JP6683649B2 - Hard coat laminated film - Google Patents

Description

The present invention relates to a hard coat laminated film. More specifically, it relates to a hard coat laminated film excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance.

2. Description of the Related Art In recent years, a touch panel, which is installed on an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display, and which can perform input by touching with a finger, a pen, or the like while seeing the display, has become widespread.

BACKGROUND ART Conventionally, a glass-based article has been used for a display face plate of a touch panel because it meets requirements such as heat resistance, dimensional stability, high transparency, high surface hardness, and high rigidity. On the other hand, glass has the following problems: low impact resistance and easy cracking; low processability; difficult handling; high specific gravity and heavy weight; and difficult to meet demands for curved and flexible displays. Therefore, materials that replace glass are being actively researched, and hard coats that have excellent surface hardness and scratch resistance on the surface of transparent resin films such as triacetyl cellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene-based polymers. A number of hard coat laminated films having the above have been proposed (for example, Patent Documents 1 and 2). However, its scratch resistance is still insufficient, and there is a demand for a hard coat laminated film capable of maintaining surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

Japanese Patent Laid-Open No. 2000-052472 JP 2000-214791 A

The object of the present invention is excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance, and is a member of an image display device such as a liquid crystal display, a plasma display, and an electroluminescence display (touch panel function is It is intended to provide a hard coat laminated film suitable for a display face plate of an image display device having the touch panel function and an image display device having the touch panel function).

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

That is, the present invention is
It has 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 that does not contain inorganic particles;
The second hard coat comprises a paint containing inorganic particles;
It is a hard coat laminated film that satisfies the following (a) and (b).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the surface of the first hard coat is 5H or more.

A second invention is the hard coat laminated film according to the first invention, wherein the pencil hardness of the surface of the first hard coat is 7H or more.

A third invention is the hard coat laminated film according to the first invention or the second invention, which further satisfies the following (C) and (D).
(C) Haze is 2.0% or less.
(D) The minimum bending radius is 40 mm or less.

A fourth invention is the hard coat laminated film according to any one of the first to third inventions, which further satisfies the following (e) and (f).
(E) The water contact angle of the surface of the first hard coat is 100 degrees or more.
(F) The water contact angle of the first hard coat surface is 100 degrees or more after the cloth is wiped back and forth 20,000 times.

5th invention, the said transparent resin film is a 1st poly (meth) acrylic imide type resin layer ((alpha) 1); an aromatic polycarbonate type resin layer ((beta)); a 2nd poly (meth) acrylic imide type resin layer ((alpha) 2). ); Is the hard coat laminated film according to any one of the first to fourth inventions, which is a transparent multilayer film laminated in this order.

A sixth invention is the hardcoat laminated film according to any one of the first to fifth inventions, wherein the first hardcoat comprises a coating material containing a silane coupling agent.

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

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

A ninth invention is the use of the hard coat laminated film according to any one of the first to eighth inventions as an image display device member.

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

The hard coat laminated film of the present invention is excellent in transparency, surface hardness, bending resistance, scratch resistance, color tone, and surface appearance. Therefore, members 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 the touch panel function), particularly an image display device having the touch panel function. It can be suitably used as a display face plate.

The hard coat laminated film of the present invention has layers of a first hard coat, a second hard coat, and a transparent resin film in this order from the surface side, and the first hard coat is made of a paint containing no inorganic particles; 2 The hard coat consists of a paint containing inorganic particles.

Inorganic particles (for example, 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; magnesium fluoride) , Metal fluoride particles such as sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles, etc.) are effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component of the paint was weak, which caused insufficient scratch resistance. Therefore, in the present invention, the first hard coat forming the outermost surface is kept free of inorganic particles to maintain scratch resistance, while the second hard coat contains inorganic particles, preferably having an average particle size of 1 This problem is solved by increasing the hardness by including inorganic fine particles of 300 nm.

Here, "not containing" the inorganic particles means not containing a significant amount of the inorganic particles. In the field of paints for forming hard coats, the significant amount of inorganic particles is usually about 1 part by mass or more per 100 parts by mass of the resin component of the paint. Therefore, “does not contain” inorganic particles means that the amount of the inorganic particles is usually less than 1 part by mass, preferably 0.1 part by mass or less, and more preferably 0.01 part by mass, relative to 100 parts by mass of the resin component of the coating material. It can also be referred to as a part or less.

Here, "comprising" inorganic particles means that the composition contains a significant amount of inorganic particles for increasing the hardness of the hard coat. In the field of paint for forming a hard coat, the amount that is significant for increasing the hardness of the hard coat is usually about 5 parts by mass or more per 100 parts by mass of the resin component of the paint. Therefore, the term “comprising” the inorganic particles means that the amount of the inorganic particles is usually 5 parts by mass or more, preferably 15 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 100 parts by mass of the resin component of the coating material. Can be paraphrased as 50 parts by mass or more.

The hard coat laminated film of the present invention has a total light transmittance (measured using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7361-1: 1997) of 85% or more. , Preferably 88% or more, more preferably 90% or more. Since the total light transmittance is 85% or more, the hard coat laminated film of the present invention can be suitably used as a member for an image display device. The higher the total light transmittance, the more preferable.

The hard coat laminated film of the present invention has a haze (measured according to JIS K 7136: 2000 using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.) of 2.0% or less, preferably It is 1.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less. When the haze is 2.0% or less, the hard coat laminated film of the present invention can be suitably used as an image display device member. The lower the haze, the more preferable.

