JP2014070105A - Surface protection sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface protection sheet including a substrate layer and an adhesive layer, capable of exhibiting efficiently and appropriately high adhesive force at high-speed peeling, and efficiently and appropriately high adhesive force even at high-speed peeling at low temperature, to an adherend having a rough surface.SOLUTION: A surface protection sheet includes a substrate layer and an adhesive layer and has an adhesive force to a SUS hair-line plate at 23°C of 1.0 N/20 mm or more as the adhesive force (180° peel off strength) at an extension speed of 10 m/min, and an adhesive force to the SUS hair-line plate at 5°C of 1.5 N/20 mm or more as the adhesive force (180° peel off strength) at an extension speed of 10 m/min.

Description

  The present invention relates to a surface protective sheet. In detail, this invention relates to the surface protection sheet containing a base material layer and an adhesion layer. The surface protective sheet of the present invention includes, for example, a metal plate, a paint plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate and other members, a polarizing film, an optical member such as a liquid crystal panel, and an electronic member. When transporting, processing, curing, etc., it is used for applications such as sticking to the surface for protection. The surface protective sheet of the present invention is particularly useful as a surface protective sheet for a SUS hairline plate having a hairline processed surface.

  The surface protective sheet is generally provided with an adhesive layer on one side of the base material layer. As a method for producing a surface protective sheet including such a base material layer and an adhesive layer, a method in which the base material layer and the adhesive layer are integrally formed by coextrusion molding has been proposed (for example, see Patent Document 1). .

  However, the conventional surface protection sheet does not have a sufficiently high adhesive force in the state of being attached to an adherend. For this reason, when processing the adherend to which the conventional surface protective sheet is attached, there is a problem that a part of the surface protective sheet is peeled off. In particular, for example, even if the adhesive strength at low speed peeling of about 0.3 m / min is high, there is a problem that the adhesive strength at high speed peeling of about 10 m / min is not high. Such a decrease in adhesive force during high-speed peeling is remarkable in a surface protective sheet using a synthetic rubber-based pressure-sensitive adhesive. On the other hand, both the adhesive strength at low speed peeling and the adhesive strength at high speed peeling are difficult to peel off if it is too high, so that these adhesive strengths are required to have a reasonably high level.

  In addition, the conventional surface protection sheet has a problem that adhesion to a rough surface is low. For example, when the surface is attached to a SUS hairline plate having a hairline processed, peeling or tearing may occur during processing. There is a problem that sufficient adhesion cannot be expressed.

  Furthermore, the conventional surface protection sheet is inferior in adhesive force in high-speed peeling at a low temperature. For example, in a low temperature environment of about 5 ° C., the surface protection sheet attached to the adherend is peeled off or torn during processing. There arises a problem that sufficient adhesiveness cannot be exhibited.

JP-A-61-103975

  An object of the present invention is a surface protective sheet comprising a base material layer and an adhesive layer, and has a sufficiently high and moderately high adhesive force in high-speed peeling even on an adherend having a rough surface, and at a low temperature. It is an object of the present invention to provide a surface protective sheet that can exhibit a sufficiently high and moderately high adhesive force even in high-speed peeling.

The surface protective sheet of the present invention is
A surface protective sheet comprising a base material layer and an adhesive layer,
The adhesive strength at 23 ° C. to the SUS hairline plate is 1.0 N / 20 mm or more as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min.
The adhesive strength at 5 ° C. to the SUS hairline plate is 1.5 N / 20 mm or more as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min.

The surface protective sheet of the present invention is
A surface protective sheet comprising a base material layer and an adhesive layer,
The adhesive layer comprises a styrenic thermoplastic elastomer and a tackifier;
The styrene-based thermoplastic elastomer has a styrene content of 5 wt% to 13 wt%,
The softening point of the tackifier is 90 ° C to 120 ° C.

  In a preferred embodiment, in the surface protective sheet of the present invention, the base material layer and the adhesive layer are integrally formed by coextrusion molding.

  In a preferred embodiment, in the surface protective sheet of the present invention, the base material layer contains a polyolefin-based resin as a main component.

  According to the present invention, it is a surface protective sheet including a base material layer and an adhesive layer, and the adhesion force in high-speed peeling is sufficiently and moderately high even for an adherend having a rough surface, and at a low temperature. Thus, it is possible to provide a surface protective sheet capable of exhibiting sufficient and moderately high adhesive force even in high-speed peeling at.

It is sectional drawing which shows typically the example of 1 structure of the surface protection sheet of this invention.

