Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/241—Polyolefin, e.g.rubber
  • C09J7/243—Ethylene or propylene polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/255—Polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to an adhesive film that is excellent in surface smoothness and excellent in slipping property, handling property and winding property and can be suitably used as a surface protective film.
• Adhesive films that have adhesiveness to the adherend surface and can be peeled off after use without contaminating the adherend are used as packaging films, surface protective films, and process films. Affixed to the surface of products, display panel members, synthetic resin panels, and objects to be protected such as substrates and parts of electrical equipment, etc., and widely used as protective films for processing, storage, transportation, shipping, etc. in use.
• Patent Documents 1 and 2 describe a film in which an adhesive is applied to the surface of a polyethylene terephthalate film or the like.
• an adhesive layer is applied off-line on a smooth film and dried.
• the adhesive film has low slipperiness and is difficult to wind. It is common to wind up as paper.
• slip paper not only increases the cost, but also requires a facility for winding the slip sheet when the adhesive film is unwound and used, so that the productivity is not sufficient.
• the object of the present invention is to solve the above-mentioned problems. That is, it is to provide an adhesive film that is excellent in surface smoothness and excellent in slipping property, handling property and winding property.
• the pressure-sensitive adhesive film of the present invention is a pressure-sensitive adhesive film provided with a pressure-sensitive adhesive layer on one side of the base film, and the back surface of the base film (the pressure-sensitive adhesive layer is not provided).
• the ten-point average roughness SRz of the surface) is 3,000 nm or less, and the thickness d of the adhesive layer is 3,000 nm or less.
• the pressure-sensitive adhesive film of the present invention is excellent in surface smoothness and excellent in slipping property, handling property and winding property, and therefore can be suitably used as a surface protective film.
• the pressure-sensitive adhesive film of the present invention is a pressure-sensitive adhesive film in which a pressure-sensitive adhesive layer is provided on one side of a base film, and the ten-point average roughness SRz of the back surface of the base film (the surface on which the pressure-sensitive adhesive layer is not provided) is 3,000 nm or less. It is. More preferably, it is 2,500 nm or less, More preferably, it is 2,000 nm or less, Most preferably, it is 1,500 nm or less. If the ten-point average roughness SRz on the back surface of the base film exceeds 3,000 nm, the surface shape of the adhesive film may be transferred to the adherend surface when the protective film is attached to the adherend and wound. is there.
• SRz is more preferably 1,000 nm.
• it is more preferably 500 nm or less, and most preferably 300 nm or less.
• SRz is preferably as small as possible.
• the lower limit of SRz is about 30 nm.
• SRz As a method of making SRz in the above range, a known technique can be used, a method of blending two or more raw materials to form surface irregularities, a method of adding easy-slip particles to the surface layer, and an unstretched film A method of forming two or more different crystal forms and forming irregularities during stretching can be used.
• the raw material composition of the film and the laminated structure of the film are set in the ranges described later, and the cast at the time of film formation (of the melt-extruded resin) It is preferable to reduce the ⁇ crystal of the cast sheet by setting the sheet forming step) condition and the longitudinal stretching condition within the ranges described below.
• the thickness d of the pressure-sensitive adhesive layer is 3,000 nm or less. More preferably, it is 1,200 nm or less, More preferably, it is 800 nm or less, More preferably, it is 600 nm or less, Most preferably, it is 400 nm or less.
• the thickness d of the pressure-sensitive adhesive layer exceeds 3,000 nm, the surface of the pressure-sensitive adhesive layer becomes smooth, and slipping between the back surface of the base film and the surface of the pressure-sensitive adhesive layer may be deteriorated and winding may be difficult. Further, the back of the adhesive layer may occur.
• the thickness d of the adhesive layer exceeds 3,000 nm, drying of the adhesive layer in the drying furnace may be insufficient, and the film may be trimmed.
• a known technique can be used as the method for setting the thickness of the adhesive layer in the above range, and it can be controlled by adjusting the solid content concentration of the solution in the adhesive layer and adjusting the coating thickness in various coating methods. If the thickness of the adhesive layer is too thin, stable coating may be difficult, or the adhesive strength may be too low to adhere to the adherend, so about 100 nm is the lower limit.
• the center average surface roughness SRa on the back surface of the base film is preferably 100 nm or less. More preferably, it is 40 nm or less, More preferably, it is 30 nm or less, Most preferably, it is 25 nm or less.
• the center average surface roughness SRa on the back surface of the base film exceeds 100 nm, the surface shape of the pressure-sensitive adhesive film may be transferred to the adherend surface when the protective film is attached to the adherend and wound. From the viewpoint of transfer of the adhesive film surface shape, SRa is preferably as small as possible, but the lower limit of SRa is substantially about 1 nm.
