面に対する接着作業性が低下してしまい、必要な基本性能を喪失してしまうという問題がある。 It has also been proposed to increase the strength of the support film to overcome the problems of sheet flexibility and strength reduction under high temperature outdoors (see, for example, Patent Document 1). However, the proposal has a problem that, as the initial strength of the support film is increased, the workability of adhesion to a curved surface of an automobile body or the like is lowered, and necessary basic performance is lost.
特開平7-118615号公報JP-A-7-118615
 本発明の課題は、曲面への接着作業性に優れるとともに、耐候性に非常に優れ、接着した状態で高温屋外下に長期間放置した場合にも十分なシート強度を保持して破損等のトラブルなく容易に剥離できる表面保護シートを提供することにある。 The problem of the present invention is that it has excellent workability for adhesion to a curved surface, and also has excellent weather resistance, and even when left in a hot outdoor environment for a long period of time, it retains sufficient sheet strength and causes troubles such as breakage. Another object of the present invention is to provide a surface protective sheet that can be easily peeled off.
 本発明の表面保護シートは、
 基材層の片面に粘着層が形成されている表面保護シートであって、
 該基材層は、ポリエチレン50~95重量%および酸化チタン5~30重量%を含む白色系層と、ポリエチレン50~99.9重量%およびカーボンブラック0.1~5重量%を含む黒色系層とを含み、
 該基材層は、150μm以下の厚さにおいて初期の降伏点強度が15~50N/25mmである。
The surface protective sheet of the present invention is
A surface protective sheet in which an adhesive layer is formed on one side of the base material layer,
The base material layer includes a white layer containing 50 to 95% by weight of polyethylene and 5 to 30% by weight of titanium oxide, and a black layer containing 50 to 99.9% by weight of polyethylene and 0.1 to 5% by weight of carbon black. Including
The base material layer has an initial yield strength of 15 to 50 N / 25 mm at a thickness of 150 μm or less.
 好ましい実施形態においては、上記基材層が紫外線吸収剤を0.1~2重量%の割合で含む。 In a preferred embodiment, the base material layer contains an ultraviolet absorber in a proportion of 0.1 to 2% by weight.
 好ましい実施形態においては、上記降伏点強度が20~35N/25mmである。 In a preferred embodiment, the yield point strength is 20 to 35 N / 25 mm.
 本発明によれば、曲面への接着作業性に優れるとともに、耐候性に非常に優れ、接着した状態で高温屋外下に長期間放置した場合にも十分なシート強度を保持して破損等のトラブルなく容易に剥離できる表面保護シートを提供することができる。 According to the present invention, it is excellent in adhesion workability to a curved surface, is extremely excellent in weather resistance, and has a sufficient sheet strength even when left in a hot outdoor environment for a long time in a bonded state. And a surface protective sheet that can be easily peeled off.
 本発明の表面保護シートは、基材層の片面に粘着層が形成されている。 In the surface protective sheet of the present invention, an adhesive layer is formed on one side of the base material layer.
 基材層は、特定の白色系層および特定の黒色系層の2層を少なくとも含む。これにより、曲面への接着作業性に優れるとともに、耐候性に非常に優れ、接着した状態で高温屋外下に長期間放置した場合にも十分なシート強度を保持して破損等のトラブルなく容易に剥離できる表面保護シートを提供することができる。 The base material layer includes at least two layers of a specific white layer and a specific black layer. As a result, it has excellent workability for adhesion to curved surfaces and extremely excellent weather resistance. Even when left in a hot outdoor environment for a long period of time, it retains sufficient sheet strength and can be easily used without any trouble such as breakage. A surface protective sheet that can be peeled can be provided.
 白色系層は、白色系の色調を示す層であり、例えば、JIS-L-1015で規定される白色度が、好ましくは60%以上、より好ましくは70%以上、さらに好ましくは80%以上、特に好ましくは85%以上である。 The white layer is a layer showing a white color tone. For example, the whiteness specified by JIS-L-1015 is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, Particularly preferably, it is 85% or more.
 白色系層は、酸化チタンを含む。白色系層中の酸化チタンの含有割合は、白色系層を形成する成分に対して5~30重量%であり、好ましくは6~20重量%であり、より好ましくは6~15重量%である。白色系層中の酸化チタンの含有割合が5重量%未満では、隠蔽力に乏しくなり、基材層や粘着層が紫外線によって劣化を受けやすくなるおそれがある。白色系層中の酸化チタンの含有割合が30重量%を超えると、押出し性等の成形性に乏しくなるおそれがある。 The white layer contains titanium oxide. The content of titanium oxide in the white layer is 5 to 30% by weight, preferably 6 to 20% by weight, and more preferably 6 to 15% by weight with respect to the components forming the white layer. . When the content of titanium oxide in the white layer is less than 5% by weight, the hiding power is poor, and the base material layer and the adhesive layer may be easily deteriorated by ultraviolet rays. When the content ratio of titanium oxide in the white layer exceeds 30% by weight, the moldability such as extrudability may be poor.
