JP6181803B2 - Active energy ray-curable resin composition and hard coat laminated film using the same - Google Patents

Description

The present invention relates to an active energy ray-curable resin composition and a hard coat laminated film using the same. More specifically, the active energy ray-curable resin composition capable of forming a hard coat excellent in transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface appearance, and a hard coat using the same The present invention relates to a laminated film.

In recent years, touch panels that are installed on image display devices such as a liquid crystal display, a plasma display, and an electroluminescence display and can be input by touching with a finger or a pen while watching the display have become widespread.

Conventionally, glass-based articles have been used for display faceplates of touch panels because they meet required characteristics such as heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity. On the other hand, glass has problems such as low impact resistance and easy cracking; low workability; difficult to handle; high specific gravity and heavy; difficult to meet demands for curved display and flexibility. Therefore, materials that replace glass have been actively studied, and the surface of a transparent resin film substrate such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene-based polymer has excellent surface hardness and scratch resistance. Many hard coat laminated bodies in which a hard coat is formed have been proposed (for example, Patent Document 1). However, its scratch resistance is still insufficient, and there is a need for a coating material for forming a hard coat that can maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

JP 2013-208896 A

An object of the present invention is to provide an active energy ray-curable resin composition capable of forming a hard coat excellent in transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface smoothness, and the use thereof. 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), particularly hard coats suitable as display face plates of touch panels It is to provide a laminated film.

As a result of diligent research, the present inventor can achieve the above-described problems with an active energy ray-curable resin composition containing a polyfunctional (meth) acrylate, a compound having a specific functional group, organic titanium, and fine particles having a specific particle size. I found.

That is, the present invention provides (A) 100 parts by mass of a polyfunctional (meth) acrylate;
(B) 0.2-4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group;
(C) 0.05 to 3 parts by mass of organic titanium; and (D) 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm;
Is an active energy ray-curable resin composition.

The second invention of the present invention is the active energy ray-curable resin composition according to the first invention, further comprising (E) 0.01 to 7 parts by mass of a water repellent.

According to a third aspect of the present invention, the active energy ray-curing property according to the second aspect is characterized in that the (E) water repellent contains a (meth) acryloyl group-containing fluoropolyether water repellent. It is a resin composition.

4th invention of this invention has a hard coat which consists of a coating material containing the active energy ray-curable resin composition of any one of 1st-3rd invention in at least one surface of a transparent resin film. A hard coat laminated film.

The fifth invention of the present invention has, in order from the outermost layer side, a first hard coat; a layer of a transparent resin film; a second hard coat; wherein the first hard coat is the first to third inventions. A hard coat laminated film comprising a paint containing the active energy ray-curable resin composition according to any one of the above.

A sixth invention of the present invention is the hard coat laminated film according to the fourth invention or the fifth invention, wherein the transparent resin film is a poly (meth) acrylimide resin film.

According to a seventh aspect of the present invention, the poly (meth) acrylimide resin film comprises a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly ( The (meth) acrylimide resin layer (α2); is a transparent multilayer film directly laminated in this order, and is a hard coat laminated film according to the sixth invention.

The eighth invention of the present invention is a hard coat laminated film for a touch panel display face plate that satisfies the following (A) to (E).
(A) Total light transmittance is 80% or more.
(B) Haze 3.0% or less.
(C) Yellowness index: 3 or less.
(D) The water contact angle of the touch surface is 100 degrees or more.
(E) Water contact angle after 20,000 reciprocating cotton wipes on the touch surface is 100 degrees or more.

9th invention of this invention is a manufacturing method of the hard coat laminated film as described in 8th invention, Comprising:
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) 0.2-4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group;
(C) 0.05 to 3 parts by mass of organic titanium; and (D) 5 to 100 parts by mass of fine particles having an average particle diameter of 1 to 300 nm;
A hard coat-forming coating composition containing an active energy ray-curable resin composition containing is applied to at least one surface of a poly (meth) acrylimide resin film to form a hard coat.

10th invention of this invention is a manufacturing method of the hard coat laminated film as described in 8th invention, Comprising:
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) 0.2-4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group;
(C) 0.05 to 3 parts by mass of organic titanium;
(D) 5 to 100 parts by mass of fine particles having an average particle size of 1 to 300 nm; and (E) 0.01 to 7 parts by mass of a water repellent agent;
A hard coat-forming coating composition containing an active energy ray-curable resin composition containing is applied to at least one surface of a poly (meth) acrylimide resin film to form a hard coat.

An eleventh aspect of the present invention is the method according to the tenth aspect, wherein the (E) water repellent comprises a (meth) acryloyl group-containing fluoropolyether water repellent.

A twelfth aspect of the present invention is a hard coat laminated film produced by the method according to any one of the ninth to eleventh aspects.

A thirteenth invention of the present invention is the use of the hard coat laminated film according to any one of the fourth to eighth and twelfth inventions as an image display device member.

A fourteenth aspect of the present invention is an image display device comprising the hard coat laminated film according to any one of the fourth to eighth and twelfth aspects.

The hard coat laminated film which has the hard coat which consists of a coating material containing the active energy ray curable resin composition of this invention is excellent in transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface appearance. Therefore, it is preferably used as a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (including an image display device having a touch panel function and an image display device not having a touch panel function), particularly as a display face plate of a touch panel. Can do.

1. Active energy ray-curable resin composition:
The active energy ray-curable resin composition of the present invention will be described.

(A) Polyfunctional (meth) acrylate:
The active energy ray-curable resin composition of the present invention contains (A) 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 has active energy such as ultraviolet rays and electron beams. It is polymerized and cured by the wire and functions 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, (Meth) acryloyl group-containing bifunctional reaction such as 2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane Monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylate; (meth) acrylates such as pentaerythritol tetra (meth) acrylate Ile group-containing tetrafunctional reactive monomers; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; and polymers (oligomers and prepolymers) having one or more of these as constituent monomers Can do. As said component A, these 1 type, or 2 or more types of mixtures can be used.

In the present specification, (meth) acrylate means acrylate or methacrylate.

(B) Compound having alkoxysilyl group and (meth) acryloyl group:
The active energy ray-curable resin composition of the present invention includes (B) a compound having an alkoxysilyl group and a (meth) acryloyl group. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. The component B is distinguished from the component A in that it has an alkoxysilyl group. The component A does not have an alkoxysilyl group. In the present specification, a compound having an alkoxysilyl group and two or more (meth) acryloyl groups in one molecule is Component B.

