Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
  • B32B2309/08—Dimensions, e.g. volume
  • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
  • B32B2309/105—Thickness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2310/00—Treatment by energy or chemical effects
  • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/202—LCD, i.e. liquid crystal displays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/204—Plasma displays
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/08—Homopolymers or copolymers of acrylic acid esters

Definitions

• the present invention relates to a hard coat film, more specifically, flat panel displays such as liquid crystal display devices, plasma display devices, electroluminescence (EL) display devices, members such as touch panels, carrier films, base films such as flexible substrates, etc. It relates to a hard coat film provided with a hard coat layer that can be used as.
• flat panel displays such as liquid crystal display devices, plasma display devices, electroluminescence (EL) display devices, members such as touch panels, carrier films, base films such as flexible substrates, etc.
• EL electroluminescence
• a display surface of a flat panel display such as a liquid crystal display (LCD) is required to be scratch-resistant so as not to be scratched during handling and reduce visibility. Therefore, it is common practice to provide scratch resistance by using a hard coat film in which a hard coat layer is provided on a base film.
• a hard coat film in which a hard coat layer is provided on a base film.
• the functional requirements for a hard coat film that maintains optical visibility and is scratch resistant have increased. rising.
• the needs for base films such as carrier films and flexible substrates have become more complex, and materials and technologies for realizing new electronics are in demand.
• a hard coat layer (functional layer) is provided on various substrate films to impart performance that cannot be obtained from the substrate film alone, and a high-performance film that can meet the demand for higher performance is required.
• polyethylene terephthalate, polyethylene naphthalate, triacetyl cellulose, and cycloolefin which are excellent in transparency, heat resistance, dimensional stability, and low moisture absorption, as well as polyimide and liquid crystal polymer, which are excellent in dimensional stability, are used as base films for optical components and electronics. It is expected to be used for parts.
• Such a hard coat film in which a hard coat layer is provided on the base film to further impart hard properties, has become excellent in adhesion between the base film and the hard coat layer along with the recent diversification of applications. Furthermore, it is required to have excellent optical properties, heat resistance, and adhesion to the laminated film.
• Patent Documents 1 and 2 disclose methods for imparting easy adhesion to a hard coat layer to a base film such as a cycloolefin film, which has particularly excellent optical properties.
• Patent Document 1 discloses a method of subjecting a substrate film surface to corona treatment, plasma treatment, UV treatment, etc.
• Patent Document 2 discloses a method of coating an anchor coating agent on a substrate film (anchor coating ) is disclosed.
• the adhesion between the base film and the hard coat layer can be improved without surface treatment of the base film or anchor coat treatment for imparting easy adhesion to the hard coat layer. It is rare.
• the hard coat film it is required to provide a laminated film (for example, a conductive film, a metal film, a metal oxide film, etc.) on the surface of the hard coat layer.
• a laminated film for example, a conductive film, a metal film, a metal oxide film, etc.
• a metal film such as Cu is formed on a hard coat film by a sputtering method or the like.
• the hard coat film is also required to have adhesion to a laminated film formed by a sputtering method or the like.
• an object of the present invention is to provide a hard coat film that is excellent in optical properties and adhesion of the hard coat layer, and that has adhesion of the laminated film formed on the hard coat film.
• the present inventors focused on the characteristics (peak area ratio) in the infrared spectrum of the resin composition contained in the hard coat layer, and found that the infrared spectrum It has been found that the above features contribute to the improvement of the adhesion of the hard coat layer and the adhesion of the laminated film formed on the hard coat film.
• the optical properties and the adhesion of the hard coat layer are excellent, and the hard coat layer having the adhesion of the laminated film formed on the hard coat film is obtained.
• the inventors have found that a coated film can be obtained, and have completed the present invention.
• the present invention has the following configurations.
• Peak area ratio 2 ((C/B) ⁇ 100) is 30% or less. (However, in infrared spectroscopic measurement of the uncured ionizing radiation curable resin composition, the peak area appearing at 1500 to 1580 cm -1 is C, and the peak area appearing at 1650 to 1800 cm -1 is B.)
• the base film is one selected from polyethylene terephthalate, cycloolefin, polyethylene naphthalate, polyimide, triacetyl cellulose, and liquid crystal polymer. coat film.