 白色系層は、ポリエチレンを含む。白色系層中のポリエチレンの含有割合は、白色系層を形成する成分に対して50~95重量%であり、好ましくは60~95重量%であり、より好ましくは65~95重量%であり、特に好ましくは70~95重量%である。白色系層中のポリエチレンの含有割合が50重量%未満では、強度に乏しくて剥離作業性に劣るものとなるおそれがある。白色系層中のポリエチレンの含有割合が95重量%を超えると、強度が過大となって柔軟性に乏しく、曲面接着性に劣るおそれがある。 The white layer contains polyethylene. The polyethylene content in the white layer is 50 to 95% by weight, preferably 60 to 95% by weight, more preferably 65 to 95% by weight, based on the components forming the white layer. Particularly preferred is 70 to 95% by weight. When the polyethylene content in the white layer is less than 50% by weight, the strength is poor and the peeling workability may be inferior. When the content ratio of polyethylene in the white layer exceeds 95% by weight, the strength is excessive and the flexibility is poor, and the curved surface adhesion may be poor.
 白色系層に含まれるポリエチレンとしては、任意の適切なポリエチレンを採用し得る。このようなポリエチレンとしては、具体的には、例えば、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、リニア低密度ポリエチレン(LLDPE)が挙げられる。このようなポリエチレンは、1種のみを用いても良いし、2種以上を用いても良い。 Any appropriate polyethylene can be adopted as the polyethylene contained in the white layer. Specific examples of such polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE). Such polyethylene may use only 1 type and may use 2 or more types.
 なお、高密度ポリエチレンは、密度が、好ましくは0.94g/cm以上である。また、低密度ポリエチレン(LDPE)やリニア低密度ポリエチレン(LLDPE)などの低密度ポリエチレンは、密度が、好ましくは0.88~0.93g/cm、より好ましくは0.895~0.920g/cmである。 The high density polyethylene preferably has a density of 0.94 g / cm 3 or more. The low density polyethylene such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) has a density of preferably 0.88 to 0.93 g / cm 3 , more preferably 0.895 to 0.920 g / cm 3 . cm 3 .
 白色系層には、ポリエチレン以外の任意の適切なその他の樹脂が含まれていても良い。このようなその他の樹脂としては、好ましくは、ポリエチレン以外のポリオレフィン樹脂であり、より好ましくは、ポリプロピレンである。 The white layer may contain any appropriate other resin other than polyethylene. Such other resin is preferably a polyolefin resin other than polyethylene, and more preferably polypropylene.
 白色系層の厚さは、目的に応じて、任意の適切な厚さを採用し得る。このような厚さは、好ましくは、1~50μmであり、より好ましくは3~40μmであり、さらに好ましくは5~30μmであり、特に好ましくは10~30μmである。 Any appropriate thickness can be adopted as the thickness of the white layer depending on the purpose. Such a thickness is preferably 1 to 50 μm, more preferably 3 to 40 μm, still more preferably 5 to 30 μm, and particularly preferably 10 to 30 μm.
 黒色系層は、黒色系の色調を示す層である。黒色系層は、カーボンブラックを含む。黒色系層中のカーボンブラックの含有割合は、黒色系層を形成する成分に対して0.1~5重量%であり、好ましくは0.1~3重量%であり、より好ましくは0.1~1重量%である。黒色系層中のカーボンブラックの含有割合が0.1重量%未満では、得られる表面保護シートに十分な耐候性を付与できないおそれがある。黒色系層中のカーボンブラックの含有割合が5重量%を超えると、押出し性等の成形性に乏しくなるおそれがある。 The black layer is a layer showing a black color tone. The black layer includes carbon black. The content ratio of carbon black in the black layer is 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.1% to the component forming the black layer. ~ 1% by weight. When the content ratio of carbon black in the black layer is less than 0.1% by weight, sufficient weather resistance may not be imparted to the resulting surface protective sheet. If the carbon black content in the black layer exceeds 5% by weight, moldability such as extrudability may be poor.
 黒色系層は、ポリエチレンを含む。黒色系層中のポリエチレンの含有割合は、黒色系層を形成する成分に対して50~99.9重量%であり、好ましくは60~99重量%であり、より好ましくは70~99重量%であり、特に好ましくは80~99重量%である。黒色系層中のポリエチレンの含有割合が50重量%未満では、強度に乏しくて剥離作業性に劣るものとなるおそれがある。黒色系層中のポリエチレンの含有割合が99.9重量%を超えると、強度が過大となって柔軟性に乏しく、曲面接着性に劣るおそれがある。 The black layer contains polyethylene. The polyethylene content in the black layer is 50 to 99.9% by weight, preferably 60 to 99% by weight, more preferably 70 to 99% by weight, based on the components forming the black layer. It is particularly preferably 80 to 99% by weight. If the polyethylene content in the black layer is less than 50% by weight, the strength is poor and the peeling workability may be poor. If the polyethylene content in the black layer exceeds 99.9% by weight, the strength becomes excessive, the flexibility is poor, and the curved surface adhesion may be poor.
 黒色系層に含まれるポリエチレンとしては、任意の適切なポリエチレンを採用し得る。このようなポリエチレンとしては、具体的には、例えば、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、リニア低密度ポリエチレン(LLDPE)が挙げられる。このようなポリエチレンは、1種のみを用いても良いし、2種以上を用いても良い。 Any appropriate polyethylene can be adopted as the polyethylene contained in the black layer. Specific examples of such polyethylene include high density polyethylene (HDPE), low density polyethylene (LDPE), and linear low density polyethylene (LLDPE). Such polyethylene may use only 1 type and may use 2 or more types.
 黒色系層には、ポリエチレン以外の任意の適切なその他の樹脂が含まれていても良い。このようなその他の樹脂としては、好ましくは、ポリエチレン以外のポリオレフィン樹脂であり、より好ましくは、ポリプロピレンである。 The black layer may contain any appropriate other resin other than polyethylene. Such other resin is preferably a polyolefin resin other than polyethylene, and more preferably polypropylene.
