WO2012073979A1 - 粘着性樹脂組成物及び粘着フィルム - Google Patents

粘着性樹脂組成物及び粘着フィルム Download PDF

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Publication number
WO2012073979A1
WO2012073979A1 PCT/JP2011/077587 JP2011077587W WO2012073979A1 WO 2012073979 A1 WO2012073979 A1 WO 2012073979A1 JP 2011077587 W JP2011077587 W JP 2011077587W WO 2012073979 A1 WO2012073979 A1 WO 2012073979A1
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Prior art keywords
pressure
sensitive adhesive
weight
film
layer
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PCT/JP2011/077587
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English (en)
French (fr)
Japanese (ja)
Inventor
茂知 山本
多賀　敦
大木　祐和
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東洋紡績株式会社
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Priority to KR1020137014007A priority Critical patent/KR101867113B1/ko
Priority to CN201180057930.5A priority patent/CN103261352B/zh
Publication of WO2012073979A1 publication Critical patent/WO2012073979A1/ja

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    • 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
    • C09J153/005—Modified block copolymers
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • 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
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene 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 an adhesive resin composition (adhesive) and an adhesive film.
  • the pressure-sensitive adhesive of the present invention can be suitably used for a pressure-sensitive adhesive film for protecting the outer surface of a prism type lens portion of a prism sheet used for optical applications. It also protects the surface of synthetic resin plates (for example, for building materials), stainless steel plates (for example, for building materials), aluminum plates, decorative plywood, steel plates, glass plates, home appliances, precision machinery, and automobile bodies during manufacturing. Therefore, to protect against damage when stacking, storing, transporting, and transporting goods in the manufacturing process, and when scratching secondary goods (for example, bending or pressing) It can also be suitably used when protecting from the like.
  • This type of pressure-sensitive adhesive film is constituted by laminating a pressure-sensitive adhesive layer on a layer serving as a base material.
  • a method for producing an adhesive film for example, a method of applying a solution-like adhesive to a base material layer composed of a synthetic resin or the like, a base material layer, an adhesive layer are melt-extruded from a plurality of extruders, and a T-die And the like, and the like.
  • coextrusion film formation by the T-die method is advantageous from the viewpoint of cost and quality.
  • a styrene-based elastomer which is one of thermoplastic elastomers can be mentioned.
  • Styrenic elastomers are not only excellent in the anchoring force of the adhesive layer to the base material layer made of polyolefin resin when forming a film, but are easy to control the adhesive force by adding a tackifier, etc. It has an advantage (Patent Document 1).
  • the covering having surface irregularities include a prism type lens portion of a prism sheet used for optical members, etc., and adhesion sufficient for use on a covering having surface irregularities such as a prism sheet. It is necessary to express force. For that purpose, the adhesive force of the adhesive layer is increased so that the adhesive force can be obtained even if the contact area is small, or the adhesive layer is softened so that the surface irregularities of the covering are eaten into the adhesive layer. It is conceivable to obtain an adhesive force by increasing the size.
  • the end portion of the film may cause troubles such as sticking to the film forming machine.
  • a tackifier to the styrenic elastomer, self-adhesive force necessary for use can be expressed on the prism sheet (see, for example, Patent Document 2), but tackifying the styrene elastomer.
  • the problem to be solved by the present invention is that when a pressure-sensitive adhesive film and a base layer resin are co-extruded by an extruder, the pressure-sensitive adhesive is insufficiently spread on the base layer.
  • the present invention is a block copolymer of a styrene polymer block and an olefin polymer block, a block copolymer of a styrene polymer block and a random copolymer block of styrene and olefin, and / or these 2 parts by weight or more of tackifying resin and less than 10 parts by weight of polyolefin resin and 2 parts by weight or more of polyolefin resin with respect to 100 parts by weight of styrene elastomer containing 5 to 15% by weight of styrene as a main component.
