JP2017141416A - Hard coat laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat laminate film that is excellent in adhesiveness between hard coat and a film base material of which a hard coat formation surface is formed from a poly(meth)acrylimide-based resin.SOLUTION: There is provided a hard coat laminate film which has a layer of a first hard coat and a layer of a transparent resin film in order from a front side, where the first hard coat is formed from a coating material containing (A) polyfunctional (meth)acrylate of 100 pts.mass and (B) an N-substituted (meth)acrylamide compound of 1-100 pts.mass, the transparent resin film has a first hard coat formation surface formed from a poly(meth)acrylimide-based resin, and the component (B) is preferably acryloyl morpholine.SELECTED DRAWING: Figure 1

Description

The present invention relates to a hard coat 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 hard coats with excellent surface hardness and scratch resistance on the surface of transparent resin films such as triacetylcellulose, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and norbornene polymers. A large number of hard coat laminated films formed with a film have been proposed (for example, Patent Documents 1 and 2). However, the adhesion between the hard coat and the film substrate is still insufficient. Further, these scratch resistances are still insufficient, and there is a need for a hard coat laminated film that can maintain 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 subject of this invention is providing the hard-coat laminated film excellent in adhesiveness with the film base material whose hard-coat and hard-coat formation surface are poly (meth) acrylimide-type resin.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a specific hard coat laminated film.

That is, the present invention has a first hard coat and a transparent resin film layer sequentially from the surface side,
The first hard coat is
(A) 100 mass parts of polyfunctional (meth) acrylate; and
(B) 1-100 parts by mass of an N-substituted (meth) acrylamide compound;
Made of paint containing;
The transparent resin film has a first hard coat forming surface made of a poly (meth) acrylimide resin;
It is a hard coat laminated film.

A second invention is the hard coat laminated film according to the first invention, wherein the component (B) is acryloylmorpholine.

According to a third invention, the coating material forming the first hard coat further includes (C) 5 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm. It is a hard coat laminated film.

4th invention has a layer of the 2nd hard coat, the 1st hard coat, and a transparent resin film in order from the surface side,
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(E) Water repellent 0.01 to 7 parts by mass; and (F) Silane coupling agent 0.01 to 10 parts by mass;
The hard coat laminated film according to any one of the first to third inventions, which is made of a paint containing no inorganic particles.

According to a fifth invention, the hard coat laminated film according to any one of the first to fourth inventions, wherein the paint forming the first hard coat further comprises (D) a leveling agent in an amount of 0.01 to 1 part by mass. It is.

In a sixth aspect of the invention, the transparent resin film comprises a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly (meth) acrylimide resin layer (α2). ); Is the hard coat laminated film according to any one of the first to fifth inventions, which is a transparent multilayer film directly laminated in this order.

A seventh invention is an article comprising the hard coat laminated film according to any one of the first to sixth inventions.

The hard coat laminated film of this invention is excellent in the adhesiveness of a hard coat and a film base material. The preferable hard coat laminated film of this invention is excellent in the adhesiveness of a hard coat and a film base material, and scratch resistance. 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 a touch panel function), particularly an image display device having a touch panel function. It can be suitably used as a display face plate. Further, the hard coat laminated film of the present invention is a vehicle window or windshield, a building window or door, a protective plate of an electronic signboard, a front panel of a home appliance such as a refrigerator, a furniture door such as a cupboard, etc. It can also be suitably used as a housing for a television, a personal computer, a tablet-type information device, a smartphone, and a show window.

In this specification, the term “film” is used as a term including a sheet. The term “resin” is used as a term including a resin mixture containing two or more resins and a resin composition containing components other than resins.

The hard coat laminated film of this invention has a 1st hard coat and the layer of a transparent resin film in an order from the surface side. The hard coat laminated film of this invention has the layer of a 2nd hard coat, a 1st hard coat, and a transparent resin film in an order from the surface side in the aspect with this invention. Here, “surface side” means that an article produced using a hard coat laminated film is closer to the outer surface (viewing surface in the case of a display faceplate) when used for on-site use. Further, in this specification, laminating a certain layer and another layer in order means laminating those layers directly and interposing one or more other layers such as anchor coats between these layers. Including both lamination.

First hard coat:
The first hard coat is made of a paint containing (A) 100 parts by mass of a polyfunctional (meth) acrylate; and (B) 1 to 100 parts by mass of an N-substituted (meth) acrylamide compound.

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule. Since the component (A) 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 such as ultraviolet rays and electron beams.

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 -Functional monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol (Meth) acryloyl group-containing tetrafunctional reactive monomers such as tetral (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth) acryloyl group containing tripentaerythritol acrylate Examples thereof include octafunctional reactive monomers and polymers (oligomers and prepolymers) containing one or more of these as constituent monomers. 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) N-substituted (meth) acrylamide compounds:
The component (B) is an N-substituted (meth) acrylamide compound. The component (B) serves to improve the adhesion between the transparent resin film and the first hard coat, the first hard coat forming surface of which is a poly (meth) acrylimide resin. Therefore, in the hard coat laminated film of the present invention, the first hard coat may be formed directly on the first hard coat forming surface of the transparent resin film. The first hard coat forming surface of the transparent resin film may not be subjected to easy adhesion treatment such as corona discharge treatment.