 黒色系層の厚さは、目的に応じて、任意の適切な厚さを採用し得る。このような厚さは、好ましくは、1~100μmであり、より好ましくは5~70μmであり、さらに好ましくは10~60μmであり、特に好ましくは20~50μmである。 Any appropriate thickness can be adopted as the thickness of the black layer according to the purpose. Such a thickness is preferably 1 to 100 μm, more preferably 5 to 70 μm, still more preferably 10 to 60 μm, and particularly preferably 20 to 50 μm.
 基材層は、好ましくは、紫外線吸収剤を含む。基材層中の紫外線吸収剤の含有割合は、基材層を形成する成分に対して、好ましくは0.1~2重量%、より好ましくは0.2~1.5重量%、さらに好ましくは0.3~1.0重量%である。基材層中の紫外線吸収剤の含有割合が0.1重量%未満では、基材層や粘着剤層が紫外線によって劣化を受けやすくなるおそれがあり、基材層中の紫外線吸収剤の含有割合が2重量%を超えると、紫外線吸収剤が基材層表面にブリードしやすくなって粉ふき現象などを生じやすくなるおそれがある。 The base material layer preferably contains an ultraviolet absorber. The content ratio of the ultraviolet absorber in the base material layer is preferably 0.1 to 2% by weight, more preferably 0.2 to 1.5% by weight, and still more preferably based on the components forming the base material layer. 0.3 to 1.0% by weight. If the content ratio of the ultraviolet absorber in the base material layer is less than 0.1% by weight, the base material layer or the pressure-sensitive adhesive layer may be easily deteriorated by ultraviolet rays, and the content ratio of the ultraviolet absorber in the base material layer If it exceeds 2% by weight, the ultraviolet absorber tends to bleed on the surface of the base material layer, which may cause a dusting phenomenon.
 紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、ヒンダードアミン系紫外線吸収剤、ベンゾエート系紫外線吸収剤などの、任意の適切な紫外線吸収剤を採用し得る。このような紫外線吸収剤の具体例としては、例えば、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、2-(3,5-ジ-t-ブチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、ポリ[{6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}]、コハク酸ジメチル・1-(2-ヒドロキシエチル)-4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン重縮合物、2,4-ジ-t-ブチルフェニル-3,5-ジ-t-ブチル-4-ヒドロキシベンゾエートなどが挙げられる。 As the UV absorber, for example, any appropriate UV absorber such as a benzotriazole UV absorber, a hindered amine UV absorber, or a benzoate UV absorber can be adopted. Specific examples of such an ultraviolet absorber include, for example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t- Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {( 2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate 1- (2-hydroxy Ethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, etc. Be
 基材層には、劣化防止等を目的に、任意の適切な添加剤を含有させても良い。このような添加剤としては、例えば、酸化防止剤;ヒンダードアミン系光安定剤等の光安定剤;帯電防止剤;酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛等の充填剤;顔料;目ヤニ防止剤;滑剤;アンチブロッキング剤;発泡剤;ポリエチレンイミンなどが挙げられる。 The base material layer may contain any appropriate additive for the purpose of preventing deterioration. Examples of such additives include antioxidants; light stabilizers such as hindered amine light stabilizers; antistatic agents; fillers such as calcium oxide, magnesium oxide, silica, and zinc oxide; pigments; A lubricant, an anti-blocking agent, a foaming agent, polyethyleneimine, and the like.
 基材層の厚さは、好ましくは10~150μm、より好ましくは20~100μm、さらに好ましくは30~50μmである。 The thickness of the base material layer is preferably 10 to 150 μm, more preferably 20 to 100 μm, and still more preferably 30 to 50 μm.
 基材層の背面側には、耐スリップ性やハンディカット性の付与を目的として凹凸加工を施していても良い。さらに、基材層の背面側には、印刷層等の各種機能層を形成しても良い。 The back surface side of the base material layer may be subjected to uneven processing for the purpose of imparting slip resistance and handy cut property. Furthermore, you may form various functional layers, such as a printing layer, in the back side of a base material layer.
 基材層は、150μm以下の厚さにおいて初期の降伏点強度が15~50N/25mmであり、好ましくは20~35N/25mmである。このような降伏点強度が15N/25mm未満では、強度に乏しくて腰(自己支持性)が弱く、接着作業時に皺が入りやすく、剥離作業性に劣るものとなるおそれがある。このような降伏点強度が50N/25mmを超えると、柔軟性に乏しくて曲面に対する接着作業性に劣るものとなるおそれがある。本発明において基材層の初期の降伏点強度は後述の方法に基づき測定される。 The substrate layer has an initial yield strength of 15 to 50 N / 25 mm, preferably 20 to 35 N / 25 mm, at a thickness of 150 μm or less. If the yield point strength is less than 15 N / 25 mm, the strength is poor, the waist (self-supporting property) is weak, wrinkles easily occur during the bonding work, and the peeling workability may be inferior. When the yield point strength exceeds 50 N / 25 mm, the flexibility is poor and the workability of bonding to a curved surface may be inferior. In the present invention, the initial yield strength of the base material layer is measured based on the method described later.
 基材層の形成方法としては、任意の適切な方法を採用し得る。このような形成方法としては、具体的には、Tダイ法やインフレーション法等の成膜方法が挙げられる。 Any appropriate method can be adopted as a method for forming the base material layer. Specific examples of such a formation method include film formation methods such as a T-die method and an inflation method.
