JP7270698B2 - Anti-glare hard-coated laminated film - Google Patents

Description

The present invention relates to an antiglare hard-coated laminated film. More particularly, it relates to an antiglare hard-coated laminated film with excellent scratch resistance.

In recent years, car navigation devices equipped with a touch panel installed on an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display, enabling input by touching with a finger or a pen while viewing the display, have become available. Widespread.

From the viewpoint of safety in the unlikely event of a traffic accident, car navigation systems use plastic display faceplates and glass display faceplates to provide a high level of impact resistance and crack resistance. Lamination of films is widely performed. In addition, the image display device of the car navigation system is provided with an anti-glare property in order to deal with the problem that light from the outside enters the screen and the light is reflected to make the displayed image difficult to see. Antiglare properties are imparted by laminating an antiglare hard-coated laminated film on the surface of a plastic display face plate or by forming an antiglare hard coat on the surface of a shatterproof film.

Many proposals have been made for antiglare hard-coated laminated films (for example, Patent Document 1). However, considering that a touch panel will be installed in a car navigation device, its scratch resistance is insufficient, and an anti-glare hard coat that can maintain surface properties such as finger slipperiness even if it is repeatedly wiped with a handkerchief. There is a need for laminated films.

Japanese Unexamined Patent Application Publication No. 2010-211150

An object of the present invention is to provide members for 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) having excellent antiglare properties. ) to provide an antiglare hard-coated laminated film suitable for the above. A further object of the present invention is to provide a device that is excellent in antiglare and scratch resistance, is often used in an environment where light from the outside enters the screen, such as a car navigation device, and has a touch panel function. An object of the present invention is to provide an antiglare hard-coated laminated film suitable as a member of

As a result of intensive research, the present inventors have found that the above-mentioned problems can be achieved with a specific hard coat 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 first hard coat is
(A) polyfunctional (meth) acrylate 100 parts by mass;
(B) water repellent agent 0.01 to 7 parts by mass;
(C) 0.01 to 10 parts by mass of a silane coupling agent; and (D) 0.1 to 5 parts by mass of fine resin particles having an average particle diameter of 0.5 to 10 μm;
and contains no inorganic particles; hard coat laminated film.

A second invention has layers of a first hard coat, a second hard coat, and a transparent resin film in order from the surface side,
The 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;
It is a hard coat laminated film according to the first invention.

A third invention is the first, wherein the (C) silane coupling agent contains 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. A hard coat laminated film according to the invention or the second invention.

A fourth invention is the hard coat laminated film according to any one of the first to third inventions, wherein the water repellent (B) comprises a (meth)acryloyl group-containing fluoropolyether water repellent. .

A fifth invention is 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's a film.

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

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

An eighth invention has a first hard coat, a second hard coat, and a resin film layer in order from the surface side,
the first hard coat comprises a paint containing no inorganic particles;
the second hard coat comprises a paint containing inorganic particles;
It is a hard coat laminated film that satisfies the following (a) to (c).
(b) The total light transmittance is 85% or more.
(b) The surface of the first hard coat has a pencil hardness of 5H or more.
(c) The Y value in the XYZ color system is 1.5 to 4.2%.

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

A tenth invention is the hard coat laminated film according to the eighth invention or the ninth invention, wherein the surface of the first hard coat has a water contact angle of 100 degrees or more after 10,000 reciprocating wipes with cotton.

An eleventh invention is use of the hard coat laminated film according to any one of the first to tenth inventions as a member of an image display device.

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

The antiglare hard-coated laminated film of the present invention is excellent in antiglare properties. A preferred antiglare hard-coated laminated film of the present invention is excellent in antiglare properties and scratch resistance. Therefore, the components 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 without a touch panel function), especially car navigation devices, etc. The device is often used in an environment where external light is incident, and can be suitably used as a member of a device having a touch panel function.

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

First hard coat:
The first hard coat forms the surface of the antiglare hard-coated laminated film of the present invention. The first hard coat forms a touch surface when the antiglare hard-coated 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 antiglare properties and scratch resistance, and functions to maintain surface properties such as finger slipperiness even after repeated wiping with a handkerchief or the like.

The first hard coat comprises (A) 100 parts by mass of a polyfunctional (meth)acrylate; (B) 0.01 to 7 parts by mass of a water repellent agent; (C) 0.01 to 10 parts by mass of a silane coupling agent; (D) A paint containing 0.1 to 5 parts by mass of fine resin particles having an average particle size of 0.5 to 10 μm and containing no inorganic particles.

Inorganic particles such as 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; 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. In addition, inorganic particles having an appropriate particle size improve antiglare properties. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes insufficient scratch resistance. Therefore, in the present invention, the first hard coat that forms the surface uses fine resin particles as particles for improving antiglare properties, and does not contain inorganic particles to maintain scratch resistance. This problem is solved by adding a large amount of specific inorganic fine particles to the second hard coat to increase the hardness.

Here, "free of" inorganic particles means not containing any significant amount of inorganic particles. In the field of hard coat-forming paints, a significant amount of inorganic particles is usually about 0.1 part by mass or more per 100 parts by mass of component (A) from the viewpoint of imparting antiglare properties. Therefore, "does not contain" inorganic particles means that the amount of inorganic particles is usually less than 0.1 parts by mass, preferably 0.05 parts by mass or less, more preferably 0 parts by mass with respect to 100 parts by mass of the component (A). It can also be rephrased as 0.01 part by mass or less.

(A) Polyfunctional (meth)acrylate:
The component (A) is a (meth)acrylate having two or more (meth)acryloyl groups in one molecule, and since it has two or more (meth)acryloyl groups in one molecule, It is polymerized and cured by 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, 2, 2′-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane and 2,2′-bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane (meth)acryloyl group-containing bifunctional reaction (meth)acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; pentaerythritol tetra(meth)acrylate (Meth)acryloyl group-containing tetrafunctional reactive monomers such as; (meth)acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth)acryloyl group-containing octafunctional reactive monomers such as tripentaerythritol acrylate and polymers (oligomers and prepolymers) having one or more of these monomers as constituent monomers. One or a mixture of two or more thereof can be used as the component (A).