The component B has a (meth) acryloyl group in the molecule, and can have a chemical bond or a strong interaction with the component D by having an alkoxysilyl group. It works to greatly improve sex. In addition, component B has a (meth) acryloyl group in the molecule or has an alkoxysilyl group in the molecule, thereby preventing chemical bonds or strong interactions and preventing troubles such as component E bleeding out. Also works.

Examples of the component B include compounds having a chemical structure represented by the general formula “(—SiO ₂ RR ′ —) n · (—SiO ₂ RR ″ —) m”. Here, n is a natural number (a positive integer), and m is 0 or a natural number. Preferably, n is a natural number of 2 to 10, and m is 0 or a natural number of 1 to 10. R is an alkoxy group such as a methoxy group (CH ₃ O—) or an ethoxy group (C ₂ H ₅ O—). R ′ is an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) CO—). R ″ is an alkyl group such as a methyl group (CH ₃ ) or an ethyl group (CH ₂ CH ₃ ).

Examples of the component B include, for example, the general formula “(—SiO ₂ (OCH ₃ ) (OCHC═CH ₂ ) —) n”, “(—SiO ₂ (OCH ₃ ) (OC (CH ₃ ) C═CH ₂ )”. -) n "," _{(- SiO 2 (OCH 3)} (OCHC = CH 2) -) n · (-SiO 2 (OCH 3) (CH 3) -) m "," _(- SiO 2 _(OCH 3) _{(OC (CH 3) C =} CH 2) -) n · (-SiO 2 (OCH 3) (CH 3) -) m "," _{(- SiO 2 (OC 2 H} 5) (OCHC = CH 2) - ) n "," _{(- SiO 2 (OC 2 H} 5) (OC (CH 3) C = CH 2) -) n "," _{(- SiO 2 (OC 2 H} 5) (OCHC = CH 2) -) _{n · (-SiO 2 (OCH 3} ) (CH 3) -) m ", and" _{(-SiO 2 (OC 2 H 5} ) _{OC (CH 3) C = CH} 2) -) n · (-SiO 2 (OCH 3) (CH 3) -) can be mentioned compounds having a chemical structure represented by m '. Here, n is a natural number (a positive integer), and m is 0 or a natural number. Preferably, n is a natural number of 2 to 10, and m is 0 or a natural number of 1 to 10.

As said component B, these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component B is 0.2 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of scratch resistance with respect to 100 parts by mass of the component A. . On the other hand, from the viewpoint of facilitating the development of water repellency, and from the viewpoint of preventing the component C from becoming excessive when the blending ratio of the component B and the component C is within a preferred range, it is preferably 4 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less.

Further, from the viewpoint of chemically bonding or strongly interacting with the component D, the blending ratio of the component B and the component D is usually 0.2 to 80 parts by mass with respect to 100 parts by mass of the component D, preferably It is 0.5-15 mass parts, More preferably, it is 2-7 mass parts.

(C) Organic titanium:
The active energy ray-curable resin composition of the present invention contains (C) organic titanium.

The component C is a component that assists the function of the component B. From the viewpoint of greatly improving the scratch resistance of the hard coat, the component B and the component C exhibit specific compatibility. The component C itself also has a chemical bond or strong interaction with the component D and the like, and functions to improve the scratch resistance of the hard coat.

Examples of the organic titanium include tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, and di-i-propoxy bis (acetyl). Acetonato) titanium, propanedioxytitanium bis (ethylacetoacetate), tri-n-butoxytitanium monostearate, di-i-propoxytitanium distearate, titanium stearate, di-i-propoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, di-n-butoxy-bis (triethanolaminato) titanium; and a polymer comprising one or more of these; and the like. As said component C, these 1 type, or 2 or more types of mixtures can be used.

Among these, alkoxy-titanium tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate are from the viewpoint of scratch resistance and color tone. preferable.

The blending amount of the component C is 0.05 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more from the viewpoint of scratch resistance with respect to 100 parts by mass of the component A. It is. On the other hand, from the viewpoint of color tone, it is 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less.

From the viewpoint of effectively assisting the function of the component B, the compounding ratio of the component B and the component C is usually 1.25 to 1500 parts by mass, preferably 100 parts by mass of the component B, preferably It is 5-150 mass parts, More preferably, it is 20-80 mass parts.

(D) Fine particles having an average particle diameter of 1 to 300 nm:
The active energy ray-curable resin composition of the present invention includes (D) fine particles having an average particle diameter of 1 to 300 nm.

The component D functions to increase the surface hardness of the hard coat. On the other hand, the interaction with the component A was weak, which caused the scratch resistance to be insufficient. Therefore, the present invention solves this problem by using the component B that can chemically bond or strongly interact with both the component A and the component D, and the component C that assists the function of the component B. .

As the component D, either inorganic fine particles or organic fine particles can be used. 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; metal fine particles; Examples of the organic fine particles include resin beads such as a styrene resin, an acrylic resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. These can be used alone or in combination of two or more.

In addition, for the purpose of increasing the dispersibility of the fine particles in the paint or increasing the surface hardness of the obtained hard coat, the surface of the fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent; aluminum Nate coupling agents; Organic compounds having an ethylenically unsaturated bond group such as (meth) acryloyl group, vinyl group and allyl group and reactive functional groups such as epoxy group; Surface treatment agents such as fatty acids and fatty acid metal salts You may use what was processed by.

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

The average particle diameter of the component D is 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less from the viewpoint of maintaining the transparency of the hard coat and ensuring the effect of improving the surface hardness of the hard coat. On the other hand, there is no particular reason for limiting the lower limit of the particle diameter, but normally available fine particles are fine, at most, about 1 nm.

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

The compounding amount of the component D is 5 parts by mass or more, preferably 20 parts by mass or more from the viewpoint of surface hardness with respect to 100 parts by mass of the component A. On the other hand, from the viewpoint of scratch resistance and transparency, it is 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

(E) Water repellent:
The active energy ray-curable resin composition of the present invention further includes (E) a water repellent agent in an amount of 0.01 to 7 parts by mass from the viewpoint of improving slipperiness, dirt adhesion prevention property, and dirt wiping property. Is preferably included.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, acrylic / ethylene copolymer wax; and silicon-based water repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane. Fluorine-containing water repellents such as fluoropolyether water repellents, fluoropolyalkyl water repellents, and the like. As Component E, one or a mixture of two or more of these may be used. be able to.

