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WO2013121845A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121845A1
WO2013121845A1 PCT/JP2013/051368 JP2013051368W WO2013121845A1 WO 2013121845 A1 WO2013121845 A1 WO 2013121845A1 JP 2013051368 W JP2013051368 W JP 2013051368W WO 2013121845 A1 WO2013121845 A1 WO 2013121845A1
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
layer
adhesive layer
weight
surface protection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/051368
Other languages
English (en)
Japanese (ja)
Inventor
公平 武田
生島　伸祐
二郎 山戸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of WO2013121845A1 publication Critical patent/WO2013121845A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional 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
    • C09J2301/162—Additional 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

Definitions

  • the present invention relates to a surface protection sheet.
  • the present invention is, for example, when 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, or a glass plate is transported, processed, or cured.
  • the present invention relates to a surface protective sheet that can be used for applications such as sticking to a surface for protection.
  • the characteristics required for the surface protective sheet include that the surface protective sheet does not float or peel off after being attached to the adherend, and that the adhesive layer does not remain on the adherend when it is peeled off.
  • the surface protection sheet attached to the adherend is subjected to harsh conditions such as high temperature or outdoor exposure before the surface protection sheet is peeled off, Even more advanced characteristics are required for the required characteristics.
  • a natural rubber pressure-sensitive adhesive in which an appropriate amount of a tackifier or the like is blended with natural rubber or modified natural rubber has been used for a pressure-sensitive adhesive layer of a surface protection sheet that is generally used.
  • a surface protective sheet is not particularly problematic for indoor use.
  • the natural rubber-based pressure-sensitive adhesive has an unsaturated double bond in its structure, and therefore, when exposed outdoors, it causes molecular cleavage by ultraviolet rays. For this reason, when peeling off the surface protection sheet in which the natural rubber-based pressure-sensitive adhesive is used, there arises a problem that the pressure-sensitive adhesive remains on the adherend. Therefore, a surface protective sheet with good weather resistance is desired.
  • an acrylic pressure-sensitive adhesive having a cohesive force increased by three-dimensionally crosslinking the acrylic copolymer with an isocyanate compound or a methylol compound in order to form an adhesive layer
  • Synthetic rubber adhesives such as polyisobutylene have been proposed.
  • these pressure-sensitive adhesives are solvent-based, there are problems in terms of safety and hygiene of the surface protection sheet, in terms of pollution and economy.
  • thermoplastic elastomers that can be co-extruded include styrene / ethylene-butylene copolymer / styrene block polymer (SEBS), styrene / ethylene-propylene copolymer / styrene block polymer (SEPS), etc.
  • SEBS styrene / ethylene-butylene copolymer / styrene block polymer
  • SEPS styrene / ethylene-propylene copolymer / styrene block polymer
  • These styrenic block copolymers have sufficient adhesion to adherend surfaces such as stainless steel plates and resin plates having a relatively smooth adherend surface.
  • these styrenic block copolymers have poor adhesiveness to adherend surfaces such as polished stainless steel plates (hairline plates) and rough resin plates.
  • a surface protective sheet having a pressure-sensitive adhesive layer using a large amount of a tackifier or the like increases its adhesive strength in a relatively short time when stored at high temperatures, such as in a warehouse in a summer or in a container. End up. Such an increase in adhesive force has a problem such as causing a peeling failure.
  • a peeling failure occurs due to the influence of a tackifier or the like.
  • An object of the present invention is a surface protective sheet in which a base material layer containing a polyolefin-based resin and an adhesive layer containing a styrene-based thermoplastic elastomer are formed by coextrusion, and has an adhesive force to various adherends. Is excellent in weather resistance, even when used outdoors or stored under high temperature, there is little increase in adhesive strength, and good peelability when peeling from the adherend.
  • the object is to provide a surface protection sheet.
  • the surface protective sheet of the present invention is A surface protection sheet in which a base material layer containing a polyolefin-based resin and an adhesive layer containing a styrene-based thermoplastic elastomer are formed by coextrusion,
  • the base material layer includes at least two layers of a white layer and a black layer,
  • the polyolefin resin is an ethylene polymer having a density of 0.88 to 0.93 g / cm 3 ;
  • the styrenic thermoplastic elastomer is a styrenic block copolymer having a maximum tan ⁇ value of dynamic viscoelasticity measurement in a measurement temperature range of ⁇ 60 to 100 ° C. or hydrogenation thereof. It is a thing.
  • the adhesive layer has a shear storage modulus at 23 ° C. of 1.0 ⁇ 10 5 to 8.0 ⁇ 10 5 Pa.
  • the adhesive layer contains a softening agent, and the number average molecular weight of the softening agent is 5000 to 100,000.
