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WO2012073979A1 - Pressure-sensitive adhesive resin composition and pressure -sensitive adhesive film - Google Patents

Pressure-sensitive adhesive resin composition and pressure -sensitive adhesive film 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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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
weight
film
layer
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Application number
PCT/JP2011/077587
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French (fr)
Japanese (ja)
Inventor
茂知 山本
多賀 敦
大木 祐和
Original Assignee
東洋紡績株式会社
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Application filed by 東洋紡績株式会社 filed Critical 東洋紡績株式会社
Priority to CN201180057930.5A priority Critical patent/CN103261352B/en
Priority to KR1020137014007A priority patent/KR101867113B1/en
Publication of WO2012073979A1 publication Critical patent/WO2012073979A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives 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
    • C09J153/005Modified block copolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241Polyolefin, e.g.rubber
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/10Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12Additional 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
    • C09J2301/122Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/006Presence of polyolefin in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/10Presence of homo or copolymers of propene
    • C09J2423/106Presence of homo or copolymers of propene in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer

Definitions

  • the present invention relates to 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)

Abstract

Provided are: a pressure-sensitive adhesive resin composition that makes it possible to laminate a pressure-sensitive adhesive layer on a base material layer by co-extrusion using an extruder without suffering from a shortage of spread and that is applicable even to a prism sheet or other substrate which, when a protective film is applied thereto, suffers from a small contact area between both; and a pressure-sensitive adhesive film. A pressure -sensitive adhesive resin composition characterized by consisting of a resin composition which contains 2 to less than 10 parts by weight of a tackifier resin and 2 to less than 10 parts by weight of a polyolefin resin relative to 100 parts by weight of a styrenic elastomer which comprises, as the main component, a block copolymer composed of a styrenic polymer block and an olefinic polymer block, a block copolymer composed of a styrenic polymer block and a styrene/olefin random copolymer block, and/or a hydrogenation product thereof and which has a styrene content of 5 to 15wt%.

Description

粘着性樹脂組成物及び粘着フィルムAdhesive resin composition and adhesive film
 本発明は粘着性樹脂組成物(粘着剤)及び粘着フィルムに関する。本発明の粘着剤は、特に光学用途に用いられているプリズムシートのプリズム型のレンズ部の外表面を保護するための粘着フィルムに好適にもちいることができる。
 また、合成樹脂板(例えば建築資材用)、ステンレス板(例えば、建築資材用)、アルミ板、化粧合板、鋼板、ガラス板、家電製品、精密機械および、製造時の自動車ボディーの表面を保護するため、物品を積み重ねたり、保管したり、輸送したり、製造工程で搬送する際の傷付きから保護するため、ならびに、物品を二次加工する(たとえば、曲げ加工やプレス加工)際の傷付きから保護する場合にも好適に用いることができる。
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.
 従来から、被覆体の表面保護を目的とした粘着フィルムは、建築資材や電気、電子製品、自動車等の加工、保管、輸送時にもちいられており、このような粘着フィルムは、良好な粘着性を有するとともに、使用後は、各表面を粘着剤で汚染することなく容易に引き剥がすことができなければならない。
 この種の粘着フィルムは、基材となる層に粘着層を積層することにより構成される。粘着フィルムの製造方法としては、例えば合成樹脂等から構成される基材層に、溶液状の粘着剤を塗工する方法、基材層、粘着層を複数の押出機から溶融押出しし、Tダイ等を用いて共押出製膜する方法等があげられる。これらの中でもTダイ法による共押出製膜がコスト、品質上の面から優位である。
Conventionally, adhesive films aimed at protecting the surface of coatings have been used during processing, storage, and transportation of building materials, electrical, electronic products, automobiles, etc. Such adhesive films have good adhesive properties. In addition, after use, each surface must be able to be easily peeled off without being contaminated with an adhesive.
This type of pressure-sensitive adhesive film is constituted by laminating a pressure-sensitive adhesive layer on a layer serving as a base material. As 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. Among these, coextrusion film formation by the T-die method is advantageous from the viewpoint of cost and quality.
 共押出製膜を行う際に、粘着層に使用される有用な樹脂として、熱可塑性エラストマーの一つであるスチレン系エラストマーが挙げられる。スチレン系エラストマーは、フィルムを製膜する際にポリオレフィン系樹脂からなる基材層に対する粘着層の投錨力が優れているのみならず、粘着付与剤の添加により粘着力の制御が容易である等の利点を有する(特許文献1)。 As a useful resin used for the adhesive layer when performing coextrusion film formation, 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).
 ところで、上記した被覆体は近年、その多様化により、被覆面が平滑なものだけでなく表面凹凸を有するものも多数見受けられる。表面凹凸を有する被覆体としては、例えば光学部材に用いられているプリズムシートのプリズム型のレンズ部等が挙げられ、プリズムシートのような表面凹凸を有する被覆体に対して、使用上充分な粘着力を発現させる必要がある。
 そのためには、接触面積が小さくても粘着力が得られるように粘着層の粘着力を高くする、もしくは粘着層を軟らかくすることにより被覆体の表面凹凸を粘着層に食込ませて接触面積を大きくすることにより粘着力を得る等が考えられる。
By the way, in recent years, due to the diversification of the above-described coverings, not only those having a smooth covering surface but also many having surface irregularities can be seen. Examples of 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.
 粘着層の自己粘着性の向上を図るには、粘着剤に適したスチレン系エラストマーに粘着付与樹脂を添加することで可能である(例えば、特許文献1等参照。)。しかし、スチレン系エラストマーに粘着付与樹脂を過剰に添加することにより構成される粘着層を基材層に押出機により共押出で積層する場合、粘着層の溶融粘度が低下し、基材層に対し延展され難く、時間がかかるという問題が生じる。また、フィードブロック法で積層する場合、粘着層が基材層に延展された後も、基材層よりも粘着層の溶融粘度が低いため、徐々にフィルム幅方向の端部で粘着層の廻り込みが発生し端部が粘着層のみとなることで、フィルム端部が製膜機に粘着する等のトラブルの原因となることもある。
 また、スチレン系エラストマーに粘着付与剤を添加することによりプリズムシートに対して使用上必要な自己粘着力を発現させることができる(例えば、特許文献2等参照。)が、スチレン系エラストマーに粘着付与剤を添加するだけでは、フィルムをロール状態としその後フィルムを繰出す際に必ずしも繰出し性が良好ではない。
In order to improve the self-adhesiveness of the pressure-sensitive adhesive layer, it is possible to add a tackifier resin to a styrene elastomer suitable for the pressure-sensitive adhesive (see, for example, Patent Document 1). However, when a pressure-sensitive adhesive layer formed by adding an excessive amount of tackifying resin to a styrene-based elastomer is laminated on the base material layer by coextrusion with an extruder, the melt viscosity of the pressure-sensitive adhesive layer decreases, It is difficult to extend and takes time. Also, when laminating by the feed block method, even after the adhesive layer is extended to the base material layer, the melt viscosity of the adhesive layer is lower than that of the base material layer. When the end portion becomes only the adhesive layer, the end portion of the film may cause troubles such as sticking to the film forming machine.
