WO2023068040A1 - ハードコートフィルムおよびその製造方法 - Google Patents

ハードコートフィルムおよびその製造方法 Download PDF

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Publication number
WO2023068040A1
WO2023068040A1 PCT/JP2022/037194 JP2022037194W WO2023068040A1 WO 2023068040 A1 WO2023068040 A1 WO 2023068040A1 JP 2022037194 W JP2022037194 W JP 2022037194W WO 2023068040 A1 WO2023068040 A1 WO 2023068040A1
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Prior art keywords
hard coat
film
compound
layer
coat layer
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Ceased
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PCT/JP2022/037194
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English (en)
French (fr)
Japanese (ja)
Inventor
雄二 中山
直樹 江草
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Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to JP2023518065A priority Critical patent/JP7315122B1/ja
Priority to CN202280070223.8A priority patent/CN118119863A/zh
Priority to KR1020247009329A priority patent/KR102725884B1/ko
Publication of WO2023068040A1 publication Critical patent/WO2023068040A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/06—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood
    • B05D7/08—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes
    • B05D7/10—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wood using synthetic lacquers or varnishes based on cellulose derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids

Definitions

  • the present invention relates to a hard coat film and its manufacturing method.
  • liquid crystal displays such as liquid crystal displays, plasma displays, EL displays, rear projection displays, CRT displays, etc. used as image display devices for televisions, computers, car navigation systems, vehicle instrument panels, mobile phones, etc., the surface of the display etc.
  • a hard coat film is used for the purpose of protection.
  • Hard coat films have excellent properties such as mechanical properties, dimensional stability, and electrical insulation.
  • Transparent plastics are widely used as substrates for applications.
  • triacetyl cellulose (TAC) films are often used for optical display materials such as displays because of their transparency, light refractive index, impact resistance, heat resistance, and durability.
  • a hard coat film is usually produced by forming a hard coat layer on a triacetyl cellulose film, which is a substrate, by coating or printing a resin composition.
  • a hard coat film for example, Patent Document 1 discloses an ionizing radiation-curable resin containing a polyfunctional monomer having two or more (meth)acryloyl groups in one molecule, a photopolymerization initiator, and a solvent.
  • a hard coat film is described in which the film thickness ratio of the mixed layer to the film thickness is 32% or more and 61% or less.
  • the hard coat film is hard because of the refractive index difference between the hard coat layer and the refractive index of the triacetyl cellulose serving as the base film, or the discontinuous change in the refractive index across the interface.
  • the light reflected on the surface of the coating layer and the light reflected on the interface between the hard coat layer and the base film interfere with each other, causing interference unevenness (rainbow unevenness), which deteriorates the visibility of the display and also reduces the aesthetic appearance of the display. There is a problem of loss.
  • Patent Document 2 discloses that a hard coat layer is formed using a solvent that dissolves or swells the base material, so that fine particles are formed at the interface between the hard coat layer and the base material. A method for discontinuously forming asperities is described.
  • Patent Document 3 discloses a method of forming a hard coat layer by applying a composition containing a solvent that dissolves or swells a substrate and an active energy ray-curable compound having a solubility parameter value within a specific range to the substrate. is stated.
  • JP 2014-058601 A Japanese Patent Application Laid-Open No. 2003-131007 JP 2007-160513 A
  • a triacetyl cellulose film is permeated with a specific composition for forming a hard coat layer to form a mixed layer with a specific ratio, so that the coating film haze and scratch resistance are not deteriorated (practically To provide a hard coat film in which interference unevenness is suppressed while maintaining a satisfactory range, and which is also excellent in adhesion.
  • a hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer contains a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D).
  • the mixed layer is a layer formed by dissolving or swelling the composition for forming a hard coat layer in the triacetyl cellulose film, A hard coat film, wherein the thickness ratio of the mixed layer to the total thickness of the hard coat layer and the mixed layer is 65% or more when the cross section of the hard coat film in the thickness direction is observed with a scanning electron microscope. .
