JP2022017317A - Antiglare hard coat laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antiglare hard coat laminated film which is excellent in antiglare property and scratch resistance, is a device such as a car navigation device that is often used in such an environment that light from the outside is incident on a screen, and is suitable as a member of a device having a touch panel function.

SOLUTION: There is provided a hard coat laminated film which has a layer of a first hard coat, a layer of a second hard coat and a layer of a transparent resin film in order from a surface side, where the first hard coat contains (A) polyfunctional (meth)acrylate of 100 pts.mass; (B) a water-repellent agent of 0.01-7 pts.mass; and (C) a silane coupling agent of 0.01-10 pts.mass, and is formed from a coating material containing no inorganic particles, and the second hard coat is formed from a coating material that contains (A) polyfunctional (meth)acrylate of 100 pts.mass, and (D) inorganic fine particles having an average particle size of 1-300 nm of 50-300 pts.mass.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to an antiglare hardcourt laminated film. More specifically, the present invention relates to an antiglare hard coat laminated film having excellent scratch resistance.

In recent years, car navigation devices equipped with touch panels that are installed on image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays and that allow input by touching with a finger or pen while looking at the display have become available. It is widespread.

In car navigation devices, from the viewpoint of safety in the event of a traffic accident, a plastic display face plate is used to provide a high level of impact resistance and crack resistance, and the surface of the glass display face plate is prevented from scattering. It is widely practiced to bond films together. Further, the image display device of the car navigation device is provided with antiglare property in order to deal with the problem that light from the outside is incident on the screen and the light is reflected to make it difficult to see the displayed image. The antiglare property is imparted by a method of laminating an antiglare hard coat laminated film on the surface of a plastic display face plate or forming an antiglare hard coat on the surface of the shatterproof film.

Many proposals have been made for antiglare hard-coated laminated films (for example, Patent Document 1). However, considering that a touch panel is mounted on a car navigation device, its scratch resistance is insufficient, and an antiglare hard coat that can maintain surface characteristics such as slipperiness even if it is repeatedly wiped with a handkerchief or the like. Laminated films are required.

Japanese Unexamined Patent Publication No. 2010-21150

The subject of the present invention includes members of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (an image display device having a touch panel function and an image display device having no touch panel function), which are excellent in antiglare property. ) Is provided as an antiglare hard coat laminated film. A further subject of the present invention is a device having excellent anti-glare and scratch resistance, which is often used in an environment where external light is incident on the screen, such as a car navigation device, and which has a touch panel function. It is an object of the present invention to provide an antiglare hard coat laminated film suitable as a member of the above.

As a result of diligent research, the present inventor has found that the above-mentioned problems can be achieved by a specific hard-coated laminated film.

That is, the present invention has a first hard coat and a layer of a transparent resin film in order from the surface side.
The above first hard coat is
(A) 100 parts by mass of polyfunctional (meth) acrylate;
(B) Water repellent 0.01 to 7 parts by mass;
(C) 0.01 to 10 parts by mass of silane coupling agent; and (D) 0.1 to 5 parts by mass of resin fine particles having an average particle diameter of 0.5 to 10 μm;
It consists of a paint containing and containing no inorganic particles; it is a hard-coated laminated film.

The second invention has a first hard coat, a second hard coat, and a layer of a transparent resin film in order from the surface side.
The above second hard coat is
(A) 100 parts by mass of polyfunctional (meth) acrylate; and (E) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm;
The hard-coated laminated film according to the first invention.

In the third aspect of the invention, the above-mentioned (C) silane coupling agent comprises one or more selected from the group consisting of a silane coupling agent having an amino group and a silane coupling agent having a mercapto group. The hard coat laminated film according to the invention or the second invention.

The fourth invention is the hard-coated laminated film according to any one of the first to third inventions, wherein the (B) water repellent agent contains a (meth) acryloyl group-containing fluoropolyether-based water repellent agent. ..

In the fifth invention, the hard coat laminate according to any one of the second to fourth inventions, wherein the paint forming the second hard coat further contains (F) 0.01 to 1 part by mass of a leveling agent; It is a film.

The sixth invention is the hard coat laminated film according to any one of the first to fifth inventions, wherein the thickness of the first hard coat is 0.5 to 5 μm.

The seventh invention is the hard coat laminated film according to any one of the second to fifth inventions, wherein the thickness of the second hard coat is 15 to 30 μm.

The eighth invention has a first hard coat, a second hard coat, and a layer of a resin film in order from the surface side.
The first hardcoat above consists of a paint that does not contain inorganic particles;
The second hard coat consists of a paint containing inorganic particles;
A hard-coated laminated film satisfying the following (a) to (c).
(B) Total light transmittance is 85% or more.
(B) The pencil hardness on the surface of the first hard coat is 5H or more.
(C) The Y value of the XYZ color system is 1.5 to 4.2%.

The ninth invention is the hard-coated laminated film according to the eighth invention, which has a minimum bending radius of 40 mm or less.

The tenth invention is the hard coat laminated film according to the eighth invention or the ninth invention, wherein the water contact angle after reciprocating 10,000 times of cotton wiping of the first hard coat surface is 100 degrees or more.

The eleventh invention is the use of the hard-coated laminated film according to any one of the first to tenth inventions as an image display device member.

A twelfth invention is an image display device including the hard-coated laminated film according to any one of the first to tenth inventions.

The antiglare hard coat laminated film of the present invention is excellent in antiglare. The preferred antiglare hardcourt laminated film of the present invention is excellent in antiglare and scratch resistance. Therefore, members of image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays (including image display devices having a touch panel function and image display devices not having a touch panel function), especially on screens of car navigation devices and the like. It is a device often used in an environment where light from the outside is incident, and can be suitably used as a member of a device having a touch panel function.

The antiglare hard coat laminated film of the present invention has a first hard coat and a layer of a transparent resin film in this order from the surface side. The antiglare hard coat laminated film of the present invention preferably has a first hard coat, a second hard coat, and a layer of a transparent resin film in order from the surface side.

1st hard court:
The first hard coat forms the surface of the antiglare hard coat laminated film of the present invention. The first hard coat forms a touch surface when the antiglare hard coat laminated film of the present invention is used as a member of an image display device having a touch panel function. The first hard coat exhibits good anti-glare properties and scratch resistance, and functions to maintain surface properties such as slipperiness even when repeatedly wiped with a handkerchief or the like.

The first hard coat is (A) 100 parts by mass of polyfunctional (meth) acrylate; (B) 0.01 to 7 parts by mass of water repellent; (C) 0.01 to 10 parts by mass of silane coupling agent; and (D) The coating material comprises 0.1 to 5 parts by mass of resin fine particles having an average particle diameter of 0.5 to 10 μm; and does not contain inorganic particles.

Inorganic particles (eg silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; fluoride Metal fluoride particles such as magnesium and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. Inorganic particles with an appropriate particle size also improve antiglare. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes the scratch resistance to be insufficient. Therefore, in the present invention, resin fine particles are used as particles for improving the antiglare property in the first hard coat forming the surface, and the scratch resistance is maintained so as not to contain inorganic particles. The second hard coat solves this problem by impregnating a large amount of specific inorganic fine particles to increase the hardness.

Here, "not containing" the inorganic particles means that the inorganic particles are not contained in a significant amount. In the field of the paint for forming a hard coat, the significant amount of the inorganic particles is usually about 0.1 part by mass or more with respect to 100 parts by mass of the above component (A) from the viewpoint of imparting antiglare property. Therefore, "not containing" means that the amount of inorganic particles is usually less than 0.1 parts by mass, preferably 0.05 parts by mass or less, and more preferably 0, with respect to 100 parts by mass of the component (A). It can be rephrased as less than 0.01 parts by mass.