  • It is an adhesive resin composition characterized by comprising a resin composition containing less than 10 parts by weight, and is particularly characterized by the content of polyolefin resin.
  • a further invention is a pressure-sensitive adhesive film, wherein the pressure-sensitive adhesive resin composition is laminated on one side of a base material layer containing a polypropylene resin as a main component.
  • the adhesive film of the present invention has a practically sufficient adhesive force as a protective film, for example, even when bonded to a covering having surface irregularities such as a prism, and even if the adhesive films are stacked, the adhesive films can block each other. It has the advantage of being less.
  • a release layer is laminated on the surface opposite to the adhesive layer made of the adhesive resin composition.
  • a base material layer mainly composed of the polypropylene resin, an adhesive layer made of an adhesive resin composition, and a release layer are laminated by coextrusion.
  • melt flow rate (MFR) at 230 ° C. and 2.16 kgf of the styrene elastomer in the adhesive layer is 0.5 to 10 g / 10 min.
  • the polypropylene resin in the base material layer has a melt flow rate (MFR) at 230 ° C. and 2.16 kgf of 1.0 to 15 g / 10 min.
  • the adhesive film is for covering a prism sheet.
  • the adhesive film is self-adhesive.
  • the pressure-sensitive adhesive resin composition (pressure-sensitive adhesive) according to the present invention can be laminated without coextruding the pressure-sensitive adhesive on the base material layer when co-extrusion is performed by an extruder, and the pressure-sensitive adhesive films are stacked. Also has the advantage of less blocking between adhesive films.
  • the adhesive film of the present invention is useful, for example, when it is attached as a protective film to an adherend having a small contact area with a film such as a prism sheet.
  • the phrase “main component” means that 90% by mass or more is the component.
  • Adhesive resin composition As the resin composition constituting the pressure-sensitive adhesive of the present invention, a mixture in which a styrene elastomer, a tackifier resin, and a polyolefin resin are mixed at a predetermined ratio is coextruded into a base material layer mainly composed of a polypropylene resin. It has good spreadability when laminated with, and when laminated by the feed block method, the adhesive layer hardly wraps around at the edge in the film width direction, and the self-adhesive strength of the obtained adhesive film to the cover It is preferable in expressing.
  • Styrenic elastomers are ABA type block polymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene copolymer-styrene, styrene-ethylene / propylene copolymer-styrene, styrene -Butadiene block, styrene-isoprene, styrene-ethylene / butylene copolymer, AB block polymer such as styrene-ethylene / propylene copolymer, styrene random copolymer such as styrene-butadiene rubber, and hydrogenation thereof You can list things.
  • the hydrogenated product of the styrene elastomer used in the present invention refers to a product in which the double bond derived from the conjugated diene of the styrene elastomer is partially or completely saturated by hydrogenation.
  • the degree of saturation is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 to 100 mol%. When the saturation is less than 80 mol%, the weather resistance and heat resistance of the pressure-sensitive adhesive layer may be insufficient.
  • the styrene component in the styrene-based elastomer is desirably 5% by weight or more and 15% by weight or less. If it is less than 5% by weight, granulation at the time of producing the resin becomes difficult, and if it exceeds 15% by weight, the adhesive strength is lowered and it becomes difficult to obtain the required adhesive strength. In addition, although an adhesive force can be raised by increasing the addition amount of tackifying resin, the extensibility of the adhesion layer at the time of coextrusion deteriorates that much. Moreover, when laminating
  • the styrene component in the styrenic elastomer is used to develop the required adhesive strength and to improve the spreadability of the adhesive layer during coextrusion and to prevent the adhesive layer from wrapping around at the end in the film width direction. Is preferably 10% by weight or more and 13% by weight or less.
  • the melt flow rate (MFR) at 230 ° C. and 2.16 kgf of the styrene elastomer used is preferably in the range of 0.5 to 10 g / 10 min, and in the range of 2.0 to 8.0 g / 10 min. This is more preferable.