Further, by adding 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. By simply adding an agent, when the film is brought into a roll state and then the film is fed out, the feeding property is not necessarily good.
特開平10-151656号公報Japanese Patent Laid-Open No. 10-151656 特開2007-332329号公報JP 2007-332329 A
 本発明が解決しようとする課題は、粘着フィルムを製造する際、粘着剤及び基材層用樹脂を押出機により共押出を行った場合に、粘着剤を基材層上に延展不足を生じることなく積層することが可能であり、かつフィルムロール状でのブロッキングが少なく、例えば、粘着フィルムとの接触面積が小さいプリズムシートなどの被着体に対する使用に好適な粘着フィルムのための粘着性樹脂組成物及びそのような粘着フィルムを提供することにある。 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. Adhesive resin composition for an adhesive film suitable for use on an adherend such as a prism sheet having a small contact area with the adhesive film, for example, which can be laminated without any problems and has little blocking in the form of a film roll It is in providing a thing and such an adhesive film.
 本発明者らは、鋭意検討した結果、粘着剤を構成する樹脂組成を所定の範囲とすることで上記の課題を解消できることを見出し、本発明に到達したものである。
 即ち、本発明は
 スチレン系重合体ブロックとオレフィン系重合体ブロックとのブロック共重合体、スチレン系重合体ブロックとスチレンとオレフィンのとのランダム共重合体ブロックとのブロック共重合体および/またはこれらの水素添加物を主成分とする、スチレン成分が5~15重量%であるスチレン系エラストマー100重量部に対して、粘着付与樹脂2重量部以上、10重量部未満、ポリオレフィン系樹脂2重量部以上、10重量部未満を含む樹脂組成物からなることを特徴する粘着性樹脂組成物であり、特にポリオレフィン系樹脂の含有量に特徴がある。
As a result of intensive studies, the present inventors have found that the above-described problems can be solved by setting the resin composition constituting the pressure-sensitive adhesive within a predetermined range, and have reached the present invention.
That is, 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.
 本発明によれば、粘着フィルムを製造する際、粘着剤及び基材層用樹脂を押出機による共押出を行った場合でも粘着剤を基材層上に延展不足を生じることなく積層した粘着フィルムを得ることができる。
 さらなる発明は、上記粘着性樹脂組成物が、ポリプロピレン系樹脂を主成分とする基材層の片面に積層されてなることを特徴とする粘着フィルムである。
 本発明の粘着フィルムは、保護フィルムとして、例えばプリズムなどの表面凹凸を有する被覆体に貼り合せても実用上充分な粘着力を有し、しかも粘着フィルム同士を重ねても粘着フィルム同士のブロッキングが少ないという利点を有している。
According to the present invention, when producing an adhesive film, an adhesive film in which an adhesive and a base layer resin are laminated on the base layer without causing insufficient extension even when coextruded by an extruder. Can be obtained.
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.
 また、前記ポリプロピレン系樹脂を主成分とする基材層において、粘着性樹脂組成物からなる粘着層とは反対面に離型層とが積層されてなることが好適である。 In addition, in the base material layer mainly composed of the polypropylene resin, it is preferable that a release layer is laminated on the surface opposite to the adhesive layer made of the adhesive resin composition.
 さらにまた、前記ポリプロピレン系樹脂を主成分とする基材層、粘着性樹脂組成物からなる粘着層、離型層とが共押出により積層されてなることが好適である。 Furthermore, it is preferable that 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.
 さらにまた、前記粘着層中のスチレン系エラストマーの230℃・2.16kgfにおけるメルトフローレート(MFR)が0.5~10g/10分であることが好適である。 Furthermore, it is preferable that the 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.
 さらにまた、前記基材層中のポリプロピレン系樹脂の230℃・2.16kgfにおけるメルトフローレート(MFR)が1.0~15g/10分であることが好適である。 Furthermore, it is preferable that 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.
 さらにまた、前記粘着フィルムがプリズムシート被覆用であることが好適である。 Furthermore, it is preferable that the adhesive film is for covering a prism sheet.
 さらにまた、前記粘着フィルムが自己粘着性であることが好適である。 Furthermore, it is preferable that the adhesive film is self-adhesive.
 本発明による粘着性樹脂組成物(粘着剤)は、押出機による共押出を行った場合に粘着剤を基材層上に延展不足を生じることなく積層可能であり、しかも粘着フィルム同士を重ねても粘着フィルム同士のブロッキングが少ないという利点を有する。
 本発明の粘着フィルムは例えば、プリズムシート等のようなフィルムとの接触面積が小さい被着体に保護フィルムとして貼付けた際に、十分な粘着力を有し有用である。
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.
測定試料の模式図である。It is a schematic diagram of a measurement sample.
 以下、本発明の粘着性樹脂組成物(粘着剤)及び粘着フィルムの実施の形態を説明する。なお、本発明で「主成分とする」という場合は、90質量%以上がその成分であることを意味する。 Hereinafter, embodiments of the adhesive resin composition (adhesive) and the adhesive film of the present invention will be described. In the present invention, the phrase “main component” means that 90% by mass or more is the component.
(粘着性樹脂組成物)
 本発明の粘着剤を構成する樹脂組成物としては、スチレン系エラストマー、粘着付与樹脂、ポリオレフィン系樹脂を所定の割合で混合されたものが、ポリプロピレン系樹脂を主成分とする基材層に共押出で積層される際の延展性が良好であり、フィードブロック法で積層する場合、粘着層がフィルム幅方向の端部で廻り込みを起こし難く、得られた粘着フィルムの被覆体への自己粘着力を発現する上で好ましい。
(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.
(スチレン系エラストマー)
 スチレン系エラストマーは、スチレン-ブタジエン-スチレン、スチレン-イソプレン-スチレン、スチレン-エチレン/ブチレン共重合体-スチレン、スチレン-エチレン/プロピレン共重合体-スチレン等のA-B-A型ブロックポリマー、スチレン-ブタジエン、スチレン-イソプレン、スチレン-エチレン/ブチレン共重合体、スチレン-エチレン/プロピレン共重合体等のA-B型ブロックポリマー、スチレン-ブタジエンラバー等のスチレン系ランダム共重合体およびそれらの水素添加物を挙げることができる。
(Styrene elastomer)
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.