 粘着層に用いられる粘着剤は、任意の適切な粘着剤を採用し得る。このような粘着剤としては、例えば、公知のゴム系粘着剤、アクリル系粘着剤、ポリエステル系粘着剤、ポリウレタン系粘着剤、ポリイソブチレン系粘着剤、スチレン系粘着剤、オレフィン系粘着剤などが挙げられる。 Arbitrary appropriate adhesive can be employ | adopted for the adhesive used for an adhesion layer. Examples of such adhesives include known rubber adhesives, acrylic adhesives, polyester adhesives, polyurethane adhesives, polyisobutylene adhesives, styrene adhesives, olefin adhesives, and the like. It is done.
 粘着層の形成に際しては、粘着特性の制御等を目的に、必要に応じて、例えば、軟化剤、オレフィン系樹脂、シリコーン系ポリマー、液状アクリル系共重合体、リン酸エステル系化合物、粘着付与剤、老化防止剤、ヒンダードアミン系光安定剤、紫外線吸収剤、ポリエチレンイミン、脂肪酸アミド、リン酸エステル、充填剤や顔料(例えば、酸化カルシウム、酸化マグネシウム、シリカ、酸化亜鉛、酸化チタンなど)などの添加剤を適宜に添加することができる。 In the formation of the adhesive layer, for the purpose of controlling adhesive properties, etc., for example, a softening agent, an olefin resin, a silicone polymer, a liquid acrylic copolymer, a phosphate ester compound, a tackifier , Antioxidants, hindered amine light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (eg calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide) An agent can be added as appropriate.
 粘着層表面には、例えば、コロナ放電処理、紫外線照射処理、火炎処理、プラズマ処理、スパッタエッチング処理などの、粘着性の制御や貼付作業性等を目的とした表面処理を必要に応じて施すこともできる。 For example, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, plasma treatment, sputter etching treatment, and other surface treatments for the purpose of adhesion control and pasting workability are performed on the adhesive layer surface as necessary. You can also.
 粘着付与剤の配合は粘着力の向上に有効である。ただし、粘着付与剤の配合量は、凝集力の低下による糊残り問題の発生を回避するため、表面保護シートが適用される被着体に応じて適宜に決定される。粘着付与剤の配合量は、粘着層に用いられる粘着剤に対し、好ましくは50重量%以下、より好ましくは30重量%以下、さらに好ましくは10重量%以下である。なお、表面保護シートが適用される被着体が金属板の場合には、粘着層の形成にあたり粘着付与剤を添加しない方が好ましい。 配合 Blending of tackifier is effective for improving adhesive strength. However, the blending amount of the tackifier is appropriately determined according to the adherend to which the surface protective sheet is applied in order to avoid the occurrence of the adhesive residue problem due to the decrease in cohesive force. The blending amount of the tackifier is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer. In addition, when the adherend to which the surface protective sheet is applied is a metal plate, it is preferable not to add a tackifier when forming the adhesive layer.
 粘着付与剤としては、例えば、脂肪族系共重合体、芳香族系共重合体、脂肪族・芳香族系共重合体系や脂環式系共重合体等の石油系樹脂、クマロン-インデン系樹脂、テルぺン系樹脂、テルぺンフェノール系樹脂、重合ロジン等のロジン系樹脂、(アルキル)フェノール系樹脂、キシレン系樹脂、これらの水添物などの、一般的に粘着剤に使用されるものを特に制限なく使用できる。粘着付与剤は、1種のみを用いても良いし、2種以上を用いても良い。これらの粘着付与剤の中でも、剥離性や耐候性などの点から、水添系の粘着付与剤が好ましい。なお、粘着付与剤は、オレフィン樹脂とのブレンド物として市販されているものを使用することもできる。 Examples of the tackifier include petroleum-based resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymer systems and alicyclic copolymers, and coumarone-indene resins. Terpene resins, terpene phenol resins, rosin resins such as polymerized rosin, (alkyl) phenol resins, xylene resins, hydrogenated products thereof, etc. Things can be used without any particular restrictions. Only one type of tackifier may be used, or two or more types may be used. Among these tackifiers, hydrogenated tackifiers are preferable from the viewpoint of peelability and weather resistance. In addition, what is marketed as a blend with an olefin resin can also be used for a tackifier.
 軟化剤の配合は粘着力の向上に有効である。軟化剤としては、例えば、低分子量のジエン系ポリマー、ポリイソブチレン、水添ポリイソプレン、水添ポリブタジエン、それらの誘導体などが挙げられる。このような誘導体としては、例えば、片末端または両末端にOH基やCOOH基を有するものを例示でき、具体的には、水添ポリブタジエンジオール、水添ポリブタジエンモノオール、水添ポリイソプレンジオール、水添ポリイソプレンモノオールなどが挙げられる。特に、被着体に対する粘着性の向上を抑制する目的からは、水添ポリブタジエンや水添ポリイソプレン等のジエン系ポリマーの水添物やオレフィン系軟化剤等が好ましい。このような軟化剤としては、具体的には、(株)クラレ製の商品名「クラプレンLIR-200」等が入手可能である。これら軟化剤は、1種のみを用いても良いし、2種以上を用いても良い。軟化剤の配合量は、粘着層に用いられる粘着剤に対し、好ましくは40重量%以下、より好ましくは20重量%以下、さらに好ましくは10重量%以下である。軟化剤の配合量が粘着層に用いられる粘着剤に対して40重量%以上であると、高温や屋外暴露時での糊残りが顕著となるおそれがある。 Softener blending is effective in improving adhesive strength. Examples of the softening agent include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and derivatives thereof. Examples of such derivatives include those having an OH group or a COOH group at one or both ends. Specifically, hydrogenated polybutadiene diol, hydrogenated polybutadiene monool, hydrogenated polyisoprene diol, water Examples thereof include polyisoprene monool. In particular, hydrogenated products of diene polymers such as hydrogenated polybutadiene and hydrogenated polyisoprene, olefinic softeners, and the like are preferable for the purpose of suppressing the improvement in adhesiveness to the adherend. As such a softening agent, specifically, trade name “Kuraprene LIR-200” manufactured by Kuraray Co., Ltd. is available. These softeners may be used alone or in combination of two or more. The blending amount of the softening agent is preferably 40% by weight or less, more preferably 20% by weight or less, and further preferably 10% by weight or less with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer. When the blending amount of the softening agent is 40% by weight or more with respect to the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer, there is a possibility that the adhesive residue at the time of high temperature or outdoor exposure becomes remarkable.