• SRa For the method of making SRa in the above range, a known technique can be used, a method of blending two or more raw materials to form surface irregularities, a method of adding easy-slip particles to the surface layer, and an unstretched film A method of forming two or more different crystal forms and forming irregularities during stretching can be used.
• the raw material composition of the film and the laminated structure of the film are within the ranges described below, and the casting conditions and longitudinal stretching conditions are within the ranges described below. It is preferable to reduce the ⁇ crystal of the cast sheet.
• the ratio of the ten-point average roughness SRz of the back surface of the base film to the thickness d of the pressure-sensitive adhesive layer, SRz / d is preferably 0.1 to 3.5. More preferably, it is 0.3 to 3.5, and still more preferably 0.5 to 3.0. If the value of SRz / d is less than 0.1, the slipperiness between the back surface of the base film and the surface of the adhesive layer may be deteriorated and winding may be difficult. When the value of SRz / d exceeds 3.5, the value of SRz increases, and the surface shape of the pressure-sensitive adhesive film may be transferred to the surface of the adherend when the protective film is attached to the adherend and wound. is there.
• the pressure-sensitive adhesive film of the present invention has the surface roughness of the base film and the thickness of the pressure-sensitive adhesive layer within the above-described ranges, so that although it has high surface smoothness, it has a certain adhesive force, It was possible to obtain a pressure-sensitive adhesive film that was excellent in handling and winding properties and was not backed. Since the pressure-sensitive adhesive film has a thick pressure-sensitive adhesive layer, the sliding property between the back surface of the base film and the surface of the pressure-sensitive adhesive layer is poor, and it has been difficult to wind up with good quality without a release film.
• the conventional adhesive film is coated with a solution of an adhesive layer on a base film, dried to the extent that the adhesive layer does not adhere to the transport roll in a drying furnace, wound into a roll with a release film, and wound.
• a general method is to age the adhesive layer after it has been taken to advance the adhesive layer.
• the adhesion between the back surface of the base film and the adhesive layer is increased during curing, and the film may be cleaved.
• both the pressure-sensitive adhesive property and the slipping property can be achieved even when a smooth base film is used, and further, the pressure-sensitive adhesive layer is cured in a drying furnace. It is possible to provide a pressure-sensitive adhesive film that is difficult to be breached even if it is wound without using a release film.
• the adhesive film of the present invention preferably has a haze of 10% or less. More preferably, it is 5% or less, more preferably 2% or less, and most preferably 1% or less. When the haze exceeds 10%, the surface roughness of the film surface is large, and the surface shape may be transferred to the adherend.
• the haze is preferably as low as possible from the viewpoint of transparency, but in practice, the lower limit is about 0.05%.
• the raw material composition of the film and the laminated structure of the film are set in a range described later to prevent deterioration of transparency due to particles and the like, and the casting conditions and longitudinal stretching conditions during film formation are described later. It is preferable that the ⁇ crystal of the cast sheet is reduced.
• Adhesive film of the present invention is preferably the longitudinal direction of the Young's modulus E MD is not less than 1 GPa.
• E MD is more preferably 1.2GPa or more, more preferably at least 1.4 GPa.
• EMD is preferably as strong as possible, but the upper limit is substantially about 10 GPa. The value of E MD to the above range, the range to be described later raw material composition of the film, also a range to be described later deposition conditions, to obtain a base film of the film was biaxially stretched at a high magnification Is preferred.
• the pressure-sensitive adhesive film of the present invention preferably has a Young's modulus E TD in the width direction of 1 GPa or more.
• E TD is less than 1 GPa, or become a film easily wrinkles on during transport, wound into a roll is pasted to a film as an adherend, such as wrinkles on the roll by the dimensional change of the film upon storage May occur.
• E TD is more preferably 1.5 GPa or more, further preferably 2.0 GPa or more, and most preferably 2.5 GPa or more.
• ETD is preferably as strong as possible, but the upper limit is substantially about 10 GPa.
• the raw material composition of the film is set in the range described later, and the film forming conditions are set in the range described below, and the base film is obtained by biaxially stretching the film at a high magnification. Is preferred.
• a direction parallel to the film forming direction is referred to as a film forming direction, a longitudinal direction, or an MD direction, and a direction perpendicular to the film forming direction in the film plane is referred to as a width direction or a TD direction.
• the adhesive film of the present invention preferably has a heat shrinkage rate of 1.0% or less after heat treatment at 110 ° C. in the width direction. More preferably, it is 0.8% or less, more preferably 0.5% or less, and most preferably 0.3% or less.