• the hard coat film has a maximum thermal shrinkage of 1.8% or less before heat treatment, and a maximum thermal shrinkage of 1.5% or less after heat treatment at 200° C. for 10 minutes.
• the hard coat film according to any one of the first to eighth inventions characterized by:
• the present invention it is possible to provide a hard coat film that is excellent in optical properties and adhesion of the hard coat layer, and further has adhesion of the laminated film formed on the hard coat film.
• the present invention is a hard coat film having a hard coat layer containing an ionizing radiation-curable resin composition on one or both sides of a base film, wherein the following condition (I), The hard coat film is characterized by satisfying (II) and (III).
• the base film of the hard coat film of the present invention will be described.
• the base film of the hard coat film is not particularly limited. can.
• Cycloolefins which are excellent in properties and low hygroscopicity, are more preferable.
• the thickness of the base film is appropriately selected according to the use of the hard coat film, but it is in the range of 10 ⁇ m to 300 ⁇ m from the viewpoint of mechanical strength, handleability, etc. more preferably in the range of 20 ⁇ m to 200 ⁇ m.
• the base film is a resin obtained by kneading a resin constituting the base film and an ultraviolet absorber for the purpose of preventing deterioration of the coating film and poor adhesion due to ultraviolet rays when used for a hard coat film.
• an ultraviolet absorber for the purpose of preventing deterioration of the coating film and poor adhesion due to ultraviolet rays when used for a hard coat film.
• the hard coat layer contains an ionizing radiation-curable resin composition.
• the hard coat layer is formed of a cured coating film of this ionizing radiation-curable resin composition.
• the resin contained in the hard coat layer particularly imparts surface hardness (pencil hardness, scratch resistance) to the hard coat layer, and can adjust the degree of cross-linking by adjusting the amount of exposure to ultraviolet rays. It is preferable to use an ionizing radiation-curable resin composition in that the surface hardness of the coating layer can be adjusted.
• the ionizing radiation-curable resin composition contains an acrylic resin containing a (meth)acryloyl group (condition (I) above).
• the ionizing radiation-curable resin composition used in the present invention is a transparent resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as "UV") or electron beams (hereinafter abbreviated as "EB”). It preferably contains an acrylic resin containing a (meth)acryloyl group, more preferably a urethane acrylate resin containing a (meth)acryloyl group.
• the present inventors focused on the characteristics (peak area ratio) in the infrared spectrum of the resin composition contained in the hard coat layer, and found that the characteristics in the infrared spectrum are: They have found that it contributes to the adhesion of the hard coat layer and the adhesion of the laminated film formed on the hard coat film.
• the ionizing radiation curable resin composition used in the present invention has a peak area (peak range area) appearing at 3250 to 3500 cm in infrared spectroscopic measurement of the uncured ionizing radiation curable resin composition. is A, and the peak area (area of the peak range) appearing at 1650 to 1800 cm -1 is B, the peak area ratio 1 ((A / B) ⁇ 100) is 5% or more. Condition (II) above).
• the peak area ratio 1 is preferably 5% to 400%.
• the peak appearing at 1650 to 1800 cm ⁇ 1 in the infrared spectrum represents the carbon-oxygen stretching vibration peak derived from the (meth)acryloyl group. Also, the peak appearing at 3250 to 3500 cm ⁇ 1 in the infrared spectroscopy spectrum is presumed to represent nitrogen-hydrogen bonds derived from amide groups or oxygen-hydrogen bonds derived from hydroxyl groups.
• the adhesion of the hard coat layer to the substrate due to the (meth)acryloyl groups and the hard coat layer Curing shrinkage within the layer maintains a balance between the interface with the base film and the peeling force in which force is applied in a different direction, making it an anchor for various base films including cycloolefin films with few polar groups. It is speculated that the adhesion of the hard coat layer to the base film can be improved without requiring modification of the layer or base film.
• the ionizing radiation curable resin composition used in the present invention has a peak area (peak range area) appearing at 1500 to 1580 cm in infrared spectroscopic measurement of the uncured ionizing radiation curable resin composition. is C, and the peak area (area of the peak range) appearing at 1650 to 1800 cm -1 is B, the peak area ratio 2 ((C/B) ⁇ 100) is 30% or less. Condition (III) above).
