WO2016052137A1 - 粘着フィルム - Google Patents
粘着フィルム Download PDFInfo
- Publication number
- WO2016052137A1 WO2016052137A1 PCT/JP2015/075797 JP2015075797W WO2016052137A1 WO 2016052137 A1 WO2016052137 A1 WO 2016052137A1 JP 2015075797 W JP2015075797 W JP 2015075797W WO 2016052137 A1 WO2016052137 A1 WO 2016052137A1
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- WO
- WIPO (PCT)
- Prior art keywords
- meth
- layer
- sensitive adhesive
- pressure
- poly
- Prior art date
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to an adhesive film. More specifically, the present invention relates to an adhesive film excellent in transparency, color tone and surface appearance, and preferably excellent in scratch resistance, surface hardness and bending resistance.
- Display face plates of image display devices include heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity.
- Glass-based articles are used because they meet the required properties.
- glass has the disadvantage of low impact resistance and easy cracking. Therefore, it has been proposed to attach various films for the purpose of preventing glass breakage to the surface of the display face plate (see, for example, Patent Documents 1 and 2).
- the scratch resistance of these films is insufficient.
- glass has disadvantages such as low workability; difficult to handle; high specific gravity and heavy; difficult to meet demands for curved display and flexibility. Therefore, materials that replace glass are actively studied.
- a glass substitute material a hard coat laminate in which a hard coat excellent in surface hardness and scratch resistance is formed on the surface of a transparent resin film substrate such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymer.
- a transparent resin film substrate such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymer.
- Patent Document 3 Many bodies have been proposed (see, for example, Patent Document 3). However, the scratch resistance of such hard coats is still insufficient.
- An object of the present invention is to provide an adhesive film which is excellent in transparency, color tone and surface appearance, and preferably excellent in scratch resistance, surface hardness and bending resistance.
- various aspects of the present invention are as follows. [1]. In order from the surface layer side, ( ⁇ ) a poly (meth) acrylimide resin film layer and ( ⁇ ) an adhesive layer, A pressure-sensitive adhesive film having a total light transmittance of 80% or more. [2].
- the ( ⁇ ) hard coat layer is (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.2 to 4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group; (2)
- the active energy ray-curable resin composition comprising (C) 0.05 to 3 parts by mass of organic titanium; and (D) 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm. ]
- the pressure-sensitive adhesive film as described in the above item [3], wherein the active energy ray-curable resin composition further comprises 0.01 to 7 parts by mass of (E) a water repellent. [5].
- the ( ⁇ ) poly (meth) acrylimide-based resin film is a first poly (meth) acrylimide-based resin layer ( ⁇ 1); an aromatic polycarbonate-based resin layer ( ⁇ ); a second poly (meth) acrylimide-based resin.
- the pressure-sensitive adhesive film as described in any one of [1] to [6] above, wherein the layer ( ⁇ 2) is a transparent multilayer film directly laminated in this order. [8].
- the pressure-sensitive adhesive film as described in any one of [1] to [7] above, wherein the ( ⁇ ) pressure-sensitive adhesive layer contains a silicon-based pressure-sensitive adhesive. [9].
- An image display member comprising the adhesive film according to any one of [1] to [8] above.
- the pressure-sensitive adhesive film of the present invention is excellent in transparency, color tone and surface appearance, and is preferably excellent in scratch resistance, surface hardness and bending resistance. Moreover, the pressure-sensitive adhesive film of the present invention has no bubble entrainment, and has good appearance maintenance and adhesiveness at the time of peeling. Therefore, this adhesive film can be suitably used as a display face plate or a protective film for a display face plate.
- FIG. 1 is a conceptual diagram of an apparatus used for forming a transparent multilayer film ( ⁇ -1) in Example 1.
- FIG. 1 is a conceptual diagram of an apparatus used for forming a transparent multilayer film ( ⁇ -1) in Example 1.
- the pressure-sensitive adhesive film of the present invention has ( ⁇ ) a poly (meth) acrylimide resin film layer and ( ⁇ ) a pressure-sensitive adhesive layer in this order from the surface layer side.
- surface layer side means that an article formed from an adhesive film having a multilayer structure is closer to the outer surface (display surface in the case of a display face plate or its protective film) when used for on-site use.
- the arrangement of one layer on the “surface side” of another layer means that these layers are in direct contact with each other and another layer or layers are interposed between the layers. Including both intervening.
- the ( ⁇ ) poly (meth) acrylimide resin film layer is a layer made of a poly (meth) acrylimide resin film.
- the pressure-sensitive adhesive film of the present invention is excellent in transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface appearance.
- the above poly (meth) acrylimide resin introduces the characteristics of excellent heat resistance and dimensional stability of polyimide resin while maintaining the characteristics of acrylic resin such as high transparency, high surface hardness and high rigidity. To a reddish brown color.
- the poly (meth) acrylimide resin is disclosed in, for example, JP-T-2011-519999.
- poly (meth) acrylimide means polyacrylimide or polymethacrylamide.
- the poly (meth) acrylimide resin is not limited except that it has high transparency and is not colored for the purpose of using the adhesive film for an optical article such as a touch panel.
- a (meth) acrylimide resin can be used.
- a yellowness index (measured using a chromaticity meter “SolidSpec-3700” (trade name) manufactured by Shimadzu Corporation in accordance with JIS K7105: 1981) is 3 or less. Can be mentioned.
- the yellowness index of the poly (meth) acrylimide resin is more preferably 2 or less, and still more preferably 1 or less.
- a preferred poly (meth) acrylimide resin has a melt mass flow rate (measured in accordance with ISO 1133 at 260 ° C. and 98.07 N) of 0.1 to 20 g. / 10 minutes.
- the melt mass flow rate of the poly (meth) acrylimide resin is more preferably 0.5 to 10 g / 10 min.
- the glass transition temperature of the poly (meth) acrylimide resin is preferably 150 ° C. or higher from the viewpoint of heat resistance.
- the glass transition temperature is more preferably 170 ° C. or higher.
- the poly (meth) acrylimide-based resin may be a thermoplastic resin other than the poly (meth) acrylimide-based resin; a pigment, an inorganic filler, an organic filler, a resin as long as it does not contradict the purpose of the present invention. Fillers; additives such as lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants may be further included. The amount of these optional components is usually about 0.01 to 10 parts by mass when the poly (meth) acrylimide resin is 100 parts by mass.
- Examples of commercially available poly (meth) acrylimide resins include “PLEXIMID TT70” (trade name) manufactured by Evonik.
- the poly (meth) acrylimide resin film is preferably a first poly (meth) acrylimide resin layer ( ⁇ 1); an aromatic polycarbonate resin layer ( ⁇ ); a second poly (meth) acrylimide resin.
- the layer ( ⁇ 2) is a transparent multilayer film directly laminated in this order. In the present specification, the present invention will be described on the assumption that the ⁇ 1 layer is disposed on the surface layer side.
- Poly (meth) acrylimide resin is excellent in surface hardness but does not have high punching resistance.
- the aromatic polycarbonate resin is excellent in punching resistance but does not have high surface hardness. Therefore, by using the above layer structure, it is possible to obtain a transparent multilayer film excellent in both surface hardness and punching resistance, combining the advantages of both.
- the layer thickness of the ⁇ 1 layer is not particularly limited, but is usually 10 ⁇ m or more, preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more, and further preferably 60 ⁇ m or more from the viewpoint of heat resistance and surface hardness of the pressure-sensitive adhesive film of the present invention. It's okay.
- the layer thickness of the ⁇ 2 layer is not particularly limited, but is preferably the same layer thickness as the ⁇ 1 layer from the viewpoint of curl resistance of the pressure-sensitive adhesive film of the present invention.
- the “same layer thickness” should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be construed that the layer thickness is the same within the range of process and quality control that is usually performed industrially. This is because the curl resistance of the multilayer film can be kept good if the layer thickness is the same within the range of the amplitude of process and quality control that is usually performed industrially.
- the layer thicknesses of 65 ⁇ m and 75 ⁇ m should be interpreted as the same. is there.
- “the same layer thickness” is also referred to as “substantially the same layer thickness”.
- the layer thickness of the ⁇ layer is not particularly limited, but may be usually 20 ⁇ m or more, preferably 40 ⁇ m or more, more preferably 60 ⁇ m or more from the viewpoint of cutting resistance of the adhesive film of the present invention.
- the poly (meth) acrylimide resin used for the ⁇ 1 layer and the ⁇ 2 layer has been described above.
- the poly (meth) acrylimide resin used for the ⁇ 1 layer and the poly (meth) acrylimide resin used for the ⁇ 2 layer have different resin characteristics, such as those having different melt mass flow rate and glass transition temperature.
- a (meth) acrylimide resin may be used.
- aromatic polycarbonate resin used for the ⁇ layer examples include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene.
- One or a mixture of two or more aromatic polycarbonate resins such as a polymer obtained by a transesterification reaction with a diester can be used.
- the aromatic polycarbonate resin include core-shell rubber.
- the core-shell rubber is 0-30 parts by mass (aromatic polycarbonate-based resin 100-70 parts by mass), preferably 0-10 parts by mass (aromatic By using it in an amount of 100 to 90 parts by mass of a polycarbonate-based resin, cutting resistance and impact resistance can be further improved.
- the core shell rubber examples include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic.
- core-shell rubbers such as acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers.
- these 1 type, or 2 or more types of mixtures can be used.
- the aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin or the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; Further, additives such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent, and a surfactant can be further included.
- the amount of these optional components is usually about 0.01 to 10 parts by mass, where the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.