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule, and has two or more (meth) acryloyl groups in one molecule, so that it can be used for ultraviolet rays, electron beams, etc. It polymerizes and cures with active energy rays to form a hard coat.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 2, Bifunctional reaction containing (meth) acryloyl group such as 2'-bis (4- (meth) acryloyloxypolyethylene oxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropylene oxyphenyl) propane Sexual monomer; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropane tri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate. (Meta) acryloyl group-containing tetrafunctional reactive monomer such as (meth) acryloyl group-containing tetrafunctional reactive monomer; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group-containing octafunctional reactive monomer such as tripentaerythritol acrylate; ; And polymers (oligomers and prepolymers) having one or more of these as constituent monomers can be mentioned. As the component (A), one kind or a mixture of two or more kinds of these can be used.

In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

(B) Water repellent:
The component (B) has a function of enhancing the slipperiness to point, the adhesion prevention property of dirt, and the wiping property of dirt.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicon-based water repellent such as silicone oil, silicone resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; Fluorohydrate-containing water repellents such as fluoropolyether-based water repellents and fluoropolyalkyl-based water repellents; and the like can be mentioned. As the component (B), one kind or a mixture of two or more kinds of these can be used.

Among these, as the component (B), a fluoropolyether-based water repellent is preferable from the viewpoint of water repellency. From the viewpoint of preventing troubles such as bleed-out of the component (B) due to a chemical bond or strong interaction between the component (A) and the component (B), the component (B) may be contained in the molecule. A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter, abbreviated as a (meth) acryloyl group-containing fluoropolyether-based water repellent) is more preferable. Further preferable as the component (B) is from the viewpoint of appropriately adjusting the chemical bond or interaction between the component (A) and the component (B) to develop good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether-based water repellent and a meta-acryloyl group-containing fluoropolyether-based water repellent.

The (meth) acryloyl group-containing fluoropolyether-based water repellent is clearly distinguished from the above-mentioned component (A) in that it contains a fluoropolyether group in the molecule. The compound having two or more (meth) acryloyl groups in one molecule and having a fluoropolyether group is a (meth) acryloyl group-containing fluoropolyether-based water repellent and is the above-mentioned component (B). ..

The blending amount of the component (B) is usually 7 parts by mass or less, preferably 4 parts by mass, from the viewpoint of preventing troubles such as bleeding out of the component (B) with respect to 100 parts by mass of the component (A). Parts or less, more preferably 2 parts by mass or less. On the other hand, from the viewpoint of obtaining the effect of using the component (B), it is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more.

(C) Silane coupling agent:
The component (C) functions to improve the adhesion between the first hard coat and the transparent resin film or the second hard coat.

The silane coupling agent includes a hydrolyzable group (for example, an alkoxy group such as a methoxy group and an ethoxy group; an acyloxy group such as an acetoxy group; a halogen group such as a chloro group; etc.), and an organic functional group (for example, an amino group, etc.). A silane compound having at least two different reactive groups (such as a mercapto group, a vinyl group, an epoxy group, a methacrylox group, an acryloxy group, and an isocyanate group). Among these, the above-mentioned component (C) includes a silane coupling agent having an amino group (a silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group (from the viewpoint of adhesion). A silane compound having a mercapto group and a hydrolyzable group) is preferable. From the viewpoint of adhesion and odor, a silane coupling agent having an amino group is more preferable.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2. -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

As the component (C), one or a mixture of two or more of these can be used.

The blending amount of the component (C) is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, from the viewpoint of surely obtaining the adhesiveness improving effect with respect to 100 parts by mass of the component (A). More preferably, it is 0.1 part by mass or more. On the other hand, from the viewpoint of the pot life of the paint, it may be usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less.

(D) Resin fine particles having an average particle diameter of 0.5 to 10 μm:
The above component (D) imparts antiglare property to the antiglare hard coat laminated film of the present invention, and even if light from the outside is incident on the screen of the image display device and this light is reflected, the display image is displayed. It works to make the image visible.

Examples of the resin fine particles include resin fine particles such as silicon-based resin, styrene-based resin, acrylic resin, fluororesin, polycarbonate-based resin, ethylene-based resin, and a cured resin of an amino-based compound and formaldehyde. .. Among these, fine particles of silicon-based resin, acrylic-based resin, and fluorine-based resin are preferable from the viewpoint of low specific density, lubricity, dispersibility, and solvent resistance. Further, from the viewpoint of improving the light diffusivity, a spherical one is preferable. As the resin fine particles, one kind or a mixture of two or more kinds of these can be used.

The average particle size of the component (D) is usually 0.5 μm or more, preferably 1 μm or more, from the viewpoint of surely obtaining antiglare property. On the other hand, from the viewpoint of maintaining the transparency of the hard coat, it is usually 10 μm or less, preferably 6 μm or less.

In the present specification, the average particle size of the resin fine particles is determined from the smaller particle size in the particle size distribution curve measured using the laser diffraction / scattering type particle size analyzer "MT3200II (trade name)" of Nikkiso Co., Ltd. The particle size is such that the cumulative total of 50% by mass is 50% by mass.

The blending amount of the component (D) is usually 0.1 to 10 parts by mass, preferably 0.2 by mass, although it depends on the level of antiglare to be imparted to 100 parts by mass of the component (A). It is up to 5 parts by mass, more preferably 0.3 to 3 parts by mass. Further, from the viewpoint of scratch resistance, it may be preferably 0.5 to 3 parts by mass.

The first hard coat forming paint is a compound having two or more isocyanate groups (-N = C = O) in one molecule and / or photopolymerization initiation from the viewpoint of improving the curability by active energy rays. It is preferable to further include the agent.

Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexylisocyanate; trimethylolpropaneadductate of tolylene diisocyanate, trimethylolpropaneadductate of hexamethylenediisocyanate, and trimethylol of isophorone diisocyanate. Polyisocyanate such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethane such as block type isocyanate of the above polyisocyanate. A cross-linking agent or the like can be given. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more of these can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as needed.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzophenone compounds such as ethyl ether, benzoin isopropyl ether and benzylmethyl ketal; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenylketone; methylanthraquinone, 2-ethylanthraquinone, 2 -Anthraquinone compounds such as amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-dipropylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenone compounds such as acetophenone dimethylketal; triazine compounds; biimidazole compounds; acylphos Examples thereof include finoxide-based compounds; titanosen-based compounds; oxime ester-based compounds; oximuphenyl acetate-based compounds; hydroxyketone-based compounds; and aminobenzoate-based compounds. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The paint for forming the first hard coat includes, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and the like. One or more additives such as a light-resistant stabilizer, an ultraviolet absorber, a heat stabilizer, and an organic colorant can be contained.

The first hard coat forming paint may contain a solvent, if desired, in order to dilute it to a concentration that is easy to apply. The solvent is particularly limited as long as it does not react with the components (A) to (D) and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like. As the solvent, one kind or a mixture of two or more kinds of these can be used.

The first hard coat forming paint can be obtained by mixing and stirring these components.

The method for forming the first hard coat using the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The thickness of the first hard coat is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 1.5 μm or more, from the viewpoint of scratch resistance and surface hardness. On the other hand, from the viewpoint of antiglare property, surface hardness, adhesion, and bending resistance, it is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less.

Second hard court:
The antiglare hard coat laminated film of the present invention preferably has a first hard coat, a second hard coat, and a layer of a transparent resin film in order from the surface side. The second hard coat serves to increase the hardness of the antiglare hard coat laminated film of the present invention, thereby increasing the surface hardness. The second hard coat comprises a coating material containing (A) 100 parts by mass of polyfunctional (meth) acrylate; and (E) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm.