Among these, the component E is preferably a fluoropolyether water repellent from the viewpoint of water repellent performance. From the viewpoint of preventing troubles such as the chemical bond or strong interaction between the component A or the component B and the component E, causing the component E to bleed out, the component E includes a (meth) acryloyl group and a fluoro A water repellent containing a compound containing a polyether group (hereinafter abbreviated as (meth) acryloyl group-containing fluoropolyether water repellent) is more preferable. Component E is an acryloyl group-containing fluoropolyether-based water repellent from the viewpoint of appropriately adjusting the chemical bond or interaction between Component A or Component B and Component E, and expressing good water repellency while maintaining high transparency. An admixture of an agent and a methacryloyl group-containing fluoropolyether water repellent may be used.

The amount of component E used is usually 7 parts by mass or less, preferably 4 parts by mass or less, from the viewpoint of preventing troubles such as bleeding out of component E with respect to 100 parts by mass of component A. Preferably it is 2 mass parts or less. The lower limit of the amount is not particularly limited because it is an optional component, but from the viewpoint of obtaining the effect of using component E, it is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass. More than a part.

In addition, the active energy ray-curable resin composition of the present invention includes a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or from the viewpoint of improving curability by active energy rays. Or it is preferable to further contain a photoinitiator.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent can be used. As the compound having two or more isocyanate groups in one molecule, one or a mixture of two or more thereof can be used. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The active energy ray-curable resin composition of the present invention includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, a weather resistance, if desired. 1 type, or 2 or more types of additives, such as a stability stabilizer, a light resistance stabilizer, a ultraviolet absorber, a heat stabilizer, a coloring agent, and a filler, may be included.

Moreover, in order to dilute to the density | concentration which is easy to apply, the active energy ray curable resin composition of this invention may contain the solvent as desired. The solvent is not particularly limited as long as it does not react with the above components A to D and other optional components or catalyze (promote) self-reaction (including degradation reaction) of these components. Examples thereof include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

The method for forming a hard coat using the hard coat forming coating material containing the active energy ray-curable resin composition of the present invention is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

2. Hard coat laminated film:
The hard coat laminated film of the present invention will be described.

The hard coat laminated film of the present invention preferably has a total light transmittance of 80% or more measured by the following method (a). By being highly transparent with a total light transmittance of 80% or more, the hard coat laminated film can be suitably used for a display face plate of a touch panel. The total light transmittance is preferably as high as possible, more preferably 85% or more, and still more preferably 90% or more.

The hard coat laminated film of the present invention preferably has a haze of 3.0% or less measured by the following method (b). By being highly transparent with a haze of 3.0% or less, the hard coat laminated film can be suitably used for a display face plate of a touch panel. The haze is preferably as low as possible, more preferably 2.0% or less, and still more preferably 1.5% or less.

The hard coat laminated film of the present invention preferably has a yellowness index of 3 or less measured by the following method (c). By having no yellowness index of 3 or less, the hard coat laminated film can be suitably used for a display face plate of a touch panel. The yellowness index is preferably as low as possible, more preferably 2 or less, and still more preferably 1 or less.

When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, preferably, the touch surface of the hard coat laminated film (the face to be touched with a finger or a pen on the touch panel display face plate to perform an input operation). The water contact angle measured by the following method (d) is 100 degrees or more. When the water contact angle is 100 degrees or more, the touch panel can be operated by sliding a finger or a pen as desired on the touch surface of the hard coat laminated film. From the viewpoint of sliding a finger or pen as desired, the water contact angle is preferably higher, more preferably 105 degrees or more. On the other hand, the upper limit of the water contact angle is not particularly limited, but about 120 degrees is usually sufficient from the viewpoint of slipperiness.

When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, the water contact angle after 20,000 reciprocating cotton swabs measured by the method (e) below on the touch surface of the hard coat laminated film is preferably 100. More than degrees. When the water contact angle after 20,000 reciprocating cotton wiping is 100 degrees or more, surface characteristics such as slipperiness can be maintained even when repeatedly wiped with a handkerchief or the like. The water contact angle after 20,000 reciprocating cotton swabs is preferably 105 degrees or more. On the other hand, although there is no upper limit of the water contact angle after 20,000 reciprocating cotton swabs, about 120 degrees is usually sufficient from the viewpoint of slipperiness.

The hard coat laminated film of the present invention can be preferably obtained by forming a hard coat made of a paint containing the active energy ray-curable resin composition of the present invention on at least one surface of the transparent resin film.

The hard coat is formed on at least one side of the transparent resin film, preferably on both sides from the viewpoint of curling resistance. Moreover, it is preferable that the coating material for forming a hard coat that forms at least the touch surface is a coating material containing the active energy ray-curable resin composition of the present invention.

The thickness of the hard coat is not particularly limited, but is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm from the viewpoints of surface hardness, rigidity, heat resistance, and dimensional stability of the hard coat laminated film of the present invention. More preferably, it may be 20 μm or more. Moreover, from a viewpoint of the cutting work aptitude and web handling property of the hard coat laminated film of this invention, Preferably it is 100 micrometers or less, More preferably, you may be 50 micrometers or less.

The said transparent resin film is a layer used as the transparent film base material for forming the said 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. For example, cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymer; acrylic resins such as polymethyl methacrylate and polyethyl methacrylate; (Meth) acrylimide resins; aromatic polycarbonate resins; polyolefin resins such as polypropylene and 4-methyl-pentene-1; polyamide resins; polyarylate resins; polymer urethane acrylate resins; and polyimide resins; And include non-stretched films, uniaxially stretched films, and biaxially stretched films. Moreover, these 1 type, or 2 or more types of laminated films are included.

The thickness of the transparent resin film is not particularly limited, and can be any thickness as desired. From the viewpoint of handleability of the hard coat laminated film of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. Moreover, from an economical viewpoint, it may be 250 micrometers or less normally, Preferably it may be 150 micrometers or less. When the hard coat laminated film of the present invention is used as a display face plate of a touch panel, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more from the viewpoint of maintaining rigidity. Moreover, from a viewpoint of meeting the request | requirement of thickness reduction of a touchscreen, it may be 1500 micrometers or less normally, Preferably it is 1200 micrometers or less, More preferably, it may be 1000 micrometers or less.