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

The minimum bending radius of the hard coat laminated film of the present invention is preferably 40 mm or less, more preferably 35 mm or less, still more preferably 30 mm or less. When the minimum bending radius is preferably 40 mm or less, the hard coat 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 is, the more preferable. Here, the minimum bending radius is a value measured according to the test (d) of the following example.

The minimum bending radius is a bending radius immediately before a crack is generated on the surface of the bent portion when the hard coat laminated film is bent, and is an index showing a bending limit. The bend radius is defined similarly to the radius of curvature.

The radius of curvature is defined as follows. The length from the point M to the point N of the curve is ΔS; the difference between the slope of the tangent line at the point M and the slope of the tangent line at the point N is Δα; a straight line that is perpendicular to the tangent line at the point M and intersects at the point M. , O is a point of intersection with a straight line that is perpendicular to the tangent line at the N point and intersects at the N point, and if ΔS is sufficiently small, the curve from the M point to the N point can be approximated to an arc. (Figure 3). The radius at this time is defined as the radius of curvature. Further, when 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 hard coat 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 hard coat laminated film of the present invention is used as a display face plate of a touch panel, the first hard coat forms a touch face. When the water contact angle of the surface of the first hard coat is 100 degrees or more, it becomes possible to slide the finger or the pen on the touch surface as desired and operate the touch panel. From the viewpoint of allowing the finger or pen to slide as desired, a higher water contact angle is preferable, and there is no particular upper limit to the water contact angle, but from the viewpoint of the sliding property of pointing, about 120 degrees is usually sufficient. Here, the water contact angle is a value measured according to the test (e) of the following examples.

The hard coat laminated film of the present invention preferably has a water contact angle of 100 degrees or more after the first hard coat surface is wiped back and forth 20,000 times. More preferably, the water contact angle after reciprocating 25,000 times with a cotton cloth is 100 degrees or more. Since the water contact angle after the cloth is wiped back and forth 20,000 times is 100 degrees or more, it is possible to maintain the surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like. The more the number of times of wiping with which the water contact angle of 100 degrees or more can be maintained, the more preferable. Here, the water contact angle after wiping is a value measured according to the test (f) in the following examples.

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

First hard court:
The first hard coat forms the surface of the hard coat laminated film of the present invention. When the hard coat laminated film of the present invention is used as a display face plate of an image display device having a touch panel function, the first hard coat forms a touch surface. The first hard coat develops good scratch resistance and functions to maintain surface properties such as slipperiness even when repeatedly wiped with a handkerchief or the like.

The coating material for forming the first hard coat is not limited except that it does not contain inorganic particles, and any coating material can be used. The preferred first hard coat-forming coating material is a coating material containing an active energy ray-curable resin and capable of being polymerized and cured by an active energy ray such as an ultraviolet ray or an electron beam to form a hard coat. You can

Examples of the active energy ray curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacrylic (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; 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) acrylo (Meth) acryloyl group-containing bifunctional reactive monomers such as luoxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomer such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomer such as pentaerythritol tetra (meth) acrylate; and dipenta Examples thereof include one or more kinds selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as erythritol hexaacrylate, or a resin containing one or more kinds of the above as constituent monomers. As the active energy ray curable resin, one kind or a mixture of two or more kinds thereof can be used. In addition, in this specification, (meth) acrylate means an acrylate or a methacrylate.

When the hard coat laminated film of the present invention is used as a member of an image display device, particularly a display face plate of an image display device having a touch panel function, transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface. From the viewpoint of appearance, the coating composition for forming the first hard coat includes (A) 100 parts by mass of polyfunctional (meth) acrylate; (B) 0.01 to 7 parts by mass of water repellent; and (C) silane coupling. A coating material containing 0.01 to 10 parts by mass of the agent and containing no inorganic particles is preferable.

(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. It functions to form a hard coat by being polymerized and cured by active energy rays.

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; trifunctional monomers containing (meth) acryloyl group such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythri (Meth) acryloyl group-containing tetrafunctional reactive monomer such as tetra (meth) acrylate; dimethaerythritol hexaacrylate or other (meth) acryloyl group-containing hexafunctional reactive monomer; and a polymer having one or more of these as constituent monomers. An example is a combination (oligomer or prepolymer). As the component (A), one kind or a mixture of two or more kinds thereof can be used.

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

(B) Water repellent:
The above-mentioned component (B) has a function of enhancing the slipperiness of pointing, the property of preventing dirt from adhering, and the property of wiping off dirt.

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

Among these, as the component (B), a fluoropolyether water repellent is preferable from the viewpoint of water repellent performance. From the viewpoint of preventing a trouble such as a chemical bond or strong interaction between the component (A) and the component (B) and bleeding out of the component (B), the component (B) has 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 preferable. More preferable as the above component (B) is from the viewpoint of appropriately controlling the chemical bond or interaction between the above component (A) and the above component (B) to exhibit good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent.

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

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

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

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

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

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

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

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

Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-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 urethane such as block isocyanate of the above polyisocyanate A crosslinking agent etc. can be mentioned. As the compound having two or more isocyanate groups in one molecule, one kind or a mixture of two or more kinds thereof can be used. In addition, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added if 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 and 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether, benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; Anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone and 2-amylanthraquinone; Thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; Alkylphenones such as acetophenone dimethylketal Compounds, triazine compounds, biimidazole compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, oxime phenylacetic acid ester compounds, hydroxyketone compounds, and aminobenzoate compounds. it can. As the photopolymerization initiator, one kind or a mixture of two or more kinds thereof can be used.

In the first hard coat forming coating composition, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, a printability improving agent, an antioxidant, a weather resistance stabilizer, One or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, organic fine particles, and an organic colorant can be contained.