• the peak area ratio 2 is preferably 25% or less.
• the peak appearing at 1500 to 1580 cm -1 of the infrared spectrum is nitrogen-hydrogen bonds derived from amide groups, carbon-hydrogen bonds derived from phenyl rings, or azo groups. It is speculated to represent the origin nitrogen-nitrogen double bond. Further, as described above, the peak appearing at 1650 to 1800 cm ⁇ 1 in the infrared spectroscopy spectrum represents the carbon-oxygen stretching vibration peak derived from the (meth)acryloyl group.
• the ionizing radiation-curable resin composition used in the present invention preferably further satisfies the following condition (IV). That is, in infrared spectroscopic measurement of the ionizing radiation curable resin composition in an uncured state, the peak area (area of the peak range) appearing at 1000 to 1120 cm -1 is D, and the peak area appearing at 1650 to 1800 cm -1 It is preferable that the peak area ratio of 3 ((D/B) ⁇ 100) is 40% or more, where (the area of the peak range) is B (condition (IV)). More preferably, the peak area ratio 3 is 50% to 400%.
• the ionizing radiation-curable resin composition used in the present invention may further contain inorganic fine particles or organic fine particles.
• the peaks appearing at 1000 to 1120 cm ⁇ 1 in the infrared spectrum are the inorganic fine particles such as nanosilica and the organic fine particles such as silicon derived from silicone resin. - presumed to represent an oxygen bond; Further, as described above, the peak appearing at 1650 to 1800 cm ⁇ 1 in the infrared spectroscopy spectrum represents the carbon-oxygen stretching vibration peak derived from the (meth)acryloyl group.
• having a peak appearing at 1000 to 1120 cm ⁇ 1 at a certain ratio or more relative to the existing ratio of (meth)acryloyl groups means that silicon-oxygen bonds with high bond energy and excellent thermal stability are abundant in the hard coat layer. Since it is synonymous with containing, it is presumed that it contributes to the improvement of the heat resistance of the hard coat layer. As a result, the deformation of the hard coat layer due to the heat applied during the formation of the laminated film formed on the hard coat film and in the subsequent process is alleviated, and the adhesion of the hard coat layer and the adhesion to the laminated film can be improved. presumed to be possible.
• the ionizing radiation-curable resin composition used in the present invention preferably further satisfies the following condition (V). That is, in infrared spectroscopic measurement of the ionizing radiation curable resin composition in the state after curing, the peak area (area of peak range) appearing at 1370 to 1435 cm -1 is E, and the peak area appearing at 1650 to 1800 cm -1 It is preferable that the peak area ratio 4 ((E/B') ⁇ 100) is 20% or less, where B' is the area of the peak range (condition (V)). The peak area ratio 4 is particularly preferably 0.5% to 10%.
• a peak appearing at 1370 to 1435 cm ⁇ 1 in the infrared spectroscopy spectrum represents a carbon-carbon double bond derived from a (meth)acryloyl group.
• the peak appearing at 1650 to 1800 cm ⁇ 1 in the infrared spectroscopy spectrum represents the carbon-oxygen stretching vibration peak derived from the (meth)acryloyl group. Therefore, the peak area ratio 4 obtained by infrared spectroscopic measurement of the ionizing radiation-curable resin composition after curing represents the abundance ratio of carbonyl groups to (meth)acryloyl groups, and indicates the degree of progress of curing of the hard coat layer. It is.
• this peak area ratio 4 the more unreacted (meth)acryloyl groups remain, and the more uncured components in the hard coat layer, the more the hard coat layer. It is presumed that the rigidity is lowered and the force for suppressing thermal deformation of the base film is lowered.
• the peak area ratio 4 is 20% or less, it is possible to suppress a decrease in rigidity of the hard coat layer and a decrease in the ability to suppress thermal deformation of the base film.
• the deformation of the hard coat layer and the base film due to the heat applied during the formation of the laminated film formed on the hard coat film and in the subsequent process is alleviated, and the adhesion of the hard coat layer and the adhesion to the laminated film are improved. presumed to be possible.