  • tackifying resin examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, coumarone / indene resins, styrene resins, and rosin resins.
  • the content of the tackifying resin in the resin composition is desirably 2 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the styrene elastomer having a styrene component of 5% by weight to 15% by weight. If the content of the tackifying resin is less than 2 parts by weight, an improvement in adhesive strength cannot be expected. When the content of the tackifying resin is excessively increased to 10 parts by weight or more, when melt extrusion is performed, the melt viscosity is significantly reduced. When an adhesive layer having a low melt viscosity is laminated by coextrusion with a polypropylene resin having a melt flow rate (MFR) at 230 ° C.
  • MFR melt flow rate
  • the content of the tackifying resin is preferably 4% by weight or more and 9% by weight or less.
  • the polyolefin-based resin is not particularly limited. Crystalline polypropylene, copolymer of propylene and a small amount of ⁇ -olefin, low density polyethylene, high density polyethylene, copolymer of ethylene and a small amount of ⁇ -olefin, ethylene and acetic acid Examples thereof include a copolymer with vinyl.
  • a polypropylene resin can be suitably used from the viewpoint of melt viscosity and the like.
  • the melt flow rate (MFR) at 230 ° C. and 2.16 kgf of the polyolefin resin used is preferably in the range of 0.5 to 10 g / 10 min, and in the range of 2.0 to 8.0 g / 10 min. This is more preferable.
  • the content of the polyolefin resin in the resin composition is in the range of 2 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the styrene elastomer having a styrene component of 5% by weight to 15% by weight.
  • the amount is 10 parts by weight or more, the adhesive strength is reduced, and sufficient adhesive strength for a covering having surface irregularities cannot be obtained, and the spreadability is also inferior.
  • the amount is less than 2 parts by weight, the film is stored in a roll state, and then, when the film is fed out, problems such as blocking occur and the film partially extends or deforms.
  • the content of the polyolefin resin is preferably 4% by weight or more and 9% by weight or less.
  • the tackifying resin used for the pressure-sensitive adhesive may contain a part of the powder depending on the type, and there is also a thing that soils the extruder during extrusion. Since such a problem is improved by using a tackifier resin as a masterbatch with a polyolefin resin, it is preferable to use a tackifier resin and a polyolefin resin as a masterbatch.
  • a crosslinking agent In the pressure-sensitive adhesive used in the present invention, a crosslinking agent, a tackifier, an inorganic or organic filler, a softener, a plasticizer, a surfactant, One or more of various additives such as coupling agents, antifoaming agents, antistatic agents, and flame retardants may be added, but the adhesive layer and the resulting adhesive film (surface protective film) are transparent. It is preferable to select and use an additive that does not inhibit the properties.
  • the pressure-sensitive adhesive layer As the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film laminated by coextrusion on the base material layer mainly composed of polypropylene resin using the above pressure-sensitive adhesive is sufficiently extended to the base material layer. Furthermore, it has the advantage that it has sufficient adhesive force to adherends such as prisms, and even when the adhesive films are stacked, the blocking between the adhesive films is small.
  • the pressure-sensitive adhesive strength of the pressure-sensitive adhesive film of the present invention is preferably in the range of 3 to 50 cN / 25 cm with respect to the prism sheet at 23 ° C. from the viewpoint of the protection performance of the prism sheet.
  • the adhesive strength is less than 3 cN / 25 cm, the prism sheet is turned over when the prism sheet is protected, and cannot function as a protective film.
  • the adhesive strength exceeds 50 cN / 25 cm, there is a possibility that the film cannot be smoothly peeled when the film is peeled from the prism sheet.
  • the adhesive strength can be appropriately set by changing the resin composition, thickness, etc. of the adhesive layer.
  • the peel strength of the pressure-sensitive adhesive surface of the pressure-sensitive adhesive film of the present invention to the release surface is preferably within a range of 100 cN / 25 cm or less at 23 ° C. from the viewpoint of the film payout property when the pressure-sensitive adhesive film is in roll form.
