JP2017100435A - Transparent resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent resin laminate which is excellent in scratch resistance, and can be suitably used as a window and a wind shield of a vehicle, a window and a door of a building, a protective plate of an electronic signboard, a front panel of household electric appliances such as a refrigerator, a door of furniture such as a cupboard, and a housing of a television, a personal computer, tablet type information equipment and a smart phone, and a show window, and the like.SOLUTION: There is provided a transparent resin laminate which has a first hard coat, 1, a second hard coat 2, and a transparent resin sheet 3 sequentially from the surface side, where the first hard coat 1 is formed from a coating material that contains (A) polyfunctional (meth)acrylate of 100 pts.mass, (B) a water-repellent agent of 0.01-7 pts.mass and (C) a silane coupling agent of 0.01-10 pts.mass and does not contain inorganic particles, and the second hard coat 2 is formed from a coating material that contains (A) a polyfunctional (meth)acrylate of 100 pts.mass and (D) inorganic fine particles having an average particle size of 1-300 nm of 50-300 pts.mass, and the transparent resin sheet 3 has a thickness of 0.5 mm or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a transparent resin laminate. More specifically, the specific gravity is small, excellent scratch resistance, vehicle windows and windshields, building windows and doors, electronic signboard protective plates, front panels of household appliances such as refrigerators, cupboards, etc. The present invention relates to a transparent resin laminate that can be suitably used as a furniture door, a television, a personal computer, a tablet-type information device, a case of a smartphone, a show window, and the like.

Conventionally, it meets the required characteristics such as transparency, rigidity, scratch resistance, and weather resistance for vehicle windows and windshields, building windows and doors, protection boards for digital signage, and show windows. For this reason, articles based on glass have been used. Also, in recent years, glass has a front panel of the door body that opens and closes the opening in the front of the main body of articles such as refrigerators, washing machines, cupboards, and clothes racks, and the opening of the main body plane due to its transparent design feeling. It attracts attention as a member constituting the flat panel of the lid body that opens and closes, particularly as a member constituting the panel surface. 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 and flexible articles. Accordingly, materials that replace glass have been actively studied, and transparent resin laminates having a transparent resin layer such as a polycarbonate resin or an acrylic resin and a hard coat layer have been proposed (for example, Patent Documents 1 and 2). ). However, its scratch resistance is still insufficient, and there is a need for a transparent resin laminate that can maintain the initial characteristics even when repeatedly wiped with a wiper or the like or repeatedly wiped with a dust cloth or the like.

JP 2014-043101 A JP, 2014-040017, A

The subject of this invention is providing the transparent resin laminated body excellent in scratch resistance. Further problems of the present invention are excellent in transparency and scratch resistance, and can maintain initial characteristics even when repeatedly wiped with a wiper or wiped with a dust cloth or the like. Windshields, building windows and doors, protection boards for digital signage, front panels of household appliances such as refrigerators, furniture doors such as cupboards, TVs, computers, tablet-type information devices, and smartphone housings An object of the present invention is to provide a transparent resin laminate that can be suitably used as a body and a show window.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by a specific transparent resin laminate.

That is, this invention has a 1st hard coat, a 2nd hard coat, and the layer of a transparent resin sheet in order from the surface side, The said 1st hard coat is,
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm;
Made of paint containing;
The transparent resin sheet has a thickness of 0.2 mm or more;
It is a transparent resin laminate.

According to a second aspect of the present invention, the (C) silane coupling agent includes 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. It is the transparent resin laminated body as described in 1st invention.

The third invention of the present invention is the transparent resin laminate according to the first or second invention, wherein the (B) water repellent comprises a (meth) acryloyl group-containing fluoropolyether water repellent. It is.

According to a fourth aspect of the present invention, in any one of the first to third aspects, the coating material forming the second hard coat further comprises (E) a leveling agent in an amount of 0.01 to 1 part by mass. It is a transparent resin laminate.

A fifth invention of the present invention has a first hard coat, a second hard coat, and a transparent resin sheet layer in order from the surface side, and the first hard coat is made of a paint containing no inorganic particles; 2 The hard coat is made of a paint containing inorganic particles; the transparent resin sheet has a thickness of 0.2 mm or more; and is a transparent resin laminate satisfying the following (a) to (c).
(A) Total light transmittance is 80% or more.
(B) Haze 5% or less.
(C) Yellowness index: 3 or less.

A sixth invention of the present invention has a first hard coat layer, a second hard coat layer, and a transparent resin sheet layer in order from the surface side, and the first hard coat is made of a paint containing no inorganic particles; 2 The hard coat is made of a paint containing inorganic particles; the transparent resin sheet has a thickness of 0.2 mm or more; and is a transparent resin laminate satisfying the following (d) and (e).
(D) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(E) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.

A seventh invention of the present invention is an article comprising the transparent resin laminate according to any one of the first to sixth inventions.