  The surface protective sheet of the present invention is a surface protective sheet including a base material layer and an adhesive layer. The surface protective sheet of the present invention may contain any appropriate other layer as long as the effects of the present invention are not impaired.

  The thickness of the base material layer is preferably 20 μm to 300 μm, more preferably 30 μm to 250 μm, still more preferably 40 μm to 200 μm, particularly preferably 45 μm to 150 μm, and most preferably 50 μm to 100 μm. is there. By adjusting the thickness of the base material layer within the above range, the base material layer is not easily torn or torn when it is peeled off after the surface protective sheet of the present invention is applied to the adherend. Since it is possible to suppress the stiffness of the layer from being increased, it is difficult for floating or the like to occur after the surface protective sheet of the present invention is applied to the adherend.

  The thickness of the adhesive layer is preferably 1 μm to 50 μm, more preferably 2 μm to 40 μm, further preferably 3 μm to 30 μm, particularly preferably 4 μm to 20 μm, and most preferably 5 μm to 10 μm. . By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, it becomes easy to control the layer structure when producing the surface protective sheet of the present invention by coextrusion molding, and the surface protection has sufficient mechanical strength. A sheet can be obtained.

  The total thickness of the surface protective sheet of the present invention is preferably 30 μm to 150 μm, more preferably 35 μm to 140 μm, still more preferably 40 μm to 130 μm, particularly preferably 45 μm to 120 μm, and most preferably. Is 50 μm to 110 μm. By adjusting the total thickness of the surface protective sheet of the present invention within the above range, a surface protective sheet having excellent mechanical properties and excellent handleability can be obtained.

  The surface protective sheet of the present invention is preferably formed by integrally forming a base material layer and an adhesive layer by coextrusion molding. As the coextrusion molding, any appropriate coextrusion molding generally used for production of films, sheets and the like can be adopted. As the coextrusion molding, for example, an inflation method, a coextrusion T-die method, or the like can be adopted. These coextrusion molding is preferable in terms of cost and productivity.

  The surface protective sheet of the present invention is excellent in adhesion to an adherend having a rough surface. Examples of such an adherend having a rough surface include an adherend having a rough surface with a surface roughness Ra of 0.210 μm to 0.310 μm. Among such adherends, the surface protective sheet of the present invention can exhibit particularly excellent effects as a surface protective sheet for a SUS hairline plate having a hairline processed surface. In the present specification, what is referred to as “SUS hairline plate” is a SUS plate having a hairline processed surface, and has a rough surface with a surface roughness Ra of 0.210 μm to 0.310 μm. In the present invention, the surface roughness Ra was measured in a direction perpendicular to the stripe direction of the hairline using a contact-type surface roughness meter (SJ400: manufactured by Mitutoyo Corporation) in a hairline processed SUS plate (measurement). Conditions: Measured according to JIS-B-0601: (2001), specifically, measured at a stylus radius of 2 μm, a cutoff value of 0.8 mm, and a measurement length of 4 mm).

  In the surface protective sheet of the present invention, the adhesive strength at 23 ° C. to the SUS hairline plate is preferably 1.0 N / 20 mm or more, more preferably as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min. 1N / 20mm to 5N / 20mm, more preferably 1N / 20mm to 4N / 20mm, and particularly preferably 1N / 20mm to 3N / 20mm. If the adhesive strength at 23 ° C. to the SUS hairline plate falls within the above range as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min, the surface protective sheet of the present invention is sufficient for high-speed peeling at room temperature. Moreover, moderately high adhesive force can be expressed. In addition, the measuring method of the various adhesive force with respect to a SUS hairline board is mentioned later.

  In the surface protective sheet of the present invention, the adhesive strength at 5 ° C. to the SUS hairline plate is preferably 1.5 N / 20 mm or more as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min, more preferably It is 1.5N / 20mm-5N / 20mm, More preferably, it is 1.5N / 20mm-4N / 20mm, Most preferably, it is 1.5N / 20mm-3.5N / 20mm. If the adhesive strength at 5 ° C. to the SUS hairline plate falls within the above range as the adhesive strength at 180 ° peel at a tensile speed of 10 m / min, the surface protective sheet of the present invention is sufficient for high-speed peeling at low temperatures. Moreover, moderately high adhesive force can be expressed. In addition, the measuring method of the various adhesive force with respect to a SUS hairline board is mentioned later.