The first hard coat-forming coating material may contain a solvent, if desired, in order to dilute it to a concentration that facilitates coating. The solvent is not particularly limited as long as it does not react with the components (A) to (C) and other optional components or catalyze (promote) self-reaction (including deterioration reaction) of these components. Not done. 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 kind or a mixture of two or more kinds can be used.

The first hard coat-forming coating material 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. Specific examples thereof include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

From the viewpoint of scratch resistance and hardness, the thickness of the first hard coat is preferably 0.5 μm or more, more preferably 1 μm or more. On the other hand, from the viewpoint of hardness and adhesion to the second hard coat, the thickness is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less.

Second hard coat The coating material for forming the second hard coat is not limited except that it contains inorganic particles, and any coating material can be used. The preferable second hard coat-forming coating material is a coating material which further contains an active energy ray-curable resin and is capable of forming a hard coat by being polymerized and cured by an active energy ray such as an ultraviolet ray or an electron beam. be able to.

The active energy ray-curable resin has been described above in the description of the first hard coat forming coating material. As the active energy ray curable resin, one kind or a mixture of two or more kinds thereof can be used.

When the hard coat laminated film of the present invention is used as a member of an image display device, particularly a display face plate of an image display device having a touch panel function, transparency, color tone, scratch resistance, surface hardness, bending resistance, and surface. From the viewpoint of appearance, the second hard coat-forming coating material includes (A) 100 parts by mass of a polyfunctional (meth) acrylate; and (D) 50-300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm. Paints are preferred.

The (A) polyfunctional (meth) acrylate has been described above in the description of the first coating material for forming a hard coat. As the component (A), one kind or a mixture of two or more kinds thereof can be used.

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

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

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

A silane coupling agent such as vinylsilane and aminosilane on the surface of the inorganic fine particles for the purpose of improving the dispersibility of the inorganic fine particles in the coating material and the surface hardness of the obtained hard coat; a titanate coupling agent. An aluminate coupling agent; an organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, an allyl group or an epoxy group; and a fatty acid or a fatty acid metal salt It is preferable to use those treated with a surface treatment agent or 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 hardness improving effect. On the other hand, the lower limit of the average particle diameter is not particularly limited, but the inorganic fine particles that are usually available are fine at most about 1 nm.

In the present specification, the average particle diameter of the inorganic fine particles is from the smaller one in the particle diameter distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. Is a particle size at which the cumulative value of 50% by mass is obtained.

From the viewpoint of surface hardness, the blending amount of the component (D) is 50 parts by mass or more, preferably 80 parts by mass or more, relative to 100 parts by mass of the 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.

(E) Leveling agent:
From the viewpoint of making the surface of the second hard coat smooth and facilitating the formation of the first hard coat, the coating composition for forming the second hard coat preferably further contains (E) a leveling agent.

Examples of the leveling agent include acrylic leveling agents, silicon leveling agents, fluorine leveling agents, silicon / acrylic copolymer leveling agents, fluorine-modified acrylic leveling agents, fluorine-modified silicon leveling agents, and functional groups for these. Examples of the leveling agent include a group (for example, an alkoxy group such as a methoxy group and an ethoxy group, an acyloxy group, a halogen group, an amino group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group). You can Among these, the component (E) is preferably a silicone / acrylic copolymer type leveling agent. As the component (E), one kind or a mixture of two or more kinds thereof can be used.

From the viewpoint of making the surface of the second hard coat smooth and making it easy to form the first hard coat, the compounding amount of the component (E) is usually 0 relative 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 that the first hard coat-forming coating material can be favorably applied on the second hard coat without being repelled, 1 part by mass or less, preferably 0.6 parts by mass or less, It may preferably be 0.4 parts by mass or less.

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

The compound having two or more isocyanate groups in one molecule has been described above in the description of the first hard coat-forming coating material. As the compound having two or more isocyanate groups in one molecule, one kind or a mixture of two or more kinds thereof can be used.

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

If desired, the second hard coat-forming coating composition contains an antistatic agent, a surfactant, a thixotropic agent, an antifouling agent, a printability improving agent, an antioxidant, a weather resistance stabilizer, and a light resistance stability. One or more kinds of additives such as an agent, an ultraviolet absorber, a heat stabilizer, a colorant, and organic fine particles can be included.

The second hard coat-forming coating material may contain a solvent, if desired, in order to dilute it to a concentration that facilitates application. As long as the above-mentioned solvent does not react with the above-mentioned component (A), the above-mentioned component (D), and other optional components or catalyze (promote) self-reactions (including deterioration reaction) of these components, There is no particular limitation. 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. Of these, 1-methoxy-2-propanol is preferred. As the solvent, one kind or a mixture of two or more kinds can be used.

The second hard coat-forming coating material can be obtained by mixing and stirring these components.

The method for 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. Specific examples thereof include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating.

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

Transparent resin film:
The transparent resin film is a layer serving as a transparent film base material on which the first hard coat and the second hard coat are formed. 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 copolymers; acrylic resins such as polymethyl methacrylate and polyethyl methacrylate; poly; (Meth) acrylic imide-based resin; aromatic polycarbonate-based resin; polypropylene and polyolefin-based resin such as 4-methyl-pentene-1; polyamide-based resin; polyarylate-based resin; polymer-type urethane acrylate-based resin; and polyimide-based resin A film such as; These films include unstretched films, uniaxially stretched films, and biaxially stretched films. In addition, these films include laminated films in which two or more of these one type or two or more types are laminated.