• the ionizing radiation-curable resin composition includes thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester, styrene-acryl, and cellulose.
• thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester, styrene-acryl, and cellulose.
• thermosetting resins such as phenolic resins, urea resins, unsaturated polyesters, epoxies, and silicon resins may be blended within a range that does not impair the effects of the present invention and the hardness and scratch resistance of the hard coat layer. .
• acetophenones such as commercially available Omnirad 651 and Omnirad 184 (both trade names: manufactured by IMG), and Omnirad 500 (trade name: IMG) ) and other benzophenones can be used, and are not particularly limited.
• the ionizing radiation-curable resin composition used in the present invention may further contain inorganic fine particles or organic fine particles.
• inorganic fine particles or organic fine particles By containing the inorganic fine particles or organic fine particles, it is possible to improve the surface hardness (scratch resistance) and surface smoothness of the hard coat layer. Furthermore, as described above, it is also possible to improve the adhesion of the laminated film.
• the average particle size of the inorganic fine particles or organic fine particles is preferably in the range of 1 to 150 nm, more preferably in the range of 10 to 100 nm. If the average particle size is less than 1 nm, it is difficult to obtain sufficient surface hardness. On the other hand, if the average particle size exceeds 150 nm, the glossiness and transparency of the hard coat layer may decrease, and the flexibility may also decrease.
• the inorganic fine particles include silica and alumina.
• a silicone resin etc. can be mentioned preferably, for example.
• the content of the inorganic fine particles or organic fine particles is preferably 1.0 to 60.0 parts by mass with respect to 100 parts by mass of the solid content of the ionizing radiation-curable resin composition. If the content is less than 1.0 parts by mass, it is difficult to obtain the effect of improving the surface hardness (scratch resistance). On the other hand, when the content exceeds 60.0 parts by mass, flexibility is lowered and haze is increased, which is not preferable.
• the hard coat film of the present invention is a hard coat film in which a hard coat layer is formed on at least one side of a substrate film using an ionizing radiation-curable resin composition that satisfies the above conditions.
• a leveling agent can be used in the hard coat layer for the purpose of improving coatability.
• known leveling agents such as fluorine-based, acrylic-based, siloxane-based, and adducts or mixtures thereof can be used. is.
• the blending amount can be in the range of 0.01 to 7 parts by mass per 100 parts by mass of the solid content of the resin of the hard coat layer.
• OCR optical transparent resin
• TSP transparent conductive member
• LCD liquid crystal module
• additives added to the hard coat layer include antifoaming agents, surface tension modifiers, antifouling agents, antioxidants, antistatic agents, ultraviolet absorbers, and light stabilizers, as long as they do not impair the effects of the present invention. You may mix
• the hard coat layer is formed by dissolving and dispersing the ionizing radiation-curable resin composition, photopolymerization initiator, and other additives in an appropriate solvent, coating the base film, and drying the coating. be done.
• the solvent can be appropriately selected according to the solubility of the resin to be blended, and any solvent that can uniformly dissolve or disperse at least the solid content (resin, photoinitiator, and other additives) may be used.
• solvents examples include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetic acid.
• aromatic solvents such as toluene, xylene and n-heptane
• aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetic acid.
• organic solvents such as ester solvents such as butyl and methyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol alone Alternatively, several types can be appropriately combined and used.
• the method of coating the hard coat layer is not particularly limited, but gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, spin coating, screen printing, spraying. After coating by a known coating method such as a coating method, it is usually dried at a temperature of about 50 to 120°C.
• the hard coat layer coating containing the ionizing radiation-curable resin composition or the like is applied to the base film, dried, and then irradiated with ionizing radiation (UV, EB, etc.) to photopolymerize the coating. occurs and a cured coating film (hard coat layer) having excellent hard properties can be obtained.
• a hard coat layer having a pencil hardness of 3B to 3H as defined in JIS K5600-5-4 is preferred.
• the irradiation dose of ionizing radiation (UV, EB, etc.) to the coating film after drying may be any irradiation dose required to give the hard coat layer sufficient hard properties, depending on the type of ionizing radiation curable resin, etc. It can be set as appropriate.