  • the peeling force exceeds 100 cN / 25 cm, problems such as partial stretching or deformation of the film occur when the film is fed when the pressure-sensitive adhesive film is rolled.
  • the peeling force can be appropriately set by forming surface irregularities on the release layer and changing the contact area between the adhesive surface and the release surface when winding as a roll. It is also possible to reduce the peel force by adding a resin having an effect of reducing the surface free energy such as a fluorine resin, a silicone resin, a 4-methyl-1-pentene polymer to the release layer. .
  • the pressure-sensitive adhesive film of the present invention can contain known additives as necessary.
  • a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improvement agent and the like may be contained.
  • the low molecular weight substance on the surface of the adhesive layer is preferably less than 1 mg / m 2 .
  • the measurement of the low molecular weight substance on the surface of the adhesive layer was carried out by the following procedure. After the surface of the adhesive layer is washed with an organic solvent that does not erode the resin constituting the adhesive layer such as ethanol, the organic solvent is removed from the cleaning solution with an evaporator, and the residue obtained by weighing the residue is washed.
  • the pressure-sensitive adhesive film of the present invention requires a base material layer mainly composed of a polypropylene resin.
  • the polypropylene resin used here include crystalline polypropylene, a random copolymer of propylene and a small amount of ⁇ -olefin, a block copolymer, and the like. More specifically, as a crystalline polypropylene resin, an n-heptane-insoluble isotactic propylene homopolymer used in ordinary extrusion molding or the like, or polypropylene containing 60% by weight or more of propylene and another ⁇ -olefin is used.
  • n-heptane insolubility 25 ° C., 60 ° It is a preferred embodiment to use a material that is compatible with an elution amount of 150 ppm or less (if the operating temperature exceeds 100 ° C., 30 PPm or less).
  • the ⁇ -olefin copolymerization component of the copolymer of propylene and other ⁇ -olefins includes ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 4 C4 or higher ⁇ -olefins such as -methyl-1-pentene are preferred.
  • the copolymer is preferably a random or block copolymer obtained by polymerizing one or more of the ⁇ -olefins exemplified above with propylene.
  • the melt flow rate (MFR) at 230 ° C.
  • the waste film produced when the film obtained in the present invention is processed into a product can be re-granulated as a recovered raw material and added to the base material layer. By using the recovered raw material, the production cost can be reduced.
  • the spreadability of the pressure-sensitive adhesive layer with respect to the base material layer is preferably 90% or more. If the spreadability of the adhesive layer is low, it takes a long time to replace the resin, and the operability deteriorates. Moreover, when laminating an adhesive layer on the order of several ⁇ m, there is a problem that unevenness in thickness tends to occur in the width direction of the film.
  • the spreadability of the adhesive layer is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more.
  • the wraparound ratio of the pressure-sensitive adhesive layer to the base material layer is preferably 3% or less. If the adhesive layer has a high wraparound rate, the film end becomes only the adhesive layer, and troubles such as sticking to the film forming machine occur and the operability deteriorates.
  • the wraparound ratio of the adhesive layer to the base material layer is more preferably 2.5% or less.
  • the thickness of the adhesive layer in the adhesive film of the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m. If the thickness of the adhesive film is less than 1 ⁇ m, stable film formation by coextrusion becomes difficult, and if it is 30 ⁇ m or more, the film is disadvantageous in terms of cost. At this time, when increasing the adhesive strength, it is preferable to increase the thickness in consideration of the viscosity. Increasing the thickness of the adhesive layer tends to increase the contact area with the adherend.
  • the thickness of the adhesive layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 3 ⁇ m or more and 15 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 8 ⁇ m or less.
  • the thickness of the base material layer in the pressure-sensitive adhesive film of the present invention is preferably 5 ⁇ m or more and less than 100 ⁇ m, and more preferably 15 ⁇ m or more and less than 25 ⁇ m.