The transparent resin laminate of the present invention is excellent in scratch resistance. The preferred transparent resin laminate of the present invention is excellent in transparency and scratch resistance, and can maintain the initial characteristics even when repeatedly wiped with a wiper or the like, or repeatedly wiped with a dust cloth or the like. Therefore, vehicle windows and windshields, building windows and doors, protection boards for electronic signboards, front panels of household appliances such as refrigerators, furniture doors such as cupboards, TVs, computers, and tablet-type information devices It can be suitably used as a housing of a smartphone, a show window, and the like.

In this specification, the term “sheet” is used as a term including a film and a plate. 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 transparent resin laminate of the present invention has layers of a first hard coat, a second hard coat, and a transparent resin sheet in order from the surface side, and has high transparency for the purpose of being used as a material replacing glass. It is not colored.

First hard coat:
The first hard coat usually forms the surface of the transparent resin laminate of the present invention. The first hard coat usually forms the surface of an article when the article is produced using the transparent resin laminate of the present invention. The first hard coat exhibits good scratch resistance and functions to maintain surface characteristics such as slipperiness even when repeatedly wiped with a handkerchief or the like.

The first hard coat is made of a paint that does not contain inorganic particles. The first hard coat is preferably (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.01 to 7 parts by mass of a water repellent agent; and (C) 0.01 to 10 parts of a silane coupling agent. And a coating material containing no part of 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; 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 present invention, the first hard coat forming the outermost surface is kept free of inorganic particles so as to retain the scratch resistance, while the second hard coat contains a large amount of specific inorganic fine particles. This problem is solved by increasing the hardness.

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.

(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. Polymerizes and cures with active energy rays to form a hard coat.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 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) Water repellent:
The component (B) functions to improve fingerprint resistance.

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 silicon oil, silicon resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents; and the like. As said component (B), these 1 type, or 2 or more types of mixtures 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 troubles 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) includes 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 (B) is to appropriately adjust the chemical bond or interaction between the component (A) and the component (B), 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 water repellent, which is the component (B). .

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). Part or less, more preferably 2 parts by weight or less. On the other hand, from the viewpoint of obtaining the effect of using the component (B), 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.

(C) Silane coupling agent:
The component (C) 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 (C), 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 (C), these 1 type, or 2 or more types of mixtures can be used.

The compounding 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 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 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 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 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 above components (A) to (C) 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 roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating, and die coating.

The thickness of the first 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 with the second hard coat, it is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less.

Second hard coat :
The second hard coat is made of a paint containing inorganic particles. The second hard coat is preferably made of a paint containing 100 parts by mass of (A) polyfunctional (meth) acrylate; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm.

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.

(D) Inorganic fine particles having an average particle size of 1 to 300 nm:
The component (D) functions to dramatically increase the surface hardness of the transparent resin laminate 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 (D), these 1 type, or 2 or more types of mixtures can be used.

The average particle size of the component (D) is usually 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of maintaining the transparency of the hard coat and ensuring the effect of improving the hardness. 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.

The compounding amount of the component (D) is usually 50 parts by mass or more, preferably 80 parts by mass or more, from the viewpoint of surface hardness with respect to 100 parts by mass of the component (A). On the other hand, from the viewpoint of transparency, it is usually 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, it is preferable that the second hard coat forming coating material 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 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 (E) is preferably a silicon / acrylic copolymer leveling agent. As said component (E), these 1 type, or 2 or more types of mixtures can be used.

The blending amount of the component (E) is usually 0 from the viewpoint of making the surface of the second hard coat smooth and easily forming the first hard coat with respect to 100 parts by mass of the component (A). 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of allowing the first hard coat-forming coating material to be satisfactorily applied without being repelled on the second hard coat, it is 1 part by mass or less, preferably 0.6 parts by mass or less, and more. Preferably it may be 0.4 parts 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, a 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. If the said solvent does not react with the said component (A), the said component (D), and other arbitrary components, or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components, There is no particular limitation. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Of these, 1-methoxy-2-propanol is preferred. 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 roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating, and die coating.

From the viewpoint of surface hardness, the thickness of the second hard coat is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and further preferably 18 μm or more. On the other hand, from the viewpoint of impact resistance, it may be preferably 30 μm or less, more preferably 27 μm or less, and even more preferably 25 μm or less.

Transparent resin sheet :
The transparent resin laminate of the present invention has the second hard coat on at least one surface of the transparent resin sheet, and further has the first hard coat thereon. The second hard coat may be formed directly on at least one surface of the transparent resin sheet, or may be formed via an anchor coat, and an arbitrary transparent layer such as a layer of a transparent resin film. You may form through. For the purpose of using the transparent resin laminate of the present invention as a material to replace glass, the transparent resin sheet is limited except that it has a predetermined range of thickness, high transparency, and no coloration. Any transparent resin sheet can be used.

The transparent resin sheet 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), preferably 80% or more. More preferably, it is 85% or more, and still more preferably 90% or more. A higher total light transmittance is preferable.

The transparent resin sheet has a haze (measured according to JIS K 7136: 2000 using a turbidimeter “NDH2000 (trade name)” manufactured by Nippon Denshoku Industries Co., Ltd.), preferably 5% or less, more preferably 3 % Or less, more preferably 2% or less. The lower the haze, the better.