  • a surface protective sheet in which a base material layer containing a polyolefin resin and an adhesive layer containing a styrene thermoplastic elastomer are formed by coextrusion, and has an adhesive force to various adherends. Is excellent in weather resistance, even when used outdoors or stored under high temperature, there is little increase in adhesive strength, and good peelability when peeling from the adherend.
  • a surface protective sheet can be provided.
  • a base material layer containing a polyolefin resin and an adhesive layer containing a styrene thermoplastic elastomer are formed by coextrusion.
  • the styrenic thermoplastic elastomer forming the adhesive layer has a styrene block co-polymer with a maximum temperature of tan ⁇ of dynamic viscoelasticity measurement in the measurement temperature range of ⁇ 60 to 100 ° C. of ⁇ 40 to ⁇ 25 ° C. A coalescence or a hydrogenated product thereof is used.
  • a styrene block copolymer showing the maximum tan ⁇ value of dynamic viscoelasticity measurement at a higher temperature than conventional is used as the styrene thermoplastic elastomer used for forming the adhesive layer.
  • the adhesiveness of the adhesive layer increases as the temperature at which the maximum tan ⁇ value is increased. Further, by adjusting the temperature showing the maximum tan ⁇ value to ⁇ 40 to ⁇ 25 ° C., moderate wettability can be obtained. For this reason, the adhesive layer in this invention has sufficient wettability and adhesiveness, even if it does not add a tackifier etc. in large quantities.
  • the surface protective sheet of the present invention having such an adhesive layer adheres well to a rough surface by adjusting the physical properties of the adhesive layer, and does not cause poor peeling even when applied to a flat surface.
  • the temperature at which the tan ⁇ value of the dynamic viscoelasticity measurement is maximized is preferably ⁇ 40 to ⁇ 30 ° C. The dynamic viscoelasticity measurement will be described in detail in the examples.
  • the shear storage modulus of the adhesive layer at 23 ° C. is preferably 1.0 ⁇ 10 5 to 8.0 ⁇ 10 5 Pa.
  • the shear storage elastic modulus of the adhesive layer at 23 ° C. which is a practical temperature range, is preferably 1.5 ⁇ 10 5 to 7.5 ⁇ 10 5 Pa, more preferably 2 0.0 ⁇ 10 5 to 7.0 ⁇ 10 5 Pa. The measurement of the shear storage elastic modulus is described in detail in the examples.
  • styrene block copolymers examples include styrene ABA block copolymers (triblock copolymers) such as styrene / butadiene / styrene copolymers (SBS) and styrene / isoprene / styrene copolymers (SIS).
  • triblock copolymers such as styrene / butadiene / styrene copolymers (SBS) and styrene / isoprene / styrene copolymers (SIS).
  • Styrenic ABAB type block 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 having repeating units Lock copolymers; and the like.
  • styrene block copolymer it is preferable to use a hydrogenated product obtained by hydrogenating an ethylenic double bond.
  • a styrene block copolymer examples include styrene / ethylene-butylene copolymer / styrene copolymer (SEBS), styrene / ethylene-propylene copolymer / styrene copolymer (SEPS), styrene / ethylene copolymer, and the like.
  • SEBSEB ethylene-butylene copolymer / styrene / ethylene-butylene copolymer copolymer
  • styrene block copolymer Only one type of styrene block copolymer may be used, or two or more types may be used.
  • the styrene block content in the styrenic block copolymer can be appropriately set to any appropriate amount, but the temperature at which the maximum tan ⁇ value of the dynamic viscoelasticity measurement is within the above range is used.
  • the styrene block content decreases, there is a possibility that adhesive residue due to insufficient cohesive force of the adhesive layer is likely to occur.
  • the styrene block content is increased, the pressure-sensitive adhesive layer formed with the styrenic block copolymer alone becomes hard, and it may not be possible to obtain good adhesion to a rough surface.
  • the styrene block content in the styrenic block copolymer is preferably 5 to 40% by weight, more preferably 7 to 30% by weight, and still more preferably 9 to 20% by weight.
  • styrenic block copolymers water of styrenic block copolymers having a repeating structure (ABA type, ABAB type, ABABA type, etc.) more than triblock copolymers composed of styrene (A) and butadiene (B) Additives (SEBS, SEBSEB, SEBSEBS, etc.) are preferred.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block in the hydrogenated styrene block copolymer is preferably 60% by weight or more, more preferably It is 70 weight% or more, More preferably, it is 75 weight% or more.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block in the hydrogenated styrene-based block copolymer is 60% by weight or more, the wettability is good, in particular, the adhesiveness is good. Adheres well to rough surfaces.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block in the hydrogenated styrene block copolymer is usually preferably 90% by weight or less.
  • the styrenic block copolymer can be mixed with other styrenic thermoplastic elastomers within the range that does not impair the object of the present invention for the purpose of adjusting the adhesiveness.
  • styrenic thermoplastic elastomers include styrene block copolymers other than those described above; styrene / butadiene copolymers (SB), styrene / isoprene copolymers (SI), styrene / ethylene-butylene copolymers.
  • AB block polymer such as polymer (SEB) and styrene / ethylene-propylene copolymer (SEP); Styrene random copolymer such as styrene / butadiene rubber (SBR); Styrene / ethylene-butylene copolymer ABC type styrene / olefin crystal block polymers such as polymers / olefin crystal copolymers (SEBC); hydrogenated products thereof, and the like.