  • the thickness of the pressure-sensitive adhesive film is less than 5 ⁇ m, there is a problem that the waist feeling is weakened, wrinkles etc. are easily formed when pasted on the cover as a protective film, and sufficient adhesive strength cannot be obtained. If it is, it will become a disadvantageous film in terms of cost.
  • a release layer is preferably formed on the surface opposite to the pressure-sensitive adhesive layer laminated on one side of the base material layer. By doing so, blocking can be further suppressed.
  • the average surface roughness SRa of the release layer surface is preferably 0.40 ⁇ m or more.
  • the average surface roughness of the surface is preferably such that SRa is 0.850 ⁇ m or less, particularly preferably 0.500 ⁇ m or more and 0.700 ⁇ m or less.
  • the thickness of the release layer is preferably 1 ⁇ m or more and less than 30 ⁇ m, and particularly preferably 3 to 10 ⁇ m.
  • a layer having a rough surface in a mat shape can be formed by using a propylene-ethylene block copolymer.
  • the same effect can be expected by mixing a polyethylene resin with homopolypropylene.
  • a layer with a rougher surface can be formed by mixing a propylene-ethylene block copolymer with a polyethylene resin.
  • the resin suitable for obtaining a mat-like surface include propylene-ethylene block copolymers such as “BC4FC” manufactured by Nippon Polypro Co., Ltd.
  • the adhesive film of the present invention is preferably in the form of a roll in terms of handling.
  • the upper limit of the width and the winding length of the film roll is not particularly limited, but from the viewpoint of ease of handling, the width is generally 1.5 m or less, and the winding length is preferably 6000 m or less when the film thickness is 30 ⁇ m.
  • a winding core a plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can usually be used.
  • the pressure-sensitive adhesive film using the pressure-sensitive adhesive of the present invention can be particularly suitably used for protecting the outer surface of the prism type lens portion of the prism sheet used for optical applications. It also protects the surface of synthetic resin plates (for example, for building materials), stainless steel plates (for example, for building materials), aluminum plates, decorative plywood, steel plates, glass plates, home appliances, precision machinery, and automobile bodies during manufacturing. Therefore, to protect against damage when stacking, storing, transporting, and transporting goods in the manufacturing process, and when scratching secondary goods (for example, bending or pressing) It can also be used when protecting from.
  • the present invention will be further described with reference to examples.
  • the present invention is not limited to the following examples without departing from the gist thereof.
  • the evaluation method of the physical property in a following example and a comparative example is as follows.
  • Adhesive layer resin is discharged at 15 kg / hour with a 40 mm ⁇ single screw extruder in a three-layer T die (feed block type, lip width 850 mm, lip gap 1 mm).
  • the base layer resin is coextruded at a discharge rate of 15 kg / hour with a 90 mm ⁇ single screw extruder
  • the release layer resin is coextruded with a discharge rate of 5 kg / hour with a 65 mm ⁇ single screw extruder.
  • the adhesive layer resin was put into a 40 mm ⁇ single screw extruder, and the spreading rate of the adhesive layer to the base material layer after 30 minutes from the beginning of the resin was measured.
  • Spreading rate laminate width of adhesive layer (mm) / 650 (mm) ⁇ 100 (%)
  • Adhesive layer resin in a three-layer T die was 15 kg / hour in a 40 mm ⁇ single screw extruder.
  • the substrate layer resin is coextruded at a discharge rate of 15 kg / hour with a 90 mm ⁇ single screw extruder and the release layer resin is discharged with a discharge rate of 5 kg / hour with a 65 mm ⁇ single screw extruder.
  • an unstretched film having a width of 650 mm is obtained.
  • the adhesive layer resin was put into a 40 mm ⁇ single screw extruder, and the wrapping ratio of both ends in the film width direction of the adhesive layer to the base material layer after 120 minutes from the beginning of the resin was measured.