 軟化剤の分子量は、任意の適切な量に適宜設定できるが、分子量が小さくなると粘着層からの被着体への物質移行や重剥離化等の原因となるおそれがあり、一方、分子量が大きくなると粘着力の向上効果に乏しくなる傾向があることから、軟化剤の数平均分子量は、好ましくは5000~10万、より好ましくは1万~5万である。 The molecular weight of the softening agent can be appropriately set to any appropriate amount, but if the molecular weight is small, there is a risk of causing material transfer or heavy peeling from the adhesive layer to the adherend, while the molecular weight is large. Therefore, the softening agent has a number average molecular weight of preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
 粘着層の厚さは、要求される粘着力などに応じて、任意の適切な厚さに適宜設定すればよい。粘着層の厚さは、好ましくは1~50μm、より好ましくは2~40μm、さらに好ましくは5~20μmである。 The thickness of the adhesive layer may be appropriately set to any appropriate thickness according to the required adhesive strength. The thickness of the adhesive layer is preferably 1 to 50 μm, more preferably 2 to 40 μm, and still more preferably 5 to 20 μm.
 本発明の表面保護シートは、任意の適切な方法によって製造し得る。本発明の表面保護シートは、好ましくは、上記基材層を形成する形成材と上記粘着層を形成する形成材を用いて、基材層と粘着層を共押出し法によって成膜することにより得られる。また、溶液タイプやエマルションタイプの粘着剤を基材層の片面に塗布する方法や、セパレータ上に形成した粘着層を基材層の片面に移着する方法によっても、本発明の表面保護シートを製造し得る。
 本発明の表面保護シートの構成としては、特に限定するものではなく、「白色系層/黒色系層/粘着層」、「黒色系層/白色系層/粘着層」のいずれの構成も採用できる。また、基材層としては、黒色系層と白色系層以外の層を形成した3層以上の層構成とすることもできる。具体的には、「透明樹脂層/白色系層/黒色系層/粘着層」などの構成とすることもできる。さらに、白色系層と黒色系層の厚みは同一であってもよく、異なる厚み(白色系層が黒色系層よりも薄い厚み構成、白色系層が黒色系層よりも厚い厚み構成)であってもよい。
The surface protective sheet of the present invention can be produced by any appropriate method. The surface protective sheet of the present invention is preferably obtained by forming the base material layer and the adhesive layer by coextrusion using the forming material for forming the base material layer and the forming material for forming the adhesive layer. It is done. The surface protective sheet of the present invention can also be obtained by applying a solution-type or emulsion-type adhesive on one side of the base material layer or transferring the adhesive layer formed on the separator to one side of the base material layer. Can be manufactured.
The structure of the surface protective sheet of the present invention is not particularly limited, and any structure of “white layer / black layer / adhesive layer” and “black layer / white layer / adhesive layer” can be adopted. . Moreover, as a base material layer, it can also be set as the layer structure of 3 or more layers which formed layers other than a black-type layer and a white-type layer. Specifically, a configuration such as “transparent resin layer / white color layer / black color layer / adhesive layer” may be employed. Furthermore, the thickness of the white layer and the black layer may be the same, and the thickness may be different (a white layer is thinner than the black layer, and a white layer is thicker than the black layer). May be.
 共押出し法としては、フィルム製造などに一般的に用いられるインフレーション法、Tダイ法等に準じて行うことができる。基材層と粘着層には必要に応じて上記表面処理を施すことができる。 As the co-extrusion method, it can be carried out according to the inflation method, T-die method and the like generally used for film production. The substrate layer and the pressure-sensitive adhesive layer can be subjected to the surface treatment as necessary.
 粘着層には必要に応じて、実用に供されるまでの間、セパレータなどを仮着して保護することもできる。なお、基材層の粘着層を付設しない面に対しては、巻戻しが容易な巻回体の形成などを目的に例えば基材層への脂肪酸アミドやポリエチレンイミン等の添加による離型処理やシリコーン系や長鎖アルキル系やフッ素系などの適宜な剥離剤からなるコート層を設けることもできる。 If necessary, the adhesive layer can be protected by temporarily attaching a separator or the like until it is put to practical use. For the surface of the base material layer where the adhesive layer is not provided, for example, a mold release treatment by adding fatty acid amide or polyethyleneimine to the base material layer for the purpose of forming a wound body that can be easily rewound. It is also possible to provide a coat layer made of an appropriate release agent such as silicone, long chain alkyl, or fluorine.