The above-mentioned transparent resin sheet preferably has a yellowness index (measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation according to JIS K 7105: 1981), preferably 3 or less, more preferably. 2 or less, more preferably 1 or less. The lower the yellowness index, the better.

The thickness of the transparent resin sheet is usually 0.2 mm or more, preferably 0.5 mm or more from the viewpoint of maintaining strength and rigidity necessary as a member that substitutes for glass, and a design having a glass-like depth. More preferably, it is 0.8 mm or more, and further preferably 1 mm or more. On the other hand, from the viewpoint of meeting the demand for weight reduction of articles, it may be usually 10 mm or less, preferably 6 mm or less, more preferably 3 mm or less.

The tensile elastic modulus of the transparent resin sheet is preferably 1500 MPa or more, more preferably 1800 MPa or more, from the viewpoint of maintaining strength and rigidity necessary for a member that substitutes for glass. There is no particular upper limit on the tensile modulus of elasticity, but since it is a resin sheet, it is at most about 10000 MPa within the normally available range. The tensile elastic modulus was measured according to JIS K7127: 1999 under the conditions of specimen type 1B and a tensile speed of 50 mm / min.

The glass transition temperature of the resin constituting the transparent resin sheet is from the viewpoint of maintaining heat resistance (including both heat resistance required when the article is manufactured and heat resistance required when the article is used). The temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher. In addition, when the said transparent resin sheet contains 2 or more types of resin as constituent resin, it is preferable that resin with the lowest glass transition temperature among these satisfy | fills the said range.

The glass transition temperature of the resin constituting the transparent resin sheet is usually 170 ° C. or lower, preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and still more preferably 140 ° C. or lower, from the viewpoint of processability at the time of article manufacture. . In addition, when the said transparent resin sheet contains 2 or more types of resin as constituent resin, it is preferable that resin with the highest glass transition temperature satisfy | fills the said range among these.

In this specification, the glass transition temperature is measured by using a Diamond DSC type differential scanning calorimeter of Perkin Elmer Japan Co., Ltd., heating the sample to 200 ° C. at a heating rate of 50 ° C./min, and at 200 ° C. for 10 minutes. After the temperature is maintained, the temperature is lowered to 50 ° C. at a rate of temperature decrease of 20 ° C./min, held at 50 ° C. for 10 minutes, and then heated to 200 ° C. at a rate of temperature increase of 20 ° C./min. The glass transition temperature appearing in the curve measured in FIG. 2 is the midpoint glass transition temperature calculated by drawing according to FIG. 2 of ASTM D3418.

The transparent resin sheet is not particularly limited. Examples of the transparent resin sheet include polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane, triacetylcellulose, and diacetyl. Cellulose resins such as cellulose and acetyl cellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene / ethylene / ethylene / propylene / styrene copolymer Styrene resins such as styrene, ethylene, butadiene and styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluorine-containing systems such as polyvinylidene fluoride Fats; it can be mentioned a transparent resin sheet such as; other, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. 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.

When the said transparent resin sheet is a lamination sheet, a lamination method is not restrict | limited, It can laminate | stack by arbitrary methods. For example, after each resin sheet is obtained by an arbitrary method, dry lamination or heat lamination is performed; each constituent material is melted by an extruder, and T-die co-processing by a feed block method, a multi-manifold method or a stack plate method is used. A method obtained by extrusion; an extrusion laminating method in which at least one resin sheet is obtained by an arbitrary method, and then another resin sheet is melt-extruded on the resin sheet; A method of applying and drying a paint containing a solvent, separating the formed resin sheet from the film substrate and transferring it onto another resin sheet, and a method of combining two or more of these; it can.

When the said transparent resin sheet is a lamination sheet, in order to improve a design feeling, you may emboss between arbitrary layers if desired.

When the said transparent resin sheet is a lamination sheet, in order to improve a design feeling, you may provide a printing layer between arbitrary layers if desired. The printing layer can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine. At this time, from the viewpoint of providing a design having a glassy depth, it is preferable to provide printing partially or using a transparent ink. Further, the print layer is not limited to 1, and may be 2 or more.

Among these, as the transparent resin sheet, from the viewpoint of mechanical properties, transparency, and non-colorability,
(A1) Acrylic resin sheet;
(A2) an aromatic polycarbonate resin sheet;
(A3) polyester resin sheet;
(A4) Any one or more laminated sheets of the transparent resin sheets (a1) to (a3);
Is preferred.

The (a1) acrylic resin sheet mainly contains an acrylic resin such as polymethyl methacrylate and polyethyl methacrylate (usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more). It is a sheet made of resin.

Examples of the acrylic resin include (meth) acrylic acid ester (co) polymers, copolymers containing structural units derived from (meth) acrylic acid esters, and modified products thereof. 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 modified substance include a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which glutaric anhydride is introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl And a polymer having an imide structure introduced therein by reacting with amine, cyclohexylamine, ammonia, etc.).