The thickness of the transparent resin film is not particularly limited and may be any thickness as desired. From the viewpoint of handleability of the hard coat laminated film of the present invention, it may be usually 20 μm or more, preferably 50 μm or more. When the hard coat laminated film of the present invention is used for applications which do not require high rigidity, it may be usually 250 μm or less, preferably 150 μm or less from the viewpoint of economy. When the hard 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. Further, from the viewpoint of meeting the demand for thinning the touch panel, it may be usually 1500 μm or less, preferably 1200 μm or less, more preferably 1000 μm or less.

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

The above-mentioned poly (meth) acrylic imide-based resin has the characteristics of high transparency, high surface hardness, and high rigidity of the acrylic-based resin, and the characteristics of the polyimide-based resin having excellent heat resistance and dimensional stability are introduced. It is a thermoplastic resin that has improved the drawback of being colored reddish brown, and is disclosed in, for example, JP-A-2011-519999. In the present specification, poly (meth) acrylimide means polyacrylimide or polymethacrylimide.

The poly (meth) acrylimide resin is not limited except that it has high transparency and is not colored, for the purpose of using the hard coat laminated film for optical articles such as touch panels. A poly (meth) acrylimide resin can be used.

As a preferable example of the poly (meth) acrylic imide-based resin, a yellowness index (measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation according to JIS K 7105: 1981) is used. The following can be mentioned. The yellowness index is more preferably 2 or less, still more preferably 1 or less. Further, from the viewpoints of extrusion load and stability of the molten film, those having a melt mass flow rate (measured in accordance with ISO1133 under the conditions of 260 ° C. and 98.07 N) of 0.1 to 20 g / 10 minutes are preferable. it can. The melt mass flow rate is more preferably 0.5 to 10 g / 10 minutes. 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 ° C. or higher.

The poly (meth) acrylic imide-based resin may be a thermoplastic resin other than the poly (meth) acrylic imide-based resin, if desired, to the extent not deviating from the object of the present invention; pigment, inorganic filler, organic filler, resin filler. An additive such as a lubricant, an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent, and a surfactant; 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.

Commercially available examples of the poly (meth) acrylic imide-based resin include "PLEXIMID TT50 (trade name)" and "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 assuming that the touch surface is formed on the α1 layer side.

Poly (meth) acrylic imide-based resins are excellent in heat resistance and surface hardness, but their machinability tends to be insufficient, whereas aromatic polycarbonate-based resins are 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 becomes possible to easily obtain a hard coat laminated film which compensates for the weak points of both and has excellent heat resistance, surface hardness, and machinability. .

The thickness of the α1 layer is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more, further preferably 80 μm or more from the viewpoint of heat resistance and surface hardness of the hard coat laminated film of the present invention. May be

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

The term "same layer thickness" should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be construed as having the same layer thickness within the range of the fluctuation range of the process / quality control that is usually performed industrially. This is because the curl resistance of the multilayer film can be kept good as long as the layer thickness is the same within the swing range of the process / quality control that is usually performed industrially. In the case of a non-stretched multilayer film produced by the T-die coextrusion method, the process and quality control are usually performed in a width of about -5 to +5 μm, and therefore the layer thickness of 65 μm and the layer thickness of 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 from the viewpoint of the 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, such as poly (meth) acrylates having different melt mass flow rates and glass transition temperatures. A (meth) acrylic imide-based 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 of the preferred embodiments.

Examples of the aromatic polycarbonate resin 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. A polymer obtained by an interfacial polymerization method with bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and other aromatic dihydroxy compounds, 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.

A core-shell rubber can be given as a preferable optional component that can be contained in the aromatic polycarbonate resin. When the total amount 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 (aromatic polycarbonate resin 100 to 70 parts by mass), preferably 0 to 10 parts by mass (aromatic). By using the polycarbonate resin in an amount of 100 to 90 parts by mass), it is possible to further improve the cutting workability and the 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, acrylonitrile / styrene / acryl. Examples thereof include core-shell rubbers such as acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. As the core shell rubber, one kind or a mixture of two or more kinds thereof can be used.

Further, the above aromatic polycarbonate-based resin, if desired, is a thermoplastic resin other than the aromatic polycarbonate-based resin or the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; a lubricant; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a 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 total amount of the aromatic polycarbonate resin and the core shell rubber is 100 parts by mass.

The method for producing the poly (meth) acrylimide resin film (including the case where the film is the transparent multilayer film) is not particularly limited. As a preferable manufacturing method, the methods described in JP-A-2005-033844 and JP-A-2015-034285 can be mentioned.

Further, when forming the second hard coat, in order to increase the adhesive strength with the second hard coat on the hard coat forming surface or both surfaces of the poly (meth) acrylimide-based resin film or the transparent multilayer film, corona in advance. You may perform easy adhesion processing, such as electric discharge processing and anchor coat formation.

The hard coat laminated film of the present invention preferably has the first hard coat, the second hard coat, the transparent resin film layer, and the third hard coat in this order from the surface side. By forming the third hard coat, both the force to curl the hard coat laminated film to one side (hereinafter, it may be abbreviated as curl force) and the force to curl the other film work together. become. Then, it is possible to suppress the occurrence of curl by offsetting these two curl forces to zero.

Further, in recent years, for the purpose of reducing the weight of an image display device, a touch panel having a two-layer structure in which a touch sensor is directly formed on the back side of a display face plate (so-called one glass solution) has been proposed. In order to further reduce the weight, a one plastic solution that replaces the so-called one glass solution has also been proposed. When the hard coat laminated film of the present invention is used for a one plastic solution that substitutes for a so-called one glass solution, the third hard coat is formed to impart suitable characteristics as a printing surface. Will be easier.