  • SEB polymer
  • SEP styrene / ethylene-propylene copolymer
  • SBR butadiene rubber
  • SEBC Styrene / ethylene-butylene copolymer ABC type styrene / olefin crystal block polymers
  • SEBC olefin crystal copolymers
  • the adhesive layer for the purpose of controlling adhesive properties, etc., for example, softener, olefin resin, silicone polymer, liquid acrylic copolymer, tackifier, anti-aging agent, hindered amine Additives such as system light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.) are added as appropriate be able to.
  • softener olefin resin, silicone polymer, liquid acrylic copolymer, tackifier, anti-aging agent, hindered amine Additives such as system light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.) are added as appropriate be able to.
  • 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 compounding amount of the tackifier is usually preferably 40% by weight or less, more preferably 30% by weight or less, and further preferably 10% by weight or less with respect to the styrene-based thermoplastic elastomer containing the styrene-based block copolymer.
  • 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 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 amount added can be set appropriately to any appropriate amount. However, as the added amount increases, the adhesive residue tends to increase at high temperatures and when exposed outdoors.
  • the amount is preferably 40% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less with respect to the pressure-sensitive adhesive composition containing a styrene-based thermoplastic elastomer containing a polymer and a softening agent.
  • the adherend to which the surface protective sheet is applied is a metal plate, it is preferable not to add a softener when forming the adhesive layer.
  • 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 base material layer contains a polyolefin resin.
  • the content ratio of the polyolefin resin in the base material layer is preferably 60% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • any appropriate polyolefin-based resin can be adopted as the polyolefin-based resin contained in the base material layer.
  • low-density polyethylene LDPE
  • linear low-density polyethylene LLDPE
  • LLDPE linear low-density polyethylene
  • LLDPE linear low-density polyethylene
  • LLDPE linear low density polyethylene
  • the polyolefin resin contained in the base material layer is preferably an ethylene polymer having a density of 0.88 to 0.93 g / cm 3 . Such a density is more preferably 0.895 to 0.920 g / cm 3 .
  • the base material layer includes at least two layers of a white layer and a black layer. Thereby, it can be set as the surface protection sheet excellent in the weather resistance.
  • 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 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.
  • the white layer contains a white pigment, the content is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the resin component forming the white layer. More preferably, it is 5 to 20% by weight.
  • the resin component forming the white layer is preferably a polyolefin resin, more preferably an ethylene polymer, and still more preferably an ethylene polymer having a density of 0.88 to 0.93 g / cm 3 .
  • preferred examples of the resin component forming the white layer include low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
  • the content 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, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • 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 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.
  • the black layer contains a black pigment, the content is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the resin component forming the black layer. More preferably, it is 0.5 to 3% by weight.
  • the resin component forming the black layer is preferably a polyolefin resin, more preferably an ethylene polymer, and still more preferably an ethylene polymer having a density of 0.88 to 0.93 g / cm 3 .
  • preferred examples of the resin component forming the black layer include low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
  • 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, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • 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 may contain any appropriate additive for the purpose of preventing deterioration.
  • additives include antioxidants; UV absorbers; light stabilizers such as hindered amine light stabilizers; antistatic agents; fillers such as calcium oxide, magnesium oxide, silica, zinc oxide, and titanium oxide. Pigments, anti-scratch agents, lubricants, anti-blocking agents, foaming agents, and polyethyleneimine.
  • any appropriate thickness can be adopted as the thickness of the base material layer depending on the purpose.
  • Such a thickness is preferably 20 to 300 ⁇ m, more preferably 30 to 250 ⁇ m, and still more preferably 40 to 200 ⁇ 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 surface protective sheet of the present invention comprises a base material layer and an adhesive layer using a forming material for forming a base material layer containing the polyolefin resin and a forming material for forming an adhesive layer containing the styrenic thermoplastic elastomer. Can be obtained by co-extrusion.
  • the base material layer includes at least two layers of a white layer and a black color layer, there are two or more forming materials for forming the base material layer.