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

As a preferable optional component that can be contained in the acrylic resin, core-shell rubber can be exemplified. When the total of the acrylic resin and the core shell rubber is 100 parts by mass, the core shell rubber is 0 to 40 parts by mass (100 to 60 parts by mass of the acrylic resin), preferably 0 to 30 parts by mass (the acrylic By using it in an amount of 100-70 parts by mass of the resin, it is possible to improve the cutting resistance and impact resistance of the (a1) acrylic resin sheet.

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 an acid ester graft copolymer, a methacrylic acid ester / acrylic acid ester rubber graft copolymer, and a methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

Other optional components that can be included in the acrylic resin composition include thermoplastic resins other than the acrylic resin and the core-shell rubber; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, and weather resistance. And additives such as stabilizers, heat stabilizers, mold release agents, antistatic agents, nucleating agents, and surfactants. The amount of these optional components is usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass when the total of the acrylic resin and the core-shell rubber is 100 parts by mass.

The (a2) aromatic polycarbonate resin sheet is a sheet made of a resin mainly containing an aromatic polycarbonate resin (usually 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more).

Examples of the aromatic polycarbonate resin include interfacial weight between an aromatic dihydroxy compound such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene. Polymer obtained by legal method; ester of aromatic dihydroxy compound such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and diester carbonate such as diphenyl carbonate And polymers obtained by an exchange reaction. As said aromatic polycarbonate-type resin, these 1 type, or 2 or more types of mixtures 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 resin and the core shell rubber is 100 parts by mass, the core shell rubber is 0 to 30 parts by mass (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably 0 to 10 parts by mass. By using it in an amount of 100 parts by weight (100 to 90 parts by mass of the aromatic polycarbonate resin), the cutting resistance and impact resistance of the (a2) aromatic polycarbonate resin sheet can be improved.

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 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 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 (a3) polyester resin sheet is a sheet made of a resin mainly containing a polyester resin such as polyethylene terephthalate (usually 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more). Includes unstretched sheets, uniaxially stretched sheets, and biaxially stretched sheets. Moreover, these 1 type, or 2 or more types of laminated sheets are included.

The (a3) polyester resin sheet is preferably mainly an amorphous or low-crystalline aromatic polyester resin (usually 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more). It is the sheet | seat which consists of resin to contain.

Examples of the amorphous or low crystalline aromatic polyester resin include aromatic polyvalent carboxylic acid components such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, ethylene glycol, diethylene glycol, neopentyl glycol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1 Polyester copolymers with polyhydric alcohol components such as 1,4-cyclohexanedimethanol can be exemplified.

Examples of the non-crystalline or low-crystalline aromatic polyester-based resin include, for example, a monomer sum of 100 mol%, terephthalic acid 50 mol% and ethylene glycol 30 to 40 mol%, 1,4-cyclohexanedimethanol 10 Glycol-modified polyethylene terephthalate (PETG) containing 20 mol%; glycol-modified polycyclohexylenedimethylene terephthalate containing 50 mol% terephthalic acid, 16-21 mol% ethylene glycol and 29-34 mol% 1,4-cyclohexanedimethanol ( PCTG); acid-modified polycyclohexylenedimethylene terephthalate (PCTA) containing 25 to 49.5 mol% terephthalic acid, 0.5 to 25 mol% isophthalic acid and 50 mol% 1,4-cyclohexanedimethanol; terephthalic acid 30 ~ 45 Acid-modified and glycol-modified polyethylene terephthalate containing 5% by mole, isophthalic acid 5-20 mole%, ethylene glycol 35-48 mole%, neopentyl glycol 2-15 mole%, diethylene glycol less than 1 mole%, bisphenol A less than 1 mole%; Terephthalic acid 45-50 mol%, isophthalic acid 5-0 mol%, 1,4-cyclohexanedimethanol 25-45 mol%, and 2,2,4,4, -tetramethyl-1,3-cyclobutanediol 25 One or a mixture of two or more of acid-modified and glycol-modified polyethylene terephthalate containing ˜5 mol% can be used.

In this specification, a Diamond DSC type differential scanning calorimeter manufactured by PerkinElmer Japan Co., Ltd. is used, and after holding the sample at 320 ° C. for 5 minutes, the sample is cooled to −50 ° C. at a temperature lowering rate of 20 ° C./min. The second melting curve (melting curve measured in the last heating step) measured by a temperature program of holding at 5 ° C. for 5 minutes and then heating to 320 ° C. at a heating rate of 20 ° C./min, Polyesters of 10 J / g or less were defined as non-crystalline, and polyesters of 10 J / g or more and 60 J / g or less were defined as low crystallinity.

The polyester-based resin can contain other components as desired, as long as the object of the present invention is not adversely affected. Optional components that can be included include thermoplastic resins other than polyester resins; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, antistatic agents, And additives such as surfactants. The compounding amount of these optional components is usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass when the polyester resin is 100 parts by mass.

A preferred optional component that can be included in the polyester resin includes core-shell rubber. By using the core-shell rubber, the impact resistance of the (a3) polyester resin sheet can be improved.