The (A) polyfunctional (meth) acrylate is described above in the description of the first hard coat forming paint. As the component (A), one kind or a mixture of two or more kinds of these can be used.

(E) Inorganic fine particles with an average particle diameter of 1 to 300 nm:
The component (E) has a function of dramatically increasing the hardness of the hard-coated laminated film of the present invention.

Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; Examples thereof include metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles; and metal fine particles; and the like.

Among these, silica and aluminum oxide fine particles are preferable, and silica fine particles are more preferable, in order to obtain a hard coat having a higher hardness. Examples of commercially available silica fine particles include Snowtex (trade name) of Nissan Chemical Industries, Ltd. and Quattron (trade name) of Fuso Chemical Industries, Ltd.

A silane coupling agent such as vinylsilane and aminosilane; a titanate-based coupling agent; Aluminate-based coupling agents; organic compounds having reactive functional groups such as ethylenically unsaturated bonding groups such as (meth) acryloyl group, vinyl group, and allyl group and epoxy groups; and surfaces of fatty acids, fatty acid metal salts, etc. It is preferable to use one treated with a treatment agent or the like.

As the component (E), one kind or a mixture of two or more kinds of these can be used.

The average particle size of the component (E) is 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of maintaining the transparency of the hard coat and surely obtaining the hardness improving effect. On the other hand, although there is no particular lower limit on the average particle size, the inorganic fine particles that are usually available are at most about 1 nm.

In the present specification, the average particle size of the inorganic fine particles is determined from the smaller particle in the particle size distribution curve measured using the laser diffraction / scattering type particle size analyzer "MT3200II (trade name)" of Nikkiso Co., Ltd. The particle size is such that the cumulative total of 50% by mass is 50% by mass.

The blending amount of the component (E) is 50 parts by mass or more, preferably 80 parts by mass or more, with respect to 100 parts by mass of the component (A) from the viewpoint of hardness. On the other hand, from the viewpoint of transparency, it is 300 parts by mass or less, preferably 200 parts by mass or less, and more preferably 160 parts by mass or less.

(F) Leveling agent:
It is preferable that the paint for forming the second hard coat further contains (F) a leveling agent from the viewpoint of smoothing the surface of the second hard coat and facilitating the formation of the first hard coat.

Examples of the leveling agent include an acrylic leveling agent, a silicon-based leveling agent, a fluorine-based leveling agent, a silicon-acrylic copolymer-based leveling agent, a fluorine-modified acrylic-based leveling agent, a fluorine-modified silicon-based leveling agent, and functional groups thereof. Examples include leveling agents into which a group (for example, an alkoxy group such as a methoxy group or an ethoxy group, an acyloxy group, a halogen group, an amino group, a vinyl group, an epoxy group, a methacrylate group, an acryloxy group, an isocyanate group, etc.) has been introduced. Can be done. Among these, as the component (F), a silicon-acrylic copolymer system leveling agent is preferable. As the component (F), one kind or a mixture of two or more kinds of these can be used.

The blending amount of the component (F) is usually 0 from the viewpoint of smoothing the surface of the second hard coat with respect to 100 parts by mass of the component (A) and facilitating the formation of the first hard coat. It is 0.01 part by mass or more, preferably 0.1 part by mass or more, and more preferably 0.2 part by mass or more. On the other hand, from the viewpoint of enabling the paint for forming the first hard coat to be satisfactorily applied onto the second hard coat without being repelled, it is more than 1 part by mass, preferably 0.6 parts by mass or less. It may be preferably 0.4 parts by mass or less.

The coating material for forming the second hard coat includes a compound having two or more isocyanate groups (-N = C = O) in one molecule and / or photopolymerization initiation from the viewpoint of improving the curability by active energy rays. It is preferable to further include the agent.

The compound having two or more isocyanate groups in one molecule is described above in the description of the first hard coat forming paint. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more of these can be used.

The photopolymerization initiator is described above in the description of the first hard coat forming paint. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The paint for forming the second hard coat includes, if desired, an antistatic agent, a surfactant, a thixo property-imparting agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light resistance stability. It can contain one or more additives such as agents, ultraviolet absorbers, heat stabilizers, colorants, and resin fine particles.

The second hard coat forming paint may contain a solvent, if desired, in order to dilute it to a concentration that is easy to apply. If the solvent does not react with the component (A), the component (E), and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. There are no particular restrictions. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like. Of these, 1-methoxy-2-propanol is preferable. As the solvent, one kind or a mixture of two or more kinds of these can be used.

The second hard coat forming paint can be obtained by mixing and stirring these components.

The method for forming the second hard coat using the second hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

From the viewpoint of hardness, the thickness of the second hard coat is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 18 μm or more. On the other hand, from the viewpoint of curl resistance and bending resistance, it is preferably 30 μm or less, more preferably 27 μm or less, still more preferably 25 μm or less.

Transparent resin film:
The transparent resin film is a layer serving as a transparent film base material for forming the first hard coat, or the first hard coat and the second hard coat on the first hard coat. The transparent resin film is not limited except that it has high transparency and is not colored, and any transparent resin film can be used. Examples of the transparent resin film include cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymers; methyl polymethacrylate, ethyl polymethacrylate, and the like. And acrylic resins such as vinylcyclohexane and methyl (meth) acrylate copolymers; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; Examples include films such as polymer-type urethane acrylate-based resins; and polyimide-based resins; These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, these films include a laminated film in which one or more of these one or more are laminated in two or more layers.

The thickness of the transparent resin film is not particularly limited and may be any thickness as desired. From the viewpoint of handleability of the antiglare hard-coated laminated film of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. When the antiglare hardcourt laminated film of the present invention is used in an application that does not require high rigidity, it may be usually 250 μm or less, preferably 150 μm or less, from the viewpoint of economy. When the hard-coated laminated film of the present invention is used as a display face plate of a car navigation device, it may be usually 100 μm or more, preferably 200 μm or more, and more preferably 300 μm or more from the viewpoint of maintaining rigidity. Further, from the viewpoint of meeting the demand for thinning of the apparatus, it may be usually 1500 μm or less, preferably 1200 μm or less, and more preferably 1000 μm or less.

The transparent resin film is preferably an acrylic resin transparent resin film.

Examples of the acrylic resin include (meth) acrylic acid ester (co) polymer, copolymer containing (meth) acrylic acid ester, and modified products thereof. In addition, (meth) acrylic means acrylic or methacrylic. Further, the (co) polymer means a polymer or a copolymer.

Examples of the (meth) acrylate (co) polymer include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, and butyl poly (meth) acrylate. Examples thereof include methyl (meth) acrylate / butyl acrylate (meth) acrylate, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, and the like.

Examples of the copolymer containing the structural unit derived from the (meth) acrylic acid ester include ethylene / (meth) acrylic acid methyl copolymer, styrene / (meth) acrylic acid methyl copolymer, vinyl cyclohexane / (. Examples thereof include a methyl acrylate copolymer, a maleic anhydride / methyl (meth) acrylate copolymer, and an N-substituted maleimide / methyl (meth) acrylate copolymer.

Examples of the modified product include a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which glutaric anhydride is introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl). A polymer having an imide structure introduced by reacting with an amine, cyclohexylamine, ammonia, etc. (hereinafter, may be referred to as a poly (meth) acrylicimide-based resin); etc. Can be done.

Examples of the transparent resin film of the acrylic resin include a film of one or a mixture of two or more of these. Further, these films include a laminated film in which one or more of these one or more are laminated in two or more layers.