The hard coat laminated film of the present invention may have any layer other than the first hard coat, the second hard coat, the transparent resin film layer, and the third hard coat, if desired. Examples of the optional layer include hard coats other than the first to third hard coats, anchor coats, pressure-sensitive adhesive layers, transparent conductive layers, high refractive index layers, low refractive index layers, and antireflection functional layers. be able to.

Production method:
The method for producing the hard coat laminated film of the present invention is not particularly limited and can be produced by any method. As a preferred manufacturing method, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example,
(1) A step of forming a wet coating film made of the second coating material for forming a hard coat on the transparent resin film;
(2) The above-mentioned wet coating film made of the above-mentioned second hard coat-forming coating material has an integrated amount of active energy rays of 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , and more preferably 10 to 160 mJ / cm 2. ² , more preferably 20 to 120 mJ / cm ² , and most preferably 30 to 100 mJ / cm ² , by irradiating the wet coating film made of the second hard coat-forming coating material in a dry-to-touch state. Forming a membrane;
(3) a step of forming a wet coating film made of the first hard coat forming coating material on the coating film in the dry-to-touch state made of the second hard coat forming coating material; and (4) the first The above wet coating film made of a hard coat-forming coating material is preheated to a temperature of 30 to 100 ° C., preferably 40 to 85 ° C., more preferably 50 to 75 ° C., and the active energy ray has a cumulative light amount of 240 to 10,000 mJ / cm 2. ² , preferably 320 to 5000 mJ / cm ² , and more preferably 360 to 2000 mJ / cm ² . I can give you a way.

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

The wet coating film formed of the second hard coat forming coating material formed in the step (1) is in a touch-free state or has no tackiness in the step (2) and directly touches the web device. However, 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 coating material is formed on the touch-free coating film made of the second hard coat-forming coating material. Will be able to.

In the present specification, “the coating film is in a dry state to the touch (state without tackiness)” means that there is no problem in handling even if the coating film directly touches the web device. .

The irradiation of the active energy ray in the step (2) depends on the characteristics of the coating material used as the second hard coat forming coating material, but from the viewpoint of surely making the coating film dry to the touch, the integrated light amount is usually 1 J. / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, more preferably 20 mJ / cm ² or more, and most preferably carried out such that 30 mJ / cm ² or more. On the other hand, from the viewpoint of adhesion between the first hard coating and second hard coating, integrated light quantity usually 230 mJ / cm ² or less, preferably 200 mJ / cm ² or less, more preferably 160 mJ / cm ² or less, more preferably 120mJ / Cm ² or less, most preferably 100 mJ / cm ² or less.

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

When irradiating with active energy rays 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. The coating film can be surely made dry to the touch. The preheating method is not particularly limited and may be any method. An example of a specific method will be described later in the description of the following step (4).

In the step (3), the method for forming the wet coating film made of the first hard coat-forming coating material is not particularly limited, and a known web coating method can be used. Specific examples thereof 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 second hard coat forming paint is also completely cured.

Although not intending to be bound by theory, it is possible to improve the adhesion between the first hard coat and the second hard coat by the method described above, because irradiation with an 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 light amount for complete curing, and is sufficient to completely cure the coating film for the first time in the above step (4). It is presumed that the above results in the complete curing of both hard coats simultaneously.

The irradiation of the active energy ray in the step (4) has a cumulative light amount of 240 mJ / cm ² or more, preferably from the viewpoint of completely curing the coating film and the adhesiveness of the first hard coat and the second hard coat. the 320 mJ / cm ² or more, more preferably carried out so that 360 mJ / cm ² or more. On the other hand, in view to obtain a hard coat laminated film are prevented from becoming those yellowing, and from the viewpoint of cost, integrated light quantity 10000 mJ / cm ² or less, preferably 5000 mJ / cm ² or less, more preferably 2000 mJ / cm ² Do the following:

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

When the active energy ray is irradiated in the step (4), the wet coating film made of the first hard coat-forming coating material has characteristics of the first hard coat-forming coating material and the second hard coat-forming coating material. Is preliminarily heated to a temperature of 30 to 100 ° C, preferably a temperature of 40 to 85 ° C, and more preferably a temperature of 50 to 75 ° C from the viewpoint of obtaining good interlayer adhesion strength. The preheating method is not particularly limited and may be any method. For example, as shown in FIG. 1, a method of controlling the surface temperature of the roll by holding the web in a roll opposite to the active energy ray irradiation device to a predetermined temperature; And a combination thereof.

Aging treatment may be performed after the step (4). The properties of the hard coat laminated film can be stabilized.

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

Measurement method (a) Total light transmittance:
According to JIS K 7361-1: 1997, it was measured using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.

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

(C) Haze;
According to JIS K 7136: 2000, it was measured using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.

(D) Minimum bending radius:
With reference to the bending formability (method B) of JIS-K6902: 2007, a test piece that was conditioned for 24 hours at a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50 ± 5% was bent at a bending temperature of 23 ° C. ± 2 ° C. and bent. The line was set in a direction perpendicular to the machine direction of the hard coat laminated film, and the bending was performed so that the first hard coat of the hard coat laminated film was on the outside to form a curved surface. The minimum bending radius was defined as the radius of the front portion of the forming jig having the smallest radius of the front portion of the forming jig in which no cracks were generated. This "front surface part" means the same term regarding the molding jig in the B method defined in Section 18.2 of JIS K6902: 2007.

(E) Water contact angle:
A method of calculating the first hard coat surface of the hard coat laminated film from the width and height of a water drop using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUSS (see JIS R 3257: 1999). It was measured at.