  In the surface protective sheet of the present invention, the adhesive strength at 10 ° C. to the SUS hairline plate is preferably 1.5 N / 20 mm or more, more preferably as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min. It is 1.5N / 20mm-5N / 20mm, More preferably, it is 1.5N / 20mm-4N / 20mm, Most preferably, it is 1.5N / 20mm-3.5N / 20mm. If the adhesive strength at 10 ° C. to the SUS hairline plate is within the above range as the adhesive strength at 180 ° peel at a tensile speed of 10 m / min, the surface protective sheet of the present invention is sufficient for high-speed peeling at low temperatures. Moreover, moderately high adhesive force can be expressed. In addition, the measuring method of the various adhesive force with respect to a SUS hairline board is mentioned later.

  The base material layer preferably contains a polyolefin resin as a main component. When the base material layer contains a polyolefin-based resin as a main component, it can have heat resistance, solvent resistance, and flexibility, and can be easily wound into a roll. The polyolefin resin contained in the base material layer may be only one type or two or more types. The base material layer may be a single layer or a plurality of layers.

  Here, the “main component” in the present invention is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. Yes, and most preferably 90% by weight or more.

  Examples of the polyolefin resin include a polyethylene resin, propylene or a propylene resin composed of a propylene component and an ethylene component, and an ethylene vinyl acetate copolymer.

  Specific examples of the polyolefin resin include, for example, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene, poly-1-butene, poly -4-methyl-1-pentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1 -Octene copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl alcohol copolymer, etc. It is done.

  When the base material layer is composed of two or more layers, each adjacent layer should be selected as a resin component that can form a strong bond with each other by melt coextrusion. Is preferred.

  The base material layer may include a white layer. When the base material layer includes a white layer, a surface protective sheet having excellent weather resistance can be obtained.

  The base material layer may include a black layer. When the base material layer includes a black layer, a surface protective sheet having excellent weather resistance can be obtained.

  The base material layer preferably includes at least two layers of a white layer and a black layer. When the base material layer includes at least two layers of a white layer and a black layer, a surface protective sheet having excellent weather resistance can be obtained.

  When the base material layer includes at least two layers of a white layer and a black layer, examples of the laminated structure of the surface protective sheet of the present invention include “white layer / black layer / adhesive layer”, “black layer” As long as the effects of the present invention are not impaired, such as “/ white color layer / adhesive layer”, any appropriate laminated structure can be adopted. FIG. 1 is a cross-sectional view schematically showing a configuration example in the case where the surface protective sheet 100 of the present invention has a laminated configuration of “white layer 21 / black layer 22 / adhesive layer 10”. The white layer 21 and the black layer 22 become the base material layer 20.

  The white layer is a layer showing a white color tone. For example, the whiteness defined by JIS-L-1015 is preferably 60% or more, more preferably 70% or more, and still more preferably. It is 80% or more, and particularly preferably 85% or more. The white layer preferably contains a white pigment. Any appropriate white pigment can be adopted as the white pigment. An example of such a white pigment is titanium oxide. When the white layer contains a white pigment, the content is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40%, with respect to the resin component forming the white layer. % By weight, more preferably 2% by weight to 30% by weight. When the content ratio of the white pigment to the resin component forming the white layer falls within the above range, a surface protective sheet having excellent weather resistance can be obtained, and extrudability and other moldability are also excellent.

The resin component forming the white layer is preferably a polyolefin resin, more preferably a propylene polymer or an ethylene polymer. Specific examples of the resin component forming the white layer include homopolypropylene, block polypropylene, random polypropylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene ( LLDPE) is preferred. The white layer preferably contains a polyethylene resin as a main component. The density of the polyethylene resin is preferably 0.880 g / cm ^{3 to} 0.940 g / cm ³ , more preferably 0.880 g / cm ^{3 to} 0.923 g / cm ³ , and still more preferably 0 .880 g / cm ^{3 to} 0.915 g / cm ³ . When the white layer contains a polyethylene resin as a main component, the base layer can have heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be easily wound into a roll. Is possible. When the white layer includes a polyethylene resin as a main component, the polyethylene resin preferably includes a low density polyethylene. When the polyethylene-based resin contains low-density polyethylene, the base material layer can sufficiently have heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be more easily wound into a roll. It becomes possible.

  The content ratio of the polyolefin resin in the white layer is preferably 60% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, and particularly preferably 85% by weight or more. Yes, most preferably 90% by weight or more. Such polyolefin resin may use only 1 type, and may use 2 or more types.