 本発明において用いられるスチレン系エラストマーの水素添加物とは、上記スチレン系エラストマーの共役ジエン由来の二重結合が水素添加により部分的にもしくは完全に飽和されているもののことを言う。飽和度としては、好ましくは80モル%以上であり、より好ましくは90モル%以上であり、特に好ましくは95~100モル%である。上記飽和度が80モル%未満であると、粘着剤層の耐候性や耐熱性が不十分となることがある。 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.
 スチレン系エラストマー中のスチレン成分は5重量%以上、15重量%以下であることが望ましい。5重量%未満であるとレジン作製時の造粒が困難となり、15重量%を超えると粘着力が低下し、必要とする粘着力を得ることが難しくなる。なお、粘着力は粘着付与樹脂の添加量を増やすことで上げることができるが、その分、共押出時の粘着層の延展性が悪化する。また、フィードブロック法で積層する場合、粘着層がフィルム幅方向の端部で廻り込みを起こし易くなる。必要とする粘着力を発現し、かつ共押出時に粘着層の延展性を良好なものとし粘着層がフィルム幅方向の端部で廻り込みを起こし難くするためには、スチレン系エラストマー中のスチレン成分が好ましくは10重量%以上、13重量%以下である。 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 | stacking by a feed block method, an adhesion layer becomes easy to raise | generate around at the edge part of a film width direction. 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.
 使用するスチレン系エラストマーの230℃・2.16kgfにおけるメルトフローレート(MFR)は、0.5~10g/10分の範囲が好ましく、2.0~8.0g/10分の範囲が製膜性の点でより好ましい。 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.
(粘着付与樹脂)
 粘着付与樹脂は、例えば脂肪族炭化水素樹脂、芳香族炭化水素樹脂、テルペン樹脂、クマロン・インデン樹脂、スチレン系樹脂、ロジン樹脂等を挙げることができる。
(Tackifying resin)
Examples of the tackifying resin include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, coumarone / indene resins, styrene resins, and rosin resins.
 樹脂組成物における粘着付与樹脂の含有量は、スチレン成分が5重量%以上、15重量%以下のスチレン系エラストマー100重量部に対し、2重量部以上、10重量部未満であることが望ましい。粘着付与樹脂の含有量が2重量部未満であると粘着力向上は見込めない。粘着付与樹脂の含有量を10重量部以上に増やし過ぎると溶融押出を行う場合、溶融粘度が著しく低下する。
 溶融粘度が低い粘着層を230℃・2.16kgfにおけるにおけるメルトフローレート(MFR)が15(g/10分)未満のポリプロピレン系樹脂を基材層として共押出により積層する場合、基材層と粘着層の間の溶融粘度差により、粘着層が基材層に対し延展され難く、時間がかかる問題が生じる。また、フィードブロック法で積層する場合、粘着層が基材層に延展された後も、基材層よりも粘着層の溶融粘度が低いため、徐々にフィルム幅方向の端部で粘着層の廻り込みが発生し端部が粘着層のみとなることで、フィルム端部が製膜機に粘着する等のトラブルの原因となることもある。しかも粘着フィルムをロール状に巻いた後、再び巻き出す際にブロッキングが生じやすいという問題もある。また被覆体を汚染する恐れもある。粘着付与樹脂の含有量は好ましくは4重量%以上9重量%以下である。
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. and 2.16 kgf of less than 15 (g / 10 min) as a base layer, Due to the difference in melt viscosity between the pressure-sensitive adhesive layers, the pressure-sensitive adhesive layer is difficult to extend with respect to the base material layer, resulting in a time-consuming problem. Also, when laminating by the feed block method, even after the adhesive layer is extended to the base material layer, the melt viscosity of the adhesive layer is lower than that of the base material layer. When the end portion becomes only the adhesive layer, the end portion of the film may cause troubles such as sticking to the film forming machine. And after winding an adhesive film in roll shape, there also exists a problem that it is easy to produce blocking when unwinding again. There is also a risk of contaminating the covering. The content of the tackifying resin is preferably 4% by weight or more and 9% by weight or less.
(ポリオレフィン系樹脂)
 ポリオレフィン系樹脂は特に限定されず、結晶性ポリプロピレン、プロピレンと少量のα-オレフィンとの共重合体、低密度ポリエチレン、高密度ポリエチレン、エチレンと少量のα-オレフィンとの共重合体、エチレンと酢酸ビニルとの共重合体等が挙げられる。中でもポリプロピレン系樹脂は基材層がポリプロピレン系樹脂で構成されるため、溶融粘度等の関係からも好適に用いることができる。
 使用するポリオレフィン系樹脂の230℃・2.16kgfにおけるメルトフローレート(MFR)は、0.5~10g/10分の範囲が好ましく、2.0~8.0g/10分の範囲が製膜性の点でより好ましい。
(Polyolefin resin)
The polyolefin-based resin is not particularly limited. Crystalline polypropylene, copolymer of propylene and a small amount of α-olefin, low density polyethylene, high density polyethylene, copolymer of ethylene and a small amount of α-olefin, ethylene and acetic acid Examples thereof include a copolymer with vinyl. Among these, since the base material layer is composed of a polypropylene resin, 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.
 樹脂組成物におけるポリオレフィン系樹脂の含有量は、スチレン成分が5重量%以上、15重量%以下のスチレン系エラストマー100重量部に対し、2重量部以上、10重量部未満の範囲である。10重量部以上であると粘着力が低下し表面凹凸を有する被覆体に対する充分な粘着力が得られず、かつ延展性も劣る。2重量部未満であるとフィルムをロール状態で保管し、その後フィルムを繰出す際にも、ブロッキングが生じてフィルムが部分的に伸長したり、変形する等の問題が生じる。ポリオレフィン系樹脂の含有量は好ましくは4重量%以上、9重量%以下である。 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. When 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. When 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.
 また、粘着剤に使用する粘着付与樹脂は、種類によっては粉体を一部含む場合があり、押出時に押出機を汚す物もある。このような問題は粘着付与樹脂をポリオレフィン系樹脂とマスターバッチ化して使用することで改善されるため、粘着付与樹脂とポリオレフィン系樹脂とをマスターバッチ化して使用するほうが好ましい。 Also, 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.
 本発明で用いられる粘着剤中には、本発明の課題達成を阻害しない範囲で必要に応じて、架橋剤、粘着性付与剤、無機もしくは有機充填剤、軟化剤、可塑剤、界面活性剤、カップリング剤、消泡剤、帯電防止剤、難燃剤等の各種添加剤の1種もしくは2種以上が添加されていても良いが、粘着剤層や得られる粘着フィルム(表面保護フィルム)の透明性を阻害しない添加剤を選択して用いることが好ましい。 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.