- the production method for obtaining the poly (meth) acrylimide resin film is not particularly limited.
- the poly (meth) acrylimide is obtained from the T die.
- Examples thereof include a method including a step of supplying and pressing a molten film of an imide resin.
- the production method in the case where the poly (meth) acrylimide resin film is a transparent multilayer film in which the ⁇ 1 layer, ⁇ layer, and ⁇ 2 layer are directly laminated in this order is not particularly limited.
- the first poly (meth) acrylimide resin layer ( ⁇ 1); the aromatic polycarbonate resin layer ( ⁇ ); the second poly (meth) acrylimide system A step of continuously co-extruding a molten film of a transparent multilayer film in which the resin layer ( ⁇ 2) is directly laminated in this order from a T-die; (B ′) rotating with a first mirror body that rotates or circulates; Or the method of supplying and throwing in the molten film of the said transparent multilayer film between the 2nd mirror surface bodies to circulate and pressing can be mentioned.
- any one can be used.
- a manifold die, a fish tail die, and a coat hanger die can be used.
- Any coextrusion apparatus can be used.
- a coextrusion apparatus such as a feed block system, a multi-manifold system, and a stack plate system can be used.
- any extruder can be used as the extruder used in the step (A) or the step (A ′).
- a single screw extruder, a same direction rotating twin screw extruder, and a different direction rotating twin screw extruder can be exemplified.
- the poly (meth) acrylimide resin is a highly hygroscopic resin, it is preferably dried before being used for film formation. Moreover, it is also preferable that the poly (meth) acrylimide resin dried by the dryer is directly transported from the dryer to the extruder and charged.
- the set temperature of the dryer is preferably 100 to 150 ° C. It is also preferable to provide a vacuum vent in the extruder (usually in the metering zone at the screw tip).
- the temperature of the T die used in the step (A) or the step (A ′) is a continuous extrusion or coextrusion of a poly (meth) acrylimide resin melt film or a transparent multilayer film melt film.
- it is preferable to set it at least 260 degreeC or more. More preferably, it is 270 degreeC or more.
- the temperature of the T die is preferably set to 350 ° C. or lower.
- the ratio (R / T) between the lip opening (R) and the thickness (T) of the resulting poly (meth) acrylimide film is usually 10 or less from the viewpoint of preventing the retardation from increasing. The following is preferable, and 2.5 or less is more preferable.
- the ratio (R / T) is preferably 1 or more, more preferably 1.1 or more, and still more preferably 1.5 or more, from the viewpoint of preventing the extrusion load from becoming excessive.
- Examples of the first mirror body used in the step (B) or the step (B ′) include a mirror roll and a mirror belt.
- a mirror roll and a mirror belt As said 2nd mirror surface body, a mirror surface roll, a mirror surface belt, etc. can be mentioned, for example.
- the above mirror roll is a roll whose surface is mirror finished.
- the material of the mirror roll include metal, ceramic, and silicon rubber.
- the surface of the mirror roll can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method, etc. for the purpose of protection from corrosion and scratches.
- the above-mentioned mirror belt is a seamless belt, usually made of metal, whose surface is mirror-finished.
- the belt is circulated between a pair of belt rollers.
- the surface of the mirror belt can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method for the purpose of protection from corrosion and scratches.
- Mirror surface processing is not limited and can be performed by any method.
- the arithmetic average roughness (Ra) of the surface of the mirror body is preferably 100 nm or less, more preferably 50 nm or less, and the ten-point average roughness (Rz) is preferably The method of making it 500 nm or less, More preferably, 250 nm or less can be mentioned.
- a poly (meth) acrylimide resin film or a transparent multilayer film excellent in transparency, surface smoothness, and appearance can be obtained by the above-described film forming method.
- the highly smooth surface state of the first mirror body and the second mirror body is a film. It can be considered that a defective portion such as a die stripe is corrected.
- the surface temperature of the first mirror body is usually 70 ° C. or higher, preferably 100 ° C. or higher. More preferably, it is 120 degreeC or more, More preferably, it is 130 degreeC or more.
- the surface temperature of the first mirror body is preferably 200 ° C. or lower, more preferably 160 ° C. or lower, in order to prevent appearance defects (peeling marks) from appearing due to peeling from the first mirror body.
- the surface temperature of the second mirror body is usually 10 ° C. or higher, preferably 20 ° C. or higher.
- the surface temperature is more preferably 60 ° C. or higher, and still more preferably 100 ° C. or higher.
- the surface temperature of the second mirror body is preferably 200 ° C. or less, and more preferably 160 ° C. or less, in order to prevent appearance defects (peeling marks) due to peeling from the second mirror body on the film.
- the surface temperature of the first mirror body is preferably higher than the surface temperature of the second mirror body. This is because the film is held in the first mirror body and sent to the next transfer roll.
- the thickness of the poly (meth) acrylimide resin film is not particularly limited, and can be any thickness as desired.
- the thickness of the poly (meth) acrylimide resin film is usually 100 ⁇ m or more, preferably 200 ⁇ m or more, more preferably 300 ⁇ m or more from the viewpoint of maintaining rigidity. It may be.
- the thickness of the poly (meth) acrylimide resin film is usually 1500 ⁇ m or less, preferably 1200 ⁇ m or less, more preferably 1000 ⁇ m or less.
- the thickness of the poly (meth) acrylimide resin film is usually 20 ⁇ m or more, preferably 50 ⁇ m or more. It's okay. Further, from the viewpoint of economy, the thickness of the poly (meth) acrylimide resin film is usually 250 ⁇ m or less, preferably 150 ⁇ m or less.
- the total light transmittance of the poly (meth) acrylimide resin film is preferable. Is 85% or more, more preferably 88% or more, still more preferably 90% or more, and most preferably 92% or more. The higher the total light transmittance of the poly (meth) acrylimide resin film, the better.
- an adhesive film that can be suitably used as an image display device member can be obtained.
- the haze of the poly (meth) acrylimide resin film is preferably 3.0%. Below, more preferably 2.1% or less, still more preferably 2.0% or less, and most preferably 1.5% or less.
- the haze of the poly (meth) acrylimide resin film is preferably as low as possible. When the poly (meth) acrylimide resin film has such a low haze, an adhesive film that can be suitably used as an image display device member can be obtained.
- the yellowness index of the poly (meth) acrylimide resin film is preferably 3 or less. More preferably, it is 2 or less, and more preferably 1 or less. The lower the yellowness index of the poly (meth) acrylimide resin film, the better. When the poly (meth) acrylimide resin film has such a low yellowness index, an adhesive film that can be suitably used as an image display device member can be obtained.
- the poly (meth) acrylimide resin film has a corona discharge treatment or anchor on at least one surface in advance in order to increase the adhesive strength when forming the ( ⁇ ) pressure-sensitive adhesive layer or the ( ⁇ ) hard coat layer. Easy adhesion treatment such as coat formation may be performed.
- good interlayer adhesion strength can be obtained by setting the wetting index (measured in accordance with JIS K6768: 1999) to usually 50 mN / m or more, preferably 60 mN / m or more. become. Further, after the corona discharge treatment, an anchor coat may be further formed.
- a film is passed between an insulated electrode and a dielectric roll, a high frequency high voltage is applied to generate a corona discharge, and the film surface is treated.
- Oxygen and the like are ionized by the corona discharge and collide with the film surface, so that the resin molecular chain is broken or the oxygen-containing functional group is added to the resin molecular chain on the film surface, and the wetting index is increased.
- the unit area and the treatment amount (S) per unit time of the corona discharge treatment are determined from the viewpoint of obtaining the above wetting index, and are usually 80 W ⁇ min / m 2 or more, preferably 120 W ⁇ min / m 2 or more. . Further, from the viewpoint of preventing the deterioration of the film, the processing amount (S) is preferably suppressed to 500 W ⁇ min / m 2 or less. More preferably, it is 400 W ⁇ min / m 2 or less.
- the processing amount (S) is defined by the following equation.
- S P / (L ⁇ V)
- S throughput (W ⁇ min / m 2 )
- P discharge power
- L length of discharge electrode
- V line speed (m / min).
- the anchor coat agent for forming the anchor coat is not limited except that it has high transparency and is not colored.
- the anchor coating agent for example, known materials such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used. Among these, from the viewpoint of improving the adhesive strength with the ( ⁇ ) pressure-sensitive adhesive layer and the ( ⁇ ) hard coat layer, a thermoplastic urethane anchor coating agent is preferable.
- a paint containing a silane coupling agent can be used as the anchor coating agent.
- Silane coupling agents include hydrolyzable groups (for example, alkoxy groups such as methoxy group and ethoxy group; acyloxy groups such as acetoxy group; halogen groups such as chloro group) and organic functional groups (for example, amino group, vinyl group) Group, epoxy group, methacryloxy group, acryloxy group, isocyanate group, and the like).
- Such a silane coupling agent functions to improve the adhesive strength with the ( ⁇ ) pressure-sensitive adhesive layer or the ( ⁇ ) hard coat layer.
- a silane coupling agent having an amino group is preferable.
- the paint containing the silane coupling agent is a paint mainly containing a silane coupling agent (50% by mass or more as a solid content). Preferably, 75% by mass or more, more preferably 90% by mass or more of the solid content of the coating material is the silane coupling agent.
- silane coupling agent having an amino group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.
- silane coupling agent having an amino group one or a mixture of two or more of these can be used.
- the method for forming the anchor coat using the anchor coat agent is not limited, and a known method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. At this time, an optional diluting solvent such as methanol, ethanol, 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone may be used as necessary. it can.