  Arbitrary appropriate thickness can be employ | adopted for the thickness of a white type | system | group layer according to the objective. Such thickness is preferably 2 μm to 100 μm, more preferably 3 μm to 80 μm, still more preferably 4 μm to 60 μm, and particularly preferably 5 μm to 50 μm.

  The black layer is a layer showing a black color tone. The black layer preferably contains a black pigment. Any appropriate black pigment can be adopted as the black pigment. An example of such a black pigment is carbon black. When the black layer contains a black pigment, the content is preferably 0.01% by weight to 10% by weight and more preferably 0.1% by weight with respect to the resin component forming the black layer. -5% by weight, more preferably 0.5-3% by weight. When the content ratio of the black pigment to the resin component forming the black layer falls within the above range, a surface protective sheet having excellent weather resistance can be obtained, and extrudability and other moldability are also excellent.

The resin component forming the black layer is preferably a polyolefin resin, more preferably a propylene polymer or an ethylene polymer. Specific examples of the resin component forming the black layer include homopolypropylene, block polypropylene, random polypropylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene ( LLDPE) is preferred. The black layer preferably contains a polyethylene resin as a main component. The density of the polyethylene resin is preferably 0.880 g / cm ^{3 to} 0.940 g / cm ³ , more preferably 0.880 g / cm ^{3 to} 0.923 g / cm ³ , and still more preferably 0 .880 g / cm ^{3 to} 0.915 g / cm ³ . When the black layer contains a polyethylene resin as a main component, the base layer can have heat resistance, solvent resistance, and flexibility, and the surface protection sheet of the present invention can be easily wound into a roll. Is possible. When the black layer includes a polyethylene resin as a main component, the polyethylene resin preferably includes a low density polyethylene and a linear low density polyethylene. When the polyethylene-based resin includes low-density polyethylene and linear low-density polyethylene, the base material layer can have sufficient heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention is rolled. It becomes possible to wind it up more easily.

  The content of the polyolefin resin in the black layer is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 85% by weight or more. Yes, most preferably 90% by weight or more. Such polyolefin resin may use only 1 type, and may use 2 or more types.

  Arbitrary appropriate thickness can be employ | adopted for the thickness of a black type | system | group layer according to the objective. Such thickness is preferably 2 μm to 100 μm, more preferably 3 μm to 80 μm, still more preferably 4 μm to 60 μm, and particularly preferably 5 μm to 50 μm.

  The base material layer may contain any appropriate additive. Examples of such additives include antioxidants, ultraviolet absorbers, anti-aging agents, light stabilizers, antistatic agents, surface lubricants, leveling agents, plasticizers, low molecular weight polymers, corrosion inhibitors, and polymerization prohibitions. Agents, silane coupling agents, inorganic and organic fillers (eg, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.), metal powders, colorants, pigments, heat stabilizers, anti-spot agents, lubricants And anti-blocking agents.

  The base material layer preferably contains a light stabilizer. When the base material layer contains a light stabilizer, sufficient weather resistance can be imparted to the surface protective sheet of the present invention.

  Any appropriate light stabilizer can be adopted as the light stabilizer as long as the effects of the present invention are not impaired. As such a light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferably exemplified.

  When the base material layer contains a light stabilizer, the content ratio of the light stabilizer is preferably 0.10% by weight or more, more preferably 0% with respect to the total weight of the surface protective sheet of the present invention. 20 wt% to 0.64 wt%, more preferably 0.30 wt% to 0.60 wt%, and particularly preferably 0.34 wt% to 0.55 wt%. When the base material layer includes a light stabilizer, if the content ratio of the light stabilizer is within the above range with respect to the total weight of the surface protective sheet of the present invention, the surface protective sheet of the present invention is more sufficient. Weather resistance can be imparted.

  A back surface treatment may be applied to the outermost layer on the side opposite to the adhesive layer of the base material layer. Any appropriate method can be adopted as the back surface processing method as long as the effects of the present invention are not impaired. Examples of the back treatment method include surface processing such as embossing and uneven processing, a method of containing a fatty acid derivative, and the like. Only one kind of such fatty acid derivative may be used, or two or more kinds thereof may be used.

  When the base material layer contains a fatty acid derivative, the content ratio of the fatty acid derivative in the base material layer is preferably 0.05% by weight to 1.00% by weight with respect to the resin component in the base material layer, More preferably, it is 0.10 weight%-0.90 weight%, More preferably, it is 0.30 weight%-0.80 weight%. If the content ratio of the fatty acid derivative in the base material layer is within the above range with respect to the resin component in the base material layer, the roll-shaped surface protection sheet of the present invention can be easily rewound. Thus, the mold release effect can be sufficiently exhibited, and the contamination of the fatty acid derivative by bleeding can be sufficiently suppressed.