(F) Scratch resistance 1 (water contact angle after wiping with cotton):
A test piece having a size of 150 mm in length and 50 mm in width so that the machine direction of the hard coat laminated film is the longitudinal direction of the test piece, and the first hard coat of the hard coat laminated film is on the surface according to JIS L. The stainless steel plate (10 mm in length, 10 mm in width, 1 mm in thickness) placed on the 0849 Gakushin tester and covered with 4 layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) on the friction terminals of the Gakushin tester And set so that the vertical and horizontal surfaces of the stainless plate come into contact with the test piece, and put a load of 350 g on the first hard coat surface of the test piece under the conditions of a friction terminal moving distance of 60 mm and a speed of 1 reciprocation / second. After rubbing back and forth 10,000 times, the water contact angle at the cotton wiping location was measured according to the method (e). When the water contact angle is 100 degrees or more, after further rubbing 5,000 times back and forth, the work of measuring the water contact angle at the cotton wiping location is repeated according to the method (e) above, and the evaluation is performed according to the following criteria. .
A: A water contact angle of 100 degrees or more even after 25,000 round trips.
B: Water contact angle of 100 degrees or more after 20,000 round trips but less than 100 degrees after 25,000 rounds.
C: Water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 rounds.
D: Water contact angle of 100 degrees or more after 10,000 round trips but less than 100 degrees after 15,000 rounds.
E: Water contact angle less than 100 degrees after 10,000 round trips.

(G) Scratch resistance 2 (Steel wool resistance)
The hard coat laminated film was placed on the JIS L 0849 Gakshin tester with the first hard coat on the surface. Subsequently, # 0000 steel wool was attached to the friction terminal of the Gakshin tester, a load of 500 g was placed thereon, the surface of the test piece was rubbed 100 times back and forth, and then the rubbed portion was visually observed. When no scratch was observed, the work of visually observing the rubbing portion was repeated after rubbing 100 times again and again, and the following criteria were used for evaluation.
A: No scratch is observed even after 500 round trips.
B: No scratches are observed after 400 round trips, but scratches can be seen after 500 round trips.
C: No scratches are observed after 300 round trips, but scratches can be seen after 400 round trips.
D: No scratches are observed after 200 round trips, but scratches can be seen after 300 round trips.
E: No scratches are observed after 100 round trips, but scratches can be seen after 200 round trips.
F: A scratch can be recognized after 100 round trips.

(H) Yellowness index;
According to JIS K 7105: 1981, it was measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation.

(I) Surface smoothness (surface appearance):
The surface (both surfaces) of the hard coat laminated film was visually observed while applying various incident angles of light of the fluorescent lamp, and evaluated according to the following criteria.
A: There is no undulation or scratch on the surface. There is no sense of cloudiness when you see the light up close.
○: There is a slight cloudy feeling when seeing through the light up close.
Δ: When viewed up close, undulations and scratches are slightly observed on the surface. There is a feeling of cloudiness.
X: Many undulations and scratches can be recognized on the surface. There is also a clear cloudy feeling.

(G) Cross-cut test (adhesion):
According to JIS K 5600-5-6: 1999, after making a cut of 100 squares (1 square = 1 mm x 1 mm) on the hard coat laminated film from the side of the first hard coat, tape for adhesion test is placed on the grid. After sticking and squeezing with fingers, it was peeled off. The evaluation standard was in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cut are completely smooth and do not peel off in any grid.
Classification 1: Small peeling of the coating film at the intersection of cuts. The cross-cut portion is clearly not affected by more than 5%.
Class 2: The coating is flaking along the edges of the cut and / or at the intersections. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Class 3: The coating film has large or partial peeling along the edge of the cut, and / or various portions of the eye are partially or completely peeled. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film has large or partial peeling along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

(L) Machinability (state of curved cutting line):
A hard coat laminated film was provided with a true circular cutting hole with a diameter of 2 mm and a true circular cutting hole with a diameter of 0.5 mm using a router processing machine that is automatically controlled by a computer. The mill used at this time was a cemented carbide four-blade blade having a cylindrical round tip, with a nick, and the blade diameter was appropriately selected according to the processing location. Subsequently, the cut end face of the cut hole having a diameter of 2 mm was visually or microscopically (100 times) observed and evaluated according to the following criteria. Similarly, with respect to a cutting hole having a diameter of 0.5 mm, the cutting end face was visually or microscopically (100 times) observed and evaluated according to the following criteria. In the table, the results of the former-the results of the latter are listed in this order.
⊚: No cracks or whiskers are observed even under a microscope. O: No cracks are observed under a microscope. However, the beard is recognized.
Δ: No crack is visually observed. However, cracks are observed under the microscope.
X: A crack is visually recognized.

(O) Shrinkage start temperature (heat resistant dimensional stability):
From the temperature-test piece length curve measured according to JIS K 7197: 1991, the change of the test piece length from increase (expansion) to decrease (contraction) at the lowest temperature side in the range of 20 ° C to the glass transition temperature of the raw material resin. The bending point (the temperature at which the length of the test piece becomes a maximum) was calculated as the shrinkage start temperature. For the measurement, a thermomechanical analyzer (TMA) "EXSTAR6100 (trade name)" manufactured by Seiko Instruments Inc. was used. The test piece had a size of 20 mm in length and 10 mm in width, and was taken so that the machine direction (MD) of the film was in the machine direction of the test piece. The condition of the test piece was adjusted 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 was not adjusted at the highest measurement temperature. . The distance between chucks was 10 mm, and the tensile load was 4.0 mN / mm ² . The temperature program was a program in which the temperature was held at 20 ° C. for 3 minutes, and then the temperature was raised to 300 ° C. at a heating rate of 5 ° C./minute.