  • the base material layer and the pressure-sensitive adhesive layer are obtained by forming the base material layer and the pressure-sensitive adhesive layer in multiple layers by a co-extrusion method using two or more kinds of the material forming the base material layer and the forming material forming the pressure-sensitive adhesive layer.
  • 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 white pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W) and 0.5% by weight of ethylene bisstearylamide (manufactured by Nippon Kasei Co., Ltd.) with respect to linear low density polyethylene (Mitsui Chemicals, Evolue SP2020) 1% by weight of carbon black (manufactured by Mitsubishi Chemical, carbon black “# 45”) with respect to low-density polyethylene (manufactured by Tosoh Corporation, Petrocene 180), and ethylenebisstearylamide (Nippon Kasei Co., Ltd.)
  • the thickness of the back substrate layer was 20 ⁇ m
  • the thickness of the intermediate substrate layer was 90 ⁇ m
  • the thickness of the adhesive layer was 5 ⁇ m.
  • the density of linear low density polyethylene (Mitsui Chemicals, Evolue SP2020) is 0.916 g / cm 3
  • the density of low density polyethylene Tosoh, Petrocene 180) is 0.922 g / cm 3. Met.
  • An adhesive layer forming material to which 5% by weight of a petroleum resin (
  • the thickness of the back substrate layer was 10 ⁇ m
  • the thickness of the intermediate substrate layer was 50 ⁇ m
  • the thickness of the adhesive layer was 10 ⁇ m.
  • the density of the low density polyethylene (Tosoh Corp., Petrocene 173) was 0.924 g / cm 3 .
  • the thickness of the back substrate layer was 20 ⁇ m
  • the thickness of the intermediate substrate layer was 90 ⁇ m
  • the thickness of the adhesive layer was 10 ⁇ m.
  • the styrene / ethylene-butylene copolymer / styrene block polymer (JSR, Dynalon 8600P) had a styrene content of 15% by weight and a proportion of the butylene structure in the ethylene-butylene copolymer block was 67% by weight. It was.
  • the styrene / ethylene-butylene copolymer / styrene block polymer (manufactured by Shell Elastomer, Kraton G1657) had a styrene content of 13% by weight.
  • a petroleum resin Arakawa Chemical Co., Alcon P-100
  • a surface protective sheet was prepared in the same manner as in Example 2 except that the material was used.
  • the styrene / ethylene-propylene copolymer / styrene block polymer (Kuraray Co., Ltd., Septon 2063) had a styrene content of 13% by weight.
  • Example 4 In Example 1, a surface protective sheet was prepared in the same manner as in Example 1 except that the white pigment and carbon black were not added to the substrate.
  • ⁇ Evaluation test ⁇ Measurement of maximum tan ⁇ temperature and storage modulus
  • the elastic modulus was measured by applying a temperature change of ⁇ 60 to 150 ° C. (heating rate 5 ° C./min) while applying a shear strain having a frequency of 1 Hz using ARES manufactured by Rheometric Scientific.
  • the measurement sample was measured by creating an adhesive layer having a thickness of about 5 mm.
  • the pressure-sensitive adhesive layer was produced by a casting method using an organic solvent or a heat press method.
  • the measurement of the shear storage elastic modulus of the adhesive layer can be measured by a method such as a method of obtaining by the difference between the shear storage elastic modulus of the surface protective sheet and the shear storage elastic modulus of the base material when these methods cannot be performed. .
  • the results are shown in Table 1.
  • the adhesive strength of the surface protective sheets obtained in Examples and Comparative Examples was measured according to JIS-Z-0237. Specifically, SUS304BA board (smooth surface) and SUS304HL board (polishing surface) were used as adherends. After cleaning the surface of the SUS plate with toluene, it was pressure-bonded with a 2 kg roller, and after 30 minutes, with an Instron type tensile tester (manufactured by Shimadzu Corp., Autograph) at a pulling speed of 300 mm / min and 180 degree peel. It was measured. At this time, the measurement environment and the storage environment were 23 ° C./50%.
  • 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 is very excellent in weather resistance, has a good adhesive force even with respect to an adherend that has been subjected to a polishing treatment, and has little increase in adhesive force even under heat resistance. It is recognized that the general peelability is good.
  • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille de protection de surface formée par la co-extrusion d'une couche de base contenant une résine polyoléfine et d'une couche adhésive contenant un élastomère thermoplastique styrène, ladite feuille de protection de surface ayant un bon pouvoir adhésif par rapport à diverses parties adhérées, une résistance aux intempéries exceptionnelle et une bonne pelabilité lorsqu'elle est pelée d'une partie adhérée, avec une petite augmentation du pouvoir adhésif même quand elle est utilisée à l'extérieur ou stockée à des températures élevées. Cette feuille de protection de surface est formée par la co-extrusion d'une couche de base contenant une résine polyoléfine et d'une couche adhésive contenant un élastomère thermoplastique styrène. La couche de base contient au moins une couche blanchâtre et une couche noirâtre et la résine polyoléfine est un polymère d'éthylène ayant une masse volumique de 0,88 à 0,93 g/cm3. L'élastomère thermoplastique styrène est un polymère à bloc de styrène ou un produit hydrogéné de celui-ci, dans lequel la température à laquelle les valeurs de tan δ pour des mesures de viscoélasticité dynamique prises dans une plage de températures mesurées de -60 à 100°C atteint un maximum est de -40 à ‑25°C.
PCT/JP2013/051368 2012-02-15 2013-01-24 Feuille de protection de surface Ceased WO2013121845A1 (fr)