The N-substituted (meth) acrylamide compound as the component (B) is not particularly limited, but may typically be a compound having a structure represented by the following general formula (1). In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₃ represents an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group or an amino group, or R ₂ and R ₃ are Together, they form a 5-membered or 6-membered ring which may have an oxygen atom as a ring member together with the nitrogen atom to which they are bonded. The “N-substituted (meth) acrylamide compound” means an N-substituted acrylamide compound or an N-substituted methacrylamide compound.

Examples of the component (B) include N-methyl (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, and N-isopropyl (meta). ) Acrylamide, N-cyclopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-methyl, N-ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide methyl ether, N-methylol (meth) acrylamide Chirueteru, N- methylol (meth) acrylamide propyl ether, N- butoxymethyl (meth) acrylamide, N- vinyl-2-pyrrolidone, may be mentioned N- vinyl -ε- caprolactam, and the like (meth) acryloyl morpholine. Among these, (meth) acryloylmorpholine, N, N-diethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide are preferable, (meth) acryloylmorpholine is more preferable, and acryloylmorpholine is more preferable. As said component (B), these 1 type, or 2 or more types of mixtures can be used.

The compounding amount of the component (B) is usually 1 part by mass or more, preferably 3 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of adhesion between the transparent resin film and the first hard coat. As mentioned above, More preferably, it is 5 mass parts or more. On the other hand, from the viewpoint of suppressing scratch resistance and hardness reduction, it is usually 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less, and still more preferably 35 parts. It may be up to 15 parts by weight, most preferably up to 15 parts by weight.

(C) Inorganic fine particles having an average particle size of 1 to 300 nm:
The component (C) functions to dramatically increase the surface 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, 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.

For the purpose of increasing the dispersibility of the inorganic fine particles in the paint or increasing the surface hardness of the obtained hard coat, the surface of the inorganic fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; 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, and an allyl group; and an epoxy group; and a fatty acid, a fatty acid metal salt, etc. It is preferable to use a material treated with a surface treatment agent or the like.

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

The average particle size of the component (C) is usually 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of reliably obtaining the effect of improving the hardness of the hard coat. On the other hand, there is no particular lower limit on the average particle diameter, but normally available inorganic fine particles are fine at most about 1 nm.

In the present specification, the average particle size of the inorganic 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. Is the particle diameter at which the accumulation of 50% by mass.

When the first hard coat forms the surface of the hard coat laminated film of the present invention, the amount of the component (C) is in terms of surface hardness with respect to 100 parts by mass of the component (A). Therefore, it may be usually 5 parts by mass or more, preferably 20 parts by mass or more. On the other hand, from the viewpoint of scratch resistance, it may be usually 100 parts by mass or less, preferably 70 parts by mass or less.

The amount of the component (C) is such that the surface hardness of the first hard coat is such that the second hard coat is further formed on the surface side of the first hard coat with respect to 100 parts by mass of the component (A). From the viewpoint, it may be preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 80 parts by mass or more. On the other hand, from the viewpoint of transparency, it may be usually 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

(D) Leveling agent:
The first hard coat forming coating material preferably further includes (D) a leveling agent from the viewpoint of making the surface good (smooth). This also facilitates the formation of the second hard coat in the aspect of forming the second hard coat of the present invention.

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 functionalities thereof. Leveling agents and the like into which groups (for example, alkoxy groups such as methoxy group and ethoxy group, acyloxy groups, halogen groups, amino groups, vinyl groups, epoxy groups, methacryloxy groups, acryloxy groups, and isocyanate groups) are introduced. Can do. Among these, the component (D) is preferably a silicon / acrylic copolymer leveling agent. As said component (D), these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component (D) is usually 0.01 parts by mass or more, preferably 0.000 parts by mass with respect to 100 parts by mass of the component (A), from the viewpoint of improving the surface of the first hard coat. It may be 1 part by mass or more, more preferably 0.2 part by mass or more. On the other hand, in the aspect of forming the second hard coat of the present invention, it is usually from the viewpoint that the second hard coat forming coating can be satisfactorily applied without being repelled on the first hard coat. It may be 1 part by mass or less, preferably 0.6 part by mass or less, more preferably 0.4 part by mass or less.

From the viewpoint of improving the curability by active energy rays, the first hard coat-forming coating material has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization initiation. It is preferable to further contain an agent.

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 first hard coat-forming coating material includes, as desired, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain-preventing agent, a printability improving agent, an antioxidant, a weathering stabilizer, One type or two or more types of additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, organic fine particles, and a colorant can be contained.

The first hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. The solvent is not particularly limited as long as it does not react with the components (A) to (D) and other optional components or catalyze (promote) the self-reaction (including degradation reaction) of these components. Not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

The said 1st hard-coat formation 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 paint is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, dip coating, spray coating, spin coating, air knife coating, and die coating.

The thickness of the first hard coat is not particularly limited, but may be usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more from the viewpoint of surface hardness. 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.

From the viewpoint of surface hardness, the thickness of the first hard coat is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 18 μm or more in the aspect of forming the second hard coat of the present invention. It may be. On the other hand, from the viewpoint of impact resistance, it may be preferably 35 μm or less, more preferably 30 μm or less, and even more preferably 25 μm or less.

Second hard coat:
The hard coat laminated film of the present invention may further have a second hard coat on the surface side of the first hard coat. That is, the hard coat laminated film of this invention has a layer of the said 2nd hard coat, the said 1st hard coat, and the said transparent resin film in an order from the surface side in a certain aspect. When the hard coat laminated film of such an aspect is used as a display face plate of an image display device having a touch panel function, the second hard coat usually forms the touch surface of the image display device. .