• the heat shrinkage rate in the width direction exceeds 1.0%, for example, the film is deformed and peeled off or wrinkled when passing through a drying process where heat is applied after bonding with another material. There is a case.
• wrinkles or the like may occur on the roll due to a dimensional change of the film.
• the lower limit of the heat shrinkage rate is not particularly limited, but the film may swell, and the lower limit is substantially about ⁇ 2.0%.
• the raw material composition of the film is set in a range described later, and the film forming conditions are set in a range described below. Is effective.
• the heat shrinkage rate refers to a film with a width of 10 mm and a length of 200 mm (measurement direction) cut out in the width direction of the film. The distance between the marked lines was measured to obtain the test length (l 0 ), and then the test piece was sandwiched between papers and taken out after heating for 60 minutes in an oven kept at 110 ° C. with zero load, and cooled at room temperature. Thereafter, the dimension (l 1 ) was measured with a universal projector and obtained by the following formula, and the average value of the five was taken as the heat shrinkage rate.
• the adhesive film of the present invention preferably has a 180 ° C. peeling force of 1 N / 25 mm or less after being bonded to a glass plate.
• the peeling force is more preferably 0.5 N / 25 mm or less, still more preferably 0.2 N / 25 mm or less, and most preferably 0.05 N / 25 mm or less. If the peeling force exceeds 1 N / 25 mm, slipping between the back surface of the base film and the surface of the adhesive layer may be deteriorated, and winding may be difficult or betrayed.
• the composition and thickness of the adhesive layer are set within the ranges described below, and the raw material composition and film forming conditions of the film are set within the ranges described below, and the surface roughness of the base film is controlled. It is effective. If the peel force is less than 0.01 N / 25 mm, the adhesive film may be peeled off during transportation after being bonded to the adherend, so the lower limit is about 0.01 N / 25 mm.
• the thickness of the pressure-sensitive adhesive film of the present invention is appropriately adjusted depending on the application and is not particularly limited, but is preferably 5 ⁇ m or more and 100 ⁇ m or less. When the thickness is less than 5 ⁇ m, handling may be difficult, and when it exceeds 100 ⁇ m, the amount of resin may increase and productivity may decrease. Even if the pressure-sensitive adhesive film of the present invention is made thin, it is excellent in strength (Young's modulus), so it can maintain handling properties. In order to make use of such characteristics, the thickness is more preferably 5 ⁇ m or more and 40 ⁇ m or less, further preferably 5 ⁇ m or more and 30 ⁇ m or less, and most preferably 5 ⁇ m or more and 25 ⁇ m or less. The thickness can be adjusted by the screw rotation speed of the extruder, the width of the unstretched sheet, the film forming speed, the stretch ratio, and the like within a range not deteriorating other physical properties.
• the base film used for the pressure-sensitive adhesive film of the present invention is not particularly limited, and the material is polyamide, aramid, polyimide, polyamideimide, cellulose, polypropylene, polyethylene, polymethylpentene, nylon, polyethylene terephthalate, etc. It can be used by mixing more than one species, but because it has excellent surface smoothness, it can obtain a high-quality film with less fish eyes and foreign materials, and it can improve handling properties such as film strength and stiffness.
• the base film is preferably composed mainly of polypropylene or polyethylene terephthalate.
• the “main component” in the present application means that the proportion of the specific component in all the components is 50% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, Most preferably, it is 99 mass% or more.
• polyethylene terephthalate is the main component when excellent surface smoothness is required for the substrate film, such as when the adherend is a soft material, or when defect detection is performed with the adherend adhered to the adherend.
• a film is used.
• polypropylene as the main component of the base film, taking advantage of the excellent releasability of polypropylene, the slipperiness between the back of the base layer and the adhesive layer surface is improved, and handling and winding properties are excellent.
• An adhesive film can be obtained.
• the base film used for the adhesive film of the present invention will be described taking as an example the case of using a polypropylene film as the base film.
• the polypropylene raw material of the polypropylene film used for the pressure-sensitive adhesive film of the present invention is not particularly limited as long as the physical properties described above are satisfied, but it is preferable to use crystalline polypropylene (hereinafter, polypropylene raw material A) from the viewpoint of strength and heat resistance.
• the polypropylene raw material A is preferably a polypropylene having a cold xylene soluble part (hereinafter referred to as CXS) of 4% by mass or less and a mesopentad fraction of 0.90 or more. If these conditions are not satisfied, film forming stability may be inferior, film strength may be reduced, and dimensional stability and heat resistance may be greatly reduced.