(粘着フィルム)
 粘着剤層として、上記粘着剤を用いて、ポリプロピレン系樹脂を主成分とする基材層に共押出で積層された粘着フィルムは、粘着剤層が基材層に十分に延展される。さらにプリズム等の被着体への粘着力を十分に有し、しかも粘着フィルム同士を重ねても粘着フィルム同士のブロッキングが少ないという利点を有する。
(Adhesive film)
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.
 本発明の粘着フィルムの粘着力は23℃において、プリズムシートに対し3~50cN/25cmの範囲であることが、プリズムシートの保護性能の点から好ましい。粘着力が3cN/25cm未満であるとプリズムシートを保護する際にめくれ等が生じ、保護フィルムとしての機能を担えない。一方、粘着力が50cN/25cmを超えるとプリズムシートからフィルムを剥離する際にスムーズに剥離できない恐れがある。粘着力は粘着層の樹脂組成や厚みなどを変更することにより、適宜設定することが可能である。 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. When 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. On the other hand, when 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.
 本発明の粘着フィルムの粘着面の離型面に対する剥離力は23℃において、100cN/25cm以下の範囲であることが、粘着フィルムをロール形態とした際のフィルムの繰出し性の点から好ましい。剥離力が100cN/25cmを超えると粘着フィルムをロール形態とした際のフィルムの繰出しにフィルムが部分的に伸長したり、変形する等の問題が生じる。剥離力は離型層に表面凹凸を形成し、ロールとして巻き取る際に粘着面と離型面との接触面積を変更することで、適宜設定することができる。また、離型層中にフッ素系樹脂、シリコーン系樹脂、4-メチル-1-ペンテン重合体等の表面自由エネルギーを下げる効果を持つ樹脂を添加することでも、剥離力を下げることが可能である。 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. When 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. .
 本発明の粘着フィルムは、公知の添加剤を必要に応じて含有させたりすることができる。例えば、滑剤、ブロッキング防止剤、熱安定剤、酸化防止剤、帯電防止剤、耐光剤、耐衝撃改良剤などを含有させたりしても良い。
 但し、粘着層表面の低分子量物質を1mg/m2未満にすることが好ましい。ここで、粘着層表面の低分子量物質の測定は、次の手順にて実施した。粘着層表面をエタノール等の粘着層を構成する樹脂を侵食しない有機溶剤を用いて洗浄後、その洗浄液から有機溶剤をエバポレーター等で除去した後、その残渣を秤量して求めた数値を洗浄した粘着層表面の表面積で割り、求めた。
 ここで、残渣が1mg/m2以上存在すると粘着層表面と被着体表面の間に異物が存在する事となり、接触面積を減らし、ファンデルワールス力を低下させる原因となる為、粘着力が低下し好ましくない。添加剤を添加する場合は、高分子型等の添加剤を選択したり、添加量及び添加方法を検討するなどして、粘着層への移行、転写がない様にすることが必要である。
The pressure-sensitive adhesive film of the present invention can contain known additives as necessary. For example, 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.
However, the low molecular weight substance on the surface of the adhesive layer is preferably less than 1 mg / m 2 . Here, 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. It was obtained by dividing by the surface area of the layer surface.
Here, if a residue is present in an amount of 1 mg / m 2 or more, foreign matter exists between the surface of the adhesive layer and the adherend surface, which reduces the contact area and lowers the van der Waals force. Decreasing and not preferable. In the case of adding an additive, it is necessary to select an additive such as a polymer type or to examine the addition amount and the addition method so that there is no transfer or transfer to the adhesive layer.
(基材層)
 本発明の粘着フィルムは、ポリプロピレン系樹脂を主成分とする基材層を必要とする。ここで用いるポリプロピレン系樹脂としては、結晶性ポリプロピレン、プロピレンと少量のα-オレフィンとのランダム共重合体、ブロック共重合体等を挙げることができる。さらに詳しくは、結晶性ポリプロピレン樹脂として、通常の押出成形などで使用するn-へプタン不溶性のアイソタクチックのプロピレン単独重合体又はプロピレンを60重量%以上含有するポリプロピレンと他のα-オレフィンとの共重合体を挙げることができ、このプロピレン単独重合体あるいはプロピレンと他のα-オレフィンとの共重合体を、単独又は混合して使用することができる。
 ここで、n-ヘプタン不溶性とは、ポリプロピレンの結晶性を指標すると同時に安全性を示すものであり、本発明では、昭和57年2月厚生省告示第20号によるn-ヘプタン不溶性(25℃、60分抽出した際の溶出分が150ppm以下〔使用温度が100℃を超えるものは30PPm以下〕)に適合するものを使用することが好ましい態様である。
(Base material layer)
The pressure-sensitive adhesive film of the present invention requires a base material layer mainly composed of a polypropylene resin. Examples of the polypropylene resin used here include crystalline polypropylene, a random copolymer of propylene and a small amount of α-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 α-olefin is used. A copolymer may be mentioned, and this propylene homopolymer or a copolymer of propylene and another α-olefin may be used alone or in combination.
Here, the insolubility of n-heptane is indicative of the crystallinity of polypropylene and at the same time shows safety. In the present invention, 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).
 プロピレンと他のα-オレフィンとの共重合体のα-オレフィン共重合成分としては、炭素数が2~8のα-オレフィン、例えば、エチレンあるいは1-ブテン、1-ペンテン、1-ヘキセン、4-メチル-1-ペンテンなどのC4以上のα-オレフィンが好ましい。
 ここで共重合体とは、プロピレンに上記に例示されるα-オレフィンを1種又は2種以上重合して得られたランダム又はブロック共重合体であることが好ましい。
 上記理由から、使用するポリプロピレン系樹脂の230℃・2.16kgfにおけるメルトフローレート(MFR)は、1.0~15g/10分の範囲が好ましく、2.0~10.0g/10分の範囲がより好ましい。
 また、プロピレンと他のα-オレフィンとの共重合体を2種以上混合して使用することもできる。
 またさらに、本発明で得られたフィルムを製品加工する際に出た屑フィルムを回収原料として再造粒し、基材層に添加することもできる。回収原料を使用することにより、生産コストを抑えることが可能である。
The α-olefin copolymerization component of the copolymer of propylene and other α-olefins includes α-olefins having 2 to 8 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 4 C4 or higher α-olefins such as -methyl-1-pentene are preferred.
Here, the copolymer is preferably a random or block copolymer obtained by polymerizing one or more of the α-olefins exemplified above with propylene.
For the above reasons, the melt flow rate (MFR) at 230 ° C. and 2.16 kgf of the polypropylene resin used is preferably in the range of 1.0 to 15 g / 10 min, and in the range of 2.0 to 10.0 g / 10 min. Is more preferable.
Further, two or more kinds of copolymers of propylene and other α-olefins can be mixed and used.
Furthermore, 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.