The second hard coat is preferably made of a paint that does not contain inorganic particles. The second hard coat is more preferably (A) polyfunctional (meth) acrylate 100 parts by mass; (E) water repellent 0.01 to 7 parts by mass; and (F) silane coupling agent 0.01 to 10 parts by mass; and a coating material that does not contain inorganic particles. By using the above-mentioned paint as the second hard coat forming paint, the second hard coat exhibits good scratch resistance and surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like. It will be possible to work to maintain.

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; fluorination Metal fluoride particles such as magnesium and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes insufficient scratch resistance. Therefore, in the aspect of forming the second hard coat of the present invention, the second hard coat forming the outermost surface keeps scratch resistance by not containing inorganic particles, while the first hard coat is formed. Has solved this problem by increasing the hardness by adding a large amount of specific inorganic fine particles.

Here, “does not contain” inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of hard coat forming paint, the significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the component (A). Therefore, “does not contain” inorganic particles means that the amount of inorganic particles is usually less than 1 part by weight, preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight with respect to 100 parts by weight of the component (A). It can be paraphrased as “parts by mass” or less.

Said (A) polyfunctional (meth) acrylate was mentioned above in description of the coating material for 1st hard-coat formation. As said component (A), these 1 type, or 2 or more types of mixtures can be used.

(E) Water repellent:
The component (E) functions to increase slipperiness, dirt adhesion prevention, and dirt wiping.

Examples of the water repellent include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; and silicon-based repellents such as silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane. Water-containing agents; fluorine-containing water-repellents such as fluoropolyether-based water repellents and fluoropolyalkyl-based water repellents; As said component (E), these 1 type, or 2 or more types of mixtures can be used.

Among these, as the component (E), a fluoropolyether water repellent is preferable from the viewpoint of water repellent performance. From the viewpoint of preventing troubles such as a chemical bond or strong interaction between the component (A) and the component (E) and bleeding out of the component (E), the component (E) is 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 component (E) is to appropriately adjust the chemical bond or interaction between the component (A) and the component (E), from the viewpoint of expressing 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 (meth) acryloyl group-containing fluoropolyether water repellent is clearly distinguished from the component (A) in that it contains a fluoropolyether group in the molecule. The compound having two or more (meth) acryloyl groups in one molecule and having a fluoropolyether group is a (meth) acryloyl group-containing fluoropolyether-based water repellent and is the component (E). .

The amount of the component (E) 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 (E). Part or less, more preferably 2 parts by weight or less. On the other hand, from the viewpoint of obtaining the use effect of the 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 or more.

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

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 mercapto group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group. Among these, as the component (F), from the viewpoint of adhesion, a silane coupling agent having an amino group (a silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group ( A silane compound having a mercapto group and a hydrolyzable group is preferred. 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, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.

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

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

The compounding amount of the component (F) is usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, from the viewpoint of surely obtaining an adhesion improving effect with respect to 100 parts by mass of the component (A). More preferably, it is 0.1 mass part 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.

From the viewpoint of improving the curability by active energy rays, the second hard coat-forming coating compound has a compound having two or more isocyanate groups (—N═C═O) in one molecule and / or photopolymerization initiation. It is preferable to further contain an agent.

The compound having two or more isocyanate groups in one molecule is 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 or a mixture of two or more thereof can be used.

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

For the second hard coat forming coating, an antistatic agent, a surfactant, a thixotropic agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light resistance stability are optionally added. One or more additives such as an agent, an ultraviolet absorber, a heat stabilizer, an organic colorant, and organic fine particles can be contained.

The second hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. The solvent reacts with the component (A), the component (D), the component (F), and other optional components, or catalyzes (accelerates) the self-reaction (including deterioration reaction) of these components. There is no particular limitation as long as it does not. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. As said solvent, these 1 type, or 2 or more types of mixtures 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 paint is not particularly limited, and a known web coating method can be used. Examples of the method include methods such as roll coating, gravure coating, reverse coating, roll brushing, dip coating, spray coating, spin coating, air knife coating, and die coating.

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

Transparent resin film:
The transparent resin film serves as a film substrate for forming the first hard coat thereon. In one aspect of the present invention, the transparent resin film serves as a film base material for forming the first hard coat and the second hard coat thereon. The transparent resin film has at least a first hard coat forming surface made of a poly (meth) acrylimide resin.

The poly (meth) acrylimide resin is a polymer in which an imide structure is introduced into an acrylic resin. 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. To a reddish brown color. A method for producing the poly (meth) acrylimide resin is not particularly limited, and examples thereof include a method of introducing an imide structure by reacting an acrylic resin with an imidizing agent.

Examples of the acrylic resin include (meth) acrylic acid ester (co) polymers and copolymers containing structural units derived from (meth) acrylic acid esters. In addition, (meth) acryl means acryl or methacryl. The (co) polymer means a polymer or a copolymer.

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

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

Examples of the imidizing agent include methylamine, cyclohexylamine, and ammonia.

The poly (meth) acrylimide resin has a high potential as a resin for a film base material of a hard coat laminated film. However, the adhesion strength with the hard coat is insufficient, and an extremely strong corona discharge treatment or a special adhesion coat or other easy adhesion treatment is required (Japanese Patent Laid-Open No. 2015-034285). In particular, when the poly (meth) acrylimide resin forms both surfaces of the film substrate, when the hard coat is formed on both surfaces of the film substrate, the adhesion of the hard coat formed later There was a problem that the strength tends to be insufficient. Although not intending to be bound by theory, it is considered that the poly (meth) acrylimide resin reduces the adhesion to the hard coat by irradiation with active energy rays.