- an optional diluting solvent such as methanol, ethanol, 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone may be used as necessary. it can.
- the anchor coating agent has an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, and a coloring agent as long as the object of the present invention is not adversely affected.
- One kind or two or more kinds of additives such as an agent, an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be contained.
- the thickness of the anchor coat is usually about 0.01 to 5 ⁇ m, preferably 0.1 to 2 ⁇ m.
- the ( ⁇ ) pressure-sensitive adhesive layer is a layer made of a composition containing an adhesive (hereinafter sometimes simply referred to as “adhesive”).
- the ( ⁇ ) pressure-sensitive adhesive layer may be formed on both sides of the ( ⁇ ) poly (meth) acrylimide resin film layer. That is, the pressure-sensitive adhesive film of the present invention has ( ⁇ ) second pressure-sensitive adhesive layer, ( ⁇ ) poly (meth) acrylimide resin film layer, and ( ⁇ ) first pressure-sensitive adhesive layer in order from the surface layer side. It may be a thing. On the ( ⁇ ) second pressure-sensitive adhesive layer, a ( ⁇ ) poly (meth) acrylimide resin film layer may be further provided.
- the pressure-sensitive adhesive film of the present invention comprises, in order from the surface layer side, ( ⁇ ) a second poly (meth) acrylimide resin film layer, ( ⁇ ) a second pressure-sensitive adhesive layer, and ( ⁇ ) a first poly (meta). It may have an acrylimide resin film layer and ( ⁇ ) a first pressure-sensitive adhesive layer.
- the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be the same or different, but are more preferably the same.
- the first poly (meth) acrylimide resin film layer and the second poly (meth) acrylimide resin film layer may be the same or different, but are more preferably the same.
- the above-mentioned pressure-sensitive adhesive for forming the above ( ⁇ ) pressure-sensitive adhesive layer is not limited except that it is excellent in transparency for the purpose of using the pressure-sensitive adhesive film of the present invention as a member for an image display device.
- the pressure-sensitive adhesive is preferably excellent in transparency and non-coloring property.
- known acrylic-based, urethane-based, rubber-based, and silicon-based pressure-sensitive adhesives can be used.
- adheresive having excellent transparency means an adhesive having a visible light transmittance of 80% or more, preferably 85% or more, more preferably 90% or more.
- the visible light transmittance is the transmittance at a wavelength of 380 to 780 nm of the adhesive measured using a spectrophotometer “SolidSpec-3700” (trade name) manufactured by Shimadzu Corporation and a quartz cell having an optical path length of 10 mm. This is a value calculated as a ratio of the integral area of the spectrum to the integral area of the transmission spectrum when it is assumed that the transmittance in the entire range of wavelengths from 380 to 780 nanometers is 100%.
- the “pressure-sensitive adhesive excellent in non-coloring property” means a pressure-sensitive adhesive having a yellowness index of 3 or less, preferably 2 or less, more preferably 1 or less.
- the yellowness index is a value measured using a chromaticity meter “SolidSpec-3700” (trade name) manufactured by Shimadzu Corporation and a quartz cell having an optical path length of 10 mm in accordance with JIS K7105: 1981.
- an acrylic pressure-sensitive adhesive is preferable from the viewpoint of light resistance and heat resistance.
- the acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive composition containing an acrylic polymer and an optional component used as desired.
- acrylic polymer examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic acid.
- the optional component that can be used in the acrylic pressure-sensitive adhesive examples include, for example, a silane coupling agent, a compound having two or more epoxy groups in one molecule, a compound having two or more isocyanate groups in one molecule, and a photopolymerization initiator.
- Organic polyvalent metal compounds, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weathering stabilizers, lightproof stabilizers, UV absorbers, A heat stabilizer, a pigment, a filler, etc. can be mentioned.
- the amount of the optional component may be about 0.01 to 10 parts by mass with 100 parts by mass of the acrylic polymer.
- the pressure-sensitive adhesive film of the present invention When used as a pressure-sensitive adhesive film that protects the surface of the display face plate, it can be applied even without human hands without causing appearance defects such as entrainment of bubbles (hereinafter referred to as “bubbleless property”). ); Even if the adhesive film is not applied with external force, it should not be displaced or peeled off due to long-term use in an environment that includes temperature changes (hereinafter referred to as “service reliability”). From the viewpoint of being able to be peeled off by human hands without leaving any adhesive residue and without causing a change in the appearance of the adhesive film (hereinafter referred to as “appearance maintenance at the time of peeling”). System adhesives are preferred.
- the silicon-based pressure-sensitive adhesive is not particularly limited.
- any of an addition reaction type silicon-based pressure-sensitive adhesive and a peroxide-curing type silicon-based pressure-sensitive adhesive can be used.
- the above addition reaction type silicon pressure-sensitive adhesive includes a silicon polymer containing an organic group capable of addition reaction such as vinyl group; an addition reaction catalyst such as platinum compound such as chloroplatinic acid, rhodium complex, and ruthenium complex; It is the adhesive composition containing the arbitrary component used according to.
- the peroxide-curable silicone-based pressure-sensitive adhesive is a pressure-sensitive adhesive composition containing a silicon-based polymer, an organic peroxide such as benzoyl peroxide, and an optional component used as desired.
- the optional component that can be used in the silicone-based pressure-sensitive adhesive examples include, for example, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weathering stabilizers, and light resistance. Mention may be made of stability stabilizers, ultraviolet absorbers, thermal stabilizers, pigments, fillers and the like.
- the amount of the optional component may be about 0.01 to 10 parts by mass with 100 parts by mass of the silicon-based polymer.
- the method for forming the ( ⁇ ) pressure-sensitive adhesive layer on at least one surface of the poly (meth) acrylimide resin film using the pressure-sensitive adhesive is not particularly limited, and any web coating method is used. can do. Examples of the web coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.
- a known diluent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate, isopropanol, 1-methoxy-2-propanol, methanol, ethanol, toluene, xylene , And acetone can be used.
- the thickness of the ( ⁇ ) pressure-sensitive adhesive layer is not particularly limited, but is usually 0.5 to 200 ⁇ m, preferably 1 to 120 ⁇ m, more preferably 5 to 50 ⁇ m in consideration of using a known web coating method. .
- the pressure-sensitive adhesive film of the present invention preferably further has ( ⁇ ) a hard coat layer on the surface layer side of the ( ⁇ ) poly (meth) acrylimide resin film layer. Scratch resistance and surface hardness can be improved.
- the ( ⁇ ) hard coat layer may be formed on both sides of the ( ⁇ ) poly (meth) acrylimide resin film layer. That is, the pressure-sensitive adhesive film of the present invention comprises, in order from the surface layer side, ( ⁇ ) a first hard coat layer, ( ⁇ ) a poly (meth) acrylimide resin film layer, ( ⁇ ) a second hard coat layer, and ( ⁇ ) It may have an adhesive layer.
- a pressure-sensitive adhesive layer is formed on ( ⁇ ) poly ( It is good also as a structure which has a (meth) acrylimide-type resin film layer.
- the pressure-sensitive adhesive film of the present invention comprises, in order from the surface layer side, ( ⁇ ) a hard coat layer, ( ⁇ ) a second poly (meth) acrylimide resin film layer, ( ⁇ ) a second pressure-sensitive adhesive layer, ( ⁇ It may have a first poly (meth) acrylimide resin film layer, and ( ⁇ ) a first pressure-sensitive adhesive layer.
- the first hard coat layer and the second hard coat layer may be the same or different, but are more preferably the same.
- the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer may be the same or different, but are more preferably the same.
- the first poly (meth) acrylimide resin film layer and the second poly (meth) acrylimide resin film layer may be the same or different, but are more preferably the same.
- the coating material for forming the ( ⁇ ) hard coat layer is not limited except that it is excellent in transparency for the purpose of using the adhesive film of the present invention as a member for an image display device, and any coating material is used. be able to.
- the hard coat layer-forming coating material is preferably excellent in transparency and non-coloring property.
- excellent transparency” and “excellent non-coloring property” conform to the above description regarding these characteristics of the pressure-sensitive adhesive.
- a preferable coating material for forming a hard coat layer includes an active energy ray-curable resin composition.
- the active energy ray-curable resin composition is capable of forming a hard coat by being polymerized and cured with active energy rays such as ultraviolet rays and electron beams.
- active energy ray curable resin composition include an active energy ray curable resin and a compound having two or more isocyanate groups (—N ⁇ C ⁇ O) in one molecule and / or photopolymerization initiation.
- a composition containing both of the agents can be mentioned.
- active energy ray-curable resin examples include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether.
- (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate , Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth
- (meth) acrylate means acrylate or methacrylate.
- Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate.
- Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates
- a crosslinking agent etc. can be mentioned. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.
- photopolymerization initiator examples include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl.
- Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkyls such
- the ( ⁇ ) hard coat layer is preferably (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.2 to 4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group; And (D) an active energy ray-curable resin composition containing 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm.
- the hard coat layer comprises (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.2 to 4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group; Active energy ray-curable resin containing 0.05 to 3 parts by mass of organic titanium; (D) 5 to 100 parts by mass of fine particles having an average particle size of 1 to 300 nm; and (E) 0.01 to 7 parts by mass of a water repellent. It consists of a composition.
- the hard coat layer has such a composition, it has excellent transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface appearance, and refers to slipperiness even when repeatedly wiped with a handkerchief or the like.
- a pressure-sensitive adhesive film that can maintain the surface characteristics such as can be obtained.