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. Mention one or a mixture of two or more core-shell rubbers such as acid ester graft copolymers, methacrylate ester / acrylate rubber graft copolymers, methacrylate ester / acrylonitrile / acrylate rubber graft copolymers Can do. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

The amount of the core-shell rubber is preferably 0.5 parts by mass or more in order to improve impact resistance when the polyester resin is 100 parts by mass. On the other hand, in order to maintain transparency, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The (a4) any one or two or more laminated sheets of the transparent resin sheets (a1) to (a3) are, for example, arbitrary co-extrusion apparatuses such as a feed block system, a multi-manifold system, and a stack plate system And coextruding into a desired layer structure; using any film forming apparatus, any one or more of the transparent resin sheets (a1) to (a3) After being obtained, these are heat laminated or dry laminated so as to have a desired layer structure; any one of the transparent resin sheets (a1) to (a3) is obtained by using an arbitrary film forming apparatus. Then, the sheet can be obtained by extrusion lamination so that the sheet has a desired layer structure.

If desired, the transparent resin sheet may be provided with a printing layer on the second hard coat forming surface or on the surface opposite to the second hard coat forming surface in order to enhance the design feeling. The printed layer is provided for imparting high designability to an article produced using the transparent resin laminate of the present invention, and prints an arbitrary pattern using an arbitrary ink and an arbitrary printing machine. Can be formed. A detailed method will be described later. In addition, from the viewpoint of providing a design having a glassy depth, when a printing layer is provided on the second hard coat forming surface, it is preferable to provide printing partially or using a transparent ink.

The transparent resin laminate of the present invention may have the first hard coat, the second hard coat, the layer of the transparent resin film, and the third hard coat in order from the surface side. By forming the third hard coat, it becomes easy to impart characteristics suitable for the back surface. FIG. 1 is a conceptual cross-sectional view showing an example of the transparent resin laminate of the present invention. In the example of FIG. 1, the first hard coat 1, the second hard coat 2, the transparent resin sheet 3, and the third hard coat 4 are provided in order from the surface side.

When forming the hard coat layer, easy adhesion such as corona discharge treatment or anchor coat formation in advance to increase the adhesive strength with the hard coat on the hard coat forming surface or both surfaces of the transparent resin sheet as the base material Processing may be performed.

As an anchor coat agent for forming the anchor coat, known materials such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used.

The method for forming the anchor coat using the anchor coat agent is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating, and die coating can be exemplified.

The thickness of the anchor coat is usually about 0.1 to 5 μm, preferably 0.5 to 2 μm.

The transparent resin laminate 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.). 80% or more, more preferably 85% or more, and still more preferably 90% or more. A higher total light transmittance is preferable.

The transparent resin laminate 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.), preferably 5% or less. Preferably it is 3% or less, More preferably, it is 2% or less. The lower the haze, the better.

The transparent resin laminate of the present invention has a yellowness index (measured using a chromaticity meter “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation according to JIS K 7105: 1981), preferably 3 or less. More preferably, it is 2 or less, More preferably, it is 1 or less. The lower the yellowness index, the better.

In the transparent resin laminate 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 an article is produced using the transparent resin laminate of the present invention, the first hard coat forms the surface of the article. When the water contact angle on the surface of the first hard coat is 100 degrees or more, fingerprint resistance (hardness of dirt such as fingerprints and ease of wiping off dirt such as fingerprints) is improved. A higher water contact angle is preferred, and there is no particular upper limit for the water contact angle. However, about 120 degrees is usually sufficient from the viewpoint of fingerprint resistance. Here, the water contact angle is a value measured according to the test (d) of the following example.

The transparent resin laminate of the present invention preferably has a water contact angle of 100 degrees or more after 20,000 cotton strokes on the surface of the first hard coat. 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, surface characteristics such as fingerprint resistance can be maintained even if the surface is 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 (e) in the following Examples.

The transparent resin laminate of the present invention uses a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under the condition of 750 g load according to JIS K 5600-5-4. Measurement) is preferably 5H or more, more preferably 6H or more, and even more preferably 7H or more. When the pencil hardness is 5H or more, the scratch resistance is particularly good. Higher pencil hardness is preferable.

Production method:
The manufacturing method in particular of the transparent resin laminated body of this invention is not restrict | limited, It can manufacture by arbitrary methods. As a preferable production 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 paint film made of the second hard coat forming paint on the transparent resin sheet;
(2) The wet coating film made of the second 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 second hard coat forming paint is applied in a dry-to-touch state. Forming a film;
(3) forming a wet paint film made of the first hard coat forming paint on the touch-dried paint film made of the second hard coat forming paint; and (4) the first 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 composed 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 roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating, and die coating.

The wet coating film made of the second 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 first hard coat forming paint is formed on the touch-dried paint film made of the second 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 second hard coat-forming paint, but from the viewpoint of ensuring that the paint film is dry to the touch, the integrated light quantity 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.

In the step (2), it is preferable to pre-dry the wet coating film made of the second hard coat forming coating material before irradiating the active energy ray. 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 (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 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 first hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating, and die coating.

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

In the step (4), it is preferable to pre-dry the wet coating film made of the first hard coat forming paint before irradiating the active energy ray. 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 (4), the wet coating film made of the first 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 transparent resin laminate can be stabilized.