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

(B) Water repellent:
The above-mentioned component (B) functions to enhance the finger-sliding property, anti-fouling property, and wiping-off property.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic/ethylene copolymer wax; silicon-based water repellents such as silicone oil, silicone resin, polydimethylsiloxane, and alkylalkoxysilane; agents; fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellants; One or a mixture of two or more thereof can be used as the component (B).

Among these, fluoropolyether-based water repellents are preferable as the component (B) from the viewpoint of water repellency. From the viewpoint of preventing problems such as chemical bonding or strong interaction between the component (A) and the component (B), causing the component (B) to bleed out, the component (B) contains A water repellent containing a compound containing a (meth)acryloyl group and a fluoropolyether group (hereinafter abbreviated as a (meth)acryloyl group-containing fluoropolyether water repellent) is more preferred. From the viewpoint of maintaining high transparency and exhibiting good water repellency by appropriately adjusting the chemical bond or interaction between component (A) and component (B), the component (B) is more preferably: It is a mixture of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent.

The (meth)acryloyl group-containing fluoropolyether water repellent is clearly distinguished from the component (A) in that it contains a fluoropolyether group in the molecule. A 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 component (B). .

The 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), the amount is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more.

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

Silane coupling agents include hydrolyzable groups (e.g., methoxy groups, alkoxy groups such as ethoxy groups; acyloxy groups such as acetoxy groups; halogen groups such as chloro groups; etc.), and organic functional groups (e.g., amino groups, silane compounds having at least two different reactive groups such as mercapto groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups; Among these, from the viewpoint of adhesion, the 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 ( A silane compound having a mercapto group and a hydrolyzable group) is preferred. A silane coupling agent having an amino group is more preferable from the viewpoint of adhesion and odor.

Silane coupling agents having an amino group include, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, Examples include N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane.

Silane coupling agents having a mercapto group include, for example, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

One or a mixture of two or more thereof can be used as the component (C).

The amount of the component (C) is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, based on 100 parts by mass of the component (A), from the viewpoint of reliably obtaining the effect of improving adhesion. More preferably, it is 0.1 parts 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, more preferably 1 part by mass or less.

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

Examples of the fine resin particles include fine resin particles such as silicone-based resins, styrene-based resins, acrylic resins, fluorine-based resins, polycarbonate-based resins, ethylene-based resins, and cured resins of amino-based compounds and formaldehyde. . Among these, from the viewpoint of low specific gravity, lubricity, dispersibility, and solvent resistance, fine particles of silicon-based resin, acrylic-based resin, and fluorine-based resin are preferred. Moreover, from the viewpoint of improving the light diffusibility, a true spherical shape is preferable. As the fine resin particles, one or a mixture of two or more of these can be used.

The average particle size of component (D) is usually 0.5 μm or more, preferably 1 μm or more, from the viewpoint of reliably obtaining antiglare properties. 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 fine resin particles is defined from the smaller particle in the particle size distribution curve measured using a laser diffraction/scattering particle size analyzer "MT3200II (trade name)" manufactured by Nikkiso Co., Ltd. is the particle diameter at which the accumulation of is 50% by mass.

The amount of component (D) blended is usually 0.1 to 10 parts by mass, preferably 0.2 parts by mass, based on 100 parts by mass of component (A), depending on the level of antiglare properties to be imparted. to 5 parts by mass, more preferably 0.3 to 3 parts by mass. From the viewpoint of scratch resistance, it may preferably be 0.5 to 3 parts by mass.

From the viewpoint of improving the curability by active energy rays, the first hard coat forming coating material contains a compound having two or more isocyanate groups (-N=C=O) in one molecule and/or a photopolymerization initiator. Further inclusion of an agent is preferred.

Examples of compounds having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, isophorone diisocyanate isocyanurate, and hexamethylene diisocyanate biuret; and urethanes such as blocked isocyanates of the above polyisocyanates A cross-linking agent and the like can be mentioned. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used. In addition, a catalyst such as dibutyltin dilaurate, dibutyltin diethylhexoate, or the like may be added at the time of cross-linking, if necessary.

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. -4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; Acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylphenyl ketone; -anthraquinone compounds such as amyl anthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; alkylphenone compounds such as acetophenone dimethyl ketal; triazine compounds; biimidazole compounds; fin oxide-based compounds; titanocene-based compounds; oxime ester-based compounds; oxime phenylacetic ester-based compounds; hydroxyketone-based compounds; As the photopolymerization initiator, one or a mixture of two or more thereof can be used.

Antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather stabilizers, One or more additives such as lightfast stabilizers, UV absorbers, heat stabilizers, and organic colorants may be included.

The paint for forming the first hard coat may optionally contain a solvent in order to dilute it to a concentration that facilitates coating. The above solvents are particularly limited as long as they do not react with the above components (A) to (D) and other optional components, and do not catalyze (promote) the self-reactions (including deterioration reactions) of these components. not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As the solvent, one or a mixture of two or more thereof can be used.

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

The method for forming the first hard coat using the first hard coat-forming coating material is not particularly limited, and a known web coating method can be used. Examples of the 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, and even 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 properties, surface hardness, adhesion and bending resistance, the thickness is preferably 5 µm or less, more preferably 4 µm or less, and even more preferably 3 µm or less.

Second hard coat:
The antiglare hard-coated laminated film of the present invention preferably has layers of a first hard coat, a second hard coat, and a transparent resin film in order from the surface side. The second hard coat serves to increase the hardness of the antiglare hard-coated laminated film of the present invention, thereby increasing the surface hardness. The second hard coat is 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.

The (A) polyfunctional (meth)acrylate was described above in the description of the first hard coat-forming coating material. One or a mixture of two or more thereof can be used as the component (A).

(E) Inorganic fine particles having an average particle size of 1 to 300 nm:
The above component (E) functions to dramatically increase the hardness of the hard coat laminated film of the present invention.