When the hard coat laminated film of the present invention contains the component (B) in a preferable amount of the first hard coat forming paint, the first hard coat formation of the transparent resin film (poly (meth) acrylimide resin) ) Even if the first hard coat is formed directly on the surface, sufficient adhesion is exhibited. Even if the first hard coat formation (poly (meth) acrylimide resin) surface of the transparent resin film is not subjected to an easy adhesion treatment such as a corona discharge treatment, sufficient adhesion is exhibited.

The transparent resin film may be a transparent single layer film of poly (meth) acrylimide resin. The transparent resin film may be a transparent multilayer film in which a layer forming the first hard coat forming surface is a poly (meth) acrylimide resin and one or more other layers made of any resin are included. The transparent resin film preferably has a first poly (meth) acrylimide resin layer (α1); an aromatic polycarbonate resin layer (β); a second poly (meth) acrylimide resin layer (α2); The transparent multilayer film may be directly laminated in this order. When the hard coat laminated film is used as a member of an image display device having a touch panel function, the present invention will be described on the assumption that the touch surface of the image display device 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 is usually 20 μm or more, preferably 40 μm or more, more preferably 60 μm or more, and still more preferably 80 μm or more, from the viewpoint of heat resistance and surface hardness of the hard coat laminated film of the present invention. It may be.

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 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 high transparency and no coloration for the purpose of using a hard coat laminated film for an optical article such as a touch panel. Any other 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 TT50 (product name)” and “PLEXIMID TT70 (product name)” manufactured by Evonik.

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 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 an acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures 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 method for producing the transparent resin film is not particularly limited. As a preferable manufacturing method, the method described in Unexamined-Japanese-Patent No. 2015-033844 and Unexamined-Japanese-Patent No. 2015-034285 can be mentioned, for example.

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 40 μm or more, more preferably 60 μm or more. When the hard coat laminated film of the present invention is used for an application that does not require high rigidity, it may be usually 250 μm or less, preferably 150 μm or less from the viewpoint of economy. When the hard coat laminated film of the present invention is used for an application requiring high rigidity such as a display face plate, it may be usually 100 μm or more, preferably 200 μm or more, more preferably 300 μm or more. Further, from the viewpoint of meeting the demand for thinning the apparatus, it may be usually 1500 μm or less, preferably 1200 μm or less, more preferably 1000 μm or less.

In addition, the preferable hard coat laminated film of this invention is corona discharge treatment beforehand in order to raise the adhesive strength with the said 1st hard coat on the said 1st hard coat formation surface or both surfaces of the said transparent resin film as mentioned above. However, there is no intention to exclude the application of the easy adhesion treatment. In other words, the hard coat laminated film of the present invention may be one in which the first hard coat forming surface or both surfaces of the transparent resin film are subjected to an easy adhesion treatment. By subjecting the first hard coat forming surface or both surfaces of the transparent resin film to easy adhesion treatment, the adhesion between the transparent resin film and the first hard coat is further improved, and the hard coat laminated film of the present invention is Even when exposed to an unexpected use environment, it can be expected to maintain adhesion.

It is preferable that the hard coat laminated film of this invention has a 3rd hard coat further on the surface on the opposite side to the said 1st hard coat formation surface of the said transparent resin film. By forming the third hard coat, both the force to curl the hard coat laminated film to one side (hereinafter sometimes abbreviated as curl force) and the force to curl to the other work both. become. The occurrence of curling can be suppressed by canceling these two curling forces to zero. The thickness of the third hard coat forming paint and the thickness of the third hard coat are not particularly limited as long as the two curling forces can be offset. The coating material and thickness for forming the third hard coat may be, for example, those described above for the first hard coat in the aspect in which the second hard coat is formed.

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

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

The hard coat laminated film of this invention may have arbitrary layers other than the said 1st hard coat, the said 2nd hard coat, the layer of the said transparent resin film, and the said 3rd hard coat as needed. Examples of the optional layer include a hard coat other than the first to third hard coats, an anchor coat, an adhesive layer, a transparent conductive layer, a high refractive index layer, a low refractive index layer, and an antireflection functional layer. be able to.

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

The hard coat laminated film of the present invention has a pencil hardness of the surface of the first hard coat side (according to JIS K 5600-5-4 under the condition of 750 g load, a pencil “Uni (trade name)” of Mitsubishi Pencil Co., Ltd. Is preferably 4H or more, more preferably 5H or more, still more preferably 6H or more, and most preferably 7H or more. When the pencil hardness is 4H or more, the hard coat laminated film of the present invention can be suitably used as an image display device member. Higher pencil hardness is preferable.

According to JIS K 5600-5-6: 1999, the hard coat laminated film of the present invention was cut into a grid of 100 squares (1 square = 1 mm × 1 mm) from the surface of the first hard coat side in the hard coat laminated film. Later, when the adhesion test tape is applied to the grid and rubbed with a finger and then peeled off, it is usually classified as 3, 3, 1, or 0, according to the criteria described in Table 1 of the JIS standard. Has an adhesion of class 2, 1 or 0, more preferably class 1 or 0, still more preferably class 0 (highest rank).