• CXS cold xylene soluble part
• the cold xylene soluble part means a polypropylene component dissolved in xylene when the sample is completely dissolved in xylene and then precipitated at room temperature, and has low stereoregularity. This is considered to correspond to a component that is difficult to crystallize due to a low molecular weight. If many such components are contained in the resin, the thermal dimensional stability of the film may be inferior. Therefore, CXS is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. CXS is preferably as low as possible, but about 0.1% by mass is the lower limit.
• CXS-containing polypropylene In order to obtain such CXS-containing polypropylene, methods such as a method for enhancing the catalytic activity in obtaining a resin, a method for washing the obtained resin with a solvent or propylene monomer itself, a method using a metallocene PP, and the like can be used.
• the mesopentad fraction of the polypropylene raw material A is preferably 0.90 or more, more preferably 0.94 or more.
• the mesopentad fraction is an index indicating the stereoregularity of the crystal phase of polypropylene measured by a nuclear magnetic resonance method (NMR method).
• NMR method nuclear magnetic resonance method
• produce the backing of an adhesion layer it is preferable.
• the upper limit of the mesopentad fraction is not particularly specified.
• a method of washing resin powder obtained with a solvent such as n-heptane there are a method of appropriately selecting a catalyst and / or a promoter, and a composition. Preferably employed.
• the polypropylene raw material A more preferably has a melt flow rate (MFR) of 1 to 10 g / 10 minutes (230 ° C., 21.18 N load), particularly preferably 2 to 5 g / 10 minutes (230 ° C., 21.18 N).
• MFR melt flow rate
• the range of (load) is preferable from the viewpoint of film forming properties and film strength.
• a method of controlling the average molecular weight or the molecular weight distribution is employed.
• the polypropylene raw material A is mainly composed of a propylene homopolymer, but may contain other unsaturated hydrocarbon copolymerization components or the like within a range not impairing the object of the present invention.
• the coalescence may be blended.
• the copolymerization amount or blend amount is preferably less than 1 mol% in copolymerization amount
• the biaxially oriented polypropylene film used for the pressure-sensitive adhesive film of the present invention may contain branched polypropylene H in addition to the polypropylene raw material A described above from the viewpoint of improving strength and improving dimensional stability.
• the branched polypropylene H as used herein is a polypropylene having 5 or less internal trisubstituted olefins per 10,000 carbon atoms. The presence of the internal trisubstituted olefin can be confirmed by the proton ratio in the 1 H-NMR spectrum. In the case of inclusion, it is preferably 0.05 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass.
• the size of the spherulite produced in the cooling (casting) step of the melt-extruded resin sheet can be controlled to be small, and a polypropylene film excellent in transparency, strength and surface smoothness can be obtained. it can.
• the melt flow rate (MFR) is preferably in the range of 1 to 20 g / 10 minutes from the viewpoint of film forming properties, and more preferably in the range of 1 to 10 g / 10 minutes. preferable.
• the melt tension is preferably in the range of 1 to 30 cN, more preferably in the range of 2 to 20 cN.
• the polypropylene film used for the pressure-sensitive adhesive film of the present invention preferably has an ethylene component content of 10% by mass or less contained in the polymer constituting the film. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
• the content of the ethylene component increases, the crystallinity decreases and the transparency is easily improved.
• the strength decreases or the heat resistance decreases and heat increases.
• the shrinkage rate may deteriorate.
• the release property of the film surface may be lowered, and the back of the adhesive layer may be easily generated.
• the content of the polypropylene polymer contained in the polymer constituting the film is preferably 95% by mass or more from the viewpoint of transparency, heat resistance, and strength. More preferably, it is 96 mass% or more, More preferably, it is 97 mass% or more, Most preferably, it is 98 mass% or more.
• various additives such as a crystal nucleating agent, an antioxidant, a thermal stabilizer, a slip agent, an antistatic agent, an antiblocking agent, and the like within a range not impairing the object of the present invention, Fillers, viscosity modifiers, anti-coloring agents, and the like can also be included.
• the selection of the type and amount of antioxidant is important from the viewpoint of the bleedout of the antioxidant. That is, the antioxidant is a phenolic compound having steric hindrance, and at least one of them is preferably a high molecular weight type having a molecular weight of 500 or more.
• BHT 2,6-di-t-butyl-p-cresol
• 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
• Irganox® 1330 manufactured by BASF molecular weight 775.2
• tetrakis [methylene-3 (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] methane for example, Irganox (registered trademark) 1010: molecular weight 1177.7 manufactured by BASF
• Irganox registered trademark
• the total content of these antioxidants is preferably in the range of 0.03 to 1.0 mass% with respect to the total amount of the polypropylene raw material.
• a polymer may deteriorate in an extrusion process and a film may color, or it may be inferior to long-term heat resistance.
• transparency may fall by the bleeding out of these antioxidants.