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

Among these, fine particles of silica and aluminum oxide are preferable, and fine particles of silica 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) manufactured by Nissan Chemical Industries, Ltd. and Quatron (trade name) manufactured by Fuso Chemical Industries, Ltd.

For the purpose of increasing the dispersibility of the inorganic fine particles in the paint or increasing the hardness of the resulting hard coat, the surfaces of the inorganic fine particles are coated with a silane-based coupling agent such as vinylsilane and aminosilane; a titanate-based coupling agent; Aluminate-based coupling agents; Organic compounds having ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, and reactive functional groups such as epoxy groups; Surfaces of fatty acids, fatty acid metal salts, etc. It is preferable to use one treated with a treating agent or the like.

One or a mixture of two or more thereof can be used as the component (E).

The average particle size of 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 reliably obtaining the effect of improving hardness. On the other hand, although there is no particular lower limit for the average particle size, generally available inorganic fine particles are at most about 1 nm.

In this specification, the average particle size of the inorganic fine particles is measured from the smaller particle in the particle size distribution curve measured using a laser diffraction/scattering particle size analyzer "MT3200II (trade name)" manufactured by Nikkiso Co., Ltd. is the particle diameter at which the accumulation of is 50% by mass.

From the viewpoint of hardness, the amount of component (E) to be blended is 50 parts by mass or more, preferably 80 parts by mass or more, per 100 parts by mass of component (A). On the other hand, from the viewpoint of transparency, it is 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

(F) leveling agent:
From the viewpoint of making the surface of the second hard coat smooth and facilitating the formation of the first hard coat, it is preferable that the paint for forming the second hard coat further contains (F) a leveling agent.

Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, fluorine leveling agents, silicone-acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicone leveling agents, and functional Examples include leveling agents into which groups (for example, alkoxy groups such as methoxy groups and ethoxy groups, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. can be done. Among these, a silicon-acrylic copolymer leveling agent is preferable as the component (F). One or a mixture of two or more thereof can be used as the component (F).

From the viewpoint of making the surface of the second hard coat smooth and facilitating the formation of the first hard coat, the compounding amount of the component (F) is usually 0 with respect to 100 parts by mass of the component (A). 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of ensuring that the first hard coat-forming coating material can be coated on the second hard coat without being repelled, it is 1 part by mass or less, preferably 0.6 parts by mass or less. Preferably, it may be 0.4 parts by mass or less.

In the second hard coat-forming coating material, from the viewpoint of improving the curability with active energy rays, a compound having two or more isocyanate groups (-N=C=O) in one molecule and/or a photopolymerization initiator Further inclusion of an agent is preferred.

The compound having two or more isocyanate groups in one molecule was 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 thereof can be used.

The photopolymerization initiator was described above in the description of the first hard coat forming coating material. As the photopolymerization initiator, one or a mixture of two or more thereof can be used.

Antistatic agents, surfactants, thixotropic agents, anti-staining agents, printability improvers, antioxidants, weather stabilizers, and light resistance stabilizers may optionally be added to the second hard coat-forming coating material. One or two or more additives such as agents, ultraviolet absorbers, heat stabilizers, colorants, and fine resin particles may be included.

The paint for forming the second hard coat may optionally contain a solvent in order to dilute it to a concentration that facilitates coating. If the solvent does not react with the component (A), the component (E), and other optional components, or does not 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, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Among these, 1-methoxy-2-propanol is preferred. As the solvent, one or a mixture of two or more thereof can be used.

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

The method of forming the second hard coat using the second hard coat-forming coating material is not particularly limited, and a known web coating method can be used. Examples of the 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, and even more preferably 18 μm or more. On the other hand, from the viewpoint of curl resistance and bending resistance, the thickness is preferably 30 μm or less, more preferably 27 μm or less, and even more preferably 25 μm or less.

Transparent resin film:
The transparent resin film is a layer that serves as a transparent film substrate for forming the first hard coat, or the first hard coat and the second hard coat thereon. The transparent resin film is not particularly limited as long as 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 copolymer; and acrylic resins such as vinylcyclohexane/(meth)methyl acrylate copolymer; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; Films such as polymer type urethane acrylate resins; and polyimide resins can be mentioned. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. These films also include laminated films obtained by laminating two or more layers of one or more of these.

The thickness of the transparent resin film is not particularly limited, and can be set to any desired thickness. From the viewpoint of handleability of the hard-coated antiglare laminated film of the present invention, the thickness is usually 20 μm or more, preferably 50 μm or more. When the antiglare hard-coated laminated film of the present invention is used for applications that do not require high rigidity, the thickness is usually 250 μm or less, preferably 150 μm or less, from the viewpoint of economy. When the hard coat laminated film of the present invention is used as a display face plate of a car navigation device, the thickness is usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more, from the viewpoint of maintaining rigidity. In addition, from the viewpoint of meeting the demand for thinner devices, the thickness is usually 1500 μm or less, preferably 1200 μm or less, and more preferably 1000 μm or less.

The transparent resin film is preferably a transparent resin film of acrylic resin.

Examples of the acrylic resin include (meth)acrylic acid ester (co)polymers, copolymers containing (meth)acrylic acid esters, and modified products thereof. In addition, (meth)acryl means acryl or methacryl. A (co)polymer means a polymer or a copolymer.

Examples of the (meth)acrylate (co)polymer include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, ( Examples thereof include methyl methacrylate/butyl (meth)acrylate copolymer and ethyl (meth)acrylate/butyl (meth)acrylate copolymer.

Examples of the copolymer containing a structural unit derived from the (meth)acrylate ester include ethylene/methyl (meth)acrylate copolymer, styrene/methyl (meth)acrylate copolymer, vinylcyclohexane/( Meth)methyl acrylate copolymer, maleic anhydride/methyl (meth)acrylate copolymer, and N-substituted maleimide/methyl (meth)acrylate copolymer can be mentioned.