The transparent resin film is more preferably a film of a vinylcyclohexane / methyl (meth) acrylate copolymer. It is an antiglare hard coat laminated film having excellent surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, and moisture resistance, and can be suitably used as a display face plate of a touch panel.

The transparent resin film is more preferably a poly (meth) acrylicimide-based resin film. It is an anti-glare hard coat laminated film with excellent surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and heat resistance dimensional stability, and is suitable as a display face plate for touch panels and transparent conductive substrates. Can be used.

The yellowness index of the acrylic resin (measured using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981) is preferably 3 or less, more preferably 2. Hereinafter, it is more preferably 1 or less. By using an acrylic resin having a yellowness index of 3 or less, an antiglare hard-coated laminated film that can be suitably used as a member of an image display device can be obtained. The lower the yellowness index, the more preferable.

The melt mass flow rate of the acrylic resin (measured at 260 ° C. and 98.07N according to ISO1133) is preferably 0.1 to 20 g / 10 minutes from the viewpoint of extrusion load and stability of the molten film. It is preferably 0.5 to 10 g / 10 minutes.

Further, the acrylic resin may be a thermoplastic resin other than the acrylic resin; a pigment, an inorganic filler, an organic filler, a resin filler; a lubricant, an antioxidant, and weather resistance stability, if desired, to the extent that it does not contradict the object of the present invention. Additives such as agents, heat stabilizers, mold release agents, antistatic agents, and surfactants; and the like can be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the acrylic resin is 100 parts by mass.

The transparent resin film is more preferably a transparent multilayer film in which a first acrylic resin layer (α1); an aromatic polycarbonate resin layer (β); a second acrylic resin layer (α2); are directly laminated in this order. It is a film. In the present specification, the present invention will be described assuming that the touch surface is formed on the α1 layer side.

Acrylic resins have excellent surface hardness but tend to have insufficient machinability, whereas aromatic polycarbonate resins have excellent machinability but tend to have insufficient surface hardness. .. Therefore, by using the transparent multilayer film having the above-mentioned layer structure, it becomes possible to easily obtain an antiglare hard-coated laminated film having excellent surface hardness and machinability by compensating for the weaknesses of both. ..

The layer thickness of the α1 layer is not particularly limited, but from the viewpoint of the surface hardness of the antiglare hard-coated laminated film of the present invention, it is usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more, still more preferably 80 μm or more. May be.

The layer thickness of the α2 layer is not particularly limited, but is preferably the same as the α1 layer from the viewpoint of curl resistance of the antiglare hard-coated laminated film of the present invention.

Here, "same layer thickness" should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be interpreted as the same layer thickness within the range of the fluctuation range of the process and quality control that is usually performed industrially. This is because the curl resistance of the multilayer film can be kept good if the layer thickness is the same within the range of the fluctuation width of the process / quality control that is usually performed industrially. In the case of a non-stretched multilayer film by the T-die coextrusion method, the process and quality control are usually performed with a width of about -5 to +5 μm, so the layer thickness of 65 μm and 75 μm should be interpreted as the same. be.

The thickness of the β layer is not particularly limited, but may be usually 20 μm or more, preferably 80 μm or more, from the viewpoint of cutting resistance of the antiglare hard-coated laminated film of the present invention.

The acrylic resin used for the α1 layer and the α2 layer is described above.

The acrylic resin used for the α1 layer and the acrylic resin used for the α2 layer may have different resin characteristics, for example, different acrylic resins such as type, melt mass flow rate, and glass transition temperature. However, from the viewpoint of curl resistance of the antiglare hard coat laminated film of the present invention, it is preferable to use one having the same resin characteristics. For example, using the same lot of the same grade is one of the preferred embodiments.

Examples of the aromatic polycarbonate-based resin used for the β layer include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and phosgen. Polymers obtained by the interfacial polymerization method with; aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and carbonic acid such as diphenylcarbonate. A polymer obtained by an ester exchange reaction with a diester; or a mixture of two or more aromatic polycarbonate-based resins can be used.

As a preferable optional component that can be contained in the aromatic polycarbonate-based resin, core-shell rubber can be mentioned. When the total of the aromatic polycarbonate resin and the core shell rubber is 100 parts by mass, the core shell rubber is 0 to 30 parts by mass (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably 0 to 10 parts by mass (aromatic). By using the amount of the polycarbonate resin (100 to 90 parts by mass), the cutting work resistance and the impact resistance can be further improved.

Examples of the core-shell rubber include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include core-shell rubbers such as acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. As the core-shell rubber, one kind or a mixture of two or more kinds of these can be used.

Further, the aromatic polycarbonate resin may be a thermoplastic resin other than the aromatic polycarbonate resin and the core shell rubber, if desired, to the extent not contrary to the object of the present invention; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, Additives such as antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants; and the like can be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

The method for producing the transparent resin film is not particularly limited. As a preferable manufacturing method when the transparent resin film is a poly (meth) acrylicimide-based resin film, the method described in JP-A-2015-033844 can be mentioned. When the transparent resin film is a transparent multilayer film in which the first acrylic resin layer (α1); the aromatic polycarbonate resin layer (β); the second acrylic resin layer (α2); are directly laminated in this order. As a preferable manufacturing method, the method described in Japanese Patent Application Laid-Open No. 2015-0833370 can be mentioned. Further, when forming the hard coat, the hard coat forming surface or both sides of the transparent resin film may be subjected to an easy adhesion treatment such as a corona discharge treatment or an anchor coat formation in advance in order to increase the adhesive strength with the hard coat. ..

It is more preferable that the antiglare hard coat laminated film of the present invention has the first hard coat, the second hard coat, the layer of the transparent resin film, and the third hard coat in order from the surface side. By forming the third hard coat, the force to curl the antiglare hard coat laminated film to one side (hereinafter, may be abbreviated as curl force) and the force to curl to the other side are obtained. Both will work. Then, the occurrence of curl can be suppressed by offsetting these two curl forces so that they become zero.

Further, in recent years, for the purpose of reducing the weight of an image display device, a touch panel having a two-layer structure (so-called one-glass solution) in which a touch sensor is directly formed on the back side of a display face plate has been proposed. A one-plastic solution that replaces the so-called one-glass solution has also been proposed for further weight reduction. When the antiglare hard-coated laminated film of the present invention is used in a one-plastic solution that replaces the so-called one-glass solution, the third hard coat is formed to obtain suitable characteristics as a printed surface. It becomes easy to give.

The antiglare hardcourt laminated film of the present invention has an arbitrary layer other than the first hardcoat, the second hardcoat, the transparent resin film layer, and the third hardcoat, if desired. May be good. Examples of the optional layer include a hard coat other than the first to third hard coats, an anchor coat, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer. be able to.

FIG. 1 is a conceptual diagram of a cross section showing an example of the antiglare hardcourt laminated film of the present invention. From the touch surface side, the first hard coat 1, the second hard coat 2, the first poly (meth) acrylicimide-based resin layer (α1) 3, the aromatic polycarbonate-based resin layer (β) 4, and the second poly (meth). ) It has an acrylicimide-based resin layer (α2) 5 and a third hard coat 6.

The antiglare hard coat laminated film of the present invention has a total light transmittance (measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Kogyo Co., Ltd. according to JIS K 7631-1: 1997). It is preferably 85% or more, more preferably 88% or more, still more preferably 90% or more. Since the total light transmittance is 85% or more, the antiglare hard-coated laminated film of the present invention can be suitably used as an image display device member. The higher the total light transmittance, the more preferable.