  • the compound (B) having one ethylenically unsaturated group consists of an initial mass (X1) of a triacetylcellulose film having a short side of 2 cm, a long side of 4 cm, and a thickness of 80 ⁇ m, and the triacetylcellulose film.
  • [(X2)/(X1) ] is 1.2 or more, the hard coat film of [1], which is a compound (b1) having one ethylenically unsaturated group.
  • the solvent (D) is the initial haze value (Y1) of a triacetylcellulose film of 10 cm short side x 10 cm long side x 80 ⁇ m thick, and the 0.1 g of (D) was added dropwise, left for 2 minutes, and then heated at 60° C. for 1 minute.
  • the haze change value [(Y2) ⁇ (Y1)] from the haze value (Y2) of the triacetyl cellulose film was 0.
  • the content of the compound (B) having one ethylenically unsaturated group is 3 to 30% by mass based on the total 100% by mass of the compound (A) and the compound (B) [1]- [3]
  • the hard coat film according to any one.
  • a method for producing a hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer comprising: A composition for forming a hard coat layer is applied onto a triacetyl cellulose film to form a mixed layer and a hard coat layer,
  • the hard coat layer-forming composition comprises a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent.
  • the mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20, A hard coat film, wherein the thickness ratio of the mixed layer to the total thickness of the hard coat layer and the mixed layer is 65% or more when the cross section of the hard coat film in the thickness direction is observed with a scanning electron microscope. manufacturing method.
  • the interference unevenness is suppressed without deteriorating the coating film haze and scratch resistance (within a practically acceptable range), and the hard coat layer has excellent adhesion.
  • (meth)acryl means “acryl or methacryl” unless otherwise specified.
  • compound (A) having three or more ethylenically unsaturated groups is “compound (A)”
  • compound (B) having one ethylenically unsaturated group is “compound (B)”.
  • compound (b1) having one ethylenically unsaturated group may be referred to as “compound (b1)”.
  • the various components appearing in this specification may be used singly or in admixture of two or more.
  • the hard coat film of the present invention is a hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer.
  • the hard coat layer contains a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D). It is formed from a composition for forming a hard coat layer containing.
  • the mass ratio of compound (B)/solvent (D) in the composition for forming a hard coat layer is 0.03 to 0.20.
  • the mixed layer is a layer formed by dissolving or swelling the hard coat layer-forming composition in the triacetyl cellulose film. and a film thickness ratio of the mixed layer to the total film thickness of the hard coat layer and the mixed layer is 65% or more.
  • the triacetylcellulose film used in the present invention may be of an optically transparent grade that can be used as a base material for a polarizing plate or the like, and the thickness of the triacetylcellulose film is not particularly limited. It is about 10 to 500 ⁇ m in terms of workability, thin layer property, etc. 20 to 250 ⁇ m is particularly preferred.
  • the hard coat layer of the present invention comprises a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D). ) is formed from a composition for forming a hard coat layer.
  • the mixed layer is a layer formed by dissolving or swelling a composition for forming a hard coat layer in a triacetyl cellulose film. Furthermore, when the cross section in the thickness direction of the hard coat film is observed with a scanning electron microscope, the thickness ratio of the mixed layer to the total thickness of the hard coat layer and the mixed layer is 65% or more.
  • the film thickness ratio is more preferably 67% or more, and still more preferably 70% or more. Moreover, from the viewpoint of hard coat properties, it is preferably 90% or less.
  • the film thickness ratio of the mixed layer is 65% or more, the interference unevenness can be reduced, the haze of the coating film and the scratch resistance can be prevented, and the adhesion can be improved. That is, it is possible to reduce the interference unevenness and further improve the adhesion while keeping the haze and scratch resistance of the coating film within the practical range. The higher the film thickness ratio, the better the reduction in interference unevenness.
  • a compound (A) having three or more ethylenically unsaturated groups a compound (B) having one ethylenically unsaturated group, and a photopolymerization initiator It is important to use a hard coat layer forming composition containing (C) and solvent (D). Furthermore, it can be controlled by the types of compound (B) and solvent (D) and their contents.