Examples of the modified product include polymers into which a lactone ring structure has been introduced by intramolecular cyclization; polymers into which glutaric anhydride has been introduced by intramolecular cyclization; and imidizing agents (e.g., methyl amine, cyclohexylamine, and ammonia. 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. These films also include laminated films obtained by laminating two or more layers of one or more of these.

The transparent resin film is more preferably a vinylcyclohexane/methyl (meth)acrylate copolymer film. The antiglare hard-coated laminated film is excellent in 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)acrylimide resin film. An anti-glare hard-coated laminated film with excellent surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and heat-resistant dimensional stability. 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. 1 or less, more preferably 1 or less. By using an acrylic resin having a yellowness index of 3 or less, it is possible to obtain an antiglare hard-coated laminated film that can be suitably used as a member of an image display device. The lower the yellowness index, the better.

The melt mass flow rate of the acrylic resin (measured under conditions of 260° C. and 98.07 N according to ISO 1133) is preferably 0.1 to 20 g/10 min, from the viewpoint of extrusion load and melt film stability. It is preferably 0.5 to 10 g/10 minutes.

In addition, the acrylic resin may optionally include thermoplastic resins other than acrylic resins; pigments, inorganic fillers, organic fillers, resin fillers; additives such as agents, heat stabilizers, release agents, antistatic agents, and surfactants; and the like. The blending amount of these optional components is usually about 0.01 to 10 parts by mass based on 100 parts by mass of the acrylic resin.

The transparent resin film is more preferably a transparent multilayer 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's a film. In this 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, while aromatic polycarbonate resins have excellent machinability but tend to have insufficient surface hardness. . Therefore, by using a transparent multilayer film having the above-described layer structure, it is possible to compensate for the weaknesses of both, and easily obtain an antiglare hard-coated laminated film excellent in both surface hardness and machinability. .

The 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, and still more preferably 80 µm or more. can be

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

Here, "the 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 process and quality control fluctuations that are normally performed industrially. This is because the curl resistance of the multi-layer film can be maintained satisfactorily as long as the layer thickness is the same within the fluctuation range of the process and quality control that are usually performed industrially. In the case of a non-stretched multilayer film produced by the T-die co-extrusion method, the process and quality are usually controlled within 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.

Although the layer thickness of the β layer is not particularly limited, it 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 has been described above.

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

Examples of aromatic polycarbonate resins used in the β layer include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and phosgene. Polymer obtained by 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 diphenyl carbonate A polymer obtained by transesterification with a diester; or a mixture of two or more aromatic polycarbonate resins such as:

Core-shell rubber can be given as a preferred optional component that can be included in the aromatic polycarbonate-based resin. 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 100 to 90 parts by mass of polycarbonate-based resin, cutting resistance and impact resistance can be further enhanced.

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

The aromatic polycarbonate-based resins may optionally include thermoplastic resins other than aromatic polycarbonate-based resins and core-shell rubbers; pigments, inorganic fillers, organic fillers, resin fillers; lubricants; Additives such as antioxidants, weather stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants; and the like may also be 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. When the transparent resin film is a poly(meth)acrylimide-based resin film, the method described in JP-A-2015-033844 can be mentioned as a preferable manufacturing method. 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. A preferable manufacturing method is the method described in JP-A-2015-083370. In forming the hard coat, the surface or both sides of the transparent resin film on which the hard coat is formed may be subjected in advance to easy-adhesion treatment such as corona discharge treatment or formation of an anchor coat in order to increase the adhesive strength with the hard coat. .

The antiglare hard-coated laminated film of the present invention more preferably has the first hard coat, the second hard coat, the transparent resin film layer, and the third hard coat in order from the surface side. By forming the third hard coat, the antiglare hard-coated laminated film is prevented from curling in one direction (hereinafter sometimes abbreviated as curling force) and in the other direction. both will work. By canceling out these two curling forces and making them zero, the occurrence of curling can be suppressed.

Further, in recent years, for the purpose of reducing the weight of the image display device, a two-layer structure touch panel (so-called one-glass solution) in which a touch sensor is directly formed on the back side of the display faceplate has been proposed. Also, for further weight reduction, a one-plastic solution has been proposed to replace the so-called one-glass solution. When the antiglare hard-coated laminated film of the present invention is used for a one-plastic solution that replaces the so-called one-glass solution, by forming the third hard coat, properties suitable as a printing surface can be obtained. easier to give.

The antiglare hard-coated laminated film of the present invention optionally has any layers other than the first hard coat, the second hard coat, the transparent resin film layer, and the third hard coat. good too. Examples of optional layers include hard coats other than the first to third hard coats, anchor coats, adhesive layers, transparent conductive layers, high refractive index layers, low refractive index layers, and antireflection functional layers. be able to.

FIG. 1 is a schematic cross-sectional view showing an example of the antiglare hard-coated laminated film of the present invention. In order from the touch surface side, the first hard coat 1, the second hard coat 2, the first poly(meth)acrylimide resin layer (α1) 3, the aromatic polycarbonate resin layer (β) 4, the second poly(meth) ) It has an acrylimide resin layer (α2) 5 and a third hard coat 6 .

The antiglare hard-coated laminated film of the present invention has a total light transmittance (measured using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7361-1:1997). It is preferably 85% or more, more preferably 88% or more, and 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 a member of an image display device. The higher the total light transmittance, the better.

The antiglare hard-coated laminated film of the present invention has a Y value of an XYZ display system based on a two-degree field of view (spectrophotometer "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation and a reflection unit "absolute reflectance measuring device Using an incident angle of 5° (trade name), specular reflection of 5 degrees (a reflection unit is installed in front of the integrating sphere. The value of specular reflection excludes diffuse light.) measured under the conditions of ) is usually 4.2% or less, preferably 3.0% or less, more preferably 2.0% or less from the viewpoint of antiglare properties. On the other hand, it is usually 1.5% or more, preferably 2.0% or more, from the viewpoint of preventing the displayed image from becoming whitish.