- the component A is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule. Since this compound has two or more (meth) acryloyl groups in one molecule, it functions to form a hard coat by polymerization and curing with active energy rays such as ultraviolet rays and electron beams.
- polyfunctional (meth) acrylate examples include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, (2) -Bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and (2) -bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane (meth) acryloyl group-containing bifunctional reaction Monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate; (meth) acrylates such as pentaerythritol tetra (meth) acrylate Examples include a rhoyl group-containing tetrafunctional reactive monomer; a (meth
- component B Compound having alkoxysilyl group and (meth) acryloyl group
- the above component B has the above component A by having a (meth) acryloyl group in the molecule, the above component D by having an alkoxysilyl group, It can bond or interact strongly and functions to greatly improve the scratch resistance of the hard coat.
- component B has a (meth) acryloyl group in the molecule or has an alkoxysilyl group, thereby causing a chemical bond or a strong interaction with component E, causing trouble such as component B bleeding out. It also works to prevent it.
- the (meth) acryloyl group means an acryloyl group or a methacryloyl group.
- the component B is distinguished from the component A in that it has an alkoxysilyl group.
- the compound of component A does not have an alkoxysilyl group.
- a compound having an alkoxysilyl group and two or more (meth) acryloyl groups in one molecule is Component B.
- Examples of the component B include compounds having a chemical structure represented by the general formula (—SiO 2 RR′—) n ⁇ (—SiO 2 RR ′′ —) m , where n is a natural number M is 0 or a natural number, preferably n is a natural number of 2 to 10, m is a natural number of 0 or 1 to 10.
- R is a methoxy group (CH 3 O—) , An ethoxy group (C 2 H 5 O—), etc.
- R ′ is an acryloyl group (CH 2 ⁇ CHCO—) or a methacryloyl group (CH 2 ⁇ C (CH 3 ) CO—).
- "Is an alkyl group such as a methyl group (CH 3 ) or an ethyl group (CH 2 CH 3 ).
- component B examples include, for example, the general formulas “(—SiO 2 (OCH 3 ) (OCHC ⁇ CH 2 ) —) n ”, “(—SiO 2 (OCH 3 ) (OC (CH 3 ) C ⁇ CH 2 )”.
- n is a natural number (a positive integer), and m is 0 or a natural number.
- n is a natural number of 2 to 10
- m is 0 or a natural number of 1 to 10.
- component B one or a mixture of two or more of these can be used.
- the blending amount of Component B is 0.2 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of scratch resistance with respect to 100 parts by mass of Component A. It's okay.
- the blending amount of the component B is It may be 4 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less.
- the blending ratio of the component B and the component D is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the component D. More preferably, it is 2 to 7 parts by mass.
- component C is a component that assists the function of the component B. From the viewpoint of greatly improving the scratch resistance of the hard coat, Component B and Component C show specific compatibility. In addition, component C itself also has a chemical bond or strong interaction with component D and the like, and functions to increase the scratch resistance of the hard coat.
- organic titanium examples include tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, and di-i-propoxybis (acetyl).
- Acetonato) titanium propanedioxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, di-n-butoxy-bis (triethanolaminato) titanium; and polymers composed of one or more of these.
- these 1 type, or 2 or more types of mixtures can be used.
- tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate of alkoxytitanium are in terms of scratch resistance and color tone. To preferred.
- the blending amount of the component C is 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more from the viewpoint of scratch resistance with respect to 100 parts by mass of the component A. It may be. On the other hand, from the viewpoint of color tone, the amount of component C may be 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1.5 parts by mass or less.
- the blending ratio of the component B and the component C is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the component B. More preferably, it is 20 to 80 parts by mass.
- component D Fine particles having an average particle size of 1 to 300 nm
- the component D functions to increase the surface hardness of the hard coat.
- the interaction with the component A was weak, which caused the scratch resistance to be insufficient. Therefore, the present invention solves this problem by using the component B that can chemically bond or strongly interact with both the component A and the component D, and the component C that assists the function of the component B. . Therefore, component D is preferably a substance that can chemically bond or strongly interact with component B, and more preferably a substance that can chemically bond or strongly interact with component B and component C. is there.
- inorganic fine particles or organic fine particles can be used.
- the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide;
- metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles;
- organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more. Any of these substance groups exemplified as component D is considered to be a substance that can at least chemically bond or strongly interact with component B.
- the surface of the fine particles is a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; Aluminate coupling agent; organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group or allyl group or epoxy group; surface treatment agent such as fatty acid or fatty acid metal salt What was processed by etc. may be used.
- silica fine particles are preferable, and fine particles of silica are more preferable.
- examples of commercially available silica fine particles include Snowtex (trade name) manufactured by Nissan Chemical Industries, Ltd. and Quattron (trade name) manufactured by Fuso Chemical Industries, Ltd.
- the average particle size of the component D is 300 nm or less from the viewpoint of maintaining the transparency of the hard coat and ensuring the effect of improving the surface hardness of the hard coat.
- the average particle size of component D is preferably 200 nm or less, and more preferably 120 nm or less.
- the fine particles that are usually available are at most about 1 nm even if they are fine.
- the average particle size of the fine particles is the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II” (trade name) manufactured by Nikkiso Co., Ltd. Is the particle diameter at which the accumulation of 50% by mass.
- the compounding amount of the component D may be 5 parts by mass or more, preferably 20 parts by mass or more from the viewpoint of surface hardness with respect to 100 parts by mass of the component A.
- the amount of component D may be 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less.
- the active energy ray-curable resin composition further includes (E) a water repellent agent 0.01 from the viewpoint of improving slipperiness, dirt adhesion prevention, and dirt wiping property. It is preferable to contain ⁇ 7 parts by mass.
- water repellent examples include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicon-based water repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane; Examples thereof include fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents.
- wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax
- silicon-based water repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane
- fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents.
- these 1 type, or 2 or more types of mixtures can be used.
- the component E is preferably a fluoropolyether water repellent from the viewpoint of water repellent performance.
- the component E includes a (meth) acryloyl group and a fluoro A water repellent containing a compound containing a polyether group (hereinafter abbreviated as (meth) acryloyl group-containing fluoropolyether water repellent) is more preferable.
- Component E is an acryloyl group-containing fluoropolyether system from the viewpoint of appropriately adjusting the chemical bond or interaction between component A or component B and component E, and expressing good water repellency while maintaining high transparency.
- An admixture of a water repellent and a methacryloyl group-containing fluoropolyether water repellent may be used.
- the blending amount is usually 7 parts by mass or less, preferably 4 parts by mass or less from the viewpoint of preventing trouble such as bleeding out of the component E with respect to 100 parts by mass of the component A. Good.
- the lower limit of the amount of component E is not particularly limited because it is an optional component, but from the viewpoint of obtaining the effect of using component E, it is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0. It may be 1 part by mass or more.
- the active energy ray-curable resin composition includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, and a weathering stabilizer, as desired.
- one or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be included.
- a solvent may be included as desired.
- the solvent is not particularly limited as long as it does not react with the components of the composition or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Examples thereof include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.
- the active energy ray-curable resin composition can be obtained by mixing and stirring these components.
- the method for forming the ( ⁇ ) hard coat layer using the hard coat forming paint containing the active energy ray-curable resin composition is not particularly limited, and a known web coating method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.
- the thickness of the ( ⁇ ) hard coat layer is not particularly limited, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of rigidity, heat resistance, and dimensional stability of the pressure-sensitive adhesive film of the present invention. More preferably, it may be 15 ⁇ m or more. Moreover, from the viewpoint of cutting workability and web handling properties of the pressure-sensitive adhesive film of the present invention, it may be preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the pressure-sensitive adhesive film of the present invention has a total light transmittance (measured using a turbidimeter “NDH2000” (trade name) of Nippon Denshoku Industries Co., Ltd. according to JIS K7361-1: 1997) of 80% or more.
- NDH2000 turbidimeter
- the total light transmittance is preferably as high as possible, preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more.
- the yellowness index of the pressure-sensitive adhesive film of the present invention is preferably 3 or less, more preferably 2 or less. More preferably, it is 1 or less. The lower the yellowness index, the better.
- the adhesive film of the present invention can be suitably used as an image display device member by having such a low yellowness index.
- Bubbleless property From a pressure-sensitive adhesive film a test piece having a size of 30 cm in length and 20 cm in width is used as a machine for a poly (meth) acrylimide resin film constituting the layer ( ⁇ ) of the pressure-sensitive adhesive film. The sample was taken so that the direction was the longitudinal direction of the test piece. A glass plate in which this test piece was left on a table by a human hand from one end portion in the horizontal direction (float plate glass having a thickness of 3 mm as defined in JIS R3202: 2011 of Test Piece Co., Ltd.). The same applies hereinafter). At this time, the presence or absence of appearance defects such as bubble entrainment and swelling were visually observed and evaluated according to the following criteria.
- (V) Yellowness Index According to JIS K7105: 1981, the yellowness index of the adhesive film was measured using a color meter “SolidSpec-3700” (trade name) manufactured by Shimadzu Corporation. If the yellowness index is 3 or less, it is good, if it is more than 3 and 4 or less, it is a little good, and if it is more than 4, it can be evaluated as bad.
- the extruder 2 As the intermediate layer ( ⁇ layer) of the transparent multilayer film, the ⁇ 1 layer; ⁇ layer; ⁇ 2 layer are directly laminated in this order, and the melted film 4 of the transparent multilayer film is co-extruded T-die of 2 types, 3 layers, multi-manifold system
- the mirror which is continuously extruded from 3 and circulates along the outer peripheral surface of the rotating mirror surface roll 5 and the pair of belt rollers 7 so that the ⁇ 1 layer is on the mirror surface roll 5 side.