The antiglare hard coat laminated film of the present invention has a Y value of an XYZ display system based on a double field (Shimazu Seisakusho Co., Ltd. specular photometer "SolidSpec-3700 (trade name)" and a reflection unit "absolute reflectance measuring device". Using an incident angle of 5 ° (trade name), according to the instructions of the spectrophotometer above, 5 degree specular reflection (install a reflection unit in front of the integrating sphere. The value of specular reflection excluding diffused light). ) Is usually 4.2% or less, preferably 3.0% or less, and more preferably 2.0% or less from the viewpoint of antiglare. On the other hand, from the viewpoint of preventing the displayed image from becoming white-brown, it is usually 1.5% or more, preferably 2.0% or more.

The antiglare hard coat laminated film of the present invention is measured by Haze (measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K 7136: 2000). From the viewpoint, it may be usually 3% or more, preferably 5% or more, although it depends on the level of antiglare to be imparted. On the other hand, from the viewpoint of preventing the displayed image from becoming white-brown, it may be usually 30% or less, preferably 25% or less.

The antiglare hard coat laminated film of the present invention is a pencil "Uni (trade name)" of Mitsubishi Pencil Co., Ltd. under the condition of a 750 g load according to the pencil hardness of the surface of the first hard coat (JIS K 5600-5-4). It is preferably 5H or more, more preferably 6H or more, and further preferably 7H or more. When the pencil hardness is 5H or more, the antiglare hard-coated laminated film of the present invention can be suitably used as an image display device member. The higher the pencil hardness, the better.

The antiglare hard-coated laminated film of the present invention has a minimum bending radius of preferably 40 mm or less, more preferably 35 mm or less, still more preferably 30 mm or less. When the minimum bending radius is preferably 40 mm or less, the antiglare hard-coated laminated film of the present invention can be easily handled as a film roll, which is advantageous in terms of manufacturing efficiency and the like. The smaller the minimum bending radius is, the more preferable. Here, the minimum bending radius is a value measured according to the test (e) of the following example.

The minimum bending radius is the bending radius immediately before cracks occur on the surface of the bent portion when the antiglare hard-coated laminated film is bent, and is an index indicating the limit of bending. The bending radius is defined in the same way as the radius of curvature.

The radius of curvature is defined as follows. The length of the curve from point M to point N is ΔS; the difference between the inclination of the tangent at point M and the inclination of the tangent at point N is Δα; the straight line that is perpendicular to the tangent at point M and intersects at point M. , The curve from point M to point N can be approximated to an arc when ΔS is sufficiently small, where O; is perpendicular to the tangent at point N and the point of intersection with the straight line intersecting at point N. (Fig. 2). The radius at this time is defined as the radius of curvature. If the radius of curvature is R, then ∠MON = Δα, and when ΔS is sufficiently small, Δα is also sufficiently small, so ΔS = RΔα holds, and R = ΔS / Δα.

In the antiglare hard coat laminated film of the present invention, the water contact angle of the surface of the first hard coat is preferably 100 degrees or more, more preferably 105 degrees or more. When the antiglare hard coat laminated film of the present invention is used as a member of a display device having a touch panel function, the first hard coat forms a touch surface. When the water contact angle of the surface of the first hard coat is 100 degrees or more, the touch panel can be operated by sliding a finger or a pen on the touch surface as desired. From the viewpoint of sliding a finger or a pen as desired, a high water contact angle is preferable, and there is no particular upper limit to the water contact angle, but from the viewpoint of pointing slipperiness, about 120 degrees is usually sufficient. Here, the water contact angle is a value measured according to the test (to) of the following example.

The antiglare hard coat laminated film of the present invention preferably has a water contact angle of 100 degrees or more after reciprocating 7500 times of cotton wiping on the surface of the first hard coat. More preferably, the water contact angle after wiping with cotton 10,000 times reciprocating is 100 degrees or more. Since the water contact angle after wiping with cotton 7500 times reciprocating is 100 degrees or more, surface characteristics such as slipperiness can be maintained even if the water is repeatedly wiped with a handkerchief or the like. It is preferable that the number of cotton wipes that can maintain a water contact angle of 100 degrees or more is large. Here, the water contact angle after wiping with cotton is a value measured according to the test (g) of the following Example.

The yellowness index of the antiglare hard coat laminated film of the present invention (measured using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation according to JIS K 7105: 1981) is preferably 3. Below, it is more preferably 2 or less, still more preferably 1 or less. When the yellowness index is 3 or less, the antiglare hard-coated laminated film of the present invention can be suitably used as an image display device member. The lower the yellowness index, the more preferable.

Production method:
The method for producing the antiglare hard-coated laminated film of the present invention is not particularly limited and can be produced by any method. As a preferable manufacturing method, for example, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example.
(1) A step of forming a wet coating film made of the second hard coat forming paint on the transparent resin film;
(2) An active energy ray is applied to the wet coating film made of the second hard coat forming paint, and the integrated light amount is 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , more preferably 10 to 160 mJ / cm. ² , more preferably 20 to 120 mJ / cm ² , most preferably 30 to 100 mJ / cm ² , and the wet coating film made of the second hard coat forming paint is applied in a dry state to the touch. The process of making a film;
(3) A step of forming a wet coating film made of the first hard coat forming paint on the paint film in a dry state to the touch made of the second hard coat forming paint; and (4) the first one. The wet coating film made of the paint for forming a hard coat is preheated to a temperature of 30 to 100 ° C., preferably a temperature of 40 to 85 ° C., more preferably a temperature of 50 to 75 ° C. ^2. A method including a step of irradiating to a temperature of 320 to 5000 mJ / cm ² , more preferably 360 to 2000 mJ / cm ² , can be mentioned.

In the step (1), the method for forming the wet coating film made of the second hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The wet coating film made of the second hard coat forming paint formed in the step (1) is in a dry state to the touch or in a non-tacky state in the step (2), and directly touches the web device. However, it does not cause handling problems such as sticking. Therefore, in the next step (3), a wet coating film made of the first hard coat forming paint is formed on the touch-dried coating film made of the second hard coat forming paint. Will be able to.

In the present specification, "the coating film is in a dry state to the touch (non-tacking state)" means that there is no problem in handling even if the coating film comes into direct contact with the web device. ..

The irradiation of the active energy rays in the above step (2) depends on the characteristics of the paint used as the second hard coat forming paint, but from the viewpoint of ensuring that the coating film is in a dry state to the touch, the integrated light amount is usually 1J. It is carried out so as to be / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, further preferably 20 mJ / cm ² or more, and most preferably 30 mJ / cm ² or more. On the other hand, from the viewpoint of the adhesion between the first hard coat and the second hard coat, the integrated light amount is usually 230 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 160 mJ / cm ² or less, still more preferable. Is 120 mJ / cm ² or less, most preferably 100 mJ / cm ² or less.

It is preferable to pre-dry the wet coating film made of the second hard coat forming paint before irradiating the active energy rays in the step (2). In the pre-drying, for example, it takes about 0.5 to 10 minutes to pass the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150 ° C, preferably a temperature of 50 to 120 ° C. This can be done by passing at a line speed, preferably 1 to 5 minutes.

When irradiating the active energy rays in the step (2), the wet coating film made of the second hard coat forming paint may be preheated to a temperature of 40 to 120 ° C, preferably a temperature of 70 to 100 ° C. The coating film can be reliably dried to the touch. The above preheating method is not particularly limited and can be performed by any method. An example of a specific method will be described later in the description of the following step (4).

In the step (3), the method for forming the wet coating film made of the first hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

The wet coating film made of the first hard coat forming paint formed in the step (3) is completely cured in the step (4). At the same time, the coating film made of the second hard coat forming paint is also completely cured.