• the thickness of the hard coat layer is not particularly limited, but is preferably in the range of 0.5 ⁇ m to 12.0 ⁇ m, more preferably in the range of 1.0 ⁇ m to 9.0 ⁇ m. preferable. If the film thickness is less than 0.5 ⁇ m, sufficient rigidity cannot be obtained for the hard coat layer, making it difficult to suppress thermal deformation. On the other hand, when the film thickness exceeds 12.0 ⁇ m, the rigidity of the hard coat layer is significantly improved, and the flexibility and crack resistance of the hard coat layer are significantly lowered, which is not preferable. The thickness of the hard coat layer can be measured by actual measurement with a micrometer.
• the arithmetic mean surface roughness (Ra) of the surface of the hard coat layer is preferably in the range of 0.5 nm to 15.0 nm, more preferably in the range of 1.0 nm to 12.0 nm. preferable.
• the arithmetic mean surface roughness (Ra) of the surface of the hard coat layer is within the above range, not only the hard properties are improved but also the adhesion of the laminated film formed on the hard coat film is improved. If the arithmetic mean surface roughness (Ra) of the surface of the hard coat layer is less than 0.5 nm, adhesion of the laminated film is lowered. Moreover, when the arithmetic mean surface roughness (Ra) is greater than 15.0 nm, the haze increases.
• the above arithmetic mean surface roughness (Ra) is defined in JIS B 0031 (1994) / JIS B 0061 (1994) appendix, the absolute deviation from the average line of the roughness curve at a certain reference length , that is, the average value of unevenness when the roughness curve portion below the average line is turned back to the positive value side.
• a specific evaluation method (measurement method) for the arithmetic mean surface roughness (Ra) in the present invention will be described later.
• the arithmetic mean surface roughness (Ra) of the hard coat layer surface is determined, for example, by the addition of inorganic or organic fine particles to the hard coat layer, the type of solvent for the hard coat layer paint, and the drying conditions when the hard coat layer is applied. can be adjusted by changing the
• the surface free energy of the hard coat layer is preferably in the range of 17.0 mJ/m 2 to 55.0 mJ/m 2 , more preferably 17.0 mJ/m 2 to 45.0 mJ/m A range of 2 is more preferred.
• the above-mentioned surface free energy is defined as "free energy possessed by a unit area of the surface", and refers to the excess energy possessed by the surface of the hard coat layer compared to the inside (bulk) of the layer.
• the higher the surface free energy of a solid the easier it is for gases and fine particles to be adsorbed, the easier it is for liquids to get wet, and the easier it is for them to adhere to other solids.
• This surface free energy can be measured by using a contact angle meter or the like and analyzing the contact angle between water and hexadecane by the Kaelble-Uy method.
• the surface free energy of the hard coat layer is specifically measured using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd., and 2 ⁇ L of water (pure water) is dropped on the surface of the primer layer. Then, the contact angle was measured after 1 second, 2 ⁇ L of n-hexadecane was dropped on the surface of the hard coat layer, and the contact angle of water and the contact angle of n-hexadecane were measured after 1 second. is a value calculated by the Kaelble-Uy method.
• the adhesion of the laminated film formed on the hard coat film is improved.
• the wettability is improved, which contributes to the improvement of the adhesion of the laminated film. If this surface free energy is less than 17.0 mJ/m 2 , there arises a problem that adhesion to the laminated film is lowered. Also, if the surface free energy is too high , stains will easily adhere and the scratch resistance will decrease. It is preferably 45.0 mJ/m 2 or less, more preferably 45.0 mJ/m 2 or less.
• the surface free energy of the hard coat layer can be adjusted, for example, by adding a leveling agent to the hard coat layer (type and amount of leveling agent added, etc.).
• the hard coat film can be annealed.
• Annealing is a method of removing residual stress in a film by heat treatment. Annealing completely crystallizes and fixes molecules, improving dimensional stability. Annealing treatment is preferably performed at a high temperature for a short period of time, preferably about 40 minutes at the longest.