Further, the hard coat of the hard coat laminated film is not limited to one layer, and may be two or more layers. The transparent resin film layer is not limited to one layer, and may be two or more layers. Furthermore, the hard coat laminated film may have an arbitrary layer other than the hard coat and the transparent resin film, if desired. Examples of the optional layer include an anchor coat layer, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer.

The transparent resin film is preferably a poly (meth) acrylimide resin film. It becomes a hard coat laminated film excellent in surface hardness, scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and dimensional stability, and can be suitably used as a display face plate of a touch panel or a transparent conductive substrate. .

The above poly (meth) acrylimide resin introduces the characteristics of excellent heat resistance and dimensional stability of polyimide resin while maintaining the characteristics of acrylic resin such as high transparency, high surface hardness and high rigidity. Is a thermoplastic resin that has improved the disadvantage of being colored reddish brown, and is disclosed in, for example, JP-T-2011-519999. In the present specification, poly (meth) acrylimide means polyacrylimide or polymethacrylamide.

As said poly (meth) acrylimide-type resin, from the objective of using a hard coat laminated film for optical articles, such as a touch panel, it is not restrict | limited except having high transparency and a thing without coloring, arbitrary Poly (meth) acrylimide resin can be used.

A preferable example of the poly (meth) acrylimide resin is a yellowness index (measured according to JIS K 7105: 1981 using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation). 3 or less can be mentioned. The yellowness index is more preferably 2 or less, and even more preferably 1 or less. From the viewpoint of the extrusion load and the stability of the molten film, it is preferable that the melt mass flow rate (measured in accordance with ISO 1133 under the conditions of 260 ° C. and 98.07 N) is 0.1 to 20 g / 10 min. it can. The melt mass flow rate is more preferably 0.5 to 10 g / 10 min. Further, the glass transition temperature of the poly (meth) acrylimide resin is preferably 150 ° C. or higher from the viewpoint of heat resistance. More preferably, it is 170 degreeC or more.

The poly (meth) acrylimide resin may be a thermoplastic resin other than the poly (meth) acrylimide resin; a pigment, an inorganic filler, an organic filler, and a resin filler, as long as it does not contradict the purpose of the present invention. An additive such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the poly (meth) acrylimide resin is 100 parts by mass.

Commercial examples of the poly (meth) acrylimide resin include “PLEXIMID TT70 (trade name)” manufactured by Evonik.

The poly (meth) acrylimide resin film is preferably a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly (meth) acrylimide resin. Layer (α2); is a transparent multilayer film directly laminated in this order. In the present specification, the present invention will be described on the assumption that the touch surface is formed on the α1 layer side.

Poly (meth) acrylimide resin is excellent in heat resistance and surface hardness, but machinability tends to be insufficient, whereas aromatic polycarbonate resin is excellent in machinability, Heat resistance and surface hardness tend to be insufficient. Therefore, by using the transparent multilayer film having the above-mentioned layer structure, it is possible to easily obtain a hard coat laminated film that compensates for the weaknesses of both and is excellent in any of heat resistance, surface hardness, and cutting workability. .

The layer thickness of the α1 layer is not particularly limited, but may be usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more from the viewpoint of heat resistance and surface hardness of the hard coat laminated film of the present invention.

The layer thickness of the α2 layer is not particularly limited, but is preferably the same layer thickness as the α1 layer from the viewpoint of curl resistance of the hard coat 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 construed that the layer thickness is the same within the range of 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 amplitude of process and quality control that is usually performed industrially. In the case of an unstretched multilayer film by the T-die coextrusion method, since the process and quality are usually controlled with a width of about -5 to +5 μm, the layer thicknesses of 65 μm and 75 μm should be interpreted as the same. is there.

The layer thickness of the β layer is not particularly limited, but may be usually 20 μm or more, preferably 80 μm or more, more preferably 120 μm or more from the viewpoint of cutting resistance of the hard coat laminated film of the present invention.

The poly (meth) acrylimide resin used for the α1 layer and the α2 layer has been described above.

The poly (meth) acrylimide-based resin used for the α1 layer and the poly (meth) acrylimide-based resin used for the α2 layer have different resin characteristics, for example, poly (meth) with different melt mass flow rate and glass transition temperature. A (meth) acrylimide resin may be used, but from the viewpoint of curl resistance of the 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 preferred embodiment.

Examples of the aromatic polycarbonate 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 phosgene. A polymer obtained by an interfacial polymerization method with an aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and carbonic acid such as diphenyl carbonate. One or a mixture of two or more aromatic polycarbonate resins such as a polymer obtained by a transesterification reaction with a diester can be used.

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

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 ester / acrylic ester rubber graft copolymers, and methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymers. One or two of these Mixtures of more than one species can be used.

The aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The compounding 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 production method for obtaining the poly (meth) acrylimide resin film is not particularly limited. For example, using a device including (A) an extruder and a T die, the poly (meth) acrylimide is obtained from the T die. A step of continuously extruding a molten film of a resin; (B) the poly (meth) acryl between the rotating or circulating first mirror body and the rotating or circulating second mirror body; And a step of supplying and pressing a molten film of an imide-based resin.

Similarly, the production method in the case where the poly (meth) acrylimide resin film is the transparent multilayer film is not particularly limited. For example, (A ′) a coextrusion apparatus including an extruder and a T die is used. , First poly (meth) acrylimide resin layer (α1); aromatic polycarbonate resin layer (β); second poly (meth) acrylimide resin layer (α2); Continuously co-extruding a molten film of a multilayer film from a T-die; (B ′) between a rotating or circulating first mirror body and a rotating or circulating second mirror body, And a step of supplying and pressing the molten film of the transparent multilayer film.

As the T die used in the step (A) or the step (A ′), any can be used, and examples thereof include a manifold die, a fish tail die, a coat hanger die, and the like.

Any coextrusion apparatus can be used, and examples thereof include a coextrusion apparatus such as a feed block system, a multi-manifold system, and a stack plate system.

Any extruder can be used as the extruder used in the step (A) or the step (A ′). For example, a single-screw extruder, a same-direction rotating twin-screw extruder, and a different-direction rotating two An example is a screw extruder.

In addition, in order to suppress deterioration of the poly (meth) acrylimide resin or the aromatic polycarbonate resin, it is one of preferable methods to purge the inside of the extruder with nitrogen.