In the antiglare hard-coated laminated film of the present invention, the haze (measured using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7136:2000) is an antiglare From the point of view, depending on the level of antiglare property to be imparted, it may be usually 3% or more, preferably 5% or more. On the other hand, from the viewpoint of preventing the displayed image from becoming whitish, it is usually 30% or less, preferably 25% or less.

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

The antiglare hard-coated laminated film of the present invention preferably has a minimum bending radius of 40 mm or less, more preferably 35 mm or less, still more preferably 30 mm or less. Since 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 production efficiency and the like. The smaller the minimum bending radius, the better. Here, the minimum bending radius is a value measured according to test (E) of the following examples.

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. A bend radius is defined similarly to a curvature radius.

The radius of curvature is defined as follows. ΔS is the length of the curve from the M point to the N point; Δα is the difference between the slope of the tangent line at the M point and the slope of the tangent line at the N point; , the intersection of a straight line that is perpendicular to the tangent at point N and intersects at point N is O; and if ΔS is sufficiently small, the curve from point M to point N can be approximated to a circular arc. (Fig. 2). The radius at this time is defined as the radius of curvature. Also, if the radius of curvature is R, ∠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-coated laminated film of the present invention, the water contact angle on the surface of the first hard coat is preferably 100 degrees or more, more preferably 105 degrees or more. When the antiglare hard-coated 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 pen on the touch surface as desired. From the viewpoint of allowing a finger or pen to slide as desired, a higher water contact angle is preferable, and there is no particular upper limit for the water contact angle. Here, the water contact angle is a value measured according to the test (vi) of the following example.

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

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

Production method:
The method for producing the antiglare hard-coated laminated film of the present invention is not particularly limited, and it can be produced by any method. As a preferable manufacturing method, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example,
(1) forming a wet coating film made of the second hard coat forming coating material on the transparent resin film;
(2) The wet coating film made of the coating material for forming the second hard coat is irradiated with an active energy ray at an integrated light amount of 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 coating material is dried to the touch. forming a membrane;
(3) forming a wet coating film made of the first hard coat-forming paint on the dry-to-the-touch coating made of the second hard coat-forming paint; and (4) the first The wet coating film made of the paint for forming a hard coat is preheated to a temperature of 30 to 100° C., preferably 40 to 85° C., more preferably 50 to 75° C., and an active energy ray is applied so that the integrated light amount is 240 to 10000 mJ / cm. ² , preferably 320 to 5000 mJ/cm ² , more preferably 360 to 2000 mJ/cm ² ;

In the step (1), the method of forming the wet coating film composed of the second hard coat-forming coating material is not particularly limited, and a known web coating method can be used. Examples of the 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 coating material formed in the step (1) becomes dry to the touch or has no tackiness in the step (2), and directly touches the web device. It will 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 dry-to-the-touch coating made of the second hard coat-forming paint. will be able to

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

The irradiation of the active energy ray in the step (2) depends on the properties of the paint used as the paint for forming the second hard coat, but from the viewpoint of ensuring that the paint film is dry to the touch, the cumulative amount of light is usually 1 J. /cm ² or more, preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, still more preferably 20 mJ/cm ² or more, most preferably 30 mJ/cm ² or more. On the other hand, from the viewpoint of adhesion between the first hard coat and the second hard coat, the integrated amount of light is usually 230 mJ/cm ² or less, preferably 200 mJ/cm ² or less, more preferably 160 mJ/cm ² or less, even more preferably. is 120 mJ/cm ² or less, most preferably 100 mJ/cm ² or less.

Before irradiating the active energy ray in the step (2), it is preferable to pre-dry the wet coating film made of the coating material for forming the second hard coat. For the preliminary drying, for example, it takes about 0.5 to 10 minutes for the web to pass through a drying oven set at a temperature of about 23 to 150° C., preferably at a temperature of 50 to 120° C., from the inlet to the outlet. , preferably by passing at a line speed of 1 to 5 minutes.

When irradiating the active energy ray in the step (2), the wet coating film made of the second hard coat forming coating material may be preheated to a temperature of 40 to 120°C, preferably 70 to 100°C. It is possible to ensure that the coating film is dry to the touch. The preheating method is not particularly limited, and any method can be used. An example of a specific method will be described later in the description of step (4) below.

In the step (3), the method of forming the wet coating film composed of the first hard coat-forming coating material is not particularly limited, and a known web coating method can be used. Examples of the 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 coating material formed in the step (3) is completely cured in the step (4). At the same time, the coating film made of the coating material for forming the second hard coat is also completely cured.

Although not intending to be bound by theory, the reason why the adhesion between the first hard coat and the second hard coat can be improved by the above method is that the irradiation of the active energy ray is performed in the step (2). is sufficient to make the coating film dry to the touch, but is suppressed to an insufficient integrated amount of light for complete curing, and in the above step (4), the integrated amount of light sufficient to completely cure the coating film is obtained for the first time. This is presumed to be because both hard coats are completely cured at the same time.

Irradiation of active energy rays in the above step (4) has an integrated light amount of 240 mJ/cm 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. /cm ² or more, more preferably 360 mJ/cm ² or more. On the other hand, from the viewpoint of preventing the obtained hard coat laminated film from yellowing and from the viewpoint of cost, the integrated amount of light is 10000 mJ/cm ² or less, preferably 5000 mJ/cm ² or less, more preferably 2000 mJ/cm ^{2 or less} . Perform as follows.

Before irradiating the active energy ray in the step (4), it is preferable to pre-dry the wet coating film made of the first hard coat forming coating material. For the preliminary drying, for example, it takes about 0.5 to 10 minutes for the web to pass through a drying oven set at a temperature of about 23 to 150° C., preferably at a temperature of 50 to 120° C., from the inlet to the outlet. , preferably by passing at a line speed of 1 to 5 minutes.