• a more preferable content is 0.05 to 0.9% by mass, and particularly preferably 0.1 to 0.8% by mass.
• a crystal nucleating agent can be added to the polypropylene raw material used for the pressure-sensitive adhesive film of the present invention as long as it does not contradict the purpose of the present invention.
• the branched polypropylene (H) has an ⁇ -crystal or ⁇ -crystal nucleating agent effect itself, but other ⁇ -crystal nucleating agents (dibenzylidene sorbitols, sodium benzoate, etc.) ), ⁇ crystal nucleating agents (amide compounds such as potassium 1,2-hydroxystearate, magnesium benzoate, N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide, quinacridone compounds, etc.), etc. .
• the addition amount is usually 0.5% by mass or less, preferably 0.1%. It is preferable to set it as mass% or less, More preferably, it is 0.05 mass% or less.
• the polypropylene film used for the pressure-sensitive adhesive film of the present invention is obtained by, for example, biaxially stretching using the above-described raw materials.
• the biaxial stretching method can be obtained by any of the inflation simultaneous biaxial stretching method, the stenter simultaneous biaxial stretching method, and the stenter sequential biaxial stretching method.
• the polypropylene film used for the pressure-sensitive adhesive film of the present invention may improve slipperiness by using easy-slip particles or the like on the surface layer.
• the film is composed of at least two layers of the surface layer (I) and the base layer (II), and the surface layer (I) contains particles, and the average particle diameter thereof is 0.7 ⁇ m or less. preferable.
• the average particle diameter exceeds 0.7 ⁇ m, the surface roughness may increase and the surface smoothness may decrease.
• voids are likely to occur at the particle interface during stretching, and the transparency is reduced, or particles added to the surface layer (I) fall off during film formation, resulting in increased surface roughness or increased haze. There is.
• the average particle diameter is more preferably 0.5 ⁇ m or less, and further preferably 0.2 ⁇ m or less. From the viewpoint of surface smoothness, the average particle size is preferably as small as possible. However, if it is less than 0.05 ⁇ m, the slipperiness may be deteriorated, or the particles may be aggregated to become coarse particles, resulting in a decrease in transparency. Moreover, you may use together 2 or more types of particle
• the particles used for the surface layer (I) are not particularly limited as long as the effects of the present invention are not impaired.
• examples of inorganic particles include silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, carbon black, and zeolite particles.
• organic particles acrylic resin particles, styrene resin particles, polyester resin particles, polyurethane resin particles, polycarbonate resin particles, polyamide resin particles, silicone resin particles, fluorine resin particles, or the above resin And copolymer resin particles of two or more types of monomers used in the synthesis.
• the polypropylene resin has low surface energy, when the particles are added and stretched, the particle interface peels off during stretching, voids are generated, haze increases, and transparency may decrease.
• the particle surface is hydrophobic, and it is preferable to use the above inorganic particles or organic particles having a silane coupling treatment on the surface, particularly silicone particles or silane coupling treatment silica particles. Is preferred.
• the particle size distribution of the particles to be used is as narrow as possible. From such a viewpoint, it is preferable to use silica particles by a sol-gel method as silica particles, and it is preferable to use silicone particles, acrylic resin particles, and styrene resin particles by a polymerization method as organic particles.
• the polypropylene film used for the pressure-sensitive adhesive film of the present invention preferably has a surface layer (I) particle content of 0.01 to 1.0% by mass. If the content is less than 0.01% by mass, the effect of reducing the friction coefficient may not be obtained. When content exceeds 1.0 mass%, a haze will raise and transparency may fall.
• the content is more preferably 0.05 to 0.7% by mass, still more preferably 0.05 to 0.65% by mass, and most preferably 0.1 to 0.6% by mass.
• the layer thickness ratio becomes 1/22/1 with a multi-manifold type A layer / B layer / A layer composite T die.
• a multi-manifold type A layer / B layer / A layer composite T die are laminated and discharged onto a casting drum to obtain a laminated unstretched sheet having a layer configuration of A layer / B layer / A layer.
• the surface temperature of the casting drum is preferably 10 to 40 ° C. from the viewpoint of transparency. Moreover, it does not matter as a 2 layer laminated structure of A layer / B layer.
• any method of an electrostatic application method, an adhesion method using the surface tension of water, an air knife method, a press roll method, an underwater casting method, etc. may be used.
• the air knife method is preferable because it is good and the surface roughness can be controlled.
• the air temperature of the air knife is 0 to 50 ° C., preferably 0 to 30 ° C., and the blowing air speed is preferably 130 to 150 m / s. Further, it is preferable to appropriately adjust the position of the air knife so that air flows downstream of the film formation so as not to cause vibration of the film.