Articles containing the transparent resin laminate of the present invention:
Although it does not restrict | limit especially as articles | goods containing the transparent resin laminated body of this invention, For example, a window, a door, etc. of a building; Television, a personal computer, a tablet-type information apparatus, a smart phone, and these housing | casings and display faceplates; 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 transparent resin laminate of the present invention, the surface of the transparent resin sheet opposite to the first hard coat and second hard coat formation surface in order to impart high designability to the obtained article. A decorative sheet may be laminated on top. In such an embodiment, the transparent resin laminate of the present invention is a panel that constitutes the front face of the door body that opens and closes the front face of the main body of articles such as refrigerators, washing machines, cupboards, and clothes racks, 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.

Examples of the colored resin sheet include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Cellulosic resin: Cellulosic resin such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene・ Styrene resins such as ethylene / ethylene / propylene / styrene copolymers and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride resins; polyvinyl chloride Fluorine-containing resins such as polyvinylidene fluoride; other colors such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone; A resin sheet can be raised. 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 opposite to the hard coat forming surface of the transparent resin sheet or / and on the front surface of the colored resin sheet, or entirely or partially. Can be applied. 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. Moreover, 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 hard coat forming surface of the transparent resin sheet. Alternatively, and / or on the surface on the front side of the colored resin sheet, vapor deposition may be performed entirely or partially by a known method.

The lamination of the transparent resin sheet 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.

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

(D) Water contact angle:
A method of calculating the first hard coat surface of the transparent resin laminate from the width and height of water droplets using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUS (see JIS R 3257: 1999). Measured with

(E) Scratch resistance 1 (water contact angle after cotton wiping):
JIS L is a test piece that is 150 mm in length and 50 mm in width and sampled so that the machine direction of the transparent resin laminate is the vertical direction of the test piece so that the first hard coat of the transparent resin laminate is on the surface. A stainless steel plate (vertical 10 mm, horizontal 10 mm) placed on the Gakushin type testing machine of 0849: 2013 and covered with 4 layers of gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) on the friction terminal of the Gakushin type testing machine , 1 mm thick), set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, put a 350 g load, and move the first hard coat surface of the test piece to the friction terminal moving distance 60 mm, speed 1 reciprocation / After rubbing back and forth 10,000 times under the condition of seconds, the water contact angle of the cotton wiping location was measured according to the method of (d) above. When the water contact angle is 100 degrees or more, after reciprocating 5,000 times, the operation of measuring the water contact angle of the cotton swab according to the above method (d) 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.

(F) Pencil hardness:
In accordance with JIS K 5600-5-4, the first hard coat surface of the transparent resin laminate was measured using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g.

(G) Scratch resistance:
The transparent resin laminate was placed on a JIS L 0849: 2013 Gakushoku-type testing machine so that the first hard coat of the transparent resin laminate was on the surface. Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type testing machine, placing a 500 g load, rubbing the surface of the test piece 100 times, and repeating the work of visually observing the friction part, Evaluation based on the 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.

(H) Surface smoothness (surface appearance):
The surface of the transparent resin laminate on the first hard coat side was visually observed while being applied with various incident angles of 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.

(Li) Cross cut test (adhesion):
In accordance with JIS K 5600-5-6: 1999, 100 square cuts (1 square = 1 mm × 1 mm) of the grid pattern from the first hard coat surface side are made in the transparent resin laminate, and then the adhesion test tape is applied to the grid pattern. After pasting and squeezing with fingers, it was peeled off. 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.

(Nu) Weather resistance:
Using a sunshine carbon arc lamp type weather resistance tester stipulated in JIS B7753: 2007, the conditions shown in Table 10 of JIS A5759: 2008 (however, the test piece is 125 mm long and 50 mm wide, laminated with transparent resin) A sample collected so that the machine direction of the body was the vertical direction of the test piece was used as it was, and was not attached to glass.), A 300-hour accelerated weather resistance test was conducted. The N number of the test was 3, and in all the tests, the transparent resin laminate was acceptable (shown as ◎ in the table) when there was no appearance change such as swelling, cracking, and peeling, otherwise it was rejected ( It was described as x in the table).

(Le) Impact resistance:
The transparent resin laminate is placed on a rectangular parallelepiped metal jig (the size is 1100 mm in length, 900 mm in width, and 200 mm in height) formed by the upper surfaces of the front plate, the back plate, and the side plates. The first hard coat surface was placed on top and installed and fixed so as to completely cover the opening of the jig. Subsequently, a metal ball having a diameter of 100 mm and a mass of 4.11 kg is placed on the apex of an equilateral triangle with a side of 130 mm marked from the height of 3000 mm above the transparent resin laminate to the vicinity of the center of the portion covering the opening of the transparent resin laminate. The metal balls were dropped once for a total of three times. The N number of the test was 3, and in all the tests, if the metal sphere did not penetrate the transparent resin laminate, it passed (indicated in the table as ◎), otherwise it was rejected (in the table, indicated as x). ).