 以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
〔実施例1〕
 MFR0.07の高密度ポリエチレン(東ソー製、ニポロンハード6900)に対し、MFR5の低密度ポリエチレン(日本ポリエチレン製、ノバテックLD-LF640MA)20重量%、白色顔料(大日精化社製、HCM2035W(酸化チタン濃度65重量%))15重量%(酸化チタン9.75重量%)、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材白層形成材料と、MFR0.07の高密度ポリエチレン(東ソー製、ニポロンハード6900)に対し、MFR5の低密度ポリエチレン(日本ポリエチレン製、ノバテックLD-LF640MA)20重量%、カーボンブラック(三菱化学製、カーボンブラック「#45」)2重量%、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材黒層形成材料とを、インフレーション法(ダイス温度240℃)により共押出して得られた厚さ30μm(白層/黒層=15μm/15μm)の基材層の黒層面にコロナ処理を行い、そのコロナ処理面に、ポリイソブチレン系粘着剤の20重量%トルエン溶液を塗工し、80℃で3分間乾燥処理して、厚さ10μmの粘着層を形成させた。このようにして、表面保護シートを作製した。
 得られた表面保護シートは、基材層の厚さが30μm、粘着層の厚さが10μmであった。
[Example 1]
20% by weight of MFR5 low density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA), white pigment (Daiichi Seika Co., Ltd., HCM2035W (titanium oxide concentration) 65 wt%)) 15 wt% (titanium oxide 9.75 wt%) and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 0.3 wt% 20% by weight of MFR5 low-density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA), carbon black (Mitsubishi) compared to the added base material white layer forming material and MFR0.07 high-density polyethylene (Tosoh, Nipolon Hard 6900) Chemical, carbon black “# 45”) 2% by weight, and A base black layer forming material to which 0.3% by weight of 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole was added was obtained by an inflation method (die temperature 240 ° C.). The black layer surface of the substrate layer having a thickness of 30 μm (white layer / black layer = 15 μm / 15 μm) obtained by coextrusion is subjected to corona treatment, and a 20 wt% toluene solution of a polyisobutylene pressure-sensitive adhesive is applied to the corona treatment surface. Was applied and dried at 80 ° C. for 3 minutes to form an adhesive layer having a thickness of 10 μm. In this way, a surface protective sheet was produced.
The obtained surface protective sheet had a base material layer thickness of 30 μm and an adhesive layer thickness of 10 μm.
〔実施例2〕
 MFR0.05の高密度ポリエチレン(東ソー製、ニポロンハード7300A)に対し、MFR5のホモポリプロピレン(日本ポリプロピレン製、ノバテックPP-FY4)10重量%、白色顔料(大日精化社製、HCM2035W(酸化チタン濃度65重量%))15重量%(酸化チタン9.75重量%)、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材白層形成材料と、MFR0.05の高密度ポリエチレン(東ソー製、ニポロンハード7300A)に対し、MFR5のホモポリプロピレン(日本ポリプロピレン製、ノバテックPP-FY4)10重量%、カーボンブラック(三菱化学製、カーボンブラック「#45」)2重量%、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材黒層形成材料とを用い、実施例1と同様に行って、表面保護シートを作製した。
 得られた表面保護シートは、基材層の厚さが30μm、粘着層の厚さが10μmであった。
[Example 2]
MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4) 10% by weight, white pigment (Daiichi Seika Co., Ltd., HCM2035W (titanium oxide concentration 65) 15 wt% (titanium oxide 9.75 wt%) and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 0.3 wt% added 10% by weight of MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4), carbon black (Mitsubishi Chemical) , Carbon black “# 45”) 2% by weight, and 2- ( -T-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and a base black layer forming material added thereto, and the same procedure as in Example 1 was carried out. Was made.
The obtained surface protective sheet had a base material layer thickness of 30 μm and an adhesive layer thickness of 10 μm.
〔実施例3〕
 MFR0.05の高密度ポリエチレン(東ソー製、ニポロンハード7300A)に対し、MFR5のホモポリプロピレン(日本ポリプロピレン製、ノバテックPP-FY4)20重量%、MFR5の低密度ポリエチレン(日本ポリエチレン製、ノバテックLD-LF640MA)10重量%、白色顔料(大日精化社製、HCM2035W(酸化チタン濃度65重量%))15重量%(酸化チタン9.75重量%)、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材白層形成材料と、MFR0.05の高密度ポリエチレン(東ソー製、ニポロンハード7300A)に対し、MFR5のホモポリプロピレン(日本ポリプロピレン製、ノバテックPP-FY4)20重量%、MFR5の低密度ポリエチレン(日本ポリエチレン製、ノバテックLD-LF640MA)10重量%、カーボンブラック(三菱化学製、カーボンブラック「#45」)2重量%、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材黒層形成材料とを、インフレーション法(ダイス温度240℃)により共押出して得られた厚さ25μm(白層/黒層=12.5μm/12.5μm)の基材層の黒層面にコロナ処理を行い、そのコロナ処理面に、アクリル系粘着剤を塗工し、80℃で3分間乾燥処理して、厚さ5μmの粘着層を形成させた。このようにして、表面保護シートを作製した。なお、アクリル系粘着剤は、2-エチルヘキシルアクリレート40重量部/エチルアクリレート50重量部/スチレン9重量部/アクリル酸1重量部を、酢酸エチル中で常法により重合処理して、重量平均分子量60万のポリマーを製造し、その溶液に三官能性イソシアネート5重量部を添加して調製したものである。
 得られた表面保護シートは、基材層の厚さが25μm、粘着層の厚さが5μmであった。
Example 3