• the non-casting drum surface of the film is further forcibly cooled to suppress the formation of ⁇ crystals on the non-casting drum surface, thereby improving the smoothness and transparency of the film.
• the cooling method for the non-casting drum surface may be any of air cooling, press roll method, underwater casting method, etc., but it is simple as equipment, easy to control surface roughness, and smooth. Air cooling with good air is preferable.
• the obtained unstretched sheet is introduced into the longitudinal stretching step.
• the longitudinal stretching step first, an unstretched sheet is brought into contact with a plurality of metal rolls maintained at 120 ° C. or more and less than 150 ° C., preheated to the stretching temperature, stretched 3 to 8 times in the longitudinal direction, and then to room temperature. Cooling.
• the stretching temperature is 150 ° C. or higher, the orientation of the film becomes weak, and the strength may decrease.
• the draw ratio is less than 3, the orientation of the film becomes weak and the strength may be lowered.
• the longitudinally uniaxially stretched film is guided to a tenter, the end of the film is gripped with a clip, and the film is horizontally stretched 7 to 13 times at a temperature of 140 to 165 ° C. If the stretching temperature is low, the film may be broken or the transparency may be lowered. If the stretching temperature is too high, the orientation of the film is weak and the strength may be lowered. Further, when the magnification is high, the film may be broken, and when the magnification is low, the orientation of the film is weak and the strength may be lowered.
• the clip is heat-fixed at a temperature of 100 ° C. or more and less than 160 ° C. while being relaxed at a relaxation rate of 2 to 20% in the width direction while holding the tension in the width direction with the clip.
• the film is guided to the outside of the tenter through a cooling process at 80 to 100 ° C. while being held tightly, the clip at the end of the film is released, the film edge is slit in the winder process, and the film product roll is wound up.
• the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention is not particularly limited, and a rubber system, a vinyl polymerization system, a condensation polymerization system, a thermosetting resin system, a silicone system, and the like can be used.
• examples of the rubber-based pressure-sensitive adhesive include butadiene-styrene copolymer system, butadiene-acrylonitrile copolymer system, and isobutylene-isoprene copolymer system.
• examples of the vinyl polymerization pressure-sensitive adhesive include acrylic, styrene, vinyl acetate-ethylene copolymer system, and vinyl chloride-vinyl acetate copolymer system.
• examples of the condensation polymerization pressure-sensitive adhesive include polyester.
• examples of the thermosetting resin-based pressure-sensitive adhesive include epoxy resin-based and urethane resin-based adhesives.
• acrylic adhesives are preferably used in consideration of excellent transparency, weather resistance, heat resistance, moist heat resistance, substrate adhesion, and the like.
• acrylic pressure-sensitive adhesives include SK Dyne (registered trademark) 1310, 1435, SK Dyne 1811L, SK Dyne 1888, SK Dyne 2094, SK Dyne 2096, SK Dyne 2137, and SK Dyne 3096 manufactured by Soken Chemical Co., Ltd.
• SK dyne 1852 and the like are preferable examples.
• a curing agent for example, in the case of isocyanate, toluene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, diphenylmethane-4 -4'-diisocyanate, diphenylmethane-2-4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4-4'-diisocyanate, dicyclohexylmethane-2-4'-diisocyanate And lysine isocyanate.
• the mixing ratio of the curing agent is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. If the amount is less than 0.1 parts by mass, curing of the pressure-sensitive adhesive layer may be insufficient in the drying furnace, and the film may be trimmed. If it exceeds 10 parts by mass, the excess curing agent may migrate to the substrate or gasify at a high temperature to cause contamination.
• an antioxidant an ultraviolet absorber, a silane coupling agent, a metal deactivator, and the like may be appropriately added to the acrylic pressure-sensitive adhesive depending on the material of the adherend (glass or functional film).
• the coating agent can be used by dissolving additives such as the above-mentioned adhesive and curing agent in a solvent.
• the solvent can be appropriately adjusted according to the drying temperature in the coater, the viscosity of the coating, and the like.
• the solid content concentration in the coating is appropriately selected depending on the viscosity of the coating and the thickness of the adhesive layer, but is preferably 5 to 20% by mass.
• the above-mentioned base film is conveyed to the coater, and the adhesive layer coating is applied.
• the surface on which the adhesive layer is applied may be either surface of the base film, but the wettability with the coating agent may be improved in advance by pretreatment such as corona treatment on the coated surface. preferable.
• the back surface of the base film is preferably not subjected to pretreatment such as corona treatment in order to improve releasability.
• the coating method (coating method) is not particularly limited, and an existing coating method such as a metabar method, a doctor blade method, a gravure method, a die method, a knife method, a reverse method, or a dip method can be employed.