(V) Cutting workability (state of curved cutting line):
Using a router machine that automatically controls with a computer, a transparent resin laminate was provided with a round cutting hole with a diameter of 2 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. Subsequently, the cutting end face of the cutting hole was observed visually or with a microscope (100 times) and evaluated according to the following criteria.
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) Water repellent:
(B-1) An acryloyl group-containing fluoropolyether water repellent “KY-1203 (trade name)” from Shin-Etsu Chemical Co., Ltd. Solid content 20% by weight.
(B-2) Solvay's methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70 (trade name)”. Solid content 70% by weight.

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

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

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

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

(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 in terms of solid content), 0.06 parts by mass of (B-2) (in terms of 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 of paint obtained by mixing and stirring. Table 1 shows the recipe. 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.

(H1-2 to 16) A paint was obtained in the same manner as (H1-1) except that the formulation was changed as shown in Table 1 or Table 2.

(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) ) A paint obtained by mixing and stirring 17 parts by mass and 200 parts by mass of the above (F-2). Table 3 shows the recipe. In addition, about said (E-1), the value of solid content conversion is described in the table | surface.

(H2-2 to 15) A paint was obtained in the same manner as (H2-1) except that the formulation was changed as shown in Table 3 or Table 4.

(A) Transparent resin sheet:
(A1-1) Acrylic resin sheet 1:
Using an acrylic resin “Optimas 6000 (trade name), glass transition temperature 119 ° C.” manufactured by Mitsubishi Gas Chemical Co., Ltd., using a device equipped with an extruder and a T die, a molten sheet of the resin is continuously formed from the T die. The molten sheet is supplied and fed between a rotating first mirror roll (the roll on the side holding the molten sheet and feeding it to the next transfer roll; the same applies hereinafter) and the rotating second mirror roll. To obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 120 ° C., a second mirror surface roll setting temperature of 110 ° C., and a T die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness index of 0.3, and a tensile modulus of 3400 MPa.

(A1-2) Acrylic resin sheet 2:
Using a poly (meth) acrylimide resin “PLEXIMID TT50 (trade name), glass transition temperature 154 ° C.” manufactured by Evonik Co., Ltd., using an apparatus equipped with an extruder and a T die, a molten sheet of the above resin from the T die Was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll, and pressed to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 140 ° C., a second mirror surface roll setting temperature of 120 ° C., and a T-die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness index of 0.3, and a tensile modulus of 4300 MPa.

(A1-3) Acrylic resin sheet 3:
A transparent resin sheet was obtained in the same manner as in the above (a1-1) except that the thickness was changed to 0.25 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 120 ° C., a second mirror surface roll setting temperature of 110 ° C., and a T die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 93%, a haze of 0.5%, a yellowness index of 0.2, and a tensile elastic modulus of 3150 MPa.

(A2-1) Aromatic polycarbonate resin sheet:
Using the aromatic polycarbonate “Caliver 301-4 (trade name), glass transition temperature 151 ° C.” of Sumika Stylon Polycarbonate Co., Ltd. and using an apparatus equipped with an extruder and a T die, the above resin is melted from the T die. The sheet was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 140 ° C., a second mirror surface roll setting temperature of 120 ° C., and a T-die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 0.6%, a yellowness index of 0.5, and a tensile modulus of 2300 MPa.

(A3-1) Polyester resin sheet 1:
Eastman Chemical Company's non-crystalline polyester resin (PETG resin) “Cadence GS1 (trade name), glass transition temperature 81 ° C.”, using an apparatus equipped with an extruder and a T die, from the T die The molten sheet of the resin is continuously extruded, and the molten sheet is supplied and pressed between the rotating first mirror roll and the rotating second mirror roll, and a transparent resin sheet having a thickness of 1 mm is obtained. Obtained. The setting conditions at this time were a first mirror surface roll setting temperature of 80 ° C., a second mirror surface roll setting temperature of 40 ° C., and a T die outlet resin temperature of 200 ° C. The obtained transparent resin sheet had a total light transmittance of 89%, a haze of 1.3%, a yellowness index of 0.4, and a tensile elastic modulus of 1500 MPa.

(A3-2) Polyester resin sheet 2:
Using Easton Chemical Company's non-crystalline polyester resin “Tritan FX200 (trade name), glass transition temperature 119 ° C.” and using an apparatus equipped with an extruder and a T die, the above resin is melted from the T die. The sheet was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror roll setting temperature of 80 ° C., a second mirror roll setting temperature of 40 ° C., and a T-die outlet resin temperature of 230 ° C. The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 1.2%, a yellowness index of 0.4, and a tensile modulus of 1500 MPa.

(A4-1) Laminated sheet 1:
Using two types and three-layer multi-manifold type co-extrusion film forming equipment equipped with an extruder and T-die, Mitsubishi Gas Chemical Co., Ltd. acrylic resin “Optimas 7500 (trade name), glass transition temperature 119 ° C.” on both outer layers First, the first mirror surface is rotated by continuously extruding a melt-laminated sheet with an intermediate layer of aromatic polycarbonate “Caliver 301-4 (trade name), glass transition temperature 151 ° C.” from Sumika Stylon Polycarbonate Co., Ltd. from a T-die. A transparent resin sheet having a total thickness of 1 mm, a thickness of both outer layers of 0.1 mm, and a thickness of the intermediate layer of 0.8 mm is supplied and pressed between the roll and the rotating second mirror roll. Got. The setting conditions at this time were a first mirror surface roll setting temperature of 120 ° C., a second mirror surface roll setting temperature of 110 ° C., and a T die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 91%, a haze of 0.6%, a yellowness index of 0.5, and a tensile elastic modulus of 2600 MPa.