20% by weight of MFR5 homopolypropylene (Nippon Polypropylene, Novatec PP-FY4) and MFR5 low density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA) with respect to MFR0.05 high density polyethylene (Tosoh, Nipolon Hard 7300A) 10% by weight, white pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W (titanium oxide concentration 65% by weight)) 15% by weight (titanium oxide 9.75% by weight), and 2- (3-t-butyl-5-methyl -2-Hydroxyphenyl) -5-chlorobenzotriazole 0.3% by weight of base material white layer forming material and MFR0.05 high density polyethylene (Tosoh Nipolon Hard 7300A), MFR5 homopolypropylene ( Nippon Polypropylene, Novatec PP-FY4) 0 wt%, MFR5 low density polyethylene (Nippon Polyethylene, Novatec LD-LF640MA) 10 wt%, carbon black (Mitsubishi Chemical, carbon black “# 45”) 2 wt%, and 2- (3-t- Thickness obtained by coextrusion with a base black layer forming material added with 0.3% by weight of butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole by an inflation method (die temperature 240 ° C.) The black layer surface of the base layer having a thickness of 25 μm (white layer / black layer = 12.5 μm / 12.5 μm) is subjected to corona treatment, and an acrylic pressure-sensitive adhesive is applied to the corona treatment surface, and then at 80 ° C. for 3 minutes. Drying treatment was performed to form a 5 μm thick adhesive layer. In this way, a surface protective sheet was produced. The acrylic pressure-sensitive adhesive was obtained by polymerizing 40 parts by weight of 2-ethylhexyl acrylate / 50 parts by weight of ethyl acrylate / 9 parts by weight of styrene / 1 part by weight of acrylic acid in an ethyl acetate by a conventional method to obtain a weight average molecular weight of 60 This was prepared by preparing 5 million polymers and adding 5 parts by weight of a trifunctional isocyanate to the solution.
The obtained surface protective sheet had a base material layer thickness of 25 μm and an adhesive layer thickness of 5 μm.
〔比較例1〕
 MFR1の高密度ポリエチレン(東ソー製、ニポロンハード5700)に対し、MFR0.05の高密度ポリエチレン(東ソー製、ニポロンハード7300A)45重量%、白色顔料(大日精化社製、HCM2035W(酸化チタン濃度65重量%))1重量%(酸化チタン0.65重量%)、および、2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール0.3重量%を添加した基材層形成材料を、インフレーション法(ダイス温度240℃)により、ブロー比5の条件で成形して得られた厚さ25μm(白層=25μm)の基材層の片面にコロナ処理を行い、そのコロナ処理面に、実施例3で得られたアクリル系粘着剤を塗工し、80℃で3分間乾燥処理して、厚さ5μmの粘着層を形成させた。このようにして、表面保護シートを作製した。
 得られた表面保護シートは、基材層の厚さが25μm、粘着層の厚さが5μmであった。
[Comparative Example 1]
MFR1 high density polyethylene (Tosoh, Nipolon Hard 5700), MFR0.05 high density polyethylene (Tosoh, Nipolon Hard 7300A) 45% by weight, white pigment (Daiichi Seika Co., Ltd., HCM2035W (Titanium oxide concentration 65% by weight) )) 1 wt% (titanium oxide 0.65 wt%) and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 0.3 wt% The material layer forming material is subjected to corona treatment on one side of a base material layer having a thickness of 25 μm (white layer = 25 μm) obtained by molding the material layer forming material under a blow ratio of 5 conditions by an inflation method (die temperature: 240 ° C.) The corona-treated surface was coated with the acrylic pressure-sensitive adhesive obtained in Example 3 and dried at 80 ° C. for 3 minutes to form a 5 μm thick pressure-sensitive adhesive layer. In this way, a surface protective sheet was produced.
The obtained surface protective sheet had a base material layer thickness of 25 μm and an adhesive layer thickness of 5 μm.
〔評価試験〕
(降伏点強度)
実施例、比較例で得た表面保護シート(幅25mm)について、引張り速度300mm/分、チャック間隔50mmの条件で引張り強度を調べた(MD方向)。試料には、初期物およびタイ国で6ヶ月間屋外暴露試験した物(タイ暴露)を用いた。その暴露試験は、表面保護シートをアクリル系クリアー塗装板(具体的には、上記アクリル系クリアー塗装板として、例えば、厚さ2mmのアルミニウム板表面に、アルミニウムホイール用アクリルメラミン塗料(日本ペイント製、スーパーラック5000AW-10クリアー)を、スプレーガンを用いて均一に塗布し、150℃で1時間乾燥させたもの等が使用できる。)に接着し、それを屋外暴露試験台に設置して、2月~8月の期間放置する条件で行った。結果を表1に示した。
〔Evaluation test〕
(Yield point strength)
About the surface protection sheet (25 mm in width) obtained in Examples and Comparative Examples, the tensile strength was examined under the conditions of a pulling speed of 300 mm / min and a chuck interval of 50 mm (MD direction). As the sample, an initial product and a product subjected to an outdoor exposure test for 6 months in Thailand (Thai exposure) were used. In the exposure test, the surface protection sheet was made of an acrylic clear coating plate (specifically, for example, the acrylic clear coating plate described above, an acrylic melamine paint for aluminum wheels (manufactured by Nippon Paint, Super rack 5000AW-10 clear) can be applied evenly using a spray gun and dried at 150 ° C. for 1 hour. The test was conducted under the condition of leaving from the month to August. The results are shown in Table 1.