- a transparent multilayer film having a good surface appearance having a total thickness of 125 ⁇ m, an ⁇ 1 layer thickness of 40 ⁇ m, a ⁇ layer thickness of 45 ⁇ m, and an ⁇ 2 layer thickness of 40 ⁇ m is supplied and pressed between the belt 6. It was. At this time, the setting conditions are that the drying temperature before film formation is 150 ° C. for ( ⁇ -1) and 100 ° C.
- Perform nitrogen purge and use vacuum vent T die 3 set temperature 300 ° C, lip opening 0.3 mm
- mirror roll 5 set temperature 130 ° C
- mirror belt 6 set temperature 120 ° C, pressure 1.4 MPa
- the speed was 9.8 m / min.
- the total light transmittance, haze, and yellowness index of the obtained transparent multilayer film were measured. The results are shown in Table 1.
- the set temperature was 130 ° C .;
- the set temperature of the mirror belt was 120 ° C .;
- the pressure of the mirror belt was 1.4 MPa;
- the take-up speed was 8.7 m / min.
- the total light transmittance, haze, and yellowness index of the obtained film were measured. The results are shown in Table 2.
- Adhesive ( ⁇ ) Adhesive ( ⁇ -1) Addition Reaction Type Silicone Adhesive “KR-3704” (trade name) 100 parts by mass of Shin-Etsu Chemical Co., Ltd., Platinum Compound-based Addition Catalyst “CAT” of Shin-Etsu Chemical Co., Ltd. It was obtained by mixing and stirring 0.5 parts by mass of “-PL-50T” (trade name) and 20 parts by mass of toluene.
- Example 1 The above ( ⁇ -1) is applied to one side of the above ( ⁇ -1) using an applicator so that the thickness after curing is 30 ⁇ m, and heat-cured under conditions of 130 ° C. for 1 minute to form an adhesive film. Obtained. The above tests (i) to (v) were performed on this adhesive film. The results are shown in Table 1.
- Example 2-14 Except that the poly (meth) acrylimide resin film shown in Table 1 or 2 was used instead of ( ⁇ -1), the same procedure as in Example 1 was carried out to prepare an adhesive film and to measure and evaluate physical properties. went. The results are shown in Table 1 or 2.
- the pressure-sensitive adhesive film of the present invention expresses physical properties suitable as a protective film for a display face plate.
- (Vii) Scratch resistance water contact angle after cotton wiping
- the test piece was sampled so that the machine direction of the poly (meth) acrylimide resin film constituting the ( ⁇ ) layer of the adhesive film was the vertical direction of the test piece in a size of 150 mm in length and 50 mm in width.
- This test piece is placed on a JIS L0849 Gakushin tester so that the hard coat surface is the surface, and four layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) are placed on the friction terminal of the Gakushin tester.
- a stainless steel plate (vertical 10 mm, horizontal 10 mm, thickness 1 mm) was attached and set so that the vertical and horizontal surfaces of the stainless steel plate were in contact with the test piece.
- the distance between chucks was 10 mm, and the temperature program was a program in which the temperature was maintained at 20 ° C. for 3 minutes and then the temperature was increased to 270 ° C. at a temperature increase rate of 5 ° C./min.
- the linear expansion coefficient was calculated from the obtained temperature-test piece length curve as a low temperature side temperature of 30 ° C. and a high temperature side temperature of 250 ° C.
- the linear expansion coefficient is very good if it is less than 20 ppm, is good if it is 20 ppm or more and less than 30 ppm, is somewhat good if it is 30 ppm or more and less than 50 ppm, and is poor if it is 50 ppm or more. be able to.
- (Xii) Minimum Bending Radius Referring to the bending formability (Method B) of JIS-K6902, the test piece was obtained by adjusting the condition at a temperature of 23 ° C. ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5% for 24 hours. About this test piece, the bending temperature is 23 ° C. ⁇ 2 ° C., the fold line is the direction perpendicular to the machine direction of the poly (meth) acrylimide resin film constituting the layer ( ⁇ ) of the adhesive film, and the hard coat of the adhesive film It was performed so that a curved surface was formed by bending the surface to the outside. Among the forming jigs in which no cracks occurred, the radius of the front part of the smallest front part radius was defined as the minimum bending radius.
- Pencil hardness was measured on the hard coat surface of the adhesive film using a pencil “Uni” (trade name) manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g according to JIS K5600-5-4. The pencil hardness can be evaluated as good if it is 6H or more, slightly good if it is 5H or more, and poor if it is less than 5H (4H or less).
- (B) Compound having alkoxysilyl group and (meth) acryloyl group: (B-1) “Shin-Etsu Silicone KR-513” (trade name) of Shin-Etsu Chemical Co., Ltd. (formula (—SiO 2 RR′—) n ⁇ (—SiO 2 RR ′′-) m ) R represents a methoxy group, R ′ represents an acryloyl group, and R ′′ represents a methyl group.) (B-2) "Shin-Etsu Silicone X-40-2655A" (trade name) (formula (-SiO 2 RR'-) n ⁇ (-SiO 2 RR "-) m , a compound represented by Shin-Etsu Chemical Co., Ltd. R is a methoxy group, R ′ is a methacryloyl group, and R ′′ is a methyl group.)
- B ′ Comparative component (B′-1) “Shin-Etsu Silicone KBM-403” (trade name) of Shin-Etsu Chemical Co., Ltd. (a compound having an alkoxysilyl group and an epoxy group, and having no (meth) acryloyl group) is there.)
- C Organic titanium (C-1) Titanium-i-propoxyoctylene glycolate “TOG” (trade name) from Nippon Soda Co., Ltd. (C-2) Tetrakis (2-ethylhexyloxy) titanium “TOT” (trade name) from Nippon Soda Co., Ltd. (C-3) Nippon Soda Co., Ltd. di-i-propoxy bis (acetylacetonato) titanium “T-50” (trade name)
- E Water repellent (E-1) Shin-Etsu Chemical Co., Ltd. acryloyl group-containing fluoropolyether water repellent “KY-1203” (trade name) (E-2) Solvay's methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70” (trade name) (E-3) DIC Corporation's acryloyl group-containing fluoropolyether water repellent "Megafac RS-91" (trade name)
- F-1 Phenylketone photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714” (trade name)
- F-2) 1-methoxy-2-propanol
- F-3) A surface conditioner “BYK-399” (trade name) of Big Chemie Japan Co., Ltd.
- F-4) BASF hydroxyketone photoinitiator ( ⁇ -hydroxyalkylphenone) “Irgacure 127” (trade name)
- the set temperature was 140 ° C .; the set temperature of the mirror surface belt was 120 ° C .; the pressure on the mirror surface belt was 1.4 MPa;
- Example 15 Corona discharge treatment was performed on both surfaces of ( ⁇ -1) under the conditions of a treatment amount of 167 W ⁇ min / m 2 (discharge power 500 W, discharge electrode length 1 m, line speed 3 m / min). The wetness index on both sides was 64 mN / m. Subsequently, a coating composition (parts by mass) shown in Table 3 as a touch surface side hard coat forming coating is applied to the surface on the ⁇ 1 layer side, and the thickness after curing is 15 ⁇ m using a die type coating apparatus. Apply the above ( ⁇ -1) as a printing surface side hard coat forming coating on the surface of the ⁇ 2 layer side, and use a die type coating apparatus so that the thickness after curing is 15 ⁇ m.
- the hard coat laminated film was obtained by coating. Subsequently, the above ( ⁇ -1) is applied on the printed surface side hard coat layer using an applicator so that the thickness after curing is 30 ⁇ m, and cured by heating at 130 ° C. for 1 minute, An adhesive film was obtained. The above tests (i) to (xv) were performed on the obtained adhesive film. The results are shown in Table 3.
- Example 16 to 28 Reference Examples 1 to 7 A pressure-sensitive adhesive film was prepared, and physical properties were measured and evaluated in the same manner as in Example 15 except that the composition of the paint for forming the touch surface side hard coat was changed as shown in any of Tables 3 to 6. The results are shown in any of Tables 3-6.
- Example 29 Except that the composition of the coating material for forming the touch surface side hard coat was changed as shown in Table 6, in the same manner as in Example 1, preparation of an adhesive film and measurement and evaluation of physical properties were performed. The results are shown in Table 6.
- Example 30 Corona discharge treatment was performed on both surfaces of the above ( ⁇ -14) under the conditions of a treatment amount of 167 W ⁇ min / m 2 (discharge power 500 W, discharge electrode length 1 m, line speed 3 m / min). The wetness index on both sides was 63 mN / m. Subsequently, a paint having a composition shown in Table 6 was applied to one surface as a touch surface-side hard coat forming paint using a die-type coating apparatus so that the thickness after curing was 15 ⁇ m. Applying the above-mentioned ( ⁇ -1) as a hard coat forming coating on the other side to a thickness of 15 ⁇ m after curing using a die-type coating device, and laminating a hard coat.
- Comparative Example 2 In the same manner as in Comparative Example 1 except that the above ( ⁇ ′-2) was used in place of the above ( ⁇ ′-1), an adhesive film was prepared, and physical properties were measured and evaluated. The results are shown in Table 6.
- Comparative Example 3 In the same manner as in Comparative Example 1 except that the above ( ⁇ ′-3) was used instead of the above ( ⁇ ′-1), an adhesive film was prepared, and physical properties were measured and evaluated. The results are shown in Table 6.