 本発明の粘着フィルムにおける粘着層の基材層に対する延展性は90%以上であることが好ましい。粘着層の延展性が低いと樹脂を置換する際に多大な時間がかかり、操業性が悪化する。また、粘着層を数μmオーダーで積層させる際にフィルムの幅方向に厚みムラが発生しやすくなるという問題がある。粘着層の延展性は90%以上であることが好ましく、93%以上であるとより好ましく、95%以上であると特に好ましい。 In the pressure-sensitive adhesive film of the present invention, 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 μm, 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.
 本発明の粘着フィルムにおける粘着層の基材層に対する廻り込み率は3%以下であることが好ましい。粘着層の廻り込み率が高いとフィルム端部が粘着層のみとなり、製膜機に粘着する等のトラブルが発生し操業性が悪化する。粘着層の基材層に対する廻り込み率は2.5%以下であるとより好ましい。 In the pressure-sensitive adhesive film of the present invention, 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.
 本発明の粘着フィルムにおける粘着層の厚さは、1μm以上、30μm未満であることが好ましい。粘着フィルムの厚さが1μm未満であると、共押出による安定製膜が困難となり、30μm以上であると、コストの面で不利なフィルムとなる。このとき、粘着力を大きくする場合は、その粘性を考慮し、厚みを大きくするのが好ましい。粘着層の厚みを大きくすることにより、被着体との接触面積が大きくなりやすい。粘着層の厚さは、2μm以上、20μm以下であることが好ましく、さらに3μm以上、15μm以下が好ましく、特に4μm以上、8μm以下が好ましい。 The thickness of the adhesive layer in the adhesive film of the present invention is preferably 1 μm or more and less than 30 μm. If the thickness of the adhesive film is less than 1 μm, stable film formation by coextrusion becomes difficult, and if it is 30 μm 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 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 8 μm or less.
 本発明の粘着フィルムにおける基材層の厚さは、5μm以上、100μm未満であることが好ましく、15μm以上、25μm未満であることがさらに好ましい。粘着フィルムの厚さが5μm未満であると、腰感が弱くなり、保護フィルムとして被覆体に貼り付けた際にシワ等が入りやすく、粘着力が十分に得られないという問題があり、100μm以上であるとコストの面で不利なフィルムとなる。 The thickness of the base material layer in the pressure-sensitive adhesive film of the present invention is preferably 5 μm or more and less than 100 μm, and more preferably 15 μm or more and less than 25 μm. When the thickness of the pressure-sensitive adhesive film is less than 5 μm, 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.
(離型層)
 本発明の粘着フィルムは、基材層の片面に積層された粘着層とは反対面に離型層を形成するのが好ましい。そうすることよってブロッキングをさらに抑えることができる。本発明の粘着層の樹脂組成を鑑みると、離型層表面の平均表面粗さSRaを0.40μm以上とするのが好ましい。表面の平均表面粗さはSRaで0.850μm以下となる様な表面にすることが好ましく、0.500μm以上、0.700μm以下が特に好ましい。離型層の厚さは、1μm以上、30μm未満であることが好ましく、3~10μmが特に好ましい。
(Release layer)
In the pressure-sensitive adhesive film of the present invention, 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. In view of the resin composition of the pressure-sensitive adhesive layer of the present invention, the average surface roughness SRa of the release layer surface is preferably 0.40 μm or more. The average surface roughness of the surface is preferably such that SRa is 0.850 μm or less, particularly preferably 0.500 μm or more and 0.700 μm or less. The thickness of the release layer is preferably 1 μm or more and less than 30 μm, and particularly preferably 3 to 10 μm.
 上記のような表面凹凸を形成するには、プロピレン-エチレンブロック共重合体を使用することによって、マット状に表面が荒れた層を形成することができる。また、ホモポリプロピレンにポリエチレン系樹脂を混合することによっても同様の効果が期待できる。加えて、プロピレン-エチレンブロック共重合体にポリエチレン系樹脂を混合することによりさらに表面が荒れた層を形成させることができる。マット状の表面を得るのに好適な樹脂としては、具体的には日本ポリプロ(株)製「BC4FC」などのプロピレン-エチレンブロック共重合体を例示することが出来る。 In order to form the surface irregularities as described above, 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. In addition, a layer with a rougher surface can be formed by mixing a propylene-ethylene block copolymer with a polyethylene resin. Specific examples of the resin suitable for obtaining a mat-like surface include propylene-ethylene block copolymers such as “BC4FC” manufactured by Nippon Polypro Co., Ltd.
 本発明の粘着フィルムはロールの形態とするのが取り扱いの上で好適である。フィルムロールの幅および巻長の上限は特に制限されるものではないが、取扱いのしやすさから、一般的には幅1.5m以下、巻長はフィルム厚み30μmの場合に6000m以下が好ましい。また、巻取りコアとしては、通常、3インチ、6インチ、8インチ等のプラスチックコアや金属製コアを使用することができる。また、加工の適性から長さ200m以上、幅450mm以上の寸法で巻き取ったフィルムロールであることが好ましい。 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 μm. Moreover, as a winding core, a plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can usually be used. Moreover, it is preferable that it is a film roll wound up by the dimension of length 200m or more and width 450mm or more from the suitability of a process.
 本発明の粘着剤を使用した粘着フィルムは、特に、光学用途に用いられているプリズムシートのプリズム型のレンズ部の外表面を保護するために好適にもちいることができる。また、合成樹脂板(例えば建築資材用)、ステンレス板(例えば、建築資材用)、アルミ板、化粧合板、鋼板、ガラス板、家電製品、精密機械および、製造時の自動車ボディーの表面を保護するため、物品を積み重ねたり、保管したり、輸送したり、製造工程で搬送する際の傷付きから保護するため、ならびに、物品を二次加工する(たとえば、曲げ加工やプレス加工)際の傷付きから保護する場合にも用いることができる。 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.
 次に実施例をあげて本発明をさらに説明する。但し、本発明は、その要旨を逸脱しない限り下記の実施例に限定されるものではない。なお、以下の実施例、比較例における物性の評価方法は以下の通りである。 Next, the present invention will be further described with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. In addition, the evaluation method of the physical property in a following example and a comparative example is as follows.