• the maximum thermal shrinkage before heat treatment is 1.8% or less, and the maximum thermal shrinkage after heat treatment at 200° C. for 10 minutes is 1.8%. It is preferably 5% or less, the maximum thermal shrinkage before heat treatment is 1.6% or less, and the maximum thermal shrinkage after heat treatment is 1.3% or less. More preferably, the maximum value of thermal shrinkage after heat treatment is 1.0% or less.
• the heat shrinkage ratio is 1.9% or more, the deformation of the hard coat film due to the heat applied during the formation of the laminated film and in the subsequent process becomes large, so the adhesion with the laminated film decreases, cracks in the laminated film, and position This causes misalignment and warping of the film substrate.
• the present invention provides a hard coat film having a hard coat layer containing an ionizing radiation-curable resin composition on one or both sides of a base film, wherein the above conditions (I), A hard coat film that satisfies (II) and (III). A coated film can be provided. Further, the hard coat film of the present invention more preferably satisfies the above conditions (IV) and/or (V).
• Example 1 Preparation of Hard Coat Layer-Forming Resin Composition (Hard Coat Layer Paint) 1] Ionizing radiation curable resin composition (23% total urethane acrylate and acrylic ester, 15% amorphous silica, 2% photopolymerization initiator, 35% propylene glycol monomethyl ether as solvent, 15% methyl ethyl ketone %, containing 10% toluene.) to which a fluorine-based leveling agent was added so that the solid content ratio was 0.1%, and a diluent (70% 1-propanol, 30% diacetone alcohol The diluent mixed in ) was adjusted to a solid content concentration of 25%. As described above, the hard coat layer-forming resin composition 1 used in this example was prepared.
• a base film containing polyethylene terephthalate as a main component (trade name “Cosmoshine A4360”, thickness 125 ⁇ m, manufactured by Toyobo Co., Ltd.) is used, and the above hard coat layers are formed on both sides of this base film.
• Resin Composition 1 was applied using a bar coater and dried with hot air in a drying oven at 80° C. for 1 minute to form a coating layer having a coating thickness of 3.0 ⁇ m (on one side). The coating thickness was the same on both sides. The coating thickness was measured using a Thin-Film Analyzer F20 (trade name) (manufactured by FILMETRICS).
• Example 2 A hard coat film of Example 2 was produced in the same manner as in Example 1, except that the coating thickness (one side) in Example 1 was 6.0 ⁇ m.
• Example 3 [Preparation of Hard Coat Layer-Forming Resin Composition (Hard Coat Layer Paint) 2] Ionizing radiation curable resin composition (urethane acrylate "FA-3352-3" (solid content 40%, manufactured by Nippon Kako Toryo Co., Ltd.)), diluent (ethyl acetate 60%, propylene glycol monomethyl ether acetate 40%) The diluent mixed in ) was adjusted to a solid content concentration of 20%. As described above, the hard coat layer-forming resin composition 2 used in this example was prepared. [Preparation of hard coat film] A hard coat film of Example 3 was produced in the same manner as in Example 1, except that the resin composition 2 for forming a hard coat layer was used.
• Example 4 A resin composition for forming a hard coat layer was prepared in the same manner as in Example 1, except that in the resin composition for forming a hard coat layer of Example 2, the amount of the fluorine-based leveling agent added was 0.3% relative to the solid content.
• a hard coat film of Example 4 was produced in the same manner as in Example 1, except that this hard coat layer-forming resin composition 3 was used.
• Example 5 After producing a hard coat film in the same manner as in Example 1, the obtained hard coat film was annealed in a drying oven at 200° C. for 10 minutes to obtain a hard coat film.
• Comparative example 1 A resin composition for forming a hard coat layer was prepared in the same manner as in Example 1, except that 15% of the amorphous silica in the ionizing radiation-curable resin composition was removed. 4 was prepared, and a hard coat film of Comparative Example 1 was produced in the same manner as in Example 1, except that this hard coat layer-forming resin composition 4 was used.
• Comparative example 2 Ionizing radiation curable resin composition (containing 95% silicone oligomer UV curable resin "KR-513" (solid content 100%, manufactured by Shin-Etsu Chemical Co., Ltd.) and 5% photopolymerization initiator) as the main ingredient , and a diluent (a mixture of 1-propanol at 40% and propyl acetate at 60%) to adjust the solid concentration to 45%.