  The fatty acid derivative refers to a compound containing a fatty acid derivative structure in the molecular structure.

  Examples of the fatty acid derivatives include saturated fatty acid bisamides, unsaturated fatty acid bisamides, aromatic bisamides, substituted ureas, and fatty acid metal salts. Specific examples of fatty acid derivatives include methylene bis stearamide, ethylene bis stearamide, ethylene bis oleate, ethylene bis behenate amide, N, N-dioleyl adipate amide, N-stearyl- N-stearyl-N′-stearylamide such as N′-stearyl urea, zinc stearate and the like can be mentioned.

  The fatty acid derivative is preferably a fatty acid amide, more preferably at least one selected from methylene bis stearic acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, N-stearyl-N′-stearyl acid amide. It is a seed.

  The fatty acid derivative preferably has a melting point of 100 ° C. or higher. A fatty acid derivative having a melting point of less than 100 ° C. has a significant transfer to the surface of the adhesive layer, and there is a risk that a decrease in adhesive strength is likely to occur.

  The adhesive layer preferably contains a thermoplastic resin as a main component. The thermoplastic resin contained in the adhesive layer may be only one type or two or more types.

  Any appropriate thermoplastic resin can be adopted as the thermoplastic resin. Examples of such thermoplastic resins include olefin resins, aromatic group-containing olefin / diene copolymers, styrene resins, ester resins, and the like. Among these thermoplastic resins, styrene resins are preferable, and styrene thermoplastic elastomers are more preferable.

  Preferred examples of the styrenic thermoplastic elastomer include hydrogenated styrene / butadiene rubber (HSBR), a styrene block copolymer, and a hydrogenated product thereof.

  Examples of styrene block copolymers include styrene ABA block copolymers (triblock copolymers) such as styrene / butadiene / styrene copolymers (SBS) and styrene / isoprene / styrene copolymers (SIS). ); Styrenic ABAB type block copolymer (tetrablock copolymer) such as styrene / butadiene / styrene / butadiene copolymer (SBSB), styrene / isoprene / styrene / isoprene copolymer (SISI); styrene / butadiene・ Styrene-based ABABA block copolymer (pentablock copolymer) such as styrene / butadiene / styrene copolymer (SBSBS), styrene / isoprene / styrene / isoprene / styrene copolymer (SISIS); Styrene group having repeating units Click copolymers; and the like.

  Examples of hydrogenated styrenic block copolymers include styrene / ethylene-butylene copolymer / styrene copolymer (SEBS), styrene / ethylene-propylene copolymer / styrene copolymer (SEPS), and styrene. -Ethylene-butylene copolymer-Styrene-ethylene-butylene copolymer copolymer (SEBSEB);

  Only one type of styrenic thermoplastic elastomer may be used, or two or more types may be used.

  The styrene content in the styrenic thermoplastic elastomer (styrene block content in the case of a styrene block copolymer) is preferably 5% by weight to 13% by weight, more preferably 1% by weight to 20% by weight, Preferably they are 2 weight%-18 weight%, Especially preferably, they are 3 weight%-15 weight%. By adjusting the styrene content within the above range, the surface protective sheet of the present invention can exhibit sufficiently and moderately high adhesive force in high-speed peeling even on an adherend having a rough surface. Adequately and moderately high adhesive strength can be expressed in high-speed peeling at low temperatures. When the styrene content decreases, there is a risk that adhesive residue due to insufficient cohesive force of the adhesive layer is likely to occur. When the styrene content increases, the pressure-sensitive adhesive layer becomes hard, and there is a possibility that good adhesion to a rough surface cannot be obtained.

  As the styrene-based thermoplastic elastomer, hydrogenation of a styrene-based block copolymer having a repeating structure (ABA type, ABAB type, ABABA type, etc.) more than a triblock copolymer composed of styrene (A) and butadiene (B). Goods (SEBS, SEBSEB, SEBSEBS, etc.) are preferred. By adopting such a styrenic thermoplastic elastomer, the adhesive force in the state of being applied to the adherend can be increased more moderately, while the adhesive force when peeling off after being attached to the adherend is more appropriate. Therefore, it can be peeled off from the adherend more easily with a slight force, and the increase in adhesive strength when exposed to an environmental load for long-term storage at relatively high temperatures is further suppressed. it can.