  • Circulation rate width (mm) / 650 (mm) ⁇ 100 (%) in which the adhesive layer wraps around both ends of the film width direction
  • Adhesive Tape / Adhesive Sheet Test Method As an adherend, an acrylic plate (Mitsubishi Rayon Co., Ltd .: Acrylite (registered trademark) 3 mm thick) 50 mm ⁇ 150 mm, two types of prism sheets with different surface treatment states (the lens part consists of a triangular prism, the height of the triangular prism) Is 25 ⁇ m, the width of the triangular prism is 50 ⁇ m), 50 mm ⁇ 150 mm is prepared.
  • an acrylic plate Mitsubishi Rayon Co., Ltd .: Acrylite (registered trademark) 3 mm thick
  • 50 mm ⁇ 150 mm As an adherend, an acrylic plate (Mitsubishi Rayon Co., Ltd .: Acrylite (registered trademark) 3 mm thick) 50 mm ⁇ 150 mm, two types of prism sheets with different surface treatment states (the lens part consists of a triangular prism, the height of the triangular prism) Is 25 ⁇ m
  • test piece As a test piece, a test piece of 150 mm is cut out in a winding direction at the time of film production and 25 mm in a direction perpendicular thereto, and a rubber roll having a mass of 2000 g (roller surface)
  • a specimen having a spring hardness of 80 Hs and a thickness of 45 mm and having a width of 45 mm and a diameter (including the rubber layer) of 95 mm is reciprocated once at a speed of 5 mm / second, and the adherend and the test piece.
  • 180 degree peeling means holding the peeling angle between the acrylic plate and the film at the time of measuring the resistance value at the time of peeling at 180 degrees.
  • a polyester sheet having a thickness of 190 ⁇ m and a size of 25 mm ⁇ 170 mm is prepared as a grip margin for the measurement sample, and the width of the paste margin is 15 mm at the end of the measurement sample obtained by pressure-bonding the adhesive film and the acrylic plate. Attached with cellophane tape (registered trademark) to make a gripping allowance for measurement.
  • a schematic diagram of the measurement sample is shown in FIG. The measurement was performed three times for one sample, and the average value was defined as the adhesive strength of the sample.
  • a test piece of 150 mm in the winding direction at the time of film production and 25 mm in a direction perpendicular thereto is cut out, and the release surface of the test piece attached to the adhesive surface and the acrylic plate with a double-sided adhesive tape is used.
  • a rubber roll having a mass of 2000 g (with a roller hardness of 80 Hs on the roller surface and a width of 45 mm and a diameter (including the rubber layer) of 95 mm covered with a rubber layer having a thickness of 6 mm) is 5 mm / second.
  • the mold was reciprocated once to crimp the release surface and the test piece.
  • the sample that was allowed to stand for 30 minutes in an environment at a temperature of 23 ° C. and a relative humidity of 65% was peeled 180 ° at a rate of 300 mm / min using “Autograph” (AGS-J) manufactured by Shimadzu Corporation.
  • the resistance value at that time was defined as a peeling force [cN / 25 mm].
  • a polyester sheet having a thickness of 190 ⁇ m and a size of 25 mm ⁇ 170 mm is prepared as a grip allowance for the measurement sample, and is attached to the end of a test piece of 150 mm ⁇ 25 mm with a cellophane tape with a width of 15 mm of the paste. It was the time to grab. The measurement was performed three times for one sample, and the average value was taken as the peel strength of the sample.
  • Example 1 Preparation of base material layer 100 wt% of a polypropylene resin (manufactured by Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 90 mm ⁇ single screw extruder to obtain a base material layer.
  • a polypropylene resin manufactured by Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min
  • Polypropylene resin (Sumitomo Chemical: FS2011DG3, MFR: 2) with respect to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) .5 g / 10 min) 8.8 parts by weight and a mixture of 8.8 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon (registered trademark) P125) are melt-extruded in a 40 mm ⁇ single-screw extruder and subjected to an adhesive layer. It was.