In the hard coat laminated film of the present invention, the water contact angle on the surface of the first hard coat side 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 surface on the first hard coat side forms a touch surface. When the water contact angle on the surface of the first hard coat side is 100 degrees or more, the touch panel can be operated by sliding a finger or a pen as desired on the touch surface. Although there is no upper limit of the water contact angle, about 120 degrees is usually sufficient from the viewpoint of sliding a finger or pen as desired. Here, the water contact angle is a value measured according to the test (g) in the following Examples.

The hard coat laminated film of the present invention preferably has a water contact angle of 100 degrees or more after 20,000 cotton swabs on the first hard coat side surface. More preferably, the water contact angle after reciprocating 25,000 cotton swabs is 100 degrees or more. When the water contact angle after 20,000 cotton reciprocations is 100 degrees or more, it is possible to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like. The larger the number of cotton wipes that can maintain a water contact angle of 100 degrees or more, the better. Here, the water contact angle after cotton wiping is a value measured according to the test (h) in the following Examples.

Production method:
The manufacturing method in particular of the hard coat laminated film of this invention is not restrict | limited, It can manufacture by arbitrary methods. As a preferable production method in the case where the hard coat laminated film of the present invention is an embodiment having layers of a second hard coat, a first hard coat, and a transparent resin film in order from the surface side, the first hard coat and the first hard coat From the viewpoint of adhesion with 2 hard coats, for example,
(1) A step of forming a wet coating film made of the first hard coat forming paint on the transparent resin film;
(2) The wet coating film made of the first hard coat forming paint has an active energy ray with an integrated light amount of 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , more preferably 10 to 160 mJ / cm. ² , more preferably 20 to 120 mJ / cm ² , most preferably 30 to 100 mJ / cm ^2, and the wet coating film made of the first hard coat forming paint is applied in a dry-to-touch state. Forming a film;
(3) forming a wet paint film made of the second hard coat forming paint on the touch-dried paint film made of the first hard coat forming paint; and (4) the second. The wet coating film comprising a hard coat forming coating 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 is integrated to 240 to 10,000 mJ / cm. ² , preferably 320 to 5000 mJ / cm ² , more preferably 360 to 2000 mJ / cm ² .

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

The wet coating film made of the first hard coat forming paint formed in the step (1) becomes dry to the touch or has no tackiness in the step (2), and directly touches the web device. However, handling problems such as sticking will no longer occur. Therefore, in the next step (3), a wet paint film made of the second hard coat forming paint is formed on the touch-dried paint film made of the first hard coat forming paint. Will be able to.

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

Irradiation with active energy rays in the step (2) depends on the characteristics of the paint used as the first hard coat-forming paint, but from the viewpoint of ensuring that the paint film is 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, the adhesion standpoint of the first hard coating and the 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 Is 120 mJ / cm ² or less, most preferably 100 mJ / cm ² or less.

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

When irradiating active energy rays in the step (2), the wet coating film made of the first hard coat forming coating material may be preheated to a temperature of 40 to 120 ° C., preferably 70 to 100 ° C. The coated film can be surely brought into a dry-to-touch state. The preheating method is not particularly limited, and can be performed by any method. An example of a specific method will be described later in the description of step (4) below.

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

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

Although not intended to be bound by theory, it is possible to improve the adhesion between the first hard coat and the second hard coat by the method described above. Then, it is sufficient to make the coating film dry to the touch, but it is suppressed to an integrated light amount that is insufficient for complete curing, and an integrated light amount sufficient to completely cure the coating film for the first time in the above step (4). It is assumed that complete curing of both hard coats is achieved simultaneously.

The irradiation of the active energy ray in the step (4) is performed in such a manner that the integrated light amount is 240 mJ / cm ² or more, preferably 320 mJ from the viewpoint of completely curing the coating film and the adhesiveness between the first hard coat and the second hard coat. / Cm ² or more, more preferably 360 mJ / cm ² or more. On the other hand, 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 Perform as follows.

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

When the active energy ray is irradiated in the step (4), the wet coating film made of the second hard coat forming paint has characteristics of the first hard coat forming paint and the second hard coat forming paint. From the viewpoint of obtaining good interlayer adhesion strength even when the temperature is greatly different, the temperature is preheated to 30 to 100 ° C, preferably 40 to 85 ° C, more preferably 50 to 75 ° C. The preheating method is not particularly limited, and can be performed by any method. For example, as shown in FIG. 3, a method of controlling the surface temperature of the roll to a predetermined temperature by holding the web on a roll facing the active energy ray irradiation apparatus; surrounding the active energy ray irradiation apparatus as an irradiation furnace; A method of controlling the temperature to a predetermined temperature; and combinations thereof.

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

Articles comprising the hard coat laminate film of the present invention:
Although it does not restrict | limit especially as articles | goods containing the hard coat laminated film of this invention, For example, it does not have image display apparatuses (an image display apparatus which has a touch panel function, and a touch panel function), such as a liquid crystal display, a plasma display, and an electroluminescent display. Image display device), and particularly an image display device having a touch panel function.

Although it does not restrict | limit especially as articles | goods containing the hard coat laminated | multilayer film of this invention, For example, a window, a door, etc. of a building; Washing machines, cupboards, clothes racks, and panels constituting them; vehicles, vehicle windows, windshields, roof windows, instrument panels, etc .; electronic signs and their protective plates; and show windows it can.