(1)粘着層の基材層への延展性の評価
 3層Tダイ(フィードブロック型、リップ幅850mm、リップギャップ1mm)内で粘着層樹脂を40mmφ単軸押出し機にて15kg/時の吐出量で、基材層樹脂を90mmφ単軸押出し機にて15kg/時の吐出量で、離型層樹脂を65mmφ単軸押出し機にて5kg/時の吐出量でそれぞれ共押出しする。押出したフィルムを温度30℃のキャスティングロールへ20m/分速度で引取ることにより、650mm幅の未延伸フィルムが得られる。粘着層樹脂を40mmφ単軸押出し機に投入し、その樹脂の代わり始めから30分経過後の基材層への粘着層の延展率を測定した。
延展率=粘着層の積層幅(mm)/650(mm)×100(%)
(1) Evaluation of spreadability of adhesive layer to base material layer Adhesive layer resin is discharged at 15 kg / hour with a 40 mmφ 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 mmφ single screw extruder, and the release layer resin is coextruded with a discharge rate of 5 kg / hour with a 65 mmφ single screw extruder. By drawing the extruded film onto a casting roll at a temperature of 30 ° C. at a speed of 20 m / min, an unstretched film having a width of 650 mm is obtained. The adhesive layer resin was put into a 40 mmφ 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 (%)
(2)粘着層の基材層への廻り込み性の評価
 3層Tダイ(フィードブロック型、リップ幅850mm、リップギャップ1mm)内で粘着層樹脂を40mmφ単軸押出し機にて15kg/時の吐出量で、基材層樹脂を90mmφ単軸押出し機にて15kg/時の吐出量で、離型層樹脂を65mmφ単軸押出し機にて5kg/時の吐出量でそれぞれ共押出しする。押出したフィルムを温度30℃のキャスティングロールへ20m/分速度で引取ることにより、650mm幅の未延伸フィルムが得られる。粘着層樹脂を40mmφ単軸押出し機に投入し、その樹脂の代わり始めから120分経過後の基材層への粘着層のフィルム幅方向の両端の廻り込み率を測定した。
廻り込み率=粘着層がフィルム幅方向の両端に廻り込んだ幅(mm)/650(mm)×100(%)
(2) Evaluation of wraparound property of adhesive layer to base material layer Adhesive layer resin in a three-layer T die (feed block type, lip width 850 mm, lip gap 1 mm) was 15 kg / hour in a 40 mmφ single screw extruder. The substrate layer resin is coextruded at a discharge rate of 15 kg / hour with a 90 mmφ single screw extruder and the release layer resin is discharged with a discharge rate of 5 kg / hour with a 65 mmφ single screw extruder. By drawing the extruded film onto a casting roll at a temperature of 30 ° C. at a speed of 20 m / min, an unstretched film having a width of 650 mm is obtained. The adhesive layer resin was put into a 40 mmφ 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
(3)粘着性の評価
 JIS-Z-0237(2000)粘着テープ・粘着シート試験方法に準拠して下記の方法にて測定した。
 被着体として、アクリル板(三菱レイヨン(株)製:アクリライト(登録商標)3mm厚)50mm×150mm、表面処理状態の異なる2種類のプリズムシート(レンズ部は三角柱からなり、三角柱の高さは25μm、三角柱の幅は50μm)50mm×150mmを準備し、試験片として、フィルム製造時の巻き取り方向に150mm、それとは直交する方向に25mmの試験片を切り出し、質量2000gのゴムロール(ローラ表面のスプリング硬さ80Hs、厚さ6mmのゴム層で被覆された、幅45mm、直径(ゴム層を含む)95mmのもの)を5mm/秒の速さで1往復させて、被着体と試験片を圧着した。圧着後、温度23℃、相対湿度65%の環境下で30分放置したものを(株)島津製作所製「オートグラフ(登録商標)」(AGS-J)を用いて、300mm/分の速度で180度剥離した際の抵抗値を粘着力[cN/25mm]とした。180度剥離とは、剥離時の抵抗値を測定する際のアクリル板とフィルムの剥離角度を180度に保持することを意味する。
 測定の際は測定試料のつかみ代として厚み190μm、サイズ25mm×170mmのポリエステルシートを準備し、上記、粘着フィルムとアクリル板を圧着した測定試料の粘着フィルム側の端に、のり代15mmの幅でセロハンテープ(登録商標)にて貼り付けて、測定の際のつかみ代とした。測定試料の模式図を図1に示す。測定は一つのサンプルに関して3回実施し、その平均値をそのサンプルの粘着力とした。
(3) Evaluation of adhesiveness Measured by the following method in accordance with JIS-Z-0237 (2000) 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 μm, the width of the triangular prism is 50 μm), 50 mm × 150 mm is prepared. 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. Was crimped. After crimping, a sample that was left for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 65% using “Autograph (registered trademark)” (AGS-J) manufactured by Shimadzu Corporation at a speed of 300 mm / min. The resistance value when peeled by 180 degrees was defined as the adhesive strength [cN / 25 mm]. 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.
At the time of measurement, a polyester sheet having a thickness of 190 μm 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.
(4)耐ブロッキング性の評価
 耐ブロッキング性の評価として、下記のように粘着フィルムの離型層と粘着層の剥離力を測定した。
 アクリル板(三菱レイヨン(株)製:アクリライト3mm厚)50mm×150mm全面に両面接着テープ(日東電工(株)製:No.535A)を貼付け、両面接着テープの他面に試験片の粘着面が来るように150mm(フィルム製造時の巻き取り方向)×50mm(フィルム製造時の巻き取り方向とは直交方向)の試験片を貼付けた。
 新たに試験片として、フィルム製造時の巻き取り方向に150mm、それとは直交する方向に25mmの試験片を切り出し、その粘着面とアクリル板に両面接着テープを介し貼付けた試験片の離型面を重ね合わせた後、質量2000gのゴムロール(ローラ表面のスプリング硬さ80Hs、厚さ6mmのゴム層で被覆された、幅45mm、直径(ゴム層を含む)95mmのもの)を5mm/秒の速さで1往復させて、離型面と試験片を圧着した。圧着後、温度23℃、相対湿度65%の環境下で30分放置したものを(株)島津製作所製「オートグラフ」(AGS-J)を用いて、300mm/分の速度で180度剥離した際の抵抗値を剥離力[cN/25mm]とした。
 測定の際は測定試料のつかみ代として厚み190μm、サイズ25mm×170mmのポリエステルシートを準備し、150mm×25mmの試験片の端に、のり代15mmの幅でセロハンテープにて貼り付けて、測定の際のつかみ代とした。測定は一つのサンプルに関して3回実施し、その平均値をそのサンプルの剥離力とした。
(4) Evaluation of blocking resistance As evaluation of blocking resistance, the peeling force of the release layer and adhesive layer of an adhesive film was measured as follows.
Acrylic board (Mitsubishi Rayon Co., Ltd .: Acrylite 3 mm thickness) 50 mm x 150 mm with a double-sided adhesive tape (Nitto Denko Co., Ltd .: No. 535A) attached to the other side of the double-sided adhesive tape A test piece of 150 mm (winding direction at the time of film production) × 50 mm (direction orthogonal to the winding direction at the time of film production) was attached.
As a new test piece, 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. After the superposition, 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. After crimping, 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].
At the time of measurement, a polyester sheet having a thickness of 190 μm 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.