• the pressure-sensitive adhesive layer thickness of the pressure-sensitive adhesive film of the present invention is a thin film of 3,000 nm or less, and the gravure method and the reverse method are preferable from the viewpoint of stably obtaining a thin coating layer.
• the drying temperature is appropriately set depending on the heat resistance of the base film and the boiling point of the solvent, but is preferably 60 to 170 ° C. If the temperature is less than 60 ° C., the adhesive layer may not be sufficiently cured and may be trimmed. When it exceeds 170 degreeC, a base film may deform
• the drying time is preferably 15 to 60 seconds. If it is less than 15 seconds, curing of the pressure-sensitive adhesive layer may not proceed sufficiently, and the film may be backed up. Exceeding 60 seconds is not preferable because productivity decreases.
• the adhesive film after drying is wound up with a winder without using a release film or the like to obtain the adhesive film roll of the present invention. Since the adhesive film of the present invention has the above-described structure, the adhesive layer is sufficiently cured, and the sliding property between the back surface of the base film and the adhesive layer surface is good. Even if it is taken, there is no problem such as being backed out or wrinkling at the time of winding, and a high-quality adhesive film roll can be obtained.
• the adhesive film of the present invention obtained as described above can be used in various applications such as packaging film, surface protective film, process film, sanitary product, agricultural product, building product, medical product, etc. Since it is excellent in smoothness, it can be preferably used as a surface protective film and a process film.
• Thickness of adhesive layer 15 points were measured using a film thickness measurement system model number F20 manufactured by Filmetrics Co., Ltd., and an average value was obtained.
• Measurement speed 0.1 mm / S Measurement range: 1000 ⁇ m in the longitudinal direction, 400 ⁇ m in the width direction
• Measurement pitch 1 ⁇ m in the longitudinal direction, 5 ⁇ m in the width direction
• Cut-off value ⁇ c 0.2 mm
• Stylus tip radius 0.5 ⁇ m.
• Peeling force was measured according to a method defined in JIS Z 0237 (2009), and a glass plate whose surface was washed with ethanol was used instead of SUS304.
• a glass plate whose surface was washed with ethanol was used instead of SUS304.
• the adhesive film of an Example and a comparative example each cut out in the strip shape of width 25mm and total length 200mm, the adhesion layer side was bonded together to the said glass plate, and it pressed using the rubber roller of mass 2kg, and it adhered uniformly. .
• the glass plate After standing for 24 hours in an atmosphere of 25 ° C. and 65% RH, the glass plate is fixed, and the stress (N / 25 mm) when peeling one end of the adhesive film 180 ° at a constant rate of 300 mm / min is measured and peeled off. Power.
• A Releasable cleanly B: Less than 10% of the area where the back line is generated C: 10% or more of the area where the back line is generated
• A It is clean and is equivalent to before applying a load.
• B Weak unevenness is confirmed.
• C Strong unevenness is confirmed.
• Example 1 Crystalline polypropylene (manufactured by Prime Polymer Co., Ltd., TF850H, MFR: 2.9 g / 10 min, mesopentad fraction: 0.94) is supplied as a base film to a uniaxial melt extruder and melted at 240 ° C. Extrusion was performed, foreign matters were removed with a 60 ⁇ m cut sintered filter, and then discharged onto a casting drum whose surface temperature was controlled at 30 ° C., and brought into close contact with the casting drum with an air knife. Thereafter, the uncooled drum surface of the sheet on the casting drum was cooled by injecting compressed air at a temperature of 30 ° C. and a pressure of 0.3 MPa to obtain an unstretched sheet.
• the sheet was preheated to 140 ° C. using a ceramic roll, and the film was stretched 4.6 times in the longitudinal direction of the film between 140 ° C. rolls provided with a peripheral speed difference.
• the end part was introduced into a tenter type stretching machine by holding it with a clip, preheated at 170 ° C. for 3 seconds, stretched 8.0 times at 165 ° C., and relaxed by 10% in the width direction at 150 ° C. Heat treatment was performed, followed by a cooling process at 100 ° C., the film was guided to the outside of the tenter, the film end clip was released, the film was wound around a core, and a base film having a thickness of 25 ⁇ m was obtained. Table 1 shows the physical properties and evaluation results of the base film.
• an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne (registered trademark) 1310) is diluted with ethyl acetate, toluene, and MEK on one side of the base film, and the solid content of the pressure-sensitive adhesive is 100 parts by mass.