Raw material (A) polyfunctional (meth) acrylate used:
(A-1) Dipentaerythritol hexaacrylate. 6 functional.
(A-2) Pentaerythritol triacrylate. Trifunctional.

(B) Water repellent:
(B-1) Acryloyl group-containing fluoropolyether-based water repellent “KY-1203 (trade name)” manufactured by Shin-Etsu Chemical Co., Ltd. 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) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane "KBM-602 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.
(C-2) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane "KBM-603 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.
(C-3) 3-aminopropyltrimethoxysilane "KBM-903 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.
(C-4) 3-mercaptopropylmethyldimethoxysilane "KBM-802 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.
(C-5) 3-glycidoxypropyltrimethoxysilane "KBM-403 (trade name)" manufactured by Shin-Etsu Chemical Co., Ltd.

(D) Inorganic 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 which are surface-treated with a silane coupling agent having a vinyl group.

(E) Leveling agent:
(E-1) Silicone / acrylic copolymer system leveling agent “Disparlon NSH-8430HF (trade name)” by Kusumoto Kasei Co., Ltd. Solid content 10% by mass.
(E-2) Silicon-acrylic copolymer system leveling agent "BYK-3550 (trade name)" manufactured by Big Chemie Japan Co., Ltd. Solid content 52 mass%.
(E-3) Acrylic polymer leveling agent "BYK-399 (trade name)" manufactured by BYK Japan KK Solid content 100% by mass.
(E-4) Silicone leveling agent "Disparon LS-480 (trade name)" of Kusumoto Kasei Co., Ltd. Solid content 100% by mass.

(F) Optional components:
(F-1) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) "SB-PI714 (trade name)" manufactured by Soho Industrial Co., Ltd.
(F-2) 1-methoxy-2-propanol.

(H1) First hard coat forming paint:
(H1-1) 100 parts by mass of (A-1), 2 parts by mass of (B-1) (0.40 parts by mass of solid content), 0.06 parts by mass of (B-2) (as solid content). 0.042 parts by mass), (C-1) 0.5 parts by mass, (F-1) 4 parts by mass, and (F-2) 100 parts by mass obtained by mixing and stirring. Table 1 shows the formulation table. In addition, about the said (B-1) and the said component (B-2), the value of solid content conversion is described in the table | surface.

A coating material was obtained in the same manner as in (H1-1) above, except that the formulation of (H1-2 to 15) was changed as shown in Table 1 or Table 2.

(H1 ′) Comparative paint for forming first hard coat:
A coating material was obtained in the same manner as in (H1-1) above, except that the formulation of (H1′-1) was changed as shown in Table 1.

(H2) Second hard coat forming paint:
(H2-1) 100 parts by mass of (A-2), 140 parts by mass of (D-1), 2 parts by mass of (E-1) (0.2 parts by mass in terms of solid content), (F-1). ) 17 mass parts, and the coating material obtained by mixing and stirring 200 mass parts of the above (F-2). Table 3 shows the formulation table. In addition, about the said (E-1), the value of solid content conversion is described in the table.

A coating material was obtained in the same manner as in (H2-1) above, except that the formulation of (H2-2 to 13) was changed as shown in Table 3 or Table 4.

(H2 ') Comparative paint for forming second hard coat:
A coating material was obtained in the same manner as in (H2-1) above, except that the formulation of (H2′-1) was changed as shown in Table 4.

(P) Transparent resin film:
(P-1) Two-kind three-layer multi-manifold type coextrusion T-die, and a device equipped with a draw-up winder equipped with a mechanism for pressing a molten film with a mirror-finished roll and a mirror-finished belt. Evonik's poly (meth) acrylic imide “PLEXIMID TT50 (trade name)” is used as both outer layers (α1 layer and α2 layer) of the multilayer resin film, and the aromatic layer of Sumika Styron Polycarbonate Co., Ltd. is used as the intermediate layer (β layer). Polycarbonate "Caliber 301-4 (trade name)" is continuously co-extruded from a co-extrusion T-die and circulated along the rotating mirror surface roll and the outer peripheral surface of the mirror surface roll so that the α1 layer is on the mirror surface roll side. A transparent resin film having a total thickness of 250 μm, an α1 layer having a layer thickness of 80 μm, a β layer having a layer thickness of 90 μm, and an α2 layer having a layer thickness of 80 μm after being supplied and pressed into a mirror surface belt Obtained. At this time, the setting conditions were a T-die setting temperature of 300 ° C., a mirror surface roll setting temperature of 130 ° C .; a mirror surface belt setting temperature of 120 ° C., and a take-up speed of 6.5 m / min.

(P-2) A transparent resin film was obtained in the same manner as in (P-1) except that the layer ratio was changed to a layer thickness of α1 layer of 60 μm, a layer thickness of β layer of 130 μm, and a layer thickness of α2 layer of 60 μm. It was

(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 a layer thickness of α1 layer of 40 μm, a layer thickness of β layer of 170 μm, and a layer thickness of α2 layer of 40 μm. It was

(P-4) Biaxially stretched polyethylene terephthalate film "Diafoil (trade name)" manufactured by Mitsubishi Plastics, Inc., thickness 250 μm.

(P-5) Acrylic resin film "Technoloy S001G (trade name)" manufactured by Sumitomo Chemical Co., Ltd., thickness 250 μm.