Although it is not intended to be bound by theory, it is possible to improve the adhesion between the first hard coat and the second hard coat by the above method by irradiating the irradiation with active energy rays in the above step (2). Is sufficient to make the coating film dry to the touch, but the integrated light intensity is insufficient to completely cure the coating film, and the integrated light intensity sufficient to completely cure the coating film for the first time in the above step (4). It is presumed that this is because the complete curing of both hard coats is achieved at the same time.

The irradiation of the active energy rays in the above step (4) has an integrated light amount of 240 mJ / cm ² or more, preferably 320 mJ, from the viewpoint of completely curing the coating film and the adhesion between the first hard coat and the second hard coat. It is performed so as to be / cm ² or more, more preferably 360 mJ / cm ² or more. On the other hand, from the viewpoint of preventing the obtained hard-coated laminated film from becoming yellowish and from the viewpoint of cost, the integrated light amount is 10,000 mJ / cm ² or less, preferably 5000 mJ / cm ² or less, more preferably 2000 mJ / cm ² . Do as follows.

It is preferable to pre-dry the wet coating film made of the first hard coat forming paint before irradiating the active energy rays in the step (4). In the pre-drying, for example, it takes about 0.5 to 10 minutes to pass the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150 ° C, preferably a temperature of 50 to 120 ° C. This can be done by passing at a line speed, preferably 1 to 5 minutes.

When irradiating the active energy rays in the step (4), the wet coating material composed of the first hard coat forming paint has the characteristics of the first hard coat forming paint and the second hard coat forming paint. From the viewpoint of obtaining good interlayer adhesion strength, the temperature is preheated to a temperature of 30 to 100 ° C., preferably a temperature of 40 to 85 ° C., and more preferably a temperature of 50 to 75 ° C. The method of preheating is not particularly limited, and any method can be used. For example, as shown in FIG. 3, a method of controlling the surface temperature of a roll to a predetermined temperature by holding a web in a roll facing the active energy ray irradiator; the periphery of the active energy ray irradiator is surrounded by an irradiation furnace and inside the irradiation furnace. A method of controlling the temperature of the above to a predetermined temperature; and a combination thereof can be mentioned.

After the above step (4), an aging process may be performed. The characteristics of the antiglare hardcourt laminated film can be stabilized.

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Measurement method (a) Total light transmittance:
Measurement was performed using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7631-1: 1997.

(B) Y value of XYZ display system based on double field of view:
Using the spectrophotometer "SolidSpec-3700 (trade name)" of Shimadzu Corporation and the reflection unit "absolute reflectance measuring device incident angle 5 ° (trade name)", follow the instructions of the spectrophotometer above and follow the instructions of the spectrophotometer. The measurement was performed under the condition of normal reflection (a reflection unit is installed in front of the integrating sphere).

(C) Haze:
According to JIS K 7136: 2000, the measurement was performed using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd.

(D) Pencil hardness:
According to JIS K 5600-5-4, the first hard-coated surface of the antiglare hard-coated laminated film was measured using a pencil "Uni (trade name)" of Mitsubishi Pencil Co., Ltd. under the condition of a load of 750 g.

(E) Minimum bending radius:
Bending at a bending temperature of 23 ° C ± 2 ° C for a test piece whose condition was adjusted for 24 hours at a temperature of 23 ° C ± 2 ° C and a relative humidity of 50 ± 5% with reference to the bending formability (method B) of JIS-K6902: 2007. The line was set in a direction perpendicular to the machine direction of the antiglare hardcoat laminated film, and was bent so that the first hardcoat of the antiglare hardcoat laminated film was on the outside to form a curved surface. Among the molded jigs in which cracks did not occur, the radius of the front portion of the one having the smallest radius of the front portion was defined as the minimum bending radius. This "front portion" means the same term for a molded jig in method B as defined in JIS K6902: 2007, paragraph 18.2.

(To) Water contact angle:
A method of calculating the first hard-coated surface of the anti-glare hard-coated laminated film from the width and height of water droplets using the automatic contact angle meter "DSA20 (trade name)" manufactured by KRUSS (JIS R 3257: 1999). See.).

(G) Scratch resistance 1 (water contact angle after cotton wiping):
A test piece with a size of 150 mm in length and 50 mm in width and collected so that the machine direction of the antiglare hardcoat laminated film is the vertical direction of the test piece is surfaced by the first hardcoat of the antiglare hardcoat laminated film. A stainless steel plate placed on a JIS L 0849: 2013 Gakushin tester and covered with four layers of gauze (Medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) on the friction terminals of the Gakushin tester. (Vertical 10 mm, horizontal 10 mm, thickness 1 mm) is attached, set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, a load of 350 g is placed, and the first hard coat surface of the test piece is moved to the friction terminal. After rubbing 10,000 times reciprocating under the conditions of 60 mm and a speed of 1 reciprocating / sec, the water contact angle of the cotton wiping portion was measured according to the above method (to). When the water contact angle was 100 degrees or more, after rubbing it back and forth 5,000 times, the work of measuring the water contact angle of the cotton-wiping part was repeated according to the method of (f) above, and the evaluation was made according to the following criteria. ..
A: The water contact angle is 100 degrees or more even after 10,000 round trips.
B: The water contact angle is 100 degrees or more after 7,500 round trips, but less than 100 degrees after 10,000 times.
C: The water contact angle is 100 degrees or more after 5000 round trips, but less than 100 degrees after 7500 rounds.
D: Water contact angle is less than 100 degrees after 5000 round trips.

(H) Scratch resistance 2 (steel wool resistance):
The antiglare hardcourt laminated film was placed on a JIS L 0849: 2013 Gakushin type tester so that the first hardcoat was on the surface. Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type tester, a load of 500 g was applied, the surface of the test piece was rubbed 100 times reciprocatingly, and then the friction portion was visually observed. When no scratches were found, after rubbing 50 times back and forth, the work of visually observing the rubbed portion was repeated and evaluated according to the following criteria.
A: No scratches are found even after 200 round trips.
B: No scratches are found after 150 round trips, but scratches can be seen after 200 round trips.
C: No scratches are found after 100 round trips, but scratches can be seen after 150 round trips.
D: The scratch can be recognized after 100 round trips.

(I) Yellowness index;
Measurement was performed using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981.

(N) Surface smoothness (surface appearance):
The surfaces (both surfaces) of the antiglare hard-coated laminated film were visually observed while applying various angles of incidence of the light of the fluorescent lamp, and evaluated according to the following criteria.
⊚: There are no waviness or scratches on the surface. Even if you look through the light up close, there is no unevenness or bumps.
◯: If you look through the light up close, there are some spots with slight unevenness. However, there are no swells, scratches, or bumps.
Δ: When viewed up close, slight waviness and scratches are observed on the surface. There are also unevenness and lumps.
X: Many swells and scratches can be seen on the surface. There are also obvious unevenness and bumps.