- Comparative Example 1 (not including the poly (meth) acrylimide resin film layer) was inferior in heat-resistant dimensional stability (linear expansion coefficient) and had insufficient surface hardness.
- Comparative Example 2 (not including the poly (meth) acrylimide resin film layer) had insufficient heat-resistant dimensional stability.
- Comparative Example 3 (not including the poly (meth) acrylimide resin film layer) had insufficient heat-resistant dimensional stability and surface hardness.
- Extruder 1 Extruder 1 2: Extruder 2 3: Co-extrusion T die of 2 types, 3 layers, multi-manifold system 4: Melted film 5: Mirror roll 6: Mirror belt 7: A pair of belt rollers
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Abstract
Description
[1].表層側から順に、(α)ポリ(メタ)アクリルイミド系樹脂フィルム層と、(γ)粘着剤層とを有し、
全光線透過率が80%以上であることを特徴とする粘着フィルム。
[2].
上記(α)ポリ(メタ)アクリルイミド系樹脂フィルム層の表層側に、更に(δ)ハードコート層を有することを特徴とする、上記[1]項に記載の粘着フィルム。
[3].
上記(δ)ハードコート層が、
(A)多官能(メタ)アクリレート100質量部;
(B)アルコキシシリル基と(メタ)アクリロイル基を有する化合物0.2~4質量部;
(C)有機チタン0.05~3質量部;及び
(D)平均粒子径1~300nmの微粒子5~100質量部
を含む活性エネルギー線硬化性樹脂組成物からなることを特徴とする上記[2]項に記載の粘着フィルム。
[4].
上記活性エネルギー線硬化性樹脂組成物が、更に、(E)撥水剤0.01~7質量部を含むことを特徴とする上記[3]項に記載の粘着フィルム。
[5].
上記(E)撥水剤が、(メタ)アクリロイル基含有フルオロポリエーテル系撥水剤を含むことを特徴とする上記[4]項に記載の粘着フィルム。
[6].
上記(α)ポリ(メタ)アクリルイミド系樹脂フィルムが、下記特性(I)及び(II)を満たすことを特徴とする上記[1]~[5]項の何れか1項に記載の粘着フィルム。
(I)全光線透過率85%以上。
(II)ヘーズ3.0%以下。
[7].
上記(α)ポリ(メタ)アクリルイミド系樹脂フィルムが、第一ポリ(メタ)アクリルイミド系樹脂層(α1);芳香族ポリカーボネート系樹脂層(β);第二ポリ(メタ)アクリルイミド系樹脂層(α2)が、この順に直接積層された透明多層フィルムであることを特徴とする上記[1]~[6]項の何れか1項に記載の粘着フィルム。
[8].
上記(γ)粘着剤層が、シリコン系粘着剤を含むことを特徴とする上記[1]~[7]項の何れか1項に記載の粘着フィルム。
[9].
上記[1]~[8]項の何れか1項に記載の粘着フィルムの、画像表示装置部材としての使用。
[10].
上記[1]~[8]項の何れか1項に記載の粘着フィルムを含む画像表示装置部材。
ここで「表層側」とは、複層構造である粘着フィルムから形成された物品が、現場での使用に供される際の外面(ディスプレイ面板またはその保護フィルムの場合の視認面)により近いことを意味する。また、本明細書において、ある一層を他の層の「表層側」に配置することは、それらの層が直接的に接すること、および、それらの層の間に別の単数又は複数の層が介在することの両方を含む。
上記(α)ポリ(メタ)アクリルイミド系樹脂フィルム層は、ポリ(メタ)アクリルイミド系樹脂フィルムからなる層である。このポリ(メタ)アクリルイミド系樹脂フィルム層を用いることによって、本発明の粘着フィルムは、透明性、色調、耐擦傷性、表面硬度、耐曲げ性、及び表面外観に優れたものになる。
また、押出負荷や溶融フィルムの安定性の観点から、好ましいポリ(メタ)アクリルイミド系樹脂として、メルトマスフローレート(ISO1133に従い、260℃、98.07Nの条件で測定。)が0.1~20g/10分のものを挙げることができる。ポリ(メタ)アクリルイミド系樹脂のメルトマスフローレートは、0.5~10g/10分がより好ましい。
更に、ポリ(メタ)アクリルイミド系樹脂のガラス転移温度は、耐熱性の観点から、150℃以上のものが好ましい。ガラス転移温度は、より好ましくは170℃以上である。
S=P/(L・V)
ここで、S:処理量(W・min/m2)、P:放電電力(W)、L:放電電極の長さ(m)、V:ライン速度(m/min)である。
上記(γ)粘着剤層は、粘着剤を含む組成物(以下、単に「粘着剤」ということがある。)からなる層である。
本発明の粘着フィルムは、好ましくは、上記(α)ポリ(メタ)アクリルイミド系樹脂フィルム層の表層側に、更に(δ)ハードコート層を有する。耐擦傷性、及び表面硬度を向上させることができる。
第1のハードコート層および第2のハードコート層は、同じであっても、異なっていてもよいが、同じであることがより好ましい。第1の粘着剤層および第2の粘着剤層は、同じであっても、異なっていてもよいが、同じであることがより好ましい。第1のポリ(メタ)アクリルイミド系樹脂フィルム層および第2のポリ(メタ)アクリルイミド系樹脂フィルム層は、同じであっても、異なっていてもよいが、同じであることがより好ましい。
上記成分Aは、1分子中に2以上の(メタ)アクリロイル基を有する(メタ)アクリレートである。この化合物は、1分子中に2以上の(メタ)アクリロイル基を有するため、紫外線や電子線等の活性エネルギー線により重合・硬化して、ハードコートを形成する働きをする。
上記成分Bは、分子内に(メタ)アクリロイル基を有することにより上記成分Aと、アルコキシシリル基を有することにより上記成分Dと、化学結合ないし強く相互作用することができ、ハードコートの耐擦傷性を大きく向上させる働きをする。また、成分Bは、分子内に(メタ)アクリロイル基を有することにより、あるいはアルコキシシリル基を有することにより、上記成分Eとも化学結合ないし強く相互作用し、成分Eがブリードアウトするなどのトラブルを防止する働きもする。ここで(メタ)アクリロイル基は、アクリロイル基又はメタクリロイル基の意味である。
なお、上記成分Bは、アルコキシシリル基を有するという点で、上記成分Aとは区別される。上記成分Aの化合物はアルコキシシリル基を有しない。本明細書において、1分子中にアルコキシシリル基と2以上の(メタ)アクリロイル基を有する化合物は、成分Bである。
上記成分Cは、上記成分Bの働きを補助する成分である。ハードコートの耐擦傷性を大きく向上させる観点において、成分Bと成分Cとは特異的な好相性を示す。また、成分C自体も、上記成分Dなどと化学結合ないし強く相互作用し、ハードコートの耐擦傷性を高める働きをする。
上記成分Dは、ハードコートの表面硬度を高める働きをする。一方、上記成分Aとの相互作用は弱く、耐擦傷性を不十分なものにする原因となっていた。そこで本発明においては、成分Aと成分Dの両方に化学結合ないし強く相互作用することのできる上記成分B、及び成分Bの働きを補助する上記成分Cを用い、この問題を解決したものである。
従って、成分Dは、好ましくは、上記成分Bと化学結合ないし強く相互作用することのできる物質であり、さらに好ましくは、上記成分B及び成分Cと化学結合ないし強く相互作用することのできる物質である。
成分Dとして例示されたこれらの物質群のいずれも、少なくとも、成分Bと化学結合ないし強く相互作用することのできる物質であると考えられる。
上記活性エネルギー線硬化性樹脂組成物には、指すべり性、汚れの付着防止性、及び汚れの拭取り性を高める観点から、更に、(E)撥水剤0.01~7質量部を含ませることが好ましい。
また、成分Eとしては、成分Aや成分Bと成分Eとの化学結合ないしは相互作用を適宜調節し、透明性を高く保ちつつ良好な撥水性を発現させる観点から、アクリロイル基含有フルオロポリエーテル系撥水剤とメタアクリロイル基含有フルオロポリエーテル系撥水剤との混和物を用いてもよい。
(i)バブルレス性
粘着フィルムから、縦30cm×横20cmの大きさの試験片を、該粘着フィルムの層(α)を構成するポリ(メタ)アクリルイミド系樹脂フィルムのマシン方向が試験片の縦方向となるように採取した。この試験片を、横方向の一方の端部から縦方向に向かって、人の手で、卓上に静置したガラス板(株式会社テストピースのJIS R3202:2011に規定する厚み3mmのフロート板ガラス。以下、同じ。)に貼り付けた。このときの気泡の巻き込み状態、膨れなどの外観不良の有無を目視観察し、以下の基準で評価した。
○(良好):気泡の巻き込みによる膨れは認められない。
△(やや不良):気泡の巻き込みによる膨れが認められる。しかし、フィルムの上から指でしごくことにより、容易に気泡を押出して膨れを無くすことができる。
×(不良):気泡の巻き込みによる膨れが認められる。しかも、フィルムの上から指でしごいても、気泡を押出し無くすことのできない膨れがある。