(5)平均表面粗さの測定
 (株)小坂研究所製の接触式三次元中心面表面粗計(型式ET-30HK)を用いて、離型層の表面の中心面平均粗さ(SRa)を次の条件で触針法により測定した。条件は下記の通りであり、3回の測定の平均値をもって値とした。
触針先端半径:0.5μm
触針圧:20mg
カットオフ値:80μm
測定長:1000μm
測定速度:100μm/秒
測定間隔:2μm
(5) Measurement of average surface roughness Center surface average roughness (SRa) of the surface of the release layer using a contact type three-dimensional center surface surface roughness meter (model ET-30HK) manufactured by Kosaka Laboratory Ltd. Was measured by the stylus method under the following conditions. The conditions were as follows, and the average value of three measurements was used as the value.
Stitch tip radius: 0.5 μm
Stylus pressure: 20mg
Cut-off value: 80 μm
Measurement length: 1000 μm
Measurement speed: 100 μm / second Measurement interval: 2 μm
(6)取り扱い性
 得られたフィルムをロールとし、ロールからフィルムを繰出す際にフィルムの抵抗が小さいものを○、大きいものを×とした。
(6) Handling property The obtained film was used as a roll, and when the film was fed out from the roll, the film having a low resistance was evaluated as ◯, and the film having a large resistance as x.
[実施例1]
(基材層の作製)
 ポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)100wt%を90mmφ単軸押出し機にて溶融押出しして基材層とした。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテック(登録商標)H1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、ポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)8.8重量部と石油樹脂(荒川化学工業製:アルコン(登録商標)P125)8.8重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
(離型層の作製)
 プロピレン-エチレンブロックコポリマー(日本ポリプロ製:BC4FC)100wt%を65mmφ単軸押出し機にて溶融押出しして離型層とした。
(フィルムの作製)
 基材層、粘着層、離型層それぞれが各押出し機にて溶融された状態のまま、250℃の3層Tダイ(フィードブロック型、リップ幅850mm、リップギャップ1mm)内で積層押出しを行った。押出したフィルムを温度30℃のキャスティングロールへ20m/min速度で引取り、冷却固化して基材層厚みが18μm、粘着層厚みが6μm、離型層厚みが6μmの3種3層未延伸フィルムを得た。
[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 mmφ single screw extruder to obtain a base material layer.
(Preparation of adhesive layer)
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 mmφ single-screw extruder and subjected to an adhesive layer. It was.
(Production of release layer)
100% by weight of propylene-ethylene block copolymer (manufactured by Nippon Polypro: BC4FC) was melt-extruded with a 65 mmφ single screw extruder to form a release layer.
(Production of film)
Lamination extrusion is performed in a three-layer T die (feed block type, lip width 850 mm, lip gap 1 mm) at 250 ° C. while the base material layer, the adhesive layer, and the release layer are melted in each extruder. It was. The extruded film is drawn onto a casting roll at a temperature of 30 ° C. at a rate of 20 m / min, cooled and solidified, and a three-layer three-layer unstretched film having a substrate layer thickness of 18 μm, an adhesive layer thickness of 6 μm, and a release layer thickness of 6 μm. Got.
[実施例2]
 粘着層、離型層は実施例1のまま、基材層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(基材層の作製)
ホモポリプロピレン樹脂(住友化学製:FLX80E4、MFR:7.5g/10min)100wt%を90mmφ単軸押出し機にて溶融押出しして基材層とした。
[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.
(Preparation of base material layer)
100 wt% of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt-extruded with a 90 mmφ single screw extruder to obtain a base material layer.
[実施例3]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)3.2重量部とポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)3.2重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[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.
(Preparation of adhesive layer)
3.2 parts by weight of a petroleum resin (Arakawa Chemical Industries: Alcon P125) with respect to 100 parts by weight of a styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) 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) was melt-extruded with a 40 mmφ single-screw extruder to obtain an adhesive layer.
[実施例4]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)8.8重量部とポリプロピレン系樹脂(住友化学製:WF836DG3:、MFR:7.0g/10min)8.8重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[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.
(Preparation of adhesive layer)
With respect to 100 parts by weight of 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 mmφ single screw extruder to obtain an adhesive layer.
[実施例5]
 離型層は実施例1のまま、基材層と粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)5.7重量部とポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)8.0重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
(基材層の作製)
 ホモポリプロピレン樹脂(住友化学社製:FLX80E4、MFR:7.5g/10min)100wt%を90mmφ単軸押出し機にて溶融押出しして基材層とした。
[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.
(Preparation of adhesive layer)
With respect to 100 parts by weight of 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) was melt-extruded with a 40 mmφ single-screw extruder to obtain an adhesive layer.
(Preparation of base material layer)
100 wt% of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt-extruded with a 90 mmφ single-screw extruder to obtain a base material layer.
[比較例1]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)17.6重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 1]
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.
(Preparation of adhesive layer)
17.6 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125) is added to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min). The mixture was melt-extruded with a 40 mmφ single screw extruder to form an adhesive layer.
[比較例2]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)21.4重量部とポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)21.4重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 2]
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.
(Preparation of adhesive layer)
21.4 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125) with respect to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) A mixture of 21.4 parts by weight of a polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mmφ single-screw extruder to obtain an adhesive layer.
[比較例3]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、ポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)17.6重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative 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.
(Preparation of adhesive layer)
Polypropylene resin (Sumitomo Chemical: FS2011DG3, MFR: 2.5 g / 10 min) with respect to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) ) 17.6 parts by weight of the mixture was melt-extruded with a 40 mmφ single screw extruder to form an adhesive layer.
[比較例4]
 離型層は実施例1のまま、粘着層と基材層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)17.6重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
(基材層の作製)
 ホモポリプロピレン樹脂(住友化学製:FLX80E4、MFR:7.5g/10min)100wt%を90mmφ単軸押出し機にて溶融押出しして基材層とした。
[Comparative Example 4]
The adhesive layer and the base material layer were changed to the following contents with the release layer being the same as in Example 1, and an unstretched film of 3 types and 3 layers was obtained by the same production method as Example 1.
(Preparation of adhesive layer)
17.6 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125) is added to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min). The mixture was melt-extruded with a 40 mmφ single screw extruder to form an adhesive layer.
(Preparation of base material layer)
100 wt% of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt-extruded with a 90 mmφ single screw extruder to obtain a base material layer.
[比較例5]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)6.4重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 5]
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.
(Preparation of adhesive layer)
6.4 parts by weight of a petroleum resin (Arakawa Chemical Industries, Ltd .: Alcon P125) is added to 100 parts by weight of a styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min). The mixture was melt-extruded with a 40 mmφ single screw extruder to form an adhesive layer.
[比較例6]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)6.3重量部とポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)18.8重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 6]
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.