When producing an article using the hard coat laminated film of the present invention, in order to impart high designability to the resulting article, the surface of the transparent resin film on the side opposite to the first hard coat forming side is provided. Further, a decorative sheet may be laminated. In such an embodiment, the hard coat laminated film of the present invention is a panel constituting the front of the door body that opens and closes the opening of the front of the main body of articles such as a refrigerator, a washing machine, a cupboard, and a clothes rack, and the main body. This is particularly effective when used as a panel constituting the flat surface of the lid that opens and closes the flat opening. The decorative sheet is not limited, and any decorative sheet can be used. As the decorative sheet, for example, any colored resin sheet can be used.

Although it does not restrict | limit especially as said colored resin sheet, For example, polyester-type resin, such as aromatic polyester and aliphatic polyester; Acrylic resin; Polycarbonate-type resin; Poly (meth) acrylimide-type resin; Polyethylene, polypropylene, and poly Polyolefin resins such as methylpentene; Cellulosic resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene Copolymers, styrene resins such as styrene / ethylene / ethylene / propylene / styrene copolymers, and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride Fats; Polyvinylidene chloride resins; Fluorine-containing resins such as polyvinylidene fluoride; Others, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone And the like. These sheets include an unstretched sheet, a uniaxially stretched sheet, and a biaxially stretched sheet. Moreover, the laminated sheet which laminated | stacked 1 or more types of these 2 or more layers is included.

The thickness of the colored resin sheet is not particularly limited, but may be usually 20 μm or more, preferably 50 μm or more, more preferably 80 μm or more. Further, from the viewpoint of meeting the demand for thinner articles, it may be usually 1500 μm or less, preferably 800 μm or less, more preferably 400 μm or less.

A printed layer may be provided on the front surface of the colored resin sheet to enhance the design feeling, if desired. The printing layer is provided for imparting high designability, and can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine.

Printing is performed directly or via an anchor coat on the surface of the transparent resin film opposite to the surface on the first hard coat forming side and / or on the front surface of the colored resin sheet. It can be applied in whole or in part. The patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, And patchwork. As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. In addition, in order to give a metallic design, aluminum, tin, titanium, indium, and oxides thereof are directly or via an anchor coat on the surface opposite to the first hard coat forming side of the transparent resin film. It may be vapor-deposited by a publicly known method on or on the front surface of the colored resin sheet.

The lamination of the transparent resin film and the decorative sheet is not particularly limited, and can be performed by any method. Examples of the method include a method of dry laminating using a known adhesive; and a method of forming a layer made of a known pressure-sensitive adhesive and then pressing them together.

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.

(D) Pencil hardness:
According to JIS K 5600-5-4, the surface of the hard coat laminated film on the first hard coat side was measured using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g.

(E) 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.

(F) Cross cut test (adhesion):
According to JIS K 5600-5-6: 1999, 100 squares (1 square = 1 mm × 1 mm) of notches on the hard coat laminated film from the surface of the first hard coat side were put into the hard coat laminated film, and then the adhesion test tape was applied to the grid. I peeled it off after sticking it on and squeezing it with my finger. Evaluation criteria were in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled 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.

(G) Water contact angle (initial water contact angle):
Method of calculating surface of first hard coat side of hard coat laminated film from width and height of water drop using automatic contact angle meter “DSA20 (trade name)” manufactured by KRUSS (see JIS R 3257: 1999) )).

(H) Scratch resistance 1 (water contact angle after cotton wiping):
A test piece taken with 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 vertical direction of the test piece so that the surface on the first hard coat side of the hard coat laminated film becomes the surface. Placed on a JIS L 0849: 2013 Gakushin type testing machine and covered with 4 layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) on the friction terminal of the Gakushin type testing machine , 10mm wide, 1mm thick), set the stainless steel plate covered with this gauze so that the vertical and horizontal surfaces are in contact with the test piece, place a 350g load, and place the surface on the first hard coat side of the test piece on the friction terminal After rubbed back and forth 10,000 times under the conditions of a moving distance of 60 mm and a speed of 1 reciprocation / second, the water contact angle of the cotton wiping site was measured according to the above method (g). When the water contact angle is 100 degrees or more, after reciprocating 5,000 times, according to the method of (G) above, the operation of measuring the water contact angle of the cotton wiping location was repeated and evaluated according to the following criteria: .
A: Water contact angle of 100 degrees or more even after 25,000 round trips.
B: Water contact angle is 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 is 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.

(Li) Scratch resistance 2 (steel wool resistance):
The hard coat laminated film was placed on a JIS L 0849: 2013 Gakushin Tester so that the first hard coat side surface was the surface. Subsequently, after # 0000 steel wool was attached to the friction terminal of the Gakushin type testing machine, a load of 500 g was placed, and the surface of the test piece was rubbed 100 times back and forth, and then the friction part was visually observed. In the case where no scratch was observed, after further rubbing 100 times, the work of visually observing the friction part was repeated and evaluated according to the following criteria.
A: No scratches are observed even after 500 round trips.
B: No scratches are observed after 400 round trips, but scratches can be observed after 500 round trips.
C: Scratches are not recognized after 300 round trips, but can be recognized after 400 round trips.
D: Scratches are not recognized after 200 round trips, but can be recognized after 300 round trips.
E: Scratches are not recognized after 100 reciprocations, but can be recognized after 200 reciprocations.
F: Scratches can be recognized after 100 reciprocations.

(Nu) 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.

(Le) 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 first hard coat side surface 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.