(Le) Go board test (adhesion):
According to JIS K 5600-5-6: 1999, make 100 squares (1 square = 1 mm x 1 mm) of notches in the grid from the first hard coat surface side in the antiglare hard coat laminated film, and then apply the adhesion test tape. It was pasted on a grid, squeezed with a finger, and then peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standards.
Classification 0: The edges of the cut are perfectly smooth and there is no peeling in any grid.
Classification 1: Small peeling of the coating at the intersection of cuts. The cross-cut area is clearly not affected by more than 5%.
Category 2: The coating is peeling off along the edges of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
Category 3: The coating is partially or wholly stripped along the edges of the cut and / or various parts of the eye are partially or wholly peeled off. The cross-cut area is clearly affected by more than 15% but not more than 35%.
Category 4: The coating is partially or wholly stripped along the edges of the cut and / or several eyes are partially or wholly peeled off. The cross-cut area is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(W) Cutting workability (state of curved cutting line):
Using a router processing machine that is automatically controlled by a computer, a perfect circular cutting hole with a diameter of 2 mm and a perfect circular cutting hole with a diameter of 0.5 mm were provided in the antiglare hard coat laminated film. The mill used at this time was a four-blade made of cemented carbide with a cylindrical round tip shape and a nick, and the blade diameter was appropriately selected according to the machining location. Subsequently, the cutting end face of the cutting hole having a diameter of 2 mm was visually or microscopically observed (100 times) and evaluated according to the following criteria. Similarly, for a cutting hole having a diameter of 0.5 mm, the cut end face was visually or microscopically observed (100 times) and evaluated according to the following criteria. The table shows the former result-the latter result in that order.
⊚: No cracks or whiskers were observed under a microscope. ○: No cracks were observed under a microscope. However, beard is recognized.
Δ: No crack was visually observed. However, cracks are observed under a microscope.
X: Cracks are also observed visually.

Raw materials used (A) Polyfunctional (meth) acrylate:
(A-1) Dipentaerythritol hexaacrylate. 6 sensuality.
(A-2) Pentaerythritol triacrylate. 3 sensuality.

(B) Water repellent:
(B-1) Acryloyl group-containing fluoropolyether-based water repellent agent "KY-1203 (trade name)" of Shin-Etsu Chemical Co., Ltd. Solid content 20% by mass.
(B-2) Solvay's fluoropolyether-based water repellent agent containing a methacryloyl group "FOMBLIN MT70 (trade name)". Solid content 70% by mass.

(C) Silane coupling agent:
(C-1) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane "KBM-602 (trade name)" of Shin-Etsu Chemical Co., Ltd.
(C-2) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane "KBM-603 (trade name)" of Shin-Etsu Chemical Co., Ltd.
(C-3) 3-Aminopropyltrimethoxysilane "KBM-903 (trade name)" of Shin-Etsu Chemical Co., Ltd.
(C-4) 3-Mercaptopropylmethyldimethoxysilane "KBM-802 (trade name)" of Shin-Etsu Chemical Co., Ltd.
(C-5) 3-glycidoxypropyltrimethoxysilane "KBM-403 (trade name)" of Shin-Etsu Chemical Co., Ltd.

(D) Resin fine particles having an average particle diameter of 0.5 to 10 μm:
(D-1) Momentive Performance Materials Co., Ltd.'s spherical silicon-based resin fine particles "Tospearl 120 (trade name)". Average particle size 2 μm.
(D-2) Momentive Performance Materials Co., Ltd.'s spherical silicon-based resin fine particles "Tospearl 130 (trade name)". Average particle size 3 μm.
(D-3) Acrylic resin fine particles "MA-180TA (trade name)" of Soken Chemical Co., Ltd. Average particle size 1.8 μm.
(D-4) Acrylic resin fine particles "MX-80H3wT (trade name)" of Soken Chemical Co., Ltd. Average particle size 0.5 μm.
(D-5) Toyobo Co., Ltd. acrylic resin fine particles "FH-S010 (trade name)". Average particle size 10 μm.

(D') Reference fine particles:
(D'-1) Silica fine particles "SO-E6 (trade name)" of Admatex Co., Ltd. Average particle size 2 μm.

(E) Inorganic fine particles with an average particle diameter of 1 to 300 nm:
(E-1) Silica fine particles having an average particle diameter of 20 nm surface-treated with a silane coupling agent having a vinyl group.

(F) Leveling agent:
(F-1) Silicon-acrylic copolymer system leveling agent "Disparon NSH-8430HF (trade name)" of Kusumoto Kasei Co., Ltd. Solid content 10% by mass.
(F-2) Silicon-acrylic copolymer system leveling agent "BYK-3550 (trade name)" of Big Chemie Japan Co., Ltd. Solid content 52% by mass.
(F-3) Acrylic polymerization system leveling agent "BYK-399 (trade name)" of Big Chemie Japan Co., Ltd. Solid content 100% by mass.
(F-4) Silicon-based leveling agent "Disparon LS-480 (trade name)" of Kusumoto Kasei Co., Ltd. Solid content 100% by mass.

(G) Optional component:
(G-1) Phenyl Ketone-based Photopolymerization Initiator (1-Hydroxycyclohexylphenylketone) "SB-PI714 (trade name)" of Souho Kogyo Co., Ltd.
(G-2) 1-methoxy-2-propanol.

(H1) First hard coat forming paint:
(H1-1) 100 parts by mass of (A-1) above, 2 parts by mass of (B-1) above (0.40 parts by mass in terms of solid content), 0.06 parts by mass of (B-2) above (converted to solid content) 0.042 parts by mass), 0.5 parts by mass of (C-1), 2 parts by mass of (D-1), 4 parts by mass of (G-1), and 100 parts by mass of (G-2). Paint obtained by mixing and stirring. Table 1 shows the formulation table. For the above (B-1) and the above component (B-2), the solid content conversion values are shown in the table.

A paint was obtained in the same manner as in (H1-1) above, except that the formulation (H1-2 to 20) was changed as shown in any one of Tables 1 to 3.

(H1') Reference 1st hard coat forming paint:
(H1'-1 to 7) A paint was obtained in the same manner as in (H1-1) above, except that the formulation was changed as shown in any one of Tables 1 to 3.

(H2) Paint for forming the second hard coat:
(H2-1) 100 parts by mass of (A-2), 140 parts by mass of (E-1), 2 parts by mass of (F-1) (0.2 parts by mass in terms of solid content), (G-1) ) 17 parts by mass and 200 parts by mass of the above (G-2) are mixed and stirred to obtain a coating material. Table 4 shows the formulation table. For the above (F-1) and the above (F-2), the values in terms of solid content are shown in the table.

(H2-2-12) A paint was obtained in the same manner as in (H2-1) above, except that the formulation was changed as shown in Table 4 or Table 5.

(H2') Reference No. 2 hard coat forming paint:
(H2'-1, 2) A paint was obtained in the same manner as in (H2-1) above, except that the formulation was changed as shown in Table 5.

(P) Transparent resin film:
(P-1) A two-kind three-layer multi-manifold coextruded T-die, and a molten film with a first mirror surface roll (a roll on the side that holds the molten film and sends it to the next transfer roll) and a second mirror surface roll. Using a device equipped with a winder (see Fig. 4) equipped with a mechanism to press the Using the imide "PLEXIMID TT50 (trade name)" as an intermediate layer (β layer), the aromatic polycarbonate "Calibre 301-4 (trade name)" of Sumika Stylon Polycarbonate Co., Ltd. is continuously co-extruded from the co-extruded T-die. , The α1 layer is supplied and charged between the rotating first mirror surface roll and the second mirror surface roll so that the α1 layer is on the first mirror surface roll side, and pressed to obtain a total thickness of 250 μm, a layer thickness of the α1 layer of 80 μm, and a β layer. A transparent resin film having a layer thickness of 90 μm and an α2 layer having a layer thickness of 80 μm was obtained. At this time, the setting conditions were a set temperature of the T die of 300 ° C., a set temperature of the first mirror surface roll of 130 ° C.; a set temperature of the second mirror surface roll of 120 ° C., and a take-up speed of 6.5 m / min.

(P-2) The above (P-) except that the acrylic resin "Optimas 7500FS (trade name)" of Mitsubishi Gas Chemical Company, Inc. was used instead of the above "PLEXIMID TT50 (trade name)" as both outer layers. A transparent resin film was obtained in the same manner as in 1).