  Hydrogenated product of styrene-based block copolymer in which the styrene-based thermoplastic elastomer has a repetitive structure (ABA type, ABAB type, ABABA type, etc.) of a triblock copolymer or more composed of styrene (A) and butadiene (B) (SEBS, SEBSEB, SEBSEBS, etc.) The proportion of the butylene structure in the ethylene-butylene copolymer block is preferably 60% by weight or more, more preferably 70% by weight or more, and even more preferably 75. % By weight or more. When the proportion of the butylene structure in the ethylene-butylene copolymer block falls within the above range, the adhesive force in the state of application to the adherend can be increased more moderately, on the other hand, after being attached to the adherend Adhesive strength at the time of peeling is a more appropriate size, therefore, it can be peeled off from the adherend more easily with a slight force, and further exposed to the environmental load of long-term storage at relatively high temperatures. In this case, the increase in adhesive strength can be further suppressed. The proportion of the butylene structure in the ethylene-butylene copolymer block is preferably 90% by weight or less.

  The pressure-sensitive adhesive layer may contain other styrenic thermoplastic elastomers within the range that does not impair the object of the present invention for the purpose of adjusting the adhesiveness.

  Other styrene thermoplastic elastomers include styrene block copolymers other than those described above; styrene / butadiene copolymers (SB), styrene / isoprene copolymers (SI), and copolymers of styrene / ethylene-butylene copolymers. AB block polymers such as polymers (SEB) and styrene / ethylene-propylene copolymer (SEP); styrene random copolymers such as styrene / butadiene rubber (SBR); styrene / ethylene-butylene copolymer Examples thereof include ABC type styrene / olefin crystal block polymers such as a polymer / olefin crystal copolymer (SEBC); hydrogenated products thereof.

  In the formation of the adhesive layer, for the purpose of controlling adhesive properties, etc., for example, softening agents, tackifiers, polyolefin resins such as those used for the base material layer, silicone polymers, liquid acrylic copolymers are used. Polymer, Phosphate ester compound, Anti-aging agent, Light stabilizer, UV absorber, Surface lubricant, Leveling agent, Plasticizer, Low molecular weight polymer, Antioxidant, Corrosion inhibitor, Polymerization inhibitor, Silane cup Additives such as ring agents, inorganic and organic fillers (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.), metal powder, colorants, pigments, heat stabilizers, etc. may be added as appropriate. it can.

  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.

  The formulation of the tackifier is effective for improving the 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 compounding amount of the tackifier is preferably 80% by weight or less, more preferably 40% by weight or less, and further preferably 20% by weight or less with respect to the base polymer of the adhesive layer.

  The softening point of the tackifier is preferably 90 ° C to 120 ° C, more preferably 70 ° C to 135 ° C, still more preferably 80 ° C to 130 ° C, and particularly preferably 85 ° C to 125 ° C. . By adjusting the softening point of the tackifier to be in the above range, the surface protective sheet of the present invention has a sufficiently high and moderately high adhesive force for high-speed peeling even on an adherend having a rough surface. Moreover, sufficient and moderately high adhesive force can be expressed in high-speed peeling at a low temperature.

  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, particularly C5 hydrogenated aromatic petroleum resins, are preferable from the viewpoints of peelability and weather resistance. In addition, what is marketed as a blend with an olefin resin can also be used for a tackifier.

  The blending of the softener is effective for improving the 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 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. Since there exists a tendency for it to become scarce at the improvement effect of adhesive force, the number average molecular weight of a softener becomes like this. Preferably it is 5000-100,000, More preferably, it is 10,000-50,000.

  When using a softener, the amount added can be appropriately set to any appropriate amount. However, as the amount added increases, the adhesive residue tends to increase at high temperatures and when exposed outdoors. On the other hand, it is preferably 100% by weight or less, more preferably 60% by weight or less, and still more preferably 40% by weight or less.

  A polyolefin-based resin may be added to the adhesive layer for the purpose of suppressing an increase in adhesive force. Examples of the polyolefin resin can be the same as those used for forming the base material layer. This polyolefin resin may be only one kind or two or more kinds. The blending amount of the polyolefin resin is preferably 50% by weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less with respect to the base polymer of the adhesive layer.

  If necessary, a separator or the like can be temporarily attached to the adhesive layer until it is put to practical use.