Furthermore, since the poly (meth) acrylimide resin is a highly hygroscopic resin, it is preferably dried before being used for film formation. It is also one of preferable methods that the poly (meth) acrylimide resin dried by a dryer is directly transported from the dryer to the extruder and charged. The set temperature of the dryer is preferably 100 to 150 ° C. It is also a preferred method to provide a vacuum vent in the metering zone of the extruder, usually at the tip of the screw.

The temperature of the T die used in the step (A) or the step (A ′) is a continuous extrusion or coextrusion of a poly (meth) acrylimide resin melt film or a transparent multilayer film melt film. In order to perform the process to perform stably, it is preferable to set it at least 260 degreeC or more. More preferably, it is 270 degreeC or more. Moreover, in order to suppress deterioration of poly (meth) acrylimide resin or aromatic polycarbonate resin, the temperature of the T die is preferably set to 350 ° C. or lower.

Further, the ratio (R / T) between the lip opening (R) and the thickness (T) of the resulting poly (meth) acrylimide film is preferably 10 or less, and preferably 5 or less, from the viewpoint of preventing the retardation from increasing. More preferred. Further, the ratio (R / T) is preferably 1 or more, more preferably 1.5 or more, from the viewpoint of preventing the extrusion load from becoming excessive.

As said 1st mirror surface body used at the said process (B) or the said process (B '), a mirror roll, a mirror belt, etc. can be mention | raise | lifted, for example. As said 2nd mirror surface body, a mirror surface roll, a mirror surface belt, etc. can be mention | raise | lifted, for example.

The mirror roll is a roll having a mirror-finished surface, and is made of metal, ceramic, silicon rubber, or the like. Further, the surface of the mirror roll can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method, etc. for the purpose of protection from corrosion and scratches.

The mirror belt is a seamless belt made of a normal metal whose surface is mirror-finished. For example, the mirror belt is circulated between a pair of belt rollers. Further, the surface of the mirror belt can be subjected to chrome plating, iron-phosphorus alloy plating, hard carbon treatment by PVD method or CVD method for the purpose of protection from corrosion and scratches.

The mirror finish is not limited and can be performed by any method. For example, by polishing using fine abrasive grains, the arithmetic average roughness (Ra) of the surface of the mirror body is preferably 100 nm or less, more preferably 50 nm or less, and the ten-point average roughness (Rz) is preferably The method of making it 500 nm or less, More preferably, 250 nm or less can be mention | raise | lifted.

Although not intended to be bound by theory, it is the first reason that a poly (meth) acrylimide resin film or a transparent multilayer film excellent in transparency, surface smoothness, and appearance can be obtained by the above-described film forming method. When the molten film of the poly (meth) acrylimide resin film or the transparent multilayer film is pressed between the mirror body and the second mirror body, the highly smooth surface state of the first mirror body and the second mirror body is a film. It can be considered that a defective portion such as a die stripe is corrected.

The surface temperature of the first mirror body is preferably 100 ° C. or higher so that the transfer of the surface state can be performed satisfactorily. More preferably, it is 120 degreeC or more, More preferably, it is 130 degreeC or more. On the other hand, the surface temperature of the first mirror body is preferably 200 ° C. or lower, more preferably 160 ° C. or lower, in order to prevent appearance defects (peeling marks) from appearing due to peeling from the first mirror body.

The surface temperature of the second mirror body is preferably set to 20 ° C. or higher so that the transfer of the surface state can be performed satisfactorily. More preferably, it is 60 degreeC or more, More preferably, it is 100 degreeC or more. On the other hand, the surface temperature of the second mirror body is preferably 200 ° C. or less, and more preferably 160 ° C. or less, in order to prevent appearance defects (peeling marks) due to peeling from the second mirror body on the film.

The surface temperature of the first mirror body is preferably higher than the surface temperature of the second mirror body. This is because the film is held in the first mirror body and sent to the next transfer roll.

Further, when forming the hard coat, adhesion to the hard coat on the hard coat forming surface or both surfaces of the poly (meth) acrylimide resin film or the transparent multilayer film, which becomes a transparent film substrate for forming the hard coat. In order to increase the strength, easy adhesion treatment such as corona discharge treatment or anchor coat formation may be performed in advance.

When the corona discharge treatment is performed, good interlayer adhesion strength can be obtained by setting the wetting index (measured in accordance with JIS K6768: 1999) to usually 50 mN / m or more, preferably 60 mN / m or more. become. Further, after the corona discharge treatment, an anchor coat may be further formed.

In the corona discharge treatment, a film is passed between an insulated electrode and a dielectric roll, a high frequency high voltage is applied to generate a corona discharge, and the film surface is treated. Oxygen and the like are ionized by the corona discharge and collide with the film surface, so that the resin molecular chain is broken or the oxygen-containing functional group is added to the resin molecular chain on the film surface, and the wetting index is increased.

The unit area and the treatment amount (S) per unit time of the corona discharge treatment are determined from the viewpoint of obtaining the above wetting index, and are usually 80 W · min / m ² or more, preferably 120 W · min / m ² or more. . Further, from the viewpoint of preventing deterioration of the film, the processing amount (S) is preferably suppressed to 500 W · min / m ² or less. More preferably, it is 400 W · min / m ² or less.

The processing amount (S) is defined by the following equation.
S = P / (L ・ V)
Here, S: treatment amount (W · min / m ² ), P: discharge power (W), L: length of discharge electrode (m), V: line speed (m / min).

The anchor coating agent for forming the anchor coat is not limited except that it has high transparency and is not colored, such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane. The well-known thing can be used. Of these, a thermoplastic urethane anchor coating agent is preferred from the viewpoint of improving the adhesive strength with the hard coat.

As the anchor coating agent, a paint containing a silane coupling agent can also be used. Silane coupling agents include hydrolyzable groups (for example, alkoxy groups such as methoxy group and ethoxy group; acyloxy groups such as acetoxy group; halogen groups such as chloro group; and the like) and organic functional groups (for example, amino groups, A silane compound having at least two different reactive groups such as a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group, and functions to improve the adhesive strength with the hard coat. Of these, a silane coupling agent having an amino group is preferred from the viewpoint of improving the adhesive strength with the hard coat.

The paint containing the silane coupling agent is a paint mainly containing a silane coupling agent (50% by mass or more as a solid content). Preferably, 75% by mass or more, more preferably 90% by mass or more of the solid content of the paint is the silane coupling agent.