(Nu) Cutting workability (state of curved cutting line):
Using a router machine that is automatically controlled by a computer, a hard-coated 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. 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 diameter 2mm, the cutting end surface was observed visually or a microscope (100 times), and the following references | standards evaluated. Similarly, about the cutting hole of diameter 0.5mm, the cutting end surface was observed visually or 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.

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

(B) N-substituted (meth) acrylamide compounds:
(B-1) Acrylylmorpholine.
(B-2) N, N-diethylacrylamide.
(B-3) N-hydroxyethylacrylamide.

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

(D) Leveling agent:
(D-1) Silicon-acrylic copolymer leveling agent “DISPARON NSH-8430HF (trade name)” from Enomoto Kasei Co., Ltd. Solid content 10% by weight.
(D-2) Silicon / acrylic copolymer leveling agent “BYK-3550 (trade name)” of Big Chemie Japan Co., Ltd. Solid content 52% by weight.
(D-3) An acrylic polymer leveling agent “BYK-399 (trade name)” of Big Chemie Japan Co., Ltd. Solid content 100 mass%.
(D-4) Silicone leveling agent “Disparon LS-480 (trade name)” from Enomoto Kasei Co., Ltd. Solid content 100 mass%.

(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.

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

(G) Optional component:
(G-1) Phenylketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714 (trade name)” of Sojyo Sangyo Co., Ltd.
(G-2) 1-methoxy-2-propanol.

(P) Transparent resin film:
(P-1) Coextruded T-die of 2 types, 3 layers, multi-manifold system, first mirror surface roll (roll on the side of holding the molten film and feeding to the next transfer roll) and second mirror surface roll Using an apparatus (see FIG. 2) equipped with a winder having a mechanism for pressing the two layers of the two-type three-layer multilayer resin film (the (α1) layer and the (α2) layer). Co-extrusion of (meth) acrylimide resin “PLEXIMID TT50 (trade name)” as an intermediate layer (β layer) and aromatic polycarbonate resin “Caliver 302-4 (trade name)” of Sumika Stylon Polycarbonate Co., Ltd. Co-extruded continuously from a T-die, supplied and charged between the rotating first mirror roll and second mirror roll so that the (α1) layer is on the first mirror roll side, and pressed to the full thickness 250 To give m, the ([alpha] 1) layer of layer thickness 80 [mu] m, the (beta) layer of layer thickness 90 [mu] m, a transparent resin film layer thickness 80 [mu] m of the ([alpha] 2) layer. At this time, the setting conditions were a T die setting temperature of 300 ° C., a first mirror surface roll setting temperature of 130 ° C .; a second mirror surface roll setting temperature of 120 ° C., and a take-up speed of 6.5 m / min.

Example 1
100 parts by mass of the component (A-1), 3 parts by mass of the component (B-1), 2 parts by mass of the component (E-1) (0.40 parts by mass in terms of solid content), and the component (E-2) 0.06 parts by mass (0.042 parts by mass in terms of solid content), 4 parts by mass of the component (G-1), and 100 parts by mass of the component (G-2) were mixed and stirred to obtain a paint. Table 1 shows the composition. In addition, about the said (E-1) and the said component (E-2), the value of solid content conversion is described in the table | surface. Next, on the surface of the (P-1) on the side of the (α2) layer side, a die-type coating apparatus is used, and the paint obtained above has a wet thickness of 21 μm (thickness after curing: 11 μm). It was applied as follows. Next, after passing the drying oven set at a furnace temperature of 90 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm Using a curing device (see FIG. 3) facing the mirror surface metal roll, a hard coat was formed by processing the mirror surface metal roll at a temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² . Similarly, a hard coat was formed on the surface of the (P-1) on the (α1) layer side to obtain a hard coat laminated film. The above tests (A) to (N) were performed using the hard coat formed later (the hard coat formed on the (α1) layer side surface of (P-1)) as the first hard coat. The results are shown in Table 1.

Examples 2-8
The procedure was the same as in Example 1 except that the formulation of the paint used was changed as shown in Table 1. The results are shown in Table 1.

The hard coat laminated film of the present invention forms a hard coat on the surface of the poly (meth) acrylimide resin without any easy adhesion treatment, but the adhesion between the hard coat and the transparent resin film is It is good. It is also excellent in transparency, surface hardness, color tone, scratch resistance, and surface smoothness.

A mode having layers of a second hard coat, a first hard coat, and a transparent resin film in order from the surface side:
Hereinafter, an example explains the case where the hard court laminated film of the present invention has the layer of the 2nd hard court, the 1st hard court, and the transparent resin film in order from the surface side.

(H1) First hard coat forming paint:
(H1-1) 100 parts by mass of the above (A-2), 12 parts by mass of the above (B-1), 140 parts by mass of the above (C-1), 2 parts by mass of the above (D-1) (0. 2 parts by weight), (G-1) 17 parts by weight, and (G-2) 200 parts by weight of a paint obtained by mixing and stirring. Table 2 shows the formulation. In addition, about said (D-1), the value of solid content conversion is described in the table | surface.

(H1-2 to 15) A paint was obtained in the same manner as (H1-1) except that the formulation was changed as shown in Table 2 or Table 3. In addition, about said (D-1) and said (D-2), the value of solid content conversion is described in the table | surface.