When irradiating the active energy ray in the step (4), the wet coating film made of the first hard coat-forming paint has the properties of the first hard coat-forming paint and the second hard coat-forming paint. From the viewpoint of obtaining good interlaminar adhesion strength even when the temperature differs greatly, the temperature is preheated to 30 to 100°C, preferably 40 to 85°C, more preferably 50 to 75°C. The preheating method is not particularly limited, and any method can be used. For example, as shown in FIG. 3, a method in which the web is held by a roll facing the active energy ray irradiation device and the surface temperature of the roll is controlled to a predetermined temperature; a method of controlling the temperature of to a predetermined temperature; and a combination thereof.

After the step (4), an aging treatment may be performed. The characteristics of the antiglare hard coat laminated film can be stabilized.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Measurement method (a) Total light transmittance:
Measured according to JIS K 7361-1:1997 using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd.

(b) Y value of XYZ display system based on 2-degree field of view:
Using a spectrophotometer "SolidSpec-3700 (trade name)" of Shimadzu Corporation and a reflection unit "absolute reflectance measuring device incident angle 5° (trade name)", 5 degrees according to the instruction manual of the above spectrophotometer It was measured under the condition of specular reflection (a reflection unit was installed in front of the integrating sphere).

(C) Haze:
Measured according to JIS K 7136:2000 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 under the condition of a load of 750 g, using a pencil "Uni (trade name)" manufactured by Mitsubishi Pencil Co., Ltd.

(e) Minimum bending radius:
With reference to JIS-K6902: 2007 bending formability (B method), the test piece was conditioned for 24 hours at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5%. The line was drawn in a direction perpendicular to the machine direction of the antiglare hard-coated laminated film, and the first hard coat of the antiglare hard-coated laminated film was bent to form a curved surface. The radius of the front portion of the smallest radius of the front portion among the forming jigs in which no cracks occurred was taken as the minimum bending radius. This "front portion" means the same term relating to the forming jig in the B method defined in JIS K6902:2007, Section 18.2.

(f) Water contact angle:
A method of calculating the first hard coat surface of the antiglare hard coat laminated film from the width and height of water droplets using an automatic contact angle meter "DSA20 (trade name)" manufactured by KRUSS (JIS R 3257: 1999 ) was measured.

(g) Scratch resistance 1 (water contact angle after wiping with cotton):
A test piece with a size of 150 mm long and 50 mm wide was taken so that the machine direction of the antiglare hard-coated laminated film was the longitudinal direction of the test piece. Place it on a JIS L 0849: 2013 Gakushin-type tester so that it becomes a stainless steel plate covered with four layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) on the friction terminal of the Gakushin-type tester. (10 mm long, 10 mm wide, 1 mm thick) is attached, the vertical and horizontal surfaces of the stainless steel plate are set in contact with the test piece, a 350 g load is placed, and the first hard coated surface of the test piece is moved by the movement distance of the friction terminal. After rubbing back and forth 10,000 times under conditions of 60 mm and a speed of 1 reciprocation/second, the water contact angle of the cotton-wiped portion was measured according to the method (vi) above. When the water contact angle was 100 degrees or more, after further rubbing 5,000 times back and forth, the operation of measuring the water contact angle at the point wiped with cotton was repeated according to the method (vi) above, and evaluated according to the following criteria. .
A: The water contact angle is 100 degrees or more even after 10,000 reciprocations.
B: The water contact angle is 100 degrees or more after 7,500 reciprocations, but less than 100 degrees after 10,000 times.
C: The water contact angle is 100 degrees or more after 5000 reciprocations, but less than 100 degrees after 7500 reciprocations.
D: The water contact angle is less than 100 degrees after 5000 reciprocations.

(h) Scratch resistance 2 (steel wool resistance):
The antiglare hard-coated laminated film was placed on a JIS L 0849:2013 Gakushin-type tester so that the first hard coat faced the surface. Subsequently, after attaching #0000 steel wool to the friction terminal of the Gakushin type testing machine, a load of 500 g was placed on the surface of the test piece, and after rubbing the surface of the test piece 100 times back and forth, the friction point was visually observed. When no scratch was observed, the work of visually observing the rubbed portion was repeated after further rubbing 50 times back and forth, and evaluation was made according to the following criteria.
A: No scratch is observed even after 200 reciprocations.
B: Scratches are not observed after 150 reciprocations, but scratches are observed after 200 reciprocations.
C: Scratches are not observed after 100 reciprocations, but scratches are observed after 150 reciprocations.
D: Scratches can be recognized after 100 reciprocations.

(i) yellowness index;
Measured according to JIS K 7105:1981 using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation.

(j) Surface smoothness (surface appearance):
The surfaces (both surfaces) of the antiglare hard-coated laminated film were visually observed while the incident angle of light from a fluorescent lamp was varied, and evaluated according to the following criteria.
A: No waviness or damage on the surface. Even if you look through the light up close, there is no unevenness or bumps.
◯: Slight unevenness is observed when viewed through light up close. However, there are no swells, scratches, or bumps.
Δ: Slight undulations and scratches are observed on the surface when viewed up close. In addition, there are irregularities and bumps.
x: A large number of undulations and scratches can be recognized on the surface. There are also obvious unevenness and bumps.

(k) Cross-cut test (adhesion):
According to JIS K 5600-5-6: 1999, 100 squares (1 square = 1 mm × 1 mm) of grid cuts were made in the antiglare hard-coated laminated film from the first hard-coated surface side, and then a tape for adhesion test was applied. After sticking to the grid and squeezing it with fingers, it was peeled off. The evaluation criteria were in accordance with Table 1 of the JIS standard.
Class 0: The edges of the cut are completely smooth, and there is no detachment on any grid mesh.
Category 1: Small delamination of the coating at the intersection of cuts. No more than 5% is clearly affected in the crosscut portion.
Category 2: The coating is peeling along the edges of the cuts and/or at the intersections. The crosscut portion is affected by clearly more than 5%, but not more than 15%.
Class 3: The coating is partially or totally peeled off along the edge of the cut and/or partially or totally peeled off in various parts of the eye. The crosscut portion is affected by clearly more than 15% but not more than 35%.
Class 4: The coating film is partially or entirely peeled off along the edge of the cut, and/or some grains are partially or entirely peeled off. The crosscut portion is affected clearly above 35% but not above 65%.
Category 5: When the degree of peeling exceeds Category 4.