  The method for producing the surface protective sheet of the present invention is preferably produced by integrally forming the base material layer and the adhesive layer by coextrusion molding. Thereby, the surface protection sheet of the laminated structure which has predetermined | prescribed thickness can be manufactured highly efficiently and cheaply. As the coextrusion molding, any appropriate coextrusion molding generally used for production of films, sheets and the like can be adopted. As the coextrusion molding, for example, an inflation method, a coextrusion T-die method, or the like can be adopted.

  According to the co-extrusion molding, the outermost surface on the opposite side of the adhesive layer of the base material layer and the adhesive layer are not in contact with each other in the melt-heated state. There is no production of by-products and no transfer of the by-products to the adhesive layer, and excellent unwinding properties are exhibited, and contamination of the adhesive layer surface can be suppressed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all.

(Density measurement)
The density (g / cm ³ ) of the resin was a value measured according to ISO 1183.

(Measurement of adhesive strength at 23 ° C, 5 ° C, 10 ° C for SUS hairline plate)
The adhesive strength at 23 ° C., 5 ° C., and 10 ° C. to the SUS hairline plate was measured according to JIS-Z-0237 (2000). Specifically, a SUS hairline plate having a surface roughness Ra in the range of 0.210 to 0.310 is used as the adherend, and after washing the surface of the SUS hairline plate with toluene, the 2 kg roller is reciprocated once. The sample for evaluation was pressure-bonded, and after 30 minutes, the tensile speed was set to 10 m / min with an Instron type tensile tester (manufactured by Shimadzu Corporation, Autograph), and the initial adhesive strength was 180 ° peel. It was measured. At this time, the measurement environment and storage environment were 23 ° C .: temperature 23 ° C./humidity 50%, 5 ° C .: temperature 5 ° C./humidity 50%, 10 ° C .: temperature 10 ° C./humidity 50%.

(Coextrusion molding conditions)
In Examples and Comparative Examples, molding was performed by an inflation method according to the following melting temperature conditions.
Base material layer: 165 ° C
Adhesive layer: 165 ° C
Coextrusion temperature: 165 ° C

[Example 1]
Low-density polyethylene (trade name: Petrocene 186R, density = 0.924 g / cm ³ ), white pigment (titanium oxide, manufactured by Dupont, trade name: Ti-Pure R103), hindered amine light stabilizer (HALS, manufactured by BASF, trade name: Tinuvin 783) was blended in the content ratio shown in Table 1 to obtain a white layer forming material.
Next, 85% by weight of low density polyethylene (manufactured by Tosoh, trade name: Petrocene 186R, density = 0.924 g / cm ³ ) and linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen FX FX307, density = 0) .890 g / cm ³ ) 10% by weight of a resin mixture containing 5% by weight of carbon black MB (manufactured by Sumika Color, trade name: Black SPEMB-865, carbon content 20%) A layer forming material was obtained.
Furthermore, HSBR (styrene content = 10% by weight, manufactured by JSR, trade name: Dynalon 1321P) and a tackifier (C5 hydrogenated aromatic petroleum resin, manufactured by Eastman Chemical, trade name: EASTOTAC C115W, softening point) = 115 ° C) 18 wt% was blended to obtain an adhesive layer forming material.
Using the white layer forming material, black layer forming material, and adhesive layer forming material obtained above, the surface of a three-layer structure (white layer / black layer / adhesive layer) by coextrusion molding by the inflation method A protective sheet (1) (thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm) was obtained.
The results are shown in Table 1.

[Example 2]
A surface protective sheet (2) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black) was carried out in the same manner as in Example 1 except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 1.

Example 3
The surface of a three-layer structure (white layer / black layer / adhesive layer) was carried out in the same manner as in Example 1 except that the blending ratio of HSBR was 80 wt% and the blending ratio of the tackifier was 20 wt%. A protective sheet (3) (thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm) was obtained.
The results are shown in Table 1.

Example 4
A surface protective sheet (4) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black) was carried out in the same manner as in Example 3 except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 1.

Example 5
The surface of a three-layer structure (white layer / black layer / adhesive layer) was carried out in the same manner as in Example 1 except that the blending ratio of HSBR was 85 wt% and the blending ratio of the tackifier was 15 wt%. A protective sheet (5) (thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm) was obtained.
The results are shown in Table 1.

Example 6
A surface protective sheet (6) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black) was carried out in the same manner as in Example 5 except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 1.