Example 1
Corona discharge treatment was performed on both sides of the above (a1-1). The wetness index on both sides was 64 mN / m. Next, on one surface of the above (a1-1), the above (H2-1) was applied so as to have a wet thickness of 40 μm (post-cured thickness 22 μm) using a die type coating apparatus. 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 (H2-1) was a touch-dried coating film. Next, using a die-type coating apparatus on the (H2-1) touch-dried coating film, the (H1-1) is made to have a wet thickness of 4 μm (post-curing 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 to form the first hard coat and the second hard coat. did. Subsequently, the third hard coat is used on the other surface of the above (a1-1), and the same paint as used for forming the second hard coat (Example 1 is the above (H2-1)) is used. Using a die-type coating apparatus, the film was formed to have a thickness of 22 μm after curing to obtain a transparent resin laminate. The above tests (i) to (wo) were conducted. The results are shown in Table 5.

Examples 2-16
The same procedure as in Example 1 was performed except that the paint shown in any one of Tables 5 to 7 was used instead of (H1-1). The results are shown in any one of Tables 5-7.

Examples 17-30
The same procedure as in Example 1 was performed except that the paint shown in any one of Tables 7 to 9 was used instead of (H2-1). The results are shown in any one of Tables 7-9.

Examples 31-36
The same procedure as in Example 1 was performed except that the transparent resin sheet shown in Table 9 was used instead of (a1-1). The results are shown in Table 9.

Examples 37-40
Except that the thickness after curing of the first hard coat was changed as shown in Table 10, everything was carried out in the same manner as in Example 1. The results are shown in Table 10. In Tables 10 to 13, the first HC means the first hard coat. Similarly, the second HC means the second hard coat.

Examples 41-44
All the examples except that the thickness after curing of the second hard coat was changed as shown in Table 10 or 11 and the thickness after curing of the third hard coat was changed to be the same as the thickness after curing of the second hard coat. 1 was performed. The results are shown in Table 10 or Table 11.

Examples 45-59
It carried out similarly to Example 1 except having changed the manufacturing conditions of the transparent resin laminated body as shown in any one of Tables 11-13. The results are shown in any one of Tables 11-13.

The preferred transparent resin laminate of the present invention is excellent in transparency, scratch resistance, color tone, slipperiness, surface hardness, rigidity, appearance, adhesion between layers, weather resistance, impact resistance, and cutting workability. Even if it is repeatedly rubbed with a cloth or wiped repeatedly with a dust cloth, the initial characteristics can be maintained. Therefore, vehicle windows and windshields, building windows and doors, protection boards for electronic signboards, front panels of household appliances such as refrigerators, furniture doors such as cupboards, TVs, computers, and tablet-type information devices It can be suitably used as a housing of a smartphone, a show window, and the like.

It is a conceptual diagram of the cross section which shows an example of the transparent resin laminated body of this invention. In an Example, it is a conceptual diagram of the apparatus used for film forming of the transparent resin sheet. In an Example, it is a conceptual diagram of the ultraviolet irradiation device used for hardening of a hard coat.

1: first hard coat 2: second hard coat 3: transparent resin sheet 4: third hard coat 5: T die 6: molten sheet 7: first mirror roll 8: second mirror roll 9: ultraviolet irradiation device 10: Mirror surface metal roll 11: Web 12: Holding angle

Claims (7)

The first hard coat, the second hard coat, and the transparent resin sheet layer in order from the surface side,
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm;
Made of paint containing;
The transparent resin sheet has a thickness of 0.2 mm or more;
Transparent resin laminate.
The transparent resin laminate according to claim 1, wherein the (C) silane coupling agent includes 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. body.
The transparent resin laminate according to claim 1, wherein the water repellent (B) includes a (meth) acryloyl group-containing fluoropolyether water repellent.
The transparent resin laminate according to any one of claims 1 to 3, wherein the coating material forming the second hard coat further comprises (E) a leveling agent in an amount of 0.01 to 1 part by mass.
The first hard coat, the second hard coat, and the transparent resin sheet layer in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
The transparent resin sheet has a thickness of 0.2 mm or more;
A transparent resin laminate satisfying the following (A) to (C).
(A) Total light transmittance is 80% or more.
(B) Haze 5% or less.
(C) Yellowness index: 3 or less.
The first hard coat, the second hard coat, and the transparent resin sheet layer in order from the surface side,
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
The transparent resin sheet has a thickness of 0.2 mm or more;
A transparent resin laminate satisfying the following (d) and (e).
(D) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(E) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.
An article comprising the transparent resin laminate according to any one of claims 1 to 6.