• Resin composition 5 for hard coat layer formation was prepared as described above.
• a hard coat film of Comparative Example 2 was produced in the same manner as in Example 1, except that the resin composition 5 for forming a hard coat layer was used.
• Comparative Example 3 Ionizing radiation curable resin composition (containing 95% polyester acrylate UV curable resin “M7300K” (solid content 100%, manufactured by Toagosei Co., Ltd.) and 5% photopolymerization initiator) as a main component and a diluent (Diluent in which 1-propanol was mixed at 40% and propyl acetate at 60%) to adjust the solid concentration to 45%.
• a diluent Dioxide in which 1-propanol was mixed at 40% and propyl acetate at 60%
• Peak area and peak area ratio of ionizing radiation-curable resin composition ATR method for uncured ionizing radiation-curable resin composition (resin used for the hard coat layer) using an infrared spectrophotometer The infrared spectroscopy spectrum (infrared absorption spectrum) was measured. An FT-IR Spectrometer Spectrum 100 (manufactured by PerkinElmer Japan) was used as an infrared spectrophotometer.
• infrared spectroscopy was performed in an environment of a temperature of 23°C and a humidity of 50%. The coated surface was brought into contact with the measurement site (sensor section) of the photometer, and the infrared spectrum was measured.
• the infrared spectroscopic spectrum (infrared absorption spectrum) was measured by the ATR method for the hard coat layer surface (ionizing radiation curable resin composition after curing) of the hard coat film using the above infrared spectrophotometer.
• the surface of the hard coat layer was brought into contact with a measurement portion (sensor portion) of an infrared spectrophotometer under an environment of temperature 23° C./humidity 30%, and the infrared spectrum was measured.
• Baselines are drawn at 1,370 to 1,435 cm -1 and 1,650 to 1,800 cm -1 on the obtained spectrum chart, in which the horizontal axis is the wavenumber (cm -1 ) and the vertical axis is the absorbance. were defined as peak areas E and B′, respectively, and the ratio ((E/B′) ⁇ 100) was defined as a peak area ratio of 4. The above results are collectively shown in Table 1.
• Optical properties Measured using a haze meter HM150 (manufactured by Murakami Color Research Laboratory) according to JIS-K-7361-1 and JIS-K-7136.
• Adhesion Adhesion was evaluated by a cross-cut peel test according to JIS-K5600-5-6. Specifically, for each hard coat film, under normal conditions (23 ° C., 50% RH), 100 cross-cuts of 1 mm 2 were prepared using a checkerboard peel test jig, and Adhesive tape No. 252 was attached thereon, pressed uniformly with a spatula, and then peeled off in the direction of 60 degrees. It should be noted that the determination was made after performing pressure bonding and peeling at the same location five times. Evaluation criteria are as follows. ⁇ : 100 pieces (no peeling) ⁇ : 99 to 90 pieces (with slight peeling) ⁇ : 89 to 0 pieces (with peeling)
• Laminate Film Adhesion Using a magnetron sputtering apparatus MSP-40T (manufactured by Vacuum Device Co., Ltd.), a Cu sputter film having a thickness of 100 nm was formed on each hard coat film. The adhesion of the laminated film was evaluated by the cross-cut peel test according to JIS-K5600-5-6 in the same manner as described above. Specifically, for the Cu sputtered film formed on each hard coat film, under normal conditions (23°C, 50% RH), 100 crosscuts of 1 mm 2 were prepared using a checkerboard peel test jig. Adhesive tape No. 252 manufactured by Sekisui Chemical Co., Ltd.
• Table 2 summarizes the evaluation results of the above surface smoothness, surface free energy, optical properties, adhesion, and laminated film adhesion.
• Thermal shrinkage rate Measured using a digital compact measuring microscope (manufactured by OLYMPUS Co., Ltd.) according to JIS-K-7133. Heat treatments were performed at 150° C. for 30 minutes and 200° C. for 30 minutes. The thermal shrinkage rate was measured in the coating direction (abbreviated as "MD") of the hard coat film and in the width direction (abbreviated as "TD") orthogonal thereto. Table 3 shows the evaluation results regarding the above thermal shrinkage rate.
• MD coating direction
• TD width direction

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