(P-6) A single-layer T-die and an apparatus equipped with a draw-up winder equipped with a mechanism for pressing a molten film with a mirror-finished roll and a mirror-finished belt are used. Caliber 301-4 (trade name) "is continuously extruded from a T-die, and is supplied between a rotating mirror surface roll and a mirror surface belt that circulates along the outer peripheral surface of the mirror surface roll, and is pressed to have a total thickness of 250 μm. To obtain a transparent resin film. At this time, the setting conditions were a T-die setting temperature of 320 ° C., a mirror surface roll setting temperature of 140 ° C .;

Example 1
Corona discharge treatment was performed on both surfaces of the above (P-1). The wetting index on both sides was 64 mN / m. Next, the above-mentioned (H2-1) was applied on the surface of the α1 layer side using a die-type coating device so that the wet thickness was 40 μm (the thickness after curing was 22 μm). Next, after passing through a drying oven set to an oven temperature of 90 ° C. at a line speed at which it takes 1 minute to pass from the inlet to the outlet, a high pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm are used. Using a curing device opposite to the mirror-finished metal roll (see FIG. 1), the treatment was performed under the conditions of the temperature of the mirror-finished metal roll of 90 ° C. and the cumulative light amount of 80 mJ / cm ² . The wet coating film of (H2-1) became a coating film in a dry state to the touch. Then, using a die-type coating device on the (H2-1) coating film in a dry state to the touch, the above (H1-1) was made to have a wet thickness of 4 μm (thickness after curing 2 μm). Applied. Next, after passing through a drying oven set to an oven temperature of 80 ° C. at a line speed at which it takes 1 minute to pass from the inlet to the outlet, a high pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm are used. Using a curing device facing the mirror-finished metal roll (see FIG. 1), the mirror-finished metal roll is treated at a temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² to form a first hard coat and a second hard coat. did. Subsequently, a third hard coat was formed on the surface of the α2 layer side, and the same paint as that used for forming the second hard coat (Example 1 above (H2-1).) Was used to apply a die method. A hard coat laminated film was obtained by using an apparatus to form a hard coat laminated film having a thickness of 22 μm after curing. The above tests (a) to (wo) were performed. The results are shown in Table 5.

Examples 2-30, Examples 1-4C
The same procedure as in Example 1 was carried out except that at least one of the paint (α), the paint (β), and the transparent resin film used was changed as shown in any one of Tables 5 to 9. The results are shown in any one of Tables 5-9.

Examples 31-53
Example 1 was repeated except that the production conditions of the hard coat laminated film were changed as shown in any one of Tables 10 to 13. The results are shown in any one of Tables 10 to 13.

The hard coat laminated film of the present invention is excellent in transparency, color tone, scratch resistance, surface hardness, and surface appearance. Therefore, it can be suitably used as a display face plate of an image display device having a touch panel function.

It is a conceptual diagram of the ultraviolet irradiation device used in the Example. It is a conceptual diagram of a cross section showing an example of the hard coat laminated film of the present invention. It is a figure explaining a curvature radius.

1: Ultraviolet irradiation device 2: Mirror surface metal roll 3: Web 4: Holding angle 5: First hard coat 6: Second hard coat 7: First poly (meth) acrylimide resin layer (α1)
8: Aromatic polycarbonate resin layer (β)
9: Second poly (meth) acrylimide resin layer (α2)
10: Third hard coat

Claims (11)

It has 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 coating material containing a silane coupling agent and containing no inorganic particles;
The second hard coat comprises a paint containing inorganic particles;
A hard coat laminated film satisfying the following (a), (b), and (e).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the surface of the first hard coat is 5H or more.
(G) When a cross-cut test is performed by making a cut in the cross-cut from the side of the first hard coat surface of the hard coat laminated film according to JIS K 5600-5-6: 1999, the first hard coat and the first hard coat The adhesiveness with the second hard coat and the adhesiveness between the second hard coat and the layer of the transparent resin film are classified into Class 0, Class 1, Class 2 or Class 3.
The hard coat laminated film according to claim 1, wherein the pencil hardness of the surface of the first hard coat is 7H or more.
The hard coat laminated film according to claim 1 or 2, further satisfying the following (C) and (D).
(C) Haze is 2.0% or less.
(D) 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 (e) and (f).
(E) The water contact angle of the surface of the first hard coat is 100 degrees or more.
(F) The water contact angle of the first hard coat surface is 100 degrees or more after the cloth is wiped back and forth 20,000 times.
The transparent resin film,
First poly (meth) acrylimide resin layer (α1);
Aromatic polycarbonate resin layer (β);
The second poly (meth) acrylimide resin layer (α2);
It is a transparent multilayer film laminated | stacked in this order, The hard-coat laminated film in any one of Claims 1-4.
The 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; Hard coat laminated film.
The hard coat laminated film according to any one of claims 1 to 6, wherein the first hard coat has a thickness of 0.5 to 5 µm.
The hard coat laminated film according to claim 1, wherein the second hard coat has a thickness of 15 to 30 μm.
Use of the hard coat laminated film according to any one of claims 1 to 8 as a member for an image display device.
An image display device comprising the hard coat laminated film according to claim 1.
A method for producing the hard coat laminated film according to any one of claims 1 to 8,
(1) A step of forming a wet coating film made of the second coating material for forming a hard coat on the transparent resin film;
(2) The wet coating film made of the second hard coat forming coating material is irradiated with an active energy ray so that the integrated light amount becomes 1 to 230 mJ / cm ^2, and the wet coating film made of the second hard coat forming coating material is applied. Making the wet coating film dry to the touch;
(3) a step of forming a wet coating film made of the first hard coat forming coating material on the coating film in the dry-to-touch state made of the second hard coat forming coating material; and (4) the first A step of preheating the wet coating film composed of the coating material for forming a hard coat to a temperature of 30 to 100 ° C. and irradiating it with an active energy ray so that the integrated light amount becomes 240 to 10,000 mJ / cm ² .
Including the method.