  • the compound (B) is a compound (b1) described later, or/and when the solvent (D) is a solvent (d1) described later, it is particularly preferable because the thickness ratio of the mixed layer is easily made 65% or more. .
  • compound (B) is compound (b1) and solvent (D) is solvent (d1).
  • substrate permeability can be improved by a manufacturing method such as adjusting the concentration of non-volatile matter in the composition for forming a hard coat layer, or allowing the composition for forming a hard coat layer to stand after being applied to a triacetyl cellulose film. It is also possible to increase the film thickness ratio of the mixed layer to 65% by mass or more.
  • composition for forming hard coat layer comprises a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent ( D).
  • Compound (B) is preferably a compound having one ethylenically unsaturated group with a mass change value [(X2)/(X1)] of 1.2 or more, which will be described later.
  • the solvent (D) is preferably a solvent having a haze change value [(Y2)-(Y1)] described later of 0.10 or more.
  • the compound (B) is a compound (b1) having one ethylenically unsaturated group with a mass change value [(X2)/(X1)] of 1.2 or more, and the solvent (D) is It is preferable that the solvent (d1) has a haze change value [(Y2) - (Y1)] of 0.10 or more. This improves the permeability of the base material and is effective in reducing interference unevenness.
  • the non-volatile content of the composition for forming a hard coat layer is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of improving substrate permeability. From the viewpoint of suppressing a decrease in coating film haze, the non-volatile content is preferably 25% by mass or more, more preferably 35% by mass or more.
  • Compound (A) is a compound having three or more ethylenically unsaturated groups.
  • Examples of the compound (A) include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, and PO-modified trimethylolpropane.
  • Compound (A) is pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate in terms of adhesion, scratch resistance, and reliability.
  • acrylates polyurethane poly(meth)acrylates, polyester poly(meth)acrylates, polyether poly(meth)acrylates, and polyacrylic poly(meth)acrylates are preferred, pentaerythritol tri(meth)acrylates, pentaerythritol tetra(meth)acrylates) More preferred are acrylates, dipentaerythritol hexa(meth)acrylates, polyurethane poly(meth)acrylates, and polyester poly(meth)acrylates. These can be combined arbitrarily. In particular, it is preferred to combine polyurethane poly(meth)acrylates with urethane and pentaerythritol poly(meth)acrylates or/and dipentaerythritol poly(meth)acrylates.
  • the content of compound (A) is preferably 25 to 60% by mass, more preferably 35 to 55% by mass, based on 100% by mass of the composition for forming a hard coat layer. Within this range, the strength of the coating film is improved, and a coating film having scratch resistance and reliability can be formed, which is preferable.
  • Compound (B) is a compound having one ethylenically unsaturated group.
  • Examples of the compound (B) include methyl (meth)acrylate, ethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dimethylamino Ester compounds such as ethyl (meth)acrylate and 2-(meth)acryloyloxyethyl acid phosphate; styrene compounds such as styrene and ⁇ -methylene; ⁇ -(me
  • the compound (B) was prepared by adding one ethylenically unsaturated group to the initial mass (X1) of a triacetylcellulose film having a short side of 2 cm, a long side of 4 cm, and a thickness of 80 ⁇ m, and the triacetylcellulose film in an environment of 25°C.
  • a compound (b1) having a mass change value [(X2)/(X1)] of 1.2 or more with respect to the mass (X2) of the triacetylcellulose film after being immersed in 35 g of the compound (B) having is preferable in that the film thickness ratio of the mixed layer can be easily controlled to 65% or more and excellent reduction in interference unevenness can be achieved.
  • the mass change value [(X2)/(X1)] is more preferably 2.0 to 10.0, still more preferably 5.0 or less.
  • the compound (B) that satisfies this condition can further improve the reduction of interference unevenness.
  • a more preferable range of [(X2)/(X1)] is 3.5 to 4.5.
