Classifications

• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • 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
  • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
• • 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
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
  • G02B27/30—Collimators
• • 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
  • B32B2250/03—3 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
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • 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
  • B32B2307/536—Hardness
• • 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
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—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
  • 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
  • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
  • B32B2333/04—Polymers of esters
• • 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
• • 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
  • B32B2457/208—Touch screens
• • 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

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 provide performance that cannot be obtained from the substrate film alone, and high-performance films that can meet the demand for higher performance are 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 after heat treatment is required not to cause deterioration in appearance, change in shape, change in optical properties (for example, haze), and the like.
• an object of the present invention is to provide a hard coat film that is excellent in optical properties, hard properties (scratch resistance, pencil hardness, etc.) and adhesion of the hard coat layer while having high heat resistance. .
• 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
• the inventors have found that the above characteristics contribute particularly to the improvement of the heat resistance of the hard coat film and the adhesion of the hard coat layer.
• the hard coat layer has excellent heat resistance, optical properties, hard properties (scratch resistance, pencil hardness, etc.), and adhesion of the hard coat layer.
• the inventors have found that an excellent hard coat film can be obtained, and have completed the present invention.
• a hard coat film comprising a hard coat layer containing an ionizing radiation-curable resin composition on each side of a base film, characterized by satisfying the following conditions (I), (II) and (III): hard coat film.
• the peak area appearing at 1000 to 1120 cm -1 is defined as A, and the peak area appearing at 1650 to 1800 cm -1 is defined as B.
• the content of the inorganic fine particles or organic fine particles is in the range of 1% by mass to 60% by mass with respect to the solid content of the ionizing radiation-curable resin composition.
• the hard coat film according to any one of the above.
• the base film is one selected from polyethylene terephthalate, cycloolefin, polyethylene naphthalate, polyimide, triacetyl cellulose, and liquid crystal polymer. coat film.
• the present invention it is possible to provide a hard coat film that is excellent in optical properties, hard properties (scratch resistance, pencil hardness, etc.), and adhesion of the hard coat layer while having high heat resistance.
• the present invention is a hard coat film in which a hard coat layer containing an ionizing radiation-curable resin composition is provided on each surface of a substrate film, wherein the following condition (I), The hard coat film is characterized by satisfying (II) and (III).
• Condition (II): The ionizing radiation-curable resin composition contains inorganic fine particles or organic fine particles.
• the peak area appearing at 1000 to 1120 cm -1 is defined as A, and the peak area appearing at 1650 to 1800 cm -1 is defined as B.
• the structure of the hard coat film of the present invention will be described in detail below.
• 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. Among them, it is preferable to use polyethylene terephthalate, cycloolefin, polyethylene naphthalate, polyimide, triacetyl cellulose, and liquid crystal polymer, which are excellent in heat resistance and dimensional stability. Cycloolefins, which are excellent in 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: In particular, they have found that it contributes to improving the heat resistance of the hard coat film and the adhesion of the hard coat layer.
• the ionizing radiation curable resin composition used in the present invention has a peak area (peak range area) appearing at 1000 to 1120 cm in infrared spectroscopic measurement of an 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) must satisfy 40% or more ( Condition (III) above).
• the peak area ratio 1 is preferably 50% to 400%.
• the ionizing radiation-curable resin composition used in the present invention further contains inorganic fine particles or organic fine particles (condition (II) above).
• 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;
• 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. It is believed that this can improve the heat resistance of the hard coat film.
• the ionizing radiation-curable resin composition used in the present invention further contains 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 also contributes to improving the heat resistance of the hard coat 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 in the range of 1 to 60% by mass, particularly in the range of 15 to 50% by mass, based on the solid content of the ionizing radiation-curable resin composition. is preferably If the content is less than 1% by mass, it is difficult to obtain the effect of improving surface hardness (scratch resistance) and the effect of improving heat resistance. On the other hand, when the content exceeds 60% by mass, the flexibility is lowered and the haze is increased, which is not preferable.
• the ionizing radiation-curable resin composition used in the present invention preferably further satisfies the following condition (IV). That is, in the infrared spectroscopic measurement of the ionizing radiation curable resin composition in an uncured state, the peak area (area of the peak range) appearing at 3250 to 3500 cm -1 is C, and the peak area appearing at 1650 to 1800 cm -1 It is preferable that the peak area ratio 2 ((C/B) ⁇ 100) is 5% or more, where B is the area of the peak range (condition (IV)). The peak area ratio 2 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 preferably further satisfies the following condition (V). That is, in the infrared spectroscopic measurement of the ionizing radiation curable resin composition in an uncured state, the peak area (area of the peak range) appearing at 1500 to 1580 cm -1 is D, and the peak area appearing at 1650 to 1800 cm -1 It is preferable that the peak area ratio 3 ((D/B) ⁇ 100) is 30% or less, where B is the area of the peak range (condition (V)).