Examples of the silane coupling agent having an amino group include 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 N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like, and one or a mixture of two or more thereof can be used. Can be used.

The method for forming the anchor coat using the anchor coat agent is not limited, and a known method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used. At this time, any dilution solvent such as methanol, ethanol, 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary. .

Further, the anchor coating agent includes an antioxidant, a weather resistance stabilizer, a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, an antistatic agent, a surfactant, and a colorant as long as the object of the present invention is not adversely affected. In addition, one or more additives such as an infrared shielding agent, a leveling agent, a thixotropic agent, and a filler may be included.

The thickness of the anchor coat is usually about 0.01 to 5 μm, preferably 0.1 to 2 μm.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measurement method (a) Total light transmittance:
According to JIS K 7361-1: 1997, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(B) Haze;
According to JIS K 7136: 2000, it measured using the turbidimeter "NDH2000 (brand name)" of Nippon Denshoku Industries Co., Ltd.

(C) Yellowness index;
In accordance with JIS K 7105: 1981, the measurement was performed using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

(D) Water contact angle:
The method of calculating the touch surface side hard coat surface of the hard coat laminated film from the width and height of water droplets using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUS (see JIS R 3257: 1999). ).

(E) Scratch resistance (water contact angle after cotton wiping):
Test specimens that are 150 mm long and 50 mm wide and have the machine direction of the hard coat laminated film aligned with the longitudinal direction of the test piece are placed so that the hard coat face on the touch surface side of the hard coat laminated film becomes the surface. Stainless steel plate (vertical 10mm, horizontal 10mm, thickness) placed on the JIS L 0849 Gakushin tester and covered with 4 layers of gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) 1mm), set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, put a 350g load, and move the test piece touch surface side hard coat surface to the friction terminal moving distance 60mm, speed 1 reciprocation / second After rubbed back and forth 20,000 times under the above conditions, the water contact angle of the cotton wiping location was measured according to the method of (d) above. If the water contact angle is 100 degrees or more, it is judged that the scratch resistance is good. When the water contact angle after 20,000 reciprocations was less than 100 degrees, the measurement was performed by changing the predetermined reciprocation count to 15,000 times and 10,000 times, and evaluated according to the following criteria.
A: Water contact angle of 100 degrees or more even after 20,000 reciprocations.
○: Water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 rounds.
Δ: Water contact angle of 100 degrees or more after 10,000 round trips, but less than 100 degrees after 15,000 rounds.
X: The water contact angle is less than 100 degrees after 10,000 reciprocations.

(F) The slipperiness to point:
The touch side hard coat surface of the hard coat laminated film was traced up and down, left and right or in a circle with an index finger, and the evaluation was made based on the impression whether or not it was possible to trace as desired. Each test was conducted by 10 people, and 2 points were given if they were traced as expected, 1 point was given if they were traced almost as expected, and 0 points were given if they were not traced as expected due to a finger being caught. Were evaluated and evaluated according to the following criteria.
◎: 16 to 20 points Δ: 10 to 15 points ×: 0 to 9 points

(G) Sliding property after wiping cotton:
According to the method of (e) above, tests and evaluations were conducted in the same manner as the slipperiness indicated in (f) above, except that the hard coat laminated film after 20,000 reciprocating cotton was used as a sample.

(H) Scratch resistance:
The hard coat laminated film was placed on a JIS L 0849 Gakushin Tester so that the touch surface side hard coat surface was the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin Tester, a load of 500 g was placed, and the surface of the test piece was rubbed 100 times. The surface was visually observed and evaluated according to the following criteria. Similarly, the printed surface side hard coat surface was tested and evaluated. In the table, the result on the touch surface side / the result on the print surface side are described.
◎: No scratch ○: There are 1 to 5 scratches Δ: There are 6 to 10 scratches ×: There are 11 or more scratches

(L) Linear expansion coefficient:
It measured according to JISK7197: 1991. A thermomechanical analyzer (TMA) “EXSTAR6000 (trade name)” manufactured by Seiko Instruments Inc. was used. The test piece was 20 mm long and 10 mm wide, and the film was collected so that the machine direction (MD) of the film was the vertical direction of the test piece. Conditioning of the test piece was performed at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% for 24 hours. For the purpose of measuring the dimensional stability as a physical property value of the film, the condition adjustment at the maximum measurement temperature was not performed. . The distance between chucks was 10 mm, and the temperature program was a program in which the temperature was maintained at 20 ° C. for 3 minutes, and then the temperature was increased to 270 ° C. at a temperature increase rate of 5 ° C./min. The linear expansion coefficient was calculated from the obtained temperature-test piece length curve as a low temperature side temperature of 30 ° C. and a high temperature side temperature of 250 ° C.

(Nu) Minimum bending radius:
JIS-K6902: With reference to the bending formability of 2007 (Method B), the test piece conditioned for 24 hours at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% was bent at a temperature of 23 ° C. ± 2 ° C. The lines were formed in a direction perpendicular to the machine direction of the hard coat laminated film, and the curved surface was formed by folding the hard coat laminated film so that the touch surface side hard coat was on the outside. Among the forming jigs in which no cracks occurred, the radius of the front part of the smallest front part radius was defined as the minimum bending radius. This “front portion” means the same term relating to a forming jig in the method B defined in JIS K6902: 2007, section 18.2.

(L) Cutting workability (state of curved cutting line):
Using a router machine that is automatically controlled by a computer, the hard coat laminated film was provided with a true circular cutting hole with a radius of 0.5 mm and a true circular cutting hole with a radius of 0.1 mm. The mill used at this time was a four-blade made of cemented carbide with a rounded tip at the tip of the cylinder, with a nick, and the blade diameter was appropriately selected according to the machining location. Then, about the cutting hole of radius 0.5mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. Similarly, about the cutting hole of radius 0.1mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. The table shows the former results-the latter results in this order.
A: No cracks or whiskers are observed even under microscopic observation. O: No cracks are observed even under microscopic observation. But beards are allowed.
(Triangle | delta): A crack is not recognized visually. However, cracks are observed by microscopic observation.
X: Cracks are recognized visually.

(E) Surface smoothness (surface appearance):
The surface (both surfaces) of the hard coat laminated film was visually observed while being applied with various incident angles of the fluorescent light, and evaluated according to the following criteria.
A: There is no wave or scratch on the surface. There is no cloudiness even when looking at the light up close.
○: There is a part with a slight cloudiness when looking closely at the light.
Δ: Slight swells and scratches are observed on the surface when viewed closely. There is also a cloudiness.
X: Many undulations and scratches can be observed on the surface. There is also a clear cloudiness.