上記試験(i)と同様にして、粘着フィルムをガラス板に貼り付けたサンプルを、冷熱衝撃試験機(湿度制御機構なし)を使用し、温度-40℃の環境に30分間曝し、次に温度80℃の環境に30分間曝す処理を1サイクルとして、13サイクルの処理を行った。処理後、サンプルを目視観察し、以下の基準で評価した。
○(良好):ガラス板からの粘着フィルムの浮き(ガラス板から粘着フィルムが剥離した箇所)は認められない。
△(やや不良):ガラス板からの粘着フィルムの浮きが、粘着フィルムの端部に認められる。
×(不良):ガラス板からの粘着フィルムの浮きが、全体的に認められる。
上記試験(i)と同様にして、粘着フィルムをガラス板に貼り付けた後、人の手で粘着フィルムをガラス板から引き剥がし、以下の基準で評価した。
○(良好):糊残りすることなく、容易にフィルムを剥がすことができる。フィルムに折れや塑性変形は生じない。
△(やや不良):糊残りすることなく、フィルムを剥がすことができる。しかし、フィルムに折れや塑性変形が生じる。
×(不良):フィルムを剥がす際に糊残りする。また、フィルムに折れや塑性変形が生じる。
JIS K7361-1:1997に従い、日本電色工業株式会社の濁度計「NDH2000」(商品名)を用いて、粘着フィルムの全光線透過率を測定した。
JIS K7105:1981に従い、株式会社島津製作所の色度計「SolidSpec-3700」(商品名)を用いて、粘着フィルムの黄色度指数を測定した。黄色度指数は、3以下であれば良好であり、3超4以下であればやや良好であり、4超であると不良であると評価することができる。
(α)ポリ(メタ)アクリルイミド系樹脂フィルム
(α-1):図1に概念図を示す構成の共押出製膜装置を使用し、エボニック社のポリ(メタ)アクリルイミド「PLEXIMID TT70」(商品名)を押出機1により透明多層フィルムの両外層(α1層とα2層)として、住化スタイロンポリカーボネート株式会社の芳香族ポリカーボネート「カリバー301-4」(商品名)を押出機2により透明多層フィルムの中間層(β層)として、α1層;β層;α2層が、この順に直接積層された透明多層フィルムの溶融フィルム4を、2種3層マルチマニホールド方式の共押出Tダイ3から連続的に押出し、α1層が鏡面ロール5側になるように、回転する鏡面ロール5と、一対のベルトローラー7の外周面に沿って循環する鏡面ベルト6との間に供給投入し、押圧して、全厚み125μm、α1層の層厚み40μm、β層の層厚み45μm、α2層の層厚み40μmの、良好な表面外観の透明多層フィルムを得た。このとき設定条件は、製膜前の乾燥温度は、(α-1)が150℃、(β-1)が100℃;押出機1の設定温度はC1/C2/C3/C4/C5/AD=260/290~290℃;押出機2の設定温度はC1/C2/C3/C4/C5/C6/AD=260/280/280/260~260/270℃;押出機1、2の何れも窒素パージを行い、真空ベントを使用;Tダイ3の設定温度300℃、リップ開度0.3mm;鏡面ロール5の設定温度130℃;鏡面ベルト6の設定温度120℃、押圧1.4MPa;引取速度9.8m/分であった。得られた透明多層フィルムの全光線透過率、ヘーズ、及び黄色度指数を測定した。結果を表1に示す。
(γ-1)信越化学工業株式会社の付加反応型シリコン系粘着剤「KR-3704」(商品名)100質量部、信越化学工業株式会社の白金化合物系付加反応触媒「CAT-PL-50T」(商品名)0.5質量部、及びトルエン20質量部を混合・攪拌して得た。
上記(α-1)の片面に、上記(γ-1)を、硬化後の厚みが30μmとなるようにアプリケーターを用いて塗布し、130℃、1分間の条件で加熱硬化し、粘着フィルムを得た。この粘着フィルムについて上記試験(i)~(v)を行った。結果を表1に示す。
上記(α-1)の替わりに表1又は2に示すポリ(メタ)アクリルイミド系樹脂フィルムを用いたこと以外は、全て実施例1と同様に、粘着フィルムの作成及び物性の測定・評価を行った。結果を表1又は2に示す。
(vi)水接触角(初期水接触角)
粘着フィルムのハードコート面について、KRUSS社の自動接触角計「DSA20」(商品名)を使用し、水滴の幅と高さとから算出する方法(JIS R3257:1999を参照)で水接触角を測定した。
縦150mm、横50mmの大きさで、粘着フィルムの(α)層を構成するポリ(メタ)アクリルイミド系樹脂フィルムのマシン方向が試験片の縦方向となるように試験片を採取した。この試験片を、ハードコート面が表面になるようにJIS L0849の学振試験機に置き、学振試験機の摩擦端子に、4枚重ねのガーゼ(川本産業株式会社の医療用タイプ1ガーゼ)で覆ったステンレス板(縦10mm、横10mm、厚み1mm)を取付け、該ステンレス板の縦横面が試験片と接触するようにセットした。このガーゼで覆ったステンレス板に350g荷重を載せ、試験片のハードコート面を、摩擦端子の移動距離60mm、速度1往復/秒の条件で往復2万回擦った後、上記(vi)の方法に従い、当該綿拭箇所の水接触角を測定した。水接触角が100度以上であれば、耐擦傷性は良好であると判断される。また、2万往復後の水接触角が100度未満のときは、所定の往復回数を1万5千回、及び1万回に変更した測定も行い、以下の基準で耐擦傷性を評価した。
◎(非常に良好):往復回数2万回後でも水接触角が100度以上である。
○(良好):往復回数1万5千回後では水接触角が100度以上だが、2万回後は100度未満である。
△(やや不良):往復回数1万回後では水接触角が100度以上だが、1万5千回後は100度未満である。
×(不良):往復回数1万回後で水接触角が100度未満である。
粘着フィルムのハードコート面を人差し指で上下左右や円状になぞり、思い通りになぞることができたか否かの印象により評価した。試験は10名が各々行い、思い通りになぞれた場合を2点、ほぼ思い通りになぞれた場合を1点、指が引っ掛かるなどして思い通りになぞれなかった場合を0点として各人の点数を集計し、以下の基準で指すべり性を評価した。
◎(良好):16~20点
△(やや不良):10~15点
×(不良):0~9点
上記(vii)の方法に従い、2万往復綿拭した後の粘着フィルムをサンプルとしたこと以外は、上記(viii)指すべり性と同様に試験し、綿拭後の指すべり性を評価した。
粘着フィルムを、ハードコート面が表面になるようにJIS L0849の学振試験機に置いた。続いて、学振試験機の摩擦端子に#0000のスチールウールを取り付けた後、500g荷重を載せ、試験片の表面を100往復擦った。上記表面を目視観察し、以下の基準で耐擦傷性(耐スチールウール性)を評価した。
◎(非常に良好):傷がない。
○(良好):1~5本の傷がある。
△(やや不良):6~10本の傷がある。
×(不良):11本以上の傷がある。
JIS K7197:1991に従い、粘着フィルムの線膨張係数を測定した。セイコーインスツル株式会社の熱機械的分析装置(TMA)「EXSTAR6000」(商品名)を用いた。試験片は、縦20mm、横10mmの大きさで、フィルムのマシン方向(MD)が試験片の縦方向となるように採取した。試験片の状態調節は、温度23℃±2℃、相対湿度50±5%で24時間とし、フィルムの物性値としての寸法安定性を測定する目的から、測定最高温度における状態調節は行わなかった。チャック間距離は10mm、温度プログラムは、温度20℃で3分間保持した後、昇温速度5℃/分で温度270℃まで昇温するプログラムとした。線膨張係数は、得られた温度-試験片長さ曲線から、低温側温度30℃、高温側温度250℃として計算した。線膨張係数は、20ppm未満であれば非常に良好であり、20ppm以上30ppm未満であれば良好であり、30ppm以上50ppm未満であればやや良好であり、50ppm以上であれば不良であると評価することができる。
JIS-K6902の曲げ成形性(B法)を参考とし、温度23℃±2℃、相対湿度50±5%にて24時間状態調節して試験片を得た。この試験片について、曲げ温度23℃±2℃、折り曲げ線は粘着フィルムの層(α)を構成するポリ(メタ)アクリルイミド系樹脂フィルムのマシン方向と直角となる方向とし、粘着フィルムのハードコート面が外側となるように折り曲げて曲面が形成されるようにして行った。クラックが発生しなかった成形ジグのうち正面部分の半径の最も小さいものの正面部分の半径を最小曲げ半径とした。
コンピュータにより自動制御を行うルーター加工機を使用し、粘着フィルムに、半径0.5mmの真円形の切削孔と半径0.1mmの真円形の切削孔を設けた。このとき使用したミルは刃先の先端形状が円筒丸型の超硬合金製4枚刃、ニック付きのものであり、刃径は加工箇所に合わせて適宜選択した。続いて半径0.5mmの切削孔について、その切削端面を目視又は顕微鏡(100倍)観察し、以下の基準で切削加工性を評価した。同様に半径0.1mmの切削孔について、その切削端面を目視又は顕微鏡(100倍)観察し、以下の基準で切削加工性を評価した。表には前者の結果-後者の結果の順に記載した。
◎(非常に良好):顕微鏡観察でもクラック、ヒゲは認められない
○(良好):顕微鏡観察でもクラックは認められない。しかしヒゲは認められる。
△(やや不良):目視でクラックは認められない。しかし顕微鏡観察ではクラックが認められる。
×(不良):目視でもクラックが認められる。
粘着フィルムのハードコート面を、蛍光灯の光の入射角をいろいろと変えて当てながら目視観察し、以下の基準で表面平滑性(表面外観)評価した。
◎(非常に良好):表面にうねりや傷がない。間近に光を透かし見ても、曇感がない。
○(良好):間近に光を透かし見ると、僅かな曇感のある箇所がある。
△(やや不良):間近に見ると、表面にうねりや傷を僅かに認める。また、曇感がある。
×(不良):表面にうねりや傷を多数認めることができる。また、明らかな曇感がある。