(l) Machinability (state of curved cutting lines):
Using a router processing machine automatically controlled by a computer, the antiglare hard-coated laminated film was provided with a perfect circular cut hole with a diameter of 2 mm and a perfect circular cut hole with a diameter of 0.5 mm. The mill used at this time had four blades made of cemented carbide with cylindrical round tips and nicks. Subsequently, the cut end face of the cut hole with a diameter of 2 mm was visually or microscopically observed (100 times) and evaluated according to the following criteria. Similarly, the cut end face of a cut hole with a diameter of 0.5 mm was visually or microscopically observed (100 times) and evaluated according to the following criteria. In the table, the results of the former are listed in the order of the results of the latter.
⊚: No cracks or whiskers observed by microscopic observation O: No cracks observed by microscopic observation. But beards are allowed.
Δ: No cracks are visually observed. However, cracks are observed by microscopic observation.
x: Cracks are 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) Shin-Etsu Chemical Co., Ltd.'s acryloyl group-containing fluoropolyether-based water repellent "KY-1203 (trade name)". Solid content 20% by mass.
(B-2) Methacryloyl group-containing fluoropolyether water repellent "FOMBLIN MT70 (trade name)" manufactured by Solvay. Solid content 70% by mass.

(C) Silane coupling agent:
(C-1) Shin-Etsu Chemical Co., Ltd. N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane “KBM-602 (trade name)”.
(C-2) Shin-Etsu Chemical Co., Ltd. N-2-(aminoethyl)-3-aminopropyltrimethoxysilane “KBM-603 (trade name)”.
(C-3) Shin-Etsu Chemical Co., Ltd. 3-aminopropyltrimethoxysilane “KBM-903 (trade name)”.
(C-4) 3-mercaptopropylmethyldimethoxysilane “KBM-802 (trade name)” from Shin-Etsu Chemical Co., Ltd.;
(C-5) Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyltrimethoxysilane “KBM-403 (trade name)”.

(D) Resin fine particles having an average particle size of 0.5 to 10 μm:
(D-1) Spherical silicon-based resin fine particles “Tospearl 120 (trade name)” from Momentive Performance Materials. Average particle size 2 μm.
(D-2) Spherical silicon-based resin fine particles “Tospearl 130 (trade name)” from Momentive Performance Materials. Average particle size 3 μm.
(D-3) Soken Chemical Co., Ltd. acrylic resin fine particles "MA-180TA (trade name)". Average particle size 1.8 μm.
(D-4) Soken Chemical Co., Ltd. acrylic resin fine particles "MX-80H3wT (trade name)". 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 microparticles:
(D'-1) Silica fine particles "SO-E6 (trade name)" from Admatechs Co., Ltd. Average particle size 2 μm.

(E) Inorganic fine particles having an average particle size 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 leveling agent “Disparon NSH-8430HF (trade name)” from Kusumoto Kasei Co., Ltd.; Solid content 10% by mass.
(F-2) Silicone-acrylic copolymer leveling agent “BYK-3550 (trade name)” from BYK-Chemie Japan. Solid content 52% by mass.
(F-3) BYK-Chemie Japan Co., Ltd. acrylic polymer leveling agent "BYK-399 (trade name)". Solid content 100% by mass.
(F-4) Silicon-based leveling agent “Disparon LS-480 (trade name)” from Kusumoto Kasei Co., Ltd.; Solid content 100% by mass.

(G) Optional ingredients:
(G-1) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexylphenylketone) “SB-PI714 (trade name)” from Sobang Industrial Co., Ltd.;
(G-2) 1-methoxy-2-propanol.

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

(H1-2 to 20) Paints were 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.

(H1′) Reference paint for forming the first hard coat:
(H1'-1 to 7) Paints were 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 second hard coat:
(H2-1) The above (A-2) 100 parts by mass, the above (E-1) 140 parts by mass, the above (F-1) 2 parts by mass (0.2 parts by mass in terms of solid content), the above (G-1 ) and 200 parts by mass of (G-2) were mixed and stirred. 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 to 12) Paints were obtained in the same manner as in (H2-1) above, except that the formulations were changed as shown in Table 4 or Table 5.

(H2′) Reference paint for forming the second hard coat:
(H2'-1, 2) Paints were obtained in the same manner as in (H2-1) above, except that the formulations were changed as shown in Table 5.

(P) Transparent resin film:
(P-1) Co-extrusion T die of 2-kind, 3-layer multi-manifold system, first mirror roll (roll on the side of holding the melted film and sending it to the next transfer roll) and second mirror roll to melt film Evonik's poly (meth) acrylic as both outer layers (α1 layer and α2 layer) of a two-kind three-layer multilayer resin film using a device (see FIG. 4) equipped with a winding machine equipped with a mechanism to press The imide "PLEXIMID TT50 (trade name)" is continuously co-extruded from a co-extrusion T-die with an aromatic polycarbonate "Caliber 301-4 (trade name)" of Sumika Styron Polycarbonate Co., Ltd. as an intermediate layer (β layer). , So that the α1 layer is on the first mirror roll side, it is supplied between the rotating first mirror roll and the second mirror roll, 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 thickness of 80 μm was obtained. At this time, the set conditions were a set temperature of the T-die of 300° C., a set temperature of the first mirror-finished roll of 130° C.; a set temperature of the second mirror-finished roll of 120° C., and a take-up speed of 6.5 m/min.

(P-2) The above (P- 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 60 μm for the α1 layer, 130 μm for the β layer, and 60 μm for the α2 layer. 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 40 μm for the α1 layer, 170 μm for the β layer, and 40 μm for the α2 layer. rice field.

(P-5) Biaxially stretched polyethylene terephthalate film "Diafoil (trade name)" manufactured by Mitsubishi Plastics, Inc., thickness 250 μm.

(P-6) Acrylic resin film “Technolloy S001G (trade name)” manufactured by Sumitomo Chemical Co., Ltd., thickness 250 μm.