  • Example 2 The adhesive layer and the release layer were the same as in Example 1, but the base material layer was changed to the following content, and an unstretched film of 3 types and 3 layers was obtained by the same production method as Example 1.
  • 100 wt% of a homopolypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min
  • Example 3 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • a mixture of 3.2 parts by weight of a polypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min
  • Example 4 The base material layer and the release layer were the same as in Example 1, but the adhesive layer was changed to the following content, and a three-kind three-layer unstretched film was obtained by the same production method as in Example 1.
  • a styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min), 8.8 parts by weight of a petroleum resin (Arakawa Chemical Industries: Alcon P125)
  • a mixture of 8.8 parts by weight of a polypropylene resin (Sumitomo Chemical Co., Ltd .: WF836DG3 :, MFR: 7.0 g / 10 min) was melt-extruded with a 40 mm ⁇ single screw extruder to obtain an adhesive layer.
  • Example 5 The base layer and the adhesive layer were changed to the following contents with the release layer remaining as in Example 1, and a three-kind and three-layer unstretched film was obtained by the same production method as in Example 1.
  • styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min), 5.7 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125)
  • a mixture of 8.0 parts by weight of a polypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min
  • the films obtained in Examples 1 to 5 have good spreadability during film formation, have a practically sufficient adhesive force when used as a protective film, and roll the film. The handleability was also good.
  • the films obtained in Comparative Examples 1 and 4 and 7 have insufficient spreadability at the time of film formation, the adhesive layer wraps around, and the film formation is not necessarily good. It was. Further, the handling property when the film was used as a roll was not necessarily good.
  • the films obtained in Comparative Examples 2 and 3 and 6 and 8 did not show adhesive strength to the prism sheet as the covering, and did not have practically necessary adhesive strength.
  • the film obtained in Comparative Example 5 was not necessarily good in terms of handleability when the film was used as a roll. Thus, all the films obtained in the comparative examples were inferior in quality and low in practicality.
  • the pressure-sensitive adhesive of the present invention can be suitably used for a pressure-sensitive adhesive film for protecting the outer surface of a prism type lens portion of a prism sheet used for optical applications. It also protects the surface of synthetic resin plates (for example, for building materials), stainless steel plates (for example, for building materials), aluminum plates, decorative plywood, steel plates, glass plates, home appliances, precision machinery, and automobile bodies during manufacturing. Therefore, to protect against damage when stacking, storing, transporting, and transporting goods in the manufacturing process, and when scratching secondary goods (for example, bending or pressing) It can be suitably used also in the case of protecting from the environment and greatly contributes to the industry.

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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)
PCT/JP2011/077587 2010-12-01 2011-11-29 粘着性樹脂組成物及び粘着フィルム WO2012073979A1 (ja)

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JP6506556B2 (ja) * 2012-10-05 2019-04-24 東洋紡株式会社 自己粘着性表面保護フィルム
JPWO2014054701A1 (ja) * 2012-10-05 2016-08-25 東洋紡株式会社 自己粘着性表面保護フィルム
WO2014168069A1 (ja) * 2013-04-11 2014-10-16 東洋紡株式会社 自己粘着性表面保護フィルム
WO2016063673A1 (ja) * 2014-10-20 2016-04-28 東レフィルム加工株式会社 組成物および積層体
JP2016183241A (ja) * 2015-03-26 2016-10-20 株式会社サンエー化研 粘着剤組成物、並びにそれを用いた粘着フィルム及び表面保護シート
CN107573862B (zh) * 2017-08-21 2021-06-22 张家港康得新光电材料有限公司 一种粘合性树脂组合物及自粘型保护膜
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CN103261352B (zh) 2016-01-27
TW201231609A (en) 2012-08-01
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