• the adhesive film was wound up 1,000 m as it was (without going through a release film) to obtain an adhesive film roll. There was no wrinkle or air biting during roll winding, and the appearance was good. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 2 In Example 1, the thickness of the pressure-sensitive adhesive layer was 1,000 nm, and the pressure-sensitive adhesive film was wound up by 1,000 m as it was (without using a release film) in the same manner as in Example 1 to obtain a pressure-sensitive adhesive film roll. There was no wrinkling at the time of winding the roll, but slight air biting occurred. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 3 In Example 1, as a base film, a PET film (Toray Industries, Inc., T60 (38 ⁇ m) was used, and the thickness of the adhesive layer was 300 nm. Otherwise, the adhesive film was directly used in the same manner as in Example 1. The film was wound up to 1,000 m (without going through a release film) to form an adhesive film roll, and there was no wrinkle or air biting during roll winding, and the appearance was good. It is shown in 1.
• Example 4 In Example 3, the pressure-sensitive adhesive layer thickness was 800 nm, and otherwise, the pressure-sensitive adhesive film was wound up by 1,000 m as it was (without using a release film) in the same manner as in Example 3 to obtain a pressure-sensitive adhesive film roll. There was no wrinkling at the time of winding the roll, but slight air biting occurred. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 5 90 parts by mass of crystalline polypropylene (PP (a)) (manufactured by Prime Polymer Co., Ltd., TF850H, MFR: 2.9 g / 10 min, mesopentad fraction: 0.94), 4-methyl-1-pentene heavy Feed the raw material (Mitsui Chemicals Co., Ltd., MX004) from the weighing hopper to the twin screw extruder so that 10 parts by mass are mixed at this ratio, melt knead at 260 ° C, and discharge from the die in a strand shape Then, it was cooled and solidified in a water bath at 25 ° C. and cut into chips to obtain a polypropylene raw material (1) for layer A.
• PP (a) manufactured by Prime Polymer Co., Ltd., TF850H, MFR: 2.9 g / 10 min, mesopentad fraction: 0.94
• the uncooled drum surface of the sheet on the casting drum was cooled by injecting compressed air at a temperature of 30 ° C. and a pressure of 0.3 MPa to obtain an unstretched sheet.
• the sheet was preheated to 145 ° C. using a ceramic roll, and stretched 4.2 times in the longitudinal direction of the film between 140 ° C. rolls provided with a peripheral speed difference.
• the end part was introduced into a tenter type stretching machine by holding it with a clip, preheated at 170 ° C. for 3 seconds, stretched 8.0 times at 165 ° C., and relaxed by 10% in the width direction at 150 ° C.
• an acrylic pressure-sensitive adhesive (“SK Dyne” (registered trademark) 1310, manufactured by Soken Chemical Co., Ltd.) is diluted with ethyl acetate, toluene, and MEK on one side of the base film to obtain a solid content of the pressure-sensitive adhesive of 100 parts by mass.
• a coating agent in which 2.0 parts by mass of a curing agent (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate D-90) was applied was applied using a gravure coater, and dried in an oven at 80 ° C. for 30 seconds to form an adhesive layer.
• a pressure-sensitive adhesive film having a thickness of 300 nm was wound up as it was (without using a release film) and wound up to 8,000 m to obtain a pressure-sensitive adhesive film roll. There was no wrinkle or air biting during roll winding, and the appearance was good.
• Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 6 In Example 1, the temperature of the casting drum was set to 50 ° C., the thickness of the adhesive layer was set to 600 nm, and other than that, the adhesive film was wound up by 1,000 m as it was (without using a release film) in the same manner as in Example 1. An adhesive film roll was obtained. There was no wrinkle or air biting during roll winding, and the appearance was good. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 1 In Example 1, the thickness of the pressure-sensitive adhesive layer was 4,500 nm. Otherwise, the pressure-sensitive adhesive film was wound up 1,000 m as it was (without using a release film) in the same manner as in Example 1 to obtain a film roll. Wrinkles were generated when the roll was wound, and it was not possible to wind it with high quality. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 2 (Comparative Example 2) In Example 3, the pressure-sensitive adhesive layer thickness was 4,500 nm, and the pressure-sensitive adhesive film was wound up by 1,000 m as it was (without using a release film) in the same manner as in Example 3 to obtain a film roll. Wrinkles were generated when the roll was wound, and it was not possible to wind it with high quality. Table 1 shows the physical properties and evaluation results of the adhesive film.
• Example 3 In Example 1, the temperature of the cast drum was set to 70 ° C., the thickness of the adhesive layer was set to 600 nm, and other than that, the adhesive film was wound up by 1,000 m as it was (without using a release film) in the same manner as in Example 1. An adhesive film roll was obtained. There were no wrinkles or air bites during roll winding, and the appearance was good, but no adhesive force was developed. Table 1 shows the physical properties and evaluation results of the adhesive film.

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• 2016
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