(H2) Second hard coat forming paint:
(H2-1) 100 parts by mass of (A-1), 2 parts by mass of (E-1) (0.40 parts by mass in terms of solids), 0.06 parts by mass of (E-2) (in terms of solids) 0.042 parts by mass), (F-1) 0.5 parts by mass, (G-1) 4 parts by mass, and (G-2) 100 parts by mass of a paint obtained by mixing and stirring. Table 1 shows the composition. In addition, about said (E-1) and said (E-2), the value of solid content conversion is described in the table | surface.

(H2-2 to 16) A paint was obtained in the same manner as in the above (H2-1) except that the formulation was changed as shown in Table 4 or Table 5. In addition, about said (E-1) and said (E-2), the value of solid content conversion is described in the table | surface.

Example 9
On the surface of the (α-1) layer side of the (P-1), a die-type coating apparatus is used so that the (H1-1) has a wet thickness of 40 μm (post-cured thickness: 22 μm). Applied. Next, after passing the drying oven set at a furnace temperature of 90 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm A curing device in which a mirror surface metal roll was placed was used (see FIG. 3), and the treatment was performed under the conditions of a mirror surface metal roll temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² to form a third hard coat. Next, a die-type coating apparatus is used on the surface of the (P-1) on the side of the (α1) layer, so that the (H1-1) has a wet thickness of 40 μm (post-curing thickness: 22 μm). It was applied as follows. Next, after passing the drying oven set at a furnace temperature of 90 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm Using a curing device in which a mirror metal roll was placed (see FIG. 3), the mirror metal roll was processed under conditions of a temperature of 90 ° C. and an integrated light amount of 80 mJ / cm ² . The wet coating film of (H1-1) was a touch-dried coating film. Next, using a die-type coating apparatus on the (H1-1) touch-dried coating film, the (H2-1) has a wet thickness of 4 μm (cured thickness: 2 μm). Applied. Next, after passing the drying furnace set at a furnace temperature of 80 ° C. at a line speed of 1 minute to pass from the inlet to the outlet, the high pressure mercury lamp type ultraviolet irradiation device and the diameter of 25.4 cm Using a curing device facing the mirror surface metal roll (see FIG. 3), the mirror surface metal roll is processed at a temperature of 60 ° C. and an integrated light quantity of 480 mJ / cm ^2. The hard coat laminated film was obtained. The above tests (i) to (wo) were conducted. The results are shown in Table 6. In the table, the first HC means the first hard coat. The second HC means the second hard coat. The third HC means the third hard coat.

Examples 10-23
A hard coat laminated film was obtained in the same manner as in Example 9 except that the coating composition for forming the first hard coat and the third hard coat was the one shown in any one of Tables 6 to 8. The above tests (i) to (wo) were conducted. The results are shown in any one of Tables 6-8.

Examples 24-38
A hard coat laminated film was obtained in the same manner as in Example 9 except that the second hard coat-forming coating material used was one shown in Table 8 or Table 9. The above tests (i) to (wo) were conducted. The results are shown in Table 8 or Table 9.

Examples 39-42
A hard coat laminated film was obtained in the same manner as in Example 9 except that the thicknesses of the first hard coat and the third hard coat were changed as shown in Table 10. The above tests (i) to (wo) were conducted. The results are shown in Table 10.

Examples 43-46
A hard coat laminated film was obtained in the same manner as in Example 9 except that the thickness of the second hard coat was changed as shown in Table 10. The above tests (i) to (wo) were conducted. The results are shown in Table 10.

The preferred hard coat laminated film of the present invention is excellent in adhesion between the hard coat and the film substrate, and excellent in transparency, surface hardness, color tone, scratch resistance, surface smoothness, bending resistance, and cutting workability. ing. 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 a touch panel function), particularly an image display device having a touch panel function. It can be suitably used as a display face plate.

It is a conceptual diagram of the section which shows an example of the hard coat lamination film of the present invention. In an Example, it is a conceptual diagram of the apparatus used for film forming of a transparent resin film. It is a conceptual diagram of the ultraviolet irradiation device used in the Example.

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

Claims (7)

The first hard coat and the transparent resin film layer in order from the surface side,
The first hard coat is
(A) 100 mass parts of polyfunctional (meth) acrylate; and
(B) 1-100 parts by mass of an N-substituted (meth) acrylamide compound;
Made of paint containing;
The transparent resin film has a first hard coat forming surface made of a poly (meth) acrylimide resin;
Hard coat laminated film.
The hard coat laminated film according to claim 1, wherein the component (B) is acryloylmorpholine.
The coating material forming the first hard coat is further (C) inorganic fine particles having an average particle diameter of 1 to 300 nm, 5 to 300 parts by mass;
The hard coat laminated film of Claim 1 or 2 containing.
Having a layer of a second hard coat, a first hard coat, and a transparent resin film in order from the surface side;
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(E) Water repellent 0.01 to 7 parts by mass; and (F) Silane coupling agent 0.01 to 10 parts by mass;
The hard coat laminated film of any one of Claims 1-3 which consists of a coating material which does not contain inorganic particle | grains.
The coating material forming the first hard coat is further (D) 0.01 to 1 part by mass of a leveling agent;
The hard coat laminated film of any one of Claims 1-4 containing.
The transparent resin film is
First poly (meth) acrylimide resin layer (α1);
Aromatic polycarbonate-based resin layer (β);
A second poly (meth) acrylimide resin layer (α2);
It is a transparent multilayer film directly laminated in this order,
The hard coat laminated film of any one of Claims 1-5.
An article comprising the hard coat laminated film according to any one of claims 1 to 6.