(W) Pencil hardness:
In accordance with JIS K 5600-5-4, measurement was performed using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g. In the table, the measurement value on the touch surface side / measurement value on the printing surface side is described.

Raw materials used (A) Multifunctional (meth) acrylate:
(A-1) Dipentaerythritol hexaacrylate. 6 sensuality.
(A-2) Ethoxylated trimethylolpropane acrylate. Trifunctional.

(B) Compound having alkoxysilyl group and (meth) acryloyl group:
(B-1) “Shin-Etsu Silicone KR-513 (trade name)” from Shin-Etsu Chemical Co., Ltd., R is a methoxy group, R ′ is an acryloyl group, and R ″ is a methyl group.
(B-2) “Shin-Etsu Silicone X-40-2655A (trade name)” of Shin-Etsu Chemical Co., Ltd., R is a methoxy group, R ′ is a methacryloyl group, and R ″ is a methyl group.

(B ′) Comparative component:
(B′-1) “Shin-Etsu Silicone KBM-403 (trade name)” from Shin-Etsu Chemical Co., Ltd., a compound having an alkoxysilyl group and an epoxy group. It does not have a (meth) acryloyl group.
(B′-2) “Shin-Etsu Silicone KBM-903 (trade name)” from Shin-Etsu Chemical Co., Ltd., a compound having an alkoxysilyl group and an amino group. It does not have a (meth) acryloyl group.

(C) Organic titanium:
(C-1) Titanium-i-propoxyoctylene glycolate “TOG (trade name)” of Nippon Soda Co., Ltd.
(C-2) Tetrakis (2-ethylhexyloxy) titanium “TOT (trade name)” manufactured by Nippon Soda Co., Ltd.
(C-3) Di-i-propoxy bis (acetylacetonato) titanium “T-50 (trade name)” manufactured by Nippon Soda Co., Ltd.

(C ′) Comparative component:
(C′-1) Tetra-n-propoxyzirconium “ZAA (trade name)” manufactured by Nippon Soda Co., Ltd.

(D) Fine particles having an average particle diameter of 1 to 300 nm:
(D-1) Silica fine particles having an average particle diameter of 20 nm.

(E) Water repellent:
(E-1) An acryloyl group-containing fluoropolyether water repellent “KY-1203 (trade name)” from Shin-Etsu Chemical Co., Ltd. Solid content 20% by weight.
(E-2) A methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70 (trade name)” from Solvay. Solid content 70% by weight.
(E-3) acryloyl group-containing fluoropolyether water repellent “Megafac RS-91 (trade name) of DIC Corporation.

Other optional ingredients:
(F-1) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714 (trade name)” of Sojyo Sangyo Co., Ltd.
(F-2) 1-methoxy-2-propanol.
(F-3) A surface conditioner “BYK-399 (trade name)” of Big Chemie Japan Co., Ltd.
(F-4) A hydroxy ketone photopolymerization initiator (α-hydroxyalkylphenone) “Irgacure 127 (trade name)” manufactured by BASF.

(Α) Poly (meth) acrylimide resin:
(Α-1) Poly (meth) acrylimide “PLEXIMID TT70 (trade name)” manufactured by Evonik.

(Β) Aromatic polycarbonate resin:
(Β-1) Aromatic polycarbonate “Caliver 301-4 (trade name)” by Sumika Stylon Polycarbonate Co., Ltd.

(Γ) Paint for forming hard coat on the printed surface side:
(Γ-1) 65 parts by mass of A-1, 35 parts by mass of A-2, 1.4 parts by mass of B-1, 0.7 parts by mass of C-1, and D-1 35 parts by mass, F-1 in 5.3 parts by mass, F-2 in 95 parts by mass, and F-3 in a composition obtained by mixing and stirring at a composition ratio of 0.5 parts by mass.

(P) Transparent resin film:
(P-1) Using a coextrusion film forming apparatus having a configuration shown in FIG. 1, the above (α-1) is used as both outer layers (α1 layer and α2 layer) of the transparent multilayer film by the extruder 1, and the above (Β-1) is used as an intermediate layer (β layer) of the transparent multilayer film by the extruder 2, and α1 layer; β layer; α2 layer; The three-layer multi-manifold coextrusion T-die 3 is continuously extruded, and the mirror roll 5 that rotates and the mirror belt 6 that circulates along the outer peripheral surface of the mirror roll so that the α1 layer is on the mirror roll 5 side. A transparent multilayer film having a total thickness of 250 μm, an α1 layer thickness of 80 μm, a β layer thickness of 90 μm, and an α2 layer thickness of 80 μm was obtained. At this time, the setting condition is that the drying temperature before film formation is (α-1) is 150 ° C and (β-1) is 100 ° C; the setting temperature of the extruder 1 is C1 / C2 / C3 / C4 / C5 / AD = 260 / 290-290 ° C; set temperature of extruder 2 is C1 / C2 / C3 / C4 / C5 / C6 / AD = 260/280/280 / 260-260 / 270 ° C; Perform nitrogen purge and use vacuum vent; T die 3 set temperature 300 ° C., lip opening 0.5 mm; mirror roll 5 set temperature 130 ° C .; mirror belt 6 set temperature 120 ° C., pressure 1.4 MPa; The speed was 6.5 m / min.

(P-2) Using (α-1) above, a 50 mm extruder (with a W flight screw of L / D = 29, CR = 1.86); a T die having a die width of 680 mm; a mirror roll (first mirror surface) Body) and a mirror belt (second mirror body) were used to obtain a film having a thickness of 250 μm using an apparatus equipped with a drawing winder equipped with a mechanism for pressing the molten film. At this time, the setting conditions of the extruder are C1 / C2 / C3 / AD = 280/300/320/320 ° C .; T die setting temperature 320 ° C .; T die lip opening 0.5 mm; The set temperature was 140 ° C .; the set temperature of the mirror belt was 120 ° C .; the pressure of the mirror belt was 1.4 MPa; the take-up speed was 5.6 m / min.

(P-3) A biaxially stretched polyethylene terephthalate film “Diafoil (trade name)” manufactured by Mitsubishi Plastics, Inc., having a thickness of 250 μm.