[Comparative Example 1]
SEBS (hydrogenated SEBS, styrene content = 15 wt%, manufactured by JSR, trade name: Dynalon 8600P) and 82 wt% tackifier (C5 hydrogenated aromatic petroleum resin, manufactured by Idemitsu Kosan, trade name: Imabu P140, softening) Surface protection sheet having a three-layer structure (white layer / black layer / adhesive layer), except that the adhesive layer forming material was obtained by blending 18% by weight (point = 140 ° C.). (C1) (Thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm) was obtained.
The results are shown in Table 2.

[Comparative Example 2]
Surface protection sheet (C2) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black), except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 2.

[Comparative Example 3]
HSBR (styrene content = 10% by weight, manufactured by JSR, trade name: Dynalon 1321P) and tackifier (C5 hydrogenated aromatic petroleum resin, manufactured by Idemitsu Kosan, trade name: Imabe P140, softening point = 140 ° C. ) 18% by weight, except that an adhesive layer forming material was obtained, and the same procedure as in Example 1 was performed, and the surface protective sheet (C3) having a three-layer structure (white layer / black layer / adhesive layer) ( Thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm).
The results are shown in Table 2.

[Comparative Example 4]
Surface protection sheet (C4) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black), except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 2.

[Comparative Example 5]
SEBS (hydrogenated SEBS, styrene content = 15 wt%, manufactured by JSR, trade name: Dynalon 8600P) and 82 wt% tackifier (C5 hydrogenated aromatic petroleum resin, Eastman Chemical, trade name: EASTOTAC C115W, (Softening point = 115 ° C.) 18% by weight, except that an adhesive layer forming material was obtained, and the same procedure as in Example 1 was performed to protect the surface of the three-layer structure (white layer / black layer / adhesive layer). A sheet (C5) (thickness: white layer / black layer / adhesive layer = 20 μm / 35 μm / 5 μm) was obtained.
The results are shown in Table 2.

[Comparative Example 6]
A surface protective sheet (C6) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black) was carried out in the same manner as Comparative Example 5 except that the thickness of the black layer was changed to 45 μm. System layer / adhesive layer = 20 μm / 45 μm / 5 μm).
The results are shown in Table 2.

[Comparative Example 7]
Surface protection sheet (C7) having a three-layer structure (white layer / black layer / adhesive layer) was performed in the same manner as Comparative Example 1 except that the thickness of the black layer was 90 μm and the thickness of the adhesive layer was 10 μm. Thickness: white layer / black layer / adhesive layer = 20 μm / 90 μm / 10 μm).
The results are shown in Table 2.

[Comparative Example 8]
Surface protection sheet (C8) having a three-layer structure (white layer / black layer / adhesive layer) is carried out in the same manner as Comparative Example 1 except that the thickness of the black layer is 70 μm and the thickness of the adhesive layer is 10 μm. Thickness: white layer / black layer / adhesive layer = 20 μm / 70 μm / 10 μm).
The results are shown in Table 2.

  From Tables 1 and 2, the surface protective sheet of the present invention has a sufficiently high and moderate adhesive force for high-speed peeling even on an adherend having a rough surface, and also for high-speed peeling at low temperatures. It can be seen that sufficient and moderately high adhesive strength can be expressed.

  The surface protective sheet of the present invention includes, for example, a metal plate, a paint plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate and other members, a polarizing film, an optical member such as a liquid crystal panel, and an electronic member. When transporting, processing, curing, etc., it is used for applications such as sticking to the surface for protection. The surface protective sheet of the present invention is particularly useful as a surface protective sheet for a SUS hairline plate having a hairline processed surface.

DESCRIPTION OF SYMBOLS 100 Surface protection sheet 10 Adhesion layer 20 Base material layer 21 White type layer 22 Black type layer

Claims (4)

A surface protective sheet comprising a base material layer and an adhesive layer,
The adhesive strength at 23 ° C. to the SUS hairline plate is 1.0 N / 20 mm or more as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min.
The adhesive strength at 5 ° C. to the SUS hairline plate is 1.5 N / 20 mm or more as the adhesive strength at 180 ° peel when the tensile speed is 10 m / min.
Surface protection sheet. A surface protective sheet comprising a base material layer and an adhesive layer,
The adhesive layer comprises a styrenic thermoplastic elastomer and a tackifier;
The styrene-based thermoplastic elastomer has a styrene content of 5 wt% to 13 wt%,
The softening point of the tackifier is 90 ° C to 120 ° C.
Surface protection sheet.   The surface protection sheet according to claim 1 or 2, wherein the base material layer and the adhesive layer are integrally formed by coextrusion molding. The surface protection sheet in any one of Claim 1 to 3 in which the said base material layer contains polyolefin resin as a main component.

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