  • Examples of the mass change value [(X2)/(X1)] of compound (B) include acryloylmorpholine (3.9), 4-hydroxybutyl acrylate (2.9), tetrahydrofurfuryl acrylate (1.5), N-vinyl- ⁇ -caprolactam (4.3), diethylacrylamide (5.2), lauryl acrylate (1.0), isobornyl acrylate (1.0), phenoxyethyl acrylate (1.1); Acryloylmorpholine, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, N-vinyl- ⁇ -caprolactam, diethylacrylamide, etc., which are compounds (b1), are preferably used.
  • Acryloylmorpholine, 4-hydroxybutyl acrylate, or N-vinyl- ⁇ -caprolactam is more preferred, and acryloylmorpholine is still more preferred, from the viewpoint of improving substrate permeability and being effective in reducing interference unevenness. is.
  • the lower limit of the content of compound (B) is preferably 3% by mass, more preferably 4% by mass, and still more preferably 5% by mass in the total 100% by mass of compound (A) and compound (B). %.
  • the upper limit of the content of the compound (B) is preferably 30% by mass, more preferably 25% by mass, and 20% by mass in the total 100% by mass of the compound (A) and the compound (B). is more preferable.
  • the content of the compound (B) is 3% by mass or more, the effect of reducing interference unevenness due to permeation into the base material is increased, and when it is 30% by mass or less, the scratch resistance is more excellent, which is preferable.
  • the photopolymerization initiator (C) is not particularly limited as long as it has a function of initiating radical polymerization by photoexcitation. etc. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, N , isoamyl N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like.
  • a known organic amine can also be added as a sensitizer.
  • the amount of the photopolymerization initiator (C) used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass in total of the compound (A) and the compound (B). Within this range, a sufficient polymerization initiation effect can be obtained, which is effective in improving adhesion and scratch resistance.
  • a sensitizer can be used in combination with the photopolymerization initiator (C) in the composition for forming a hard coat layer in the present invention.
  • Examples of sensitizers include amine-based sensitizers, anthracene-based sensitizers, and thioxanthone-based sensitizers.
  • a sensitizer can be used alone or in combination of two or more.
  • Amine sensitizers include, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, N, N-dimethylbenzylamine, 4'-bis(diethylamino)benzophenone and the like.
  • anthracene-based sensitizers include 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-bis(2-ethylhexyloxy)anthracene and the like.
  • thioxanthone sensitizers include thioxanthone sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
  • the sensitizer is preferably a thioxanthone-based sensitizer or the like.
  • a sensitizer When a sensitizer is used, its content is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of compound (A) and compound (B).
  • Solvent (D) is, for example, dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, propylene glycol monomethyl ether.
  • ethers such as Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone; esters such as ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, ⁇ -butyrolactone; In addition, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, Acetylacetone, diacetone alcohol, methyl acetoacetate,
  • the solvent (D) is the initial haze value (Y1) of a triacetyl cellulose film of 10 cm short side ⁇ 10 cm long side ⁇ 80 ⁇ m thick, and the triacetyl cellulose film in an environment of 25 ° C., the solvent (D) is 0. 1 g is dropped and left for 2 minutes, then heated at 60° C. for 1 minute, and then the haze value (Y2) of the triacetyl cellulose film is measured.
  • the obtained haze change value [(Y2) - (Y1)] is 0.10 or more, the film thickness ratio of the mixed layer can be easily controlled to 65% or more, and it can be excellent in reducing interference unevenness. is preferred.
  • the haze change value [(Y2)-(Y1)] is more preferably 0.10 or more and 0.80 or less, and still more preferably 0.45 or less.
  • the solvent (D) that satisfies this condition is effective in improving substrate permeability and reducing interference unevenness without lowering the haze or scratch resistance of the coating film.
  • Examples of the haze change value [(Y2) - (Y1)] of the solvent (D) are dimethyl carbonate (0.15), ethyl acetate (0.47), acetone (0.81), methyl ethyl ketone (0.42). , 1,3-dioxolane (0.48), methyl isobutyl ketone (0.01), isopropyl alcohol (0.04), propylene glycol monomethyl ether (0.00), solvent (d1), dimethyl carbonate , ethyl acetate, acetone, methyl ethyl ketone or 1,3-dioxolane are preferably used. More preferably, dimethyl carbonate, methyl ethyl ketone, 1,3-dioxolane, or ethyl acetate, more preferably dimethyl carbonate or methyl ethyl ketone.