JIS K5600-5-4に従い、750g荷重の条件で、三菱鉛筆株式会社の鉛筆「ユニ」(商品名)を用い、粘着フィルムのハードコート面について鉛筆硬度を測定した。鉛筆硬度は、6H以上であれば良好であり、5H以上であればやや良好であり、5H未満(4H以下)であれば不良であると評価することができる。
(A)多官能(メタ)アクリレート
(A-1)ジペンタエリスリトールヘキサアクリレート(6官能)
(A-2)エトキシ化トリメチロールプロパンアクリレート(3官能)
(B-1)信越化学工業株式会社の「信越シリコーンKR-513」(商品名)(式(-SiO2RR’-)n・(-SiO2RR”-)mで表される化合物であり、Rはメトキシ基、R’はアクリロイル基、R”はメチル基である。)
(B-2)信越化学工業株式会社の「信越シリコーンX-40-2655A」(商品名)(式(-SiO2RR’-)n・(-SiO2RR”-)mで表される化合物であり、Rはメトキシ基、R’はメタクリロイル基、R”はメチル基である。)
(B’-1)信越化学工業株式会社の「信越シリコーンKBM-403」(商品名)(アルコキシシリル基とエポキシ基を有し、(メタ)アクリロイル基を有しない化合物である。)
(B’-2)信越化学工業株式会社の「信越シリコーンKBM-903」(商品名)(アルコキシシリル基とアミノ基を有し、(メタ)アクリロイル基を有しない化合物である。)
(C-1)日本曹達株式会社のチタニウム-i-プロポキシオクチレングリコレート「TOG」(商品名)
(C-2)日本曹達株式会社のテトラキス(2-エチルヘキシルオキシ)チタン「TOT」(商品名)
(C-3)日本曹達株式会社のジ-i-プロポキシ・ビス(アセチルアセトナト)チタン「T-50」(商品名)
(C’-1)日本曹達株式会社のテトラ-n-プロポキシジルコニウム「ZAA」(商品名)
(D-1)平均粒子径20nmのシリカ微粒子
(E-1)信越化学工業株式会社のアクリロイル基含有フルオロポリエーテル系撥水剤「KY-1203」(商品名)
(E-2)ソルベイ(Solvay)社のメタクリロイル基含有フルオロポリエーテル系撥水剤「FOMBLIN MT70」(商品名)
(E-3)DIC株式会社のアクリロイル基含有フルオロポリエーテル系撥水剤「メガファックRS-91」(商品名)
(F-1)双邦實業股分有限公司のフェニルケトン系光重合開始剤(1-ヒドロキシシクロヘキシルフェニルケトン)「SB-PI714」(商品名)
(F-2)1-メトキシ-2-プロパノール
(F-3)ビッグケミー・ジャパン株式会社の表面調整剤「BYK-399」(商品名)
(F-4)BASF社のヒドロキシケトン系光重合開始剤(α-ヒドロキシアルキルフェノン)「イルガキュア127」(商品名)
(ε-1)上記(A-1)65質量部、上記(A-2)35質量部、上記(B-1)1.4質量部、上記(C-1)0.7質量部、上記(D-1)35質量部、上記(F-1)5.3質量部、上記(F-2)95質量部、及び上記(F-3)0.5質量の配合組成比で混合・攪拌して得た塗料を用いた。
(α’-1)三菱樹脂株式会社の二軸延伸ポリエチレンテレフタレート系フィルム「ダイヤホイル」(商品名)、厚み125μmを用いた。
上記(α-1)の両面に処理量167W・min/m2(放電電力500W、放電電極の長さ1m、ライン速度3m/min)の条件で、コロナ放電処理を行った。両面とも濡れ指数は64mN/mであった。続いて、α1層側の面にはタッチ面側ハードコート形成用塗料として表3に示す配合組成(質量部)の塗料を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布し;α2層側の面には印刷面側ハードコート形成用塗料として上記(ε-1)を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布して、ハードコート積層フィルムを得た。続いて、印刷面側ハードコート層の上に、上記(γ-1)を、硬化後の厚みが30μmとなるようにアプリケーターを用いて塗布し、130℃、1分間の条件で加熱硬化し、粘着フィルムを得た。得られた粘着フィルムについて上記試験(i)~(xv)を行った。結果を表3に示す。
タッチ面側ハードコート形成用塗料の配合組成を表3~6の何れかに示すように変更したこと以外は、全て実施例15と同様に、粘着フィルムの作成及び物性測定・評価を行った。結果を表3~6の何れかに示す。
タッチ面側ハードコート形成用塗料の配合組成を表6に示すように変更したこと以外は、全て実施例1と同様に、粘着フィルムの作成及び物性測定・評価を行った。結果を表6に示す。
上記(α-14)の両面に処理量167W・min/m2(放電電力500W、放電電極の長さ1m、ライン速度3m/min)の条件で、コロナ放電処理を行った。両面とも濡れ指数は63mN/mであった。続いて、一方の面にはタッチ面側ハードコート形成用塗料として、表6に示す配合組成の塗料を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布し;他方の面には印刷面側ハードコート形成用塗料として上記(ε-1)を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布して、ハードコート積層フィルムを得た。続いて、印刷面側ハードコート層の上に、上記(γ-1)を、硬化後の厚みが30μmとなるようにアプリケーターを用いて塗布し、130℃、1分間の条件で加熱硬化し、粘着フィルムを得た。得られた粘着フィルムについて上記試験(i)~(xv)を行った。結果を表6に示す。
上記(α’-1)の一方の面にはタッチ面側ハードコート形成用塗料として、表6に示す配合組成の塗料を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布し;他方の面には印刷面側ハードコート形成用塗料として上記(ε-1)を、ダイ方式の塗工装置を使用して、硬化後厚みが15μmとなるように塗布して、ハードコート積層体を得た。続いて、印刷面側ハードコート層の上に、上記(γ-1)を、硬化後の厚みが30μmとなるようにアプリケーターを用いて塗布し、130℃、1分間の条件で加熱硬化し、粘着フィルムを得た。得られた粘着フィルムについて上記試験(i)~(xv)を行った。結果を表6に示す。なお、線膨張係数は、試験片の収縮が大きく、測定値を得ることができなかった。
上記(α’-1)に替えて、上記(α’-2)を用いたこと以外は、全て比較例1と同様に、粘着フィルムの作成及び物性測定・評価を行った。結果を表6に示す。
上記(α’-1)に替えて、上記(α’-3)を用いたこと以外は、全て比較例1と同様に、粘着フィルムの作成及び物性測定・評価を行った。結果を表6に示す。
2:押出機2
3:2種3層マルチマニホールド方式の共押出Tダイ
4:溶融フィルム
5:鏡面ロール
6:鏡面ベルト
7:一対のベルトローラー
Claims (10)
- 表層側から順に、(α)ポリ(メタ)アクリルイミド系樹脂フィルム層と、(γ)粘着剤層とを有し、
全光線透過率が80%以上であることを特徴とする粘着フィルム。 - 上記(α)ポリ(メタ)アクリルイミド系樹脂フィルム層の表層側に、更に(δ)ハードコート層を有することを特徴とする請求項1に記載の粘着フィルム。
- 上記(δ)ハードコート層が、
(A)多官能(メタ)アクリレート100質量部;
(B)アルコキシシリル基と(メタ)アクリロイル基を有する化合物0.2~4質量部;
(C)有機チタン0.05~3質量部;及び
(D)平均粒子径1~300nmの微粒子5~100質量部
を含む活性エネルギー線硬化性樹脂組成物からなることを特徴とする請求項2に記載の粘着フィルム。 - 上記活性エネルギー線硬化性樹脂組成物が、更に、(E)撥水剤0.01~7質量部を含むことを特徴とする請求項3に記載の粘着フィルム。
- 上記(E)撥水剤が、(メタ)アクリロイル基含有フルオロポリエーテル系撥水剤を含むことを特徴とする請求項4に記載の粘着フィルム。
- 上記(α)ポリ(メタ)アクリルイミド系樹脂フィルムが、下記特性(I)及び(II)を満たすことを特徴とする請求項1~5の何れか1項に記載の粘着フィルム。
(I)全光線透過率85%以上。
(II)ヘーズ3.0%以下。 - 上記(α)ポリ(メタ)アクリルイミド系樹脂フィルムが、第一ポリ(メタ)アクリルイミド系樹脂層(α1);芳香族ポリカーボネート系樹脂層(β);第二ポリ(メタ)アクリルイミド系樹脂層(α2)が、この順に直接積層された透明多層フィルムであることを特徴とする請求項1~6の何れか1項に記載の粘着フィルム。
- 上記(γ)粘着剤層が、シリコン系粘着剤を含むことを特徴とする請求項1~7の何れか1項に記載の粘着フィルム。
- 請求項1~8の何れか1項に記載の粘着フィルムの、画像表示装置部材としての使用。
- 請求項1~8の何れか1項に記載の粘着フィルムを含む画像表示装置部材。
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US20170306188A1 (en) | 2017-10-26 |
TWI663240B (zh) | 2019-06-21 |
US10689530B2 (en) | 2020-06-23 |
KR102468458B1 (ko) | 2022-11-17 |
JP2016074878A (ja) | 2016-05-12 |
CN107075320A (zh) | 2017-08-18 |
TW201614025A (en) | 2016-04-16 |
JP6153977B2 (ja) | 2017-06-28 |
KR20170063646A (ko) | 2017-06-08 |
CN107075320B (zh) | 2019-11-26 |
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