(曲面接着性)
 実施例、比較例で得た表面保護シートを、半径500cmの塗装板に接着する際における作業性を調べ、次の基準で評価した。結果を表1に示した。
○:皺を生じないで接着処理しやすかった。
△:皺が入りやすく、皺を生じない接着処理に作業慣れを要した。
×:皺入りを回避できず、接着処理しにくかった。
(Curved surface adhesion)
Workability at the time of bonding the surface protective sheets obtained in Examples and Comparative Examples to a coated plate having a radius of 500 cm was examined and evaluated according to the following criteria. The results are shown in Table 1.
○: Adhesion treatment was easy without generating wrinkles.
(Triangle | delta): The work process was required for the adhesion process which is easy to enter a wrinkle and does not produce a wrinkle.
X: It was difficult to avoid wrinkling and difficult to adhere.
(長期剥離性)
 実施例、比較例で得た表面保護シートを半径500cmの塗装板に接着してそれを屋外に6ヶ月間暴露した後における剥離作業性を調べ、次の基準で評価した。結果を表1に示した。
○:シートが切れずにスムーズに剥離できた。
△:シートが時々切れて剥離しにくかった。
×:シートが非常に切れやすかった。
(Long-term peelability)
The surface protective sheets obtained in the examples and comparative examples were adhered to a coated plate having a radius of 500 cm, and the peeling workability after the exposure to the outdoors for 6 months was examined and evaluated according to the following criteria. The results are shown in Table 1.
○: The sheet could be smoothly peeled without being cut.
(Triangle | delta): The sheet | seat sometimes cut and it was hard to peel.
X: The sheet was very easy to cut.
(耐候性の測定)
 実施例および比較例で得られた表面保護シートを幅20mmの短冊状にカットして評価用サンプルを作製した。このサンプルを、SUS430BA板に、2kgのローラーを1往復させて圧着した後、サンシャイン・カーボン・ウェザーメーター(スガ試験機株式会社製品)に1000時間投入し、次いで、サンプルの一端から100mmの長さまでを0.3m/分の引張速度で180°方向に剥離した。
 上記の結果を、以下の基準で評価した。結果を表1に示した。
○:サンプルが千切れず、極めて良好に剥離できた。
×:基材の劣化によりサンプルが途中で千切れた、もしくは、粘着剤が被着体に残って汚染した。
(Measurement of weather resistance)
The surface protection sheets obtained in Examples and Comparative Examples were cut into strips having a width of 20 mm to prepare evaluation samples. This sample was pressed against a SUS430BA plate by reciprocating a 2 kg roller, and then put into a sunshine carbon weather meter (product of Suga Test Instruments Co., Ltd.) for 1000 hours, and then from one end of the sample to a length of 100 mm Was peeled in the 180 ° direction at a tensile speed of 0.3 m / min.
The above results were evaluated according to the following criteria. The results are shown in Table 1.
○: The sample was not broken and could be peeled off very well.
X: The sample was broken in the middle due to deterioration of the substrate, or the adhesive remained on the adherend and was contaminated.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1より、本発明の表面保護シートは、曲面への接着作業性に優れるとともに、耐候性に非常に優れ、接着した状態で高温屋外下に長期間放置した場合にも十分なシート強度を保持して破損等のトラブルなく容易に剥離できることが判る。 From Table 1, the surface protective sheet of the present invention has excellent workability for adhesion to curved surfaces and extremely excellent weather resistance, and retains sufficient sheet strength even when left in a hot outdoor environment for a long time. Thus, it can be easily peeled off without any trouble such as breakage.
 本発明の表面保護シートは、例えば、金属板、塗装した金属板、アルミサッシ、樹脂板、化粧鋼板、塩化ビニルラミネート鋼板、ガラス板等の部材を運搬、加工または養生する際等に、それら部材表面に貼り付けて保護する用途等に用いることができる。
 

 
The surface protective sheet of the present invention is, for example, a member such as a metal plate, a painted metal plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate, etc. It can be used for purposes such as attaching to the surface to protect.


Claims (3)

  1.  基材層の片面に粘着層が形成されている表面保護シートであって、
     該基材層は、ポリエチレン50~95重量%および酸化チタン5~30重量%を含む白色系層と、ポリエチレン50~99.9重量%およびカーボンブラック0.1~5重量%を含む黒色系層とを含み、
     該基材層は、150μm以下の厚さにおいて初期の降伏点強度が15~50N/25mmである、
     表面保護シート。
    A surface protective sheet in which an adhesive layer is formed on one side of the base material layer,
    The base material layer includes a white layer containing 50 to 95% by weight of polyethylene and 5 to 30% by weight of titanium oxide, and a black layer containing 50 to 99.9% by weight of polyethylene and 0.1 to 5% by weight of carbon black. Including
    The base material layer has an initial yield strength of 15 to 50 N / 25 mm at a thickness of 150 μm or less.
    Surface protection sheet.
  2.  前記基材層が紫外線吸収剤を0.1~2重量%の割合で含む、請求項1に記載の表面保護シート。 The surface protective sheet according to claim 1, wherein the base material layer contains an ultraviolet absorber in a proportion of 0.1 to 2% by weight.
  3.  前記降伏点強度が20~35N/25mmである、請求項1に記載の表面保護シート。

     

     
    The surface protective sheet according to claim 1, wherein the yield point strength is 20 to 35 N / 25 mm.



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