JP6780941B2 - Transparent resin laminate - Google Patents

Description

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

Conventionally, windows and windshields of vehicles, windows and doors of buildings, protective plates for electronic signboards, show windows, etc. meet the required characteristics such as transparency, rigidity, scratch resistance, and weather resistance. Therefore, articles based on glass have been used. In recent years, glass has been used to open the front panel of the door body that opens and closes the opening on the front of the main body of articles such as refrigerators, washing machines, cupboards, and clothes racks, and the opening on the flat surface of the main body because of its transparent design. It is attracting attention as a member that constitutes a flat panel of a lid that opens and closes, particularly as a member that constitutes a panel surface. On the other hand, glass has problems such as low impact resistance and easy cracking; low workability; difficult handling; high specific gravity and heavy; difficult to meet the demand for curved surface and flexibility of articles. Therefore, 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 demand for a transparent resin laminate that can maintain its initial characteristics even if it is repeatedly rubbed with a wiper or the like or wiped repeatedly with a rag or the like.

Japanese Unexamined Patent Publication No. 2014-043101 Japanese Unexamined Patent Publication No. 2014-040017

An object of the present invention is to provide a transparent resin laminate having excellent scratch resistance. A further problem of the present invention is that it has excellent transparency and scratch resistance, and can maintain the initial characteristics even if it is repeatedly rubbed with a wiper or wiped with a cloth, so that it can be used for a vehicle window or the like. Windshields, windows and doors of buildings, protective plates for electronic signs, front panels of home appliances such as refrigerators, doors for furniture such as cupboards, TVs, personal 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 or the like and a show window or the like.

As a result of diligent research, the present inventor has found that the above-mentioned problems can be achieved by a specific transparent resin laminate.

That is, 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 the first hard coat is
(A) 100 parts by mass of polyfunctional (meth) acrylate;
(B) Water repellent agent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consists of a paint that contains and does not contain inorganic particles;
The second hard coat is
(A) 100 parts by mass of 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;
Consists of paint containing;
The transparent resin sheet has a thickness of 0.2 mm or more;
It is a transparent resin laminate.

In the second aspect of the present invention, the above-mentioned (C) silane coupling agent comprises 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. The transparent resin laminate according to the first invention.

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

The fourth invention of the present invention is described in any one of the first to third inventions, wherein the coating material forming the second hard coat further contains (E) 0.01 to 1 part by mass of a leveling agent; It is a transparent resin laminate.

A fifth aspect of the present invention has layers of a first hard coat, a second hard coat, and a transparent resin sheet in this order from the surface side, and the first hard coat comprises 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).
(B) Total light transmittance of 80% or more.
(B) Haze 5% or less.
(C) Yellowness index 3 or less.

The sixth invention of the present invention has a first hard coat, a second hard coat, and a layer of a transparent resin sheet in this order from the surface side, and the first hard coat comprises 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 wiping the surface of the first hard coat 20,000 times back and forth is 100 degrees or more.

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

The transparent resin laminate of the present invention has excellent scratch resistance. The preferable transparent resin laminate of the present invention is excellent in transparency and scratch resistance, and can maintain its initial characteristics even if it is repeatedly rubbed with a wiper or the like or wiped repeatedly with a rag or the like. Therefore, windows and windshields of vehicles, windows and doors of buildings, protective plates for electronic signs, front panels of home appliances such as refrigerators, doors of furniture such as cupboards, TVs, personal computers, tablet-type information devices, etc. , And a housing of a smartphone, a show window, and the like.

As used herein, the term "sheet" is used as a term that also includes films and boards. The term "resin" is used as a term that also includes a resin mixture containing two or more resins and a resin composition containing components other than the resin.

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 in place of glass. It is not colored.

1st 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 properties such as slipperiness even when repeatedly wiped with a handkerchief or the like.

The first hard coat is made of a paint containing no inorganic particles. The first hard coat is preferably (A) 100 parts by mass of polyfunctional (meth) acrylate; (B) 0.01 to 7 parts by mass of water repellent; and (C) 0.01 to 10 parts by mass of silane coupling agent. It consists of a paint containing parts by mass; and containing no inorganic particles.

Inorganic particles (eg 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; fluoride 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 above component (A) is weak, which causes the scratch resistance to be insufficient. Therefore, in the present invention, the first hard coat forming the outermost surface is prevented from containing inorganic particles to maintain 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, "not containing" inorganic particles means that it does not contain a significant amount of inorganic particles. In the field of paints for forming hard coats, the significant amount of inorganic particles is usually about 1 part by mass or more with respect to 100 parts by mass of the component (A). Therefore, "not containing" means that the amount of inorganic particles is usually less than 1 part by mass, preferably 0.1 parts by mass or less, more preferably 0.01, based on 100 parts by mass of the component (A). In other words, it is less than the mass part.

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule, and since it has two or more (meth) acryloyl groups in one molecule, it can be used for ultraviolet rays, electron beams, etc. It functions to form a hard coat by polymerizing and curing with active energy rays.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 2, Bifunctional reaction containing (meth) acryloyl group such as 2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropylene oxyphenyl) propane Sexual monomer; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) acrylate. Etc. (meth) acryloyl group-containing tetrafunctional reactive monomer; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group-containing octafunctional reactive monomer such as trypentaerythritol acrylate. And polymers (oligomers and prepolymers) having one or more of these as constituent monomers can be mentioned. As the component (A), one kind or a mixture of two or more kinds of these can be used.

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

(B) Water repellent:
The component (B) serves to enhance 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 silicone oil, silicone resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; fluoropolyether-based water repellents, fluoropolyalkyl-based water repellents and other fluorophilic water-repellent agents; and the like can be mentioned. As the component (B), one kind or a mixture of two or more kinds of these can be used.

Among these, as the component (B), a fluoropolyether-based water repellent is preferable from the viewpoint of water repellency. From the viewpoint of preventing troubles such as bleed-out of the component (B) due to a chemical bond or strong interaction between the component (A) and the component (B), the component (B) may be included in the molecule. A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter, abbreviated as a (meth) acryloyl group-containing fluoropolyether-based water repellent) is more preferable. More preferable as the component (B) is from the viewpoint of appropriately adjusting the chemical bond or interaction between the component (A) and the component (B) to develop good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether-based water repellent and a meta-acryloyl group-containing fluoropolyether-based water repellent. The (meth) acryloyl group-containing fluoropolyether-based water repellent is clearly distinguished from the above 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 above-mentioned component (B). ..

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

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

Silane coupling agents include hydrolyzable groups (eg, alkoxy groups such as methoxy and ethoxy groups; acyloxy groups such as acetoxy groups; halogen groups such as chloro groups; etc.), and organic functional groups (eg, amino groups, etc.). 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, the component (C) includes a silane coupling agent having an amino group (silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group (from the viewpoint of adhesion). A silane compound having a mercapto group and a hydrolyzable group) is preferable. From the viewpoint of adhesion and odor, a silane coupling agent having an amino group is more preferable.

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

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

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

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

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

Examples of the compound having two or more isocyanate groups in one molecule include methylenebis-4-cyclohexylisocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and trimethylol of isophorone diisocyanate. Polyisocyanate such