• the peak area ratio 3 is particularly preferably 0.5% to 10%.
• 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 (VI). 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 (VI)). 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, and improve the heat resistance of the hard coat film. also contribute to
• 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 hard coat film of the present invention is a hard coat film in which hard coat layers are formed on both sides of a base 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.
• 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.
• aromatic solvents such as toluene, xylene and n-heptane
• aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl
• 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 amount of ionizing radiation (UV, EB, etc.) applied to the coating film after drying may be any amount required to give the hard coat layer sufficient hard properties, and may vary depending on the type of ionizing radiation-curable resin, etc. It can be set as appropriate.
• the hard coat film of the present invention is a hard coat film in which hard coat layers are provided on both sides of a substrate film.
• the thickness of the hard coat layer is not particularly limited, but the thickness of the hard coat layer A on one side of the base film is DA , and the thickness of the hard coat layer B on the other side is When D B , the film thicknesses D A and D B of the hard coat layers A and B are preferably in the range of 0.5 ⁇ m to 12.0 ⁇ m, particularly in the range of 1.0 ⁇ m to 9.0 ⁇ m. Preferably. If the film thickness is less than 0.5 ⁇ m, the hard coat layer does not have sufficient rigidity, and it becomes difficult for the hard coat layer to suppress thermal deformation of the base film.
• 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. It is more preferable that the film thickness is in the range of 5.0 ⁇ m to 7.0 ⁇ m in order to maintain a balance between the two.
• the film thickness ratio ((D A /D B ) ⁇ 100) of the hard coat layer A and the hard coat layer B is preferably in the range of 50% to 150%, more preferably in the range of 80% to 120%. is particularly preferred.
• the film thickness ratio of the hard coat layer A and the hard coat layer B is within the above ratio, curling of the hard coat layers A and B due to curing shrinkage is offset, which is preferable.
• the present invention provides a hard coat film comprising a hard coat layer containing an ionizing radiation-curable resin composition on each side of a base film, wherein the conditions (I), It is a hard coat film that satisfies (II) and (III), and according to the present invention, while having high heat resistance, optical properties, hard properties (scratch resistance, pencil hardness, etc.) It is possible to provide a hard coat film that is also excellent in terms of properties. Further, the hard coat film of the present invention more preferably satisfies the above conditions (IV) and/or (V) and/or (VI).
• 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.
• Comparative example 1 Ionizing radiation curable resin composition (95% polyester acrylate UV curable resin "M7300K” (solid content 100%, manufactured by Toagosei Co., Ltd.) and 5% photopolymerization initiator), the solid content ratio A fluorine-based leveling agent was added to a concentration of 0.1% as the main component, and the solid concentration was adjusted to 45% with a diluent (a mixture of 40% 1-propanol and 60% propyl acetate). As described above, the hard coat layer-forming resin composition 2 was prepared. A hard coat film of Comparative Example 1 was produced in the same manner as in Example 1, except that the resin composition 2 for forming a hard coat layer was used.
• 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.
• 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 pasted on it, and after pressing it evenly with a spatula, it was peeled off in the 60-degree direction, and after crimping and peeling at the same place five times, the number of remaining hard coat layers was reduced to 3. graded. Evaluation criteria are as follows. ⁇ : 100 pieces (no peeling) ⁇ : 99 to 90 pieces (with slight peeling) ⁇ : 89 to 0 pieces (with peeling)
• Table 1 summarizes the evaluation results regarding the above optical properties, scratch resistance, pencil hardness, and adhesion.
• each hard coat film is placed on a stainless steel plate (in the case of the reference example, the base film is placed on a stainless steel plate), and a constant temperature dryer DY300 ( After heat treatment for a certain period of time in a drying oven (manufactured by Yamato Scientific Co., Ltd.), the appearance, deformation, and ⁇ haze of the film after heat treatment were evaluated.
• the heat treatment was performed in three ways: 150° C. for 30 minutes, 200° C. for 30 minutes, and 240° C. for 10 minutes.
• [ ⁇ Haze] A value obtained by subtracting the haze of each film before heat treatment (untreated) from the haze of each film after heat treatment was defined as ⁇ haze ( ⁇ Haze).
• the haze was measured using a haze meter HM150 (manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS-K-7136 as described above.
• Table 2 summarizes the results of the heat resistance evaluation described above.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Laminated Bodies (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Surface Treatment Of Optical Elements (AREA)
• Electroluminescent Light Sources (AREA)
• Devices For Indicating Variable Information By Combining Individual Elements (AREA)
• Liquid Crystal (AREA)
• Paints Or Removers (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=83459524

Family Applications (1)

Country Status (5)

Cited By (3)

Citations (6)

Family Cites Families (2)

• 2022
  • 2022-03-29 JP JP2023509460A patent/JP7302116B2/ja active Active
  • 2022-03-29 KR KR1020237033496A patent/KR20240017775A/ko active Pending
  • 2022-03-29 US US18/284,713 patent/US20240166833A1/en active Pending
  • 2022-03-29 CN CN202280025421.2A patent/CN117561461A/zh active Pending
  • 2022-03-29 WO PCT/JP2022/015704 patent/WO2022210792A1/ja not_active Ceased

Patent Citations (6)

Also Published As

Similar Documents

Legal Events