(Preparation of adhesive layer)
With respect to 100 parts by weight of a styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min), 6.3 parts by weight of a petroleum resin (Arakawa Chemical Industries: Alcon P125) A mixture obtained by mixing 18.8 parts by weight of a polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.
[比較例7]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1221、スチレン共重合比12wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)18.8重量部とポリプロピレン系樹脂(住友化学製:WF836DG3、MFR:7.0g/10min)6.3重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 7]
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.
(Preparation of adhesive layer)
With respect to 100 parts by weight of a styrene elastomer (Asahi Kasei Chemicals: Tuftec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min), 18.8 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125) A mixture of 6.3 parts by weight of a polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: WF836DG3, MFR: 7.0 g / 10 min) was melt-extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.
[比較例8]
 基材層、離型層は実施例1のまま、粘着層を下記の内容に変更して、実施例1と同様の製法で3種3層の未延伸フィルムを得た。
(粘着層の作製)
 スチレン系エラストマー(旭化成ケミカルズ製:タフテックH1062、スチレン共重合比18wt%、MFR:4.5g/10min)100重量部に対して、石油樹脂(荒川化学工業製:アルコンP125)8.8重量部とポリプロピレン系樹脂(住友化学製:FS2011DG3、MFR:2.5g/10min)8.8重量部を混合したものを、40mmφ単軸押出し機にて溶融押出しして粘着層とした。
[Comparative Example 8]
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.
(Preparation of adhesive layer)
With respect to 100 parts by weight of styrene elastomer (Asahi Kasei Chemicals: Tuftec H1062, styrene copolymerization ratio 18 wt%, MFR: 4.5 g / 10 min), 8.8 parts by weight of petroleum resin (Arakawa Chemical Industries: Alcon P125) A mixture obtained by mixing 8.8 parts by weight of a polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.
 上記結果を表1、2、3に示す。 The above results are shown in Tables 1, 2, and 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表1から明らかなように実施例1~5で得られたフィルムは、フィルム製膜時の延展性が良好で、保護フィルムとして使用した際に実用上充分な粘着力を有し、フィルムをロールとした際の取り扱い性も良好であった。 As is apparent from Table 1, 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.
 一方、比較例1及び4及び7で得られたフィルムは、フィルム製膜時の延展性が不充分であり、粘着層の回り込みが発生し、製膜性が必ずしも良好とは言えない結果となった。また、フィルムをロールとした際の取り扱い性に関しても必ずしも良好とは言えない結果となった。比較例2及び3及び6及び8で得られたフィルムは、被覆体であるプリズムシートに粘着力を示さず、実用上必要な粘着力を有していない結果となった。比較例5で得られたフィルムはフィルムをロールとした際の取り扱い性に関しても必ずしも良好とは言えない結果となった。このように比較例で得られたフィルムはいずれも品質が劣り、実用性が低いものであった。 On the other hand, 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.
 本発明の粘着剤は、特に光学用途に用いられているプリズムシートのプリズム型のレンズ部の外表面を保護するための粘着フィルムに好適にもちいることができる。
 また、合成樹脂板(例えば建築資材用)、ステンレス板(例えば、建築資材用)、アルミ板、化粧合板、鋼板、ガラス板、家電製品、精密機械および、製造時の自動車ボディーの表面を保護するため、物品を積み重ねたり、保管したり、輸送したり、製造工程で搬送する際の傷付きから保護するため、ならびに、物品を二次加工する(たとえば、曲げ加工やプレス加工)際の傷付きから保護する場合にも好適に用いることができ、産業界に寄与することが大である。
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.

Claims (8)

  1.  スチレン系重合体ブロックとオレフィン系重合体ブロックとのブロック共重合体、スチレン系重合体ブロックとスチレンとオレフィンとのランダム共重合体ブロックとのブロック共重合体、および/またはこれらの水素添加物を主成分とする、スチレン成分が5~15重量%であるスチレン系エラストマー100重量部に対して、粘着付与樹脂2重量部以上、10重量部未満、ポリオレフィン系樹脂2重量部以上、10重量部未満を含む樹脂組成物からなることを特徴する粘着性樹脂組成物。 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 a hydrogenated product thereof. 2 parts by weight or more and less than 10 parts by weight of a tackifying resin, 2 parts by weight or more and less than 10 parts by weight of a polyolefin resin with respect to 100 parts by weight of a styrene elastomer having a styrene component of 5 to 15% by weight as a main component An adhesive resin composition comprising a resin composition comprising:
  2.  請求項1に記載の粘着性樹脂組成物が、ポリプロピレン系樹脂を主成分とする基材層の片面に積層されてなることを特徴とする粘着フィルム。 A pressure-sensitive adhesive film, wherein the pressure-sensitive adhesive composition according to claim 1 is laminated on one side of a base material layer mainly composed of a polypropylene resin.
  3.  ポリプロピレン系樹脂を主成分とする基材層の粘着性樹脂組成物からなる粘着層とは反対面に離型層が積層されてなることを特徴とする請求項2に記載の粘着フィルム。 3. The pressure-sensitive adhesive film according to claim 2, wherein a release layer is laminated on the surface opposite to the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition of the base material layer mainly composed of polypropylene resin.
  4.  ポリプロピレン系樹脂を主成分とする基材層、粘着性樹脂組成物からなる粘着層、離型層とが共押出により積層されてなることを特徴とする請求項3に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 3, wherein a base material layer mainly composed of a polypropylene resin, a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive resin composition, and a release layer are laminated by coextrusion.
  5.  前記粘着層中のスチレン系エラストマーの230℃・2.16kgfにおけるメルトフローレート(MFR)が0.5~10g/10分である請求項2~4のいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 2 to 4, wherein the styrene elastomer in the pressure-sensitive adhesive layer has a melt flow rate (MFR) at 230 ° C and 2.16 kgf of 0.5 to 10 g / 10 minutes.
  6.  前記基材層中のポリプロピレン系樹脂の230℃・2.16kgfにおけるメルトフローレート(MFR)が1.0~15g/10分である請求項2~5のいずれかに記載の粘着フィルム。 6. The pressure-sensitive adhesive film according to claim 2, wherein 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 minutes.
  7.  プリズムシート被覆用である請求項2~6のいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 2 to 6, which is used for covering a prism sheet.
  8.  自己粘着性である請求項2~7のいずれかに記載の粘着フィルム。 The adhesive film according to any one of claims 2 to 7, which is self-adhesive.
PCT/JP2011/077587 2010-12-01 2011-11-29 Pressure-sensitive adhesive resin composition and pressure -sensitive adhesive film WO2012073979A1 (en)

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CN103261352A (en) 2013-08-21
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KR101867113B1 (en) 2018-06-12
TWI443172B (en) 2014-07-01

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