(P-4) Acrylic resin film “Technoloy S001G (trade name)” from Sumitomo Chemical Co., Ltd., thickness 250 μm.

(P-5) Using (β-1) above, a 50 mm extruder (with a W flight screw of L / D = 29, CR = 1.86); a T die having a die width of 680 mm; a mirror surface roll (first mirror surface) Body) and a mirror belt (second mirror body) were used to obtain a film having a thickness of 250 μm using an apparatus equipped with a drawing winder equipped with a mechanism for pressing the molten film. At this time, the setting conditions of the extruder are C1 / C2 / C3 / AD = 280/300/320/320 ° C .; T die setting temperature 320 ° C .; T die lip opening 0.5 mm; The set temperature was 140 ° C .; the set temperature of the mirror belt was 120 ° C .; the pressure of the mirror belt was 1.4 MPa; the take-up speed was 5.6 m / min.

Example 1
Corona discharge treatment was performed on both sides of p-1 under the conditions of a treatment amount of 167 W · min / m ² (discharge power 500 W, discharge electrode length 1 m, line speed 3 m / min). The wetness index on both sides was 64 mN / m. Subsequently, a coating composition (parts by mass) shown in Table 1 as a coating material for forming the touch surface side hard coat is applied to the surface on the α1 layer side, and the thickness after curing is 25 μm using a die-type coating device. The above-mentioned γ-1 is applied to the surface on the α2 layer side as a printing surface side hard coat forming coating using a die-type coating device so that the thickness after curing is 25 μm. Thus, a hard coat laminated film was obtained. The above tests (i) to (wa) were conducted. The results are shown in Table 1.

Examples 2-14, Comparative Examples 1-7
All of the procedures were performed in the same manner as in Example 1 except that the composition of the paint for forming the touch surface side hard coat was changed as shown in any one of Tables 1 to 4. The results are shown in any one of Tables 1 to 4.

Example 15
Corona discharge treatment was performed on both surfaces of p-2 under the conditions of a treatment amount of 167 W · min / m ² (discharge power: 500 W, discharge electrode length: 1 m, line speed: 3 m / min). The wetness index on both sides was 63 mN / m. Subsequently, a paint having a composition shown in Table 4 was applied to one surface as a touch surface-side hard coat forming paint using a die-type coating apparatus so that the thickness after curing was 25 μm. Applying the above-mentioned γ-1 as a printing surface side hard coat-forming coating on the other surface using a die-type coating device so that the thickness after curing is 25 μm. Obtained. The above tests (i) to (wa) were conducted. The results are shown in Table 4.

Example 16
On one side of the p-3, a paint having a composition shown in Table 4 is used as a touch surface-side hard coat-forming paint so that the thickness after curing is 25 μm using a die-type coating device. Apply γ-1 as a printing surface side hard coat forming coating on the other surface using a die coating device so that the thickness after curing is 25 μm, and hard coat lamination Got the body. The above tests (i) to (wa) were conducted. The results are shown in Table 4. In the test (I), the test piece was greatly contracted, and the measured value could not be obtained.

Example 17
The same procedure as in Example 16 was performed except that p-4 was used instead of p-3 as the transparent resin film. The results are shown in Table 4.

Example 18
A transparent resin film was prepared in the same manner as in Example 16 except that p-5 was used instead of p-3. The results are shown in Table 4.

Example 19
The same procedure as in Example 1 was performed except that the composition of the paint for forming the touch surface side hard coat was changed as shown in Table 4. The results are shown in Table 4.

The hard coat laminated film having a hard coat made of a paint containing the active energy ray-curable resin composition of the present invention has transparency, color tone, scratch resistance (cotton wiping resistance and steel wool resistance), surface hardness, Excellent bendability and surface appearance. On the other hand, the comparative example 1 which does not contain the component C is inferior to cotton-wiping resistance. Comparative Example 2 in which component C exceeds the specified amount is inferior in color tone. Comparative Example 3 in which Component B is less than the specified amount is inferior in cotton wiping resistance. In Comparative Example 4 in which Component B exceeds the specified amount, water repellency is hardly exhibited. The comparative example 5 which uses the compound which has an alkoxy silyl group and an epoxy group instead of the component B, and does not have a (meth) acryloyl group is inferior to cotton-wiping resistance. The comparative example 6 which uses the compound which has an alkoxy silyl group and an amino group instead of the component B, and does not have a (meth) acryloyl group is inferior in color tone. Comparative Example 7 using tetra-n-propoxyzirconium instead of Component C is inferior in cotton wiping resistance.

It is a conceptual diagram of the apparatus used for film forming of a transparent resin film (p-1).

1: Extruder 1
2: Extruder 2
3: Co-extrusion T die of 2 types, 3 layers, multi-manifold system 4: Melted film 5: Mirror roll 6: Mirror belt 7: A pair of belt rollers

Claims (7)

On at least one side of the transparent resin film,
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) 0.2-4 parts by mass of a compound having an alkoxysilyl group and a (meth) acryloyl group;
(C) 0.05 to 3 parts by mass of organic titanium;
(D) 5 to 100 parts by mass of fine particles having an average particle size of 1 to 300 nm; and
(E) Water repellent 0.01 to 7 parts by mass;
Having a hard coat made of paint, including
A hard coat laminated film satisfying the following (a) to (e).
(A) Total light transmittance is 80% or more.
(B) Haze 3.0% or less.
(C) Yellowness index: 3 or less.
(D) The water contact angle of the touch surface is 100 degrees or more.
(E) Water contact angle after 20,000 reciprocating cotton wipes on the touch surface is 100 degrees or more.
The hard coat laminated film according to claim 1, wherein the water repellent (E) includes a (meth) acryloyl group-containing fluoropolyether water repellent.
The (C) organic titanium is one selected from the group consisting of tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate The hard coat laminated film of Claim 1 or 2 containing the above .
The hard coat laminated film according to claim 1, wherein the transparent resin film is a poly (meth) acrylimide resin film.
The poly (meth) acrylimide resin film is
First poly (meth) acrylimide resin layer (α1);
Aromatic polycarbonate-based resin layer (β);
A second poly (meth) acrylimide resin layer (α2);
The hard coat laminated film according to claim 4, which is a transparent multilayer film directly laminated in this order.
Use of the hard coat laminated film according to any one of claims 1 to 5 as an image display device member.
The image display apparatus containing the hard coat laminated film of any one of Claims 1-5.