  • the total content of the compound (B) and solvent (D) is preferably 40 to 80% by mass, more preferably 40 to 70% by mass, based on 100% by mass of the composition for forming a hard coat layer. , 45 to 65 mass % is more preferred.
  • it is 40% by mass or more, the substrate permeability is high, and the adhesion is further improved.
  • it is 80% by mass or less, the substrate permeability is not too high, and the coating film has haze or scratch resistance. Aggravation can be further suppressed.
  • the mass ratio of compound (B)/solvent (D) is preferably 0.03 to 0.20, more preferably 0.05 to 0.15. When it is 0.03 or more, the base material permeability is sufficient, and the effect of reducing interference unevenness is further improved. When it is 0.20 or less, the scratch resistance is further improved.
  • composition for forming a hard coat layer in the present invention may contain other additives as necessary.
  • Other additives include, for example, plasticizers, surface conditioners, light stabilizers, antioxidants, and polymerization inhibitors.
  • the hard coat film can be produced by a conventionally known method such as coating a hard coat layer-forming composition on a triacetyl cellulose film, and is not particularly limited.
  • a conventionally known method such as coating a hard coat layer-forming composition on a triacetyl cellulose film, and is not particularly limited.
  • the solvent is dried if necessary.
  • the applied composition for forming a hard coat layer is cross-linked and cured to obtain a hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer.
  • a hard coat film is obtained in which the thickness ratio of the mixed layer to the total thickness of the hard coat layer and the mixed layer is 65% or more. It is also preferable to apply the composition for forming a hard coat layer to a triacetyl cellulose film and allow it to stand still, because this improves the permeability to the substrate and makes it easier for the film thickness ratio of the mixed layer to be 65% by mass or more.
  • Coating methods include bar coating, blade coating, spin coating, reverse coating, dyeing, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, and dipping.
  • the active energy ray it is possible to use electron beams and ultraviolet rays emitted from light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps.
  • light sources such as xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, and tungsten lamps.
  • the thickness of the hard coat layer is not particularly limited as long as it has hard coat properties, and is usually 1 to 20 ⁇ m, preferably 2 to 15 ⁇ m.
  • the total thickness of the hard coat layer and the mixed layer is not particularly limited, but is preferably 0.5 to 100 ⁇ m, more preferably 1.1 to 30 ⁇ m, and still more preferably 1.2 to 25 ⁇ m in order to reduce interference unevenness. be.
  • the thickness of the hard coat film is not particularly limited, it is preferably 50 to 300 ⁇ m, more preferably 81 to 100 ⁇ m, still more preferably 82 to 95 ⁇ m.
  • the mass change value [(X2)/(X1)] of compound (B) was obtained by the following method. First, the initial mass (X1) of a triacetyl cellulose film having a short side of 2 cm, a long side of 4 cm, and a thickness of 80 ⁇ m was measured. Then, this triacetyl cellulose film was immersed in 35 g of compound (B) having one ethylenically unsaturated group in an environment of 25° C. for 2 hours. After that, the triacetylcellulose film was taken out and lightly wiped with Kimtowel, and then the mass (X2) of the triacetylcellulose film was measured. As the triacetylcellulose film, an 80 ⁇ m-thick triacetylcellulose film (manufactured by Fuji Film Co., Ltd.) was used (this film was also used for haze, which will be described later).
  • the haze change value [(Y2)-(Y1)] of the solvent (D) was obtained by the following method. First, the initial haze value (Y1) of a triacetyl cellulose film having a short side of 10 cm, a long side of 10 cm, and a thickness of 80 ⁇ m was determined. Next, 0.1 g of the solvent (D) was added dropwise to the triacetyl cellulose film in an environment of 25° C. and left for 2 minutes. After that, the film was heated at 60° C. for 1 minute, returned to normal temperature, and then the haze value (Y2) of the triacetyl cellulose film was measured.