(P-3) A transparent resin film was obtained in the same manner as in (P-1) above, except that the layer ratio was changed to the layer thickness of the α1 layer 60 μm, the layer thickness of the β layer 130 μm, and the layer thickness of the α2 layer 60 μm. rice field.

(P-4) A transparent resin film was obtained in the same manner as in (P-1) above, except that the layer ratio was changed to a layer thickness of the α1 layer of 40 μm, a layer thickness of the β layer of 170 μm, and a layer thickness of the α2 layer of 40 μm. rice field.

(P-5) Mitsubishi Plastics Co., Ltd. biaxially stretched polyethylene terephthalate film "Diafoil (trade name)", thickness 250 μm.

(P-6) Sumitomo Chemical Co., Ltd. acrylic resin film "Technoloy S001G (trade name)", thickness 250 μm.

(P-7) A pull with a mechanism for pressing the molten film with a single-layer T-die, a first mirror surface roll (a roll on the side that holds the molten film and sends it to the next transfer roll), and a second mirror surface roll. Using a device equipped with a winder, the aromatic polycarbonate "Calibre 301-4 (trade name)" of Sumika Stylon Polycarbonate Co., Ltd. is continuously extruded from the T-die, and the first mirror surface roll and the second mirror surface are rotated. It was supplied and charged between the rolls and pressed to obtain a transparent resin film having a total thickness of 250 μm. At this time, the setting conditions were a set temperature of the T die of 320 ° C., a set temperature of the first mirror surface roll of 140 ° C.; a set temperature of the second mirror surface roll of 120 ° C., and a take-up speed of 5.6 m / min.

Example 1
Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides. Next, the above (H2-1) was applied onto the surface on the α1 layer side using a die-type coating device so as to have a wet thickness of 40 μm (thickness after curing 22 μm). Next, after passing the drying furnace set to the furnace temperature of 90 ° C. at a line speed that takes 1 minute to pass from the inlet to the outlet, a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm are used. Using a curing device facing the mirror metal roll (see FIG. 3), the treatment was performed under the conditions that the temperature of the mirror metal roll was 90 ° C. and the integrated light amount was 80 mJ / cm ² . The wet coating film of the above (H2-1) became a coating film in a dry state to the touch. Next, a die-type coating device is used on the coating film in a dry state to the touch of (H2-1) so that the wet thickness of (H1-1) is 4 μm (thickness after curing is 2 μm). Applied. Next, after passing the drying furnace set to the furnace temperature of 80 ° C. at a line speed that takes 1 minute to pass from the inlet to the outlet, a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm are used. Using a curing device facing the mirror surface metal roll (see FIG. 1), the mirror surface metal roll is treated under the conditions of a temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² to form a first hard coat and a second hard coat. did. Subsequently, a third hard coat was applied onto the surface on the α2 layer side, and the same paint used for forming the second hard coat (Example 1 is the above (H2-1)) was used for die-based coating. Using the apparatus, it was formed so as to have a thickness of 22 μm after curing, and a hard-coated laminated film was obtained. The above tests (a) to (wo) were performed. The results are shown in Table 6.

Examples 2 to 20, Examples 1C to 7C
All were carried out in the same manner as in Example 1 except that the paint shown in any one of Tables 6 to 9 was used instead of the above (H1-1). The results are shown in any one of Tables 6-9.

Examples 21-31, Examples 8C, 9C
All were carried out in the same manner as in Example 1 except that the paint shown in any one of Tables 10 to 12 was used instead of the above (H2-1). The results are shown in any one of Tables 10 to 12.

Examples 32-36
The procedure was the same as in Example 1 except that the transparent resin film shown in Table 12 was used instead of the above (P-1). The results are shown in Table 12.

Example 37-40
The same procedure as in Example 1 was carried out except that the thickness of the first hard coat after curing was changed as shown in Table 13. The results are shown in Table 13.

Examples 41-44
All examples except that the post-curing thickness of the second hard coat was changed as shown in Table 13 or 14, and the post-cured thickness of the third hard coat was changed to the same as the post-cured thickness of the second hard coat. It was done in the same manner as 1. The results are shown in Table 13 or Table 14.

Example 45-59
The same procedure as in Example 1 was carried out except that the production conditions of the hard-coated laminated film were changed as shown in any one of Tables 14 to 16. The results are shown in any one of Tables 14 to 16.

The preferred antiglare hardcourt laminated film of the present invention is excellent in antiglare, scratch resistance, surface hardness, and slipperiness. Further, the bending resistance, the color tone, the appearance, the interlayer adhesion strength, and the cutting workability are also good. Therefore, members of image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays (including image display devices having a touch panel function and image display devices not having a touch panel function), especially on screens of car navigation devices and the like. It is a device often used in an environment where light from the outside is incident, and can be suitably used as a member of a device having a touch panel function.

It is sectional drawing which shows an example of the antiglare hard coat laminated film of this invention. It is a figure explaining the radius of curvature. It is a conceptual diagram of the ultraviolet irradiation apparatus used in an Example. It is a conceptual diagram of the film forming apparatus used in an Example.

1: 1st hard coat 2: 2nd hard coat 3: 1st poly (meth) acrylicimide-based resin layer (α1)
4: Aromatic polycarbonate resin layer (β)
5: Second poly (meth) acrylicimide-based resin layer (α2)
6: Third hard coat 7: Ultraviolet irradiation device 8: Mirror metal roll 9: Web 10: Holding angle 11: Molten resin film 12: T die 13: First mirror surface roll 14: Second mirror surface roll

Claims (11)

It has a first hard coat, a second hard coat, and a layer of a transparent resin film in order from the surface side.
The first hard coat comprises a polyfunctional (meth) acrylate, a water repellent, and a paint containing resin fine particles having an average particle diameter of 1 to 10 μm (excluding 1 μm) and containing no inorganic particles;
The second hard coat is made from a paint containing (A) 100 parts by mass of polyfunctional (meth) acrylate and (E) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm (excluding 300 parts by mass). Nari;
A hard-coated laminated film that satisfies the following (1) to (3).
(1) Total light transmittance is 85% or more.
(2) The pencil hardness of the surface of the first hard coat is 5H or more.
(3) The Y value of the XYZ color system is 1.5 to 4.2%.
The hard-coated laminated film according to claim 1, further satisfying the following (4).
(4) The water contact angle after wiping the surface of the first hard coat 7500 times reciprocating with cotton is 100 degrees or more.
The hard-coated laminated film according to claim 1 or 2, further satisfying the following (5).
(5) The minimum bending radius is 40 mm or less.
The hard-coated laminated film according to any one of claims 1 to 3, further satisfying the following (6).
(6) The yellowness index is 3 or less.
13. Hardcourt laminated film.
The hardcoat laminated film according to any one of claims 1 to 5, wherein the pencil hardness of the surface of the first hardcoat is 6H or more.
Any of claims 1 to 6, wherein the second hard coat comprises a coating material containing 100 parts by mass of (A) polyfunctional (meth) acrylate and (E) 50 to 200 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm. The hard coat laminated film according to item 1.
The hardcoat laminated film according to any one of claims 1 to 7, wherein the thickness of the first hardcoat is 0.5 to 5 μm.
The hardcoat laminated film according to any one of claims 1 to 8, wherein the thickness of the second hardcoat is 10 to 30 μm.
Use of the hard-coated laminated film according to any one of claims 1 to 9 as an image display device member.
An image display device including the hard-coated laminated film according to any one of claims 1 to 9.

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