Applications Claiming Priority (2)

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CN2012100362484A CN103254821A (zh) 2012-02-15 2012-02-15 表面保护片
CN201210036248.4 2012-02-15

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WO2013121845A1 true WO2013121845A1 (fr) 2013-08-22

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CN110062697A (zh) * 2016-12-09 2019-07-26 3M创新有限公司 聚合物多层膜
US20230083934A1 (en) * 2020-02-28 2023-03-16 Kitagawa Industries Co., Ltd. Black Elastomer Molded Article

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5469156U (fr) * 1977-10-27 1979-05-16
JPS63106737U (fr) * 1986-12-26 1988-07-09
JPH06271821A (ja) * 1993-03-23 1994-09-27 Lintec Corp 再剥離型粘着保護テープ
JP2005089547A (ja) * 2003-09-16 2005-04-07 Nitto Denko Corp 表面保護シート
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4115791B2 (ja) * 2002-03-05 2008-07-09 日東電工株式会社 表面保護シート

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5469156U (fr) * 1977-10-27 1979-05-16
JPS63106737U (fr) * 1986-12-26 1988-07-09
JPH06271821A (ja) * 1993-03-23 1994-09-27 Lintec Corp 再剥離型粘着保護テープ
JP2005089547A (ja) * 2003-09-16 2005-04-07 Nitto Denko Corp 表面保護シート
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム

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