  • Components A to D used in Table 1 are shown below.
  • ⁇ M405 Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.: Aronix M405, a hexafunctional monomer)
  • ⁇ PET30 Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD PET30, trifunctional monomer)
  • Example 1 As the compound (A), 50 parts of a urethane prepolymer (Kyoeisha Chemical Co., Ltd.: UA-306H, 6-functional urethane acrylate) mainly composed of a 2:1 adduct of pentaerythritol triacrylate and hexamethylene diisocyanate, di Pentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.: Aronix M405, hexafunctional monomer) 30 parts, pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD PET30, trifunctional monomer) 10 parts, as compound (B) , Acryloyl morpholine (manufactured by KJ Chemicals Co., Ltd.: AC ⁇ O, monofunctional monomer) 10 parts, as a photopolymerization initiator (C), diphenyl-2,4,6
  • the resulting composition for forming a hard coat layer was coated on a triacetyl cellulose film (manufactured by Fuji Film Co., Ltd.) with a thickness of 80 ⁇ m using a bar coater No. 10 and dried in a hot air oven for 1 minute.
  • ultraviolet rays were irradiated from a high-pressure mercury lamp with an output of 80 w/cm to cure the coating layer to obtain a hard coat film having a triacetyl cellulose film, a mixed layer, and a hard coat layer.
  • the total thickness of the hard coat layer and mixed layer was 9.0 ⁇ m, and the thickness of the hard coat film was 87.0 ⁇ m.
  • the film thickness ratio of the mixed layer to the total film thickness of the hard coat layer and the mixed layer was 70.5%.
  • Examples 2 to 20 Comparative Examples 1 to 11> As shown in Tables 1 to 3, hard coat layer-forming compositions of Examples 2 to 20 and Comparative Examples 1 to 11 were prepared in the same manner as in Example 1, except that the composition and amount (parts by mass) were changed. was produced to obtain a hard coat film. Tables 1 to 3 show the total thickness of the hard coat layer and mixed layer of the obtained hard coat film, the thickness of the hard coat film, and the thickness ratio of the mixed layer to the total thickness of the hard coat layer and mixed layer. It was shown to.
  • the film thickness ( ⁇ m) of the obtained hard coat film was measured using a Digimicro (manufactured by Nikon, model: MH-15M).
  • Adhesion evaluation 1 A tape adhesion test was carried out using the obtained hard coat film.
  • the tape adhesion test was carried out according to JISK5600. Insert a cutter knife so as to form a total of 100 squares of 10 squares ⁇ 10 squares at intervals of 1 mm width to a depth that reaches the base material but does not cut the hard coat film, and cellophane tape (25 mm width, manufactured by Nichiban Co., Ltd.). was attached to the surface of the coating film, and then the cellophane tape was rapidly peeled off by hand to evaluate the state of the remaining squares.
  • ⁇ Evaluation criteria +++: No peeling (very good). ++: Edges of squares are slightly chipped (good). +: Peeling of 1 to 5 squares is observed (practically no problem). NG: Peeling of 6 squares or more is observed (not practical).
  • Adhesion evaluation 2 After performing the above-mentioned adhesion evaluation 1, a cellophane tape peeling test was additionally performed twice (three times in total) on the same place, and the state of the remaining squares was evaluated according to the following criteria. . ⁇ Evaluation criteria +++: No peeling (very good). ++: Edges of squares are slightly chipped (good). +: Peeling of 1 to 5 squares is observed (practically no problem). NG: Peeling of 6 squares or more is observed (not practical).
  • a compound (A) having three or more ethylenically unsaturated groups, a compound (B) having one ethylenically unsaturated group, a photopolymerization initiator (C), and a solvent (D has a hard coat layer and a mixed layer formed from a hard coat layer-forming composition containing 0.20, and the film thickness ratio of the mixed layer to the total film thickness of the hard coat layer and the mixed layer is 65% or more. It was confirmed that an excellent hard coat film having haze, scratch resistance, interference unevenness, and adhesion was obtained.

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