(P-7) A puller equipped with a single-layer T die and a mechanism for pressing the melted film with the first mirror roll (the roll on the side of holding the melted film and sending it to the next transfer roll) and the second mirror roll Using a device equipped with a winding machine, Sumika Styron Polycarbonate Co., Ltd.'s aromatic polycarbonate "Caliber 301-4 (trade name)" is continuously extruded from a T-die, and the rotating first mirror surface roll and second mirror surface are extruded. A transparent resin film having a total thickness of 250 μm was obtained by feeding and pressing between rolls. At this time, the set conditions were a set temperature of the T-die of 320° C., a set temperature of the first mirror-finished roll of 140° C.; a set temperature of the second mirror-finished roll of 120° C., and a take-up speed of 5.6 m/min.

Example 1
Both sides of the above (P-1) were subjected to corona discharge treatment. The wetting index was 64 mN/m on both sides. Next, the above (H2-1) was coated on the α1 layer side using a die-type coating device so as to give a wet thickness of 40 μm (thickness after curing: 22 μm). Next, after passing through a drying furnace set to a temperature of 90 ° C. at a line speed that takes 1 minute to pass from the entrance to the exit, a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm Using a curing device with a mirror-finished metal roll facing each other (see FIG. 3), processing was performed under the conditions of a mirror-finished metal roll temperature of 90° C. and an integrated light intensity of 80 mJ/cm ² . The wet coating film of (H2-1) was dry to the touch. Next, using a die-type coating device on the dry-to-the-touch coating of (H2-1), apply the above (H1-1) to a wet thickness of 4 μm (thickness after curing of 2 μm). applied. Next, after passing through a drying furnace set at an internal temperature of 80 ° C. at a line speed that takes 1 minute to pass from the entrance to the exit, a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm Using a curing device in which a specular metal roll is placed (see Fig. 1), the temperature of the specular metal roll is 60°C and the integrated light intensity is 480mJ/ ^cm2 to form the first hard coat and the second hard coat. bottom. Subsequently, a third hard coat is applied on the surface of the α2 layer side, using the same paint as that used to form the second hard coat (Example 1 is (H2-1) above), and die-coating. A hard coat laminate film was obtained by using a device to form a film having a thickness of 22 μm after curing. The above tests (i) to (wo) were performed. Table 6 shows the results.

Examples 2-20, Examples 1C-7C
Everything was 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 (H1-1). The results are shown in any one of Tables 6-9.

Examples 21-31, Examples 8C, 9C
Everything was 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 (H2-1). The results are shown in any one of Tables 10-12.

Examples 32-36
Everything was carried out in the same manner as in Example 1, except that the transparent resin film shown in Table 12 was used instead of (P-1). Table 12 shows the results.

Examples 37-40
Everything was carried out in the same manner as in Example 1, except that the post-curing thickness of the first hard coat 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 Table 14, and the post-curing thickness of the third hard coat was changed to be the same as the post-curing thickness of the second hard coat. Same as 1. The results are shown in Table 13 or Table 14.

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

A preferred antiglare hard-coated laminated film of the present invention is excellent in antiglare properties, scratch resistance, surface hardness, and finger sliding properties. Furthermore, the bending resistance, color tone, appearance, interlayer adhesion strength, and machinability are also good. Therefore, the components 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 without a touch panel function), especially car navigation devices, etc. The device is often used in an environment where external light is incident, and can be suitably used as a member of a device having a touch panel function.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of the antiglare hard-coated laminated film of the present invention; It is a figure explaining a curvature radius. 1 is a conceptual diagram of an ultraviolet irradiation device used in Examples. FIG. 1 is a conceptual diagram of a film forming apparatus used in Examples. FIG.

1: First hard coat 2: Second hard coat 3: First poly(meth)acrylimide resin layer (α1)
4: Layer of aromatic polycarbonate resin (β)
5: Second poly(meth)acrylimide resin layer (α2)
6: Third hard coat 7: Ultraviolet irradiation device 8: Mirror surface 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 (10)

Having a layer of a first hard coat, a second hard coat, and a transparent resin film in order from the surface side,
The first hard coat comprises a paint containing polyfunctional (meth)acrylate, a water repellent, and fine resin particles having an average particle size of 0.5 to 10 μm and containing no inorganic particles;
Here, the blending amount of the fine resin particles having an average particle diameter of 0.5 to 10 μm is 0.3 to 15 parts by mass with respect to 100 parts by mass of the polyfunctional (meth)acrylate;
The thickness of the first hard coat is 1 to 4 μm;
The second hard coat is 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). becomes;
A hard coat laminated film that satisfies the following (1) to (3).
(1) The total light transmittance is 85% or more.
(2) The surface of the first hard coat has a pencil hardness of 5H or more.
(3) The Y value in the XYZ color system is 4.2% or less.
The hard coat laminated film according to claim 1, further satisfying the following (4).
(4) The water contact angle of the surface of the first hard coat after 7500 reciprocating wipings with cotton is 100 degrees or more.
3. The hard coat laminated film according to claim 1, further satisfying the following (5).
(5) The minimum bending radius is 40 mm or less.
The hard coat laminated film according to any one of claims 1 to 3, further satisfying the following (6).
(6) A yellowness index of 3 or less.
5. The hard coat laminated film according to any one of claims 1 to 4, wherein the first hard coat contains fine resin particles having an average particle size of 1 to 6 μm and is made of a paint containing no inorganic particles.
The hard coat laminated film according to any one of claims 1 to 5, wherein the surface of the first hard coat has a pencil hardness of 6H or more.
7. Any one of claims 1 to 6, wherein the second hard coat comprises (A) 100 parts by mass of 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. 2. The hard coat laminated film according to item 1.
The hard coat laminated film according to any one of claims 1 to 7 , wherein the second hard coat has a thickness of 10 to 30 µm.
Use of the hard coat laminated film according to any one of claims 1 to 8 as a member of an image display device.
An image display device comprising the hard coat laminated film according to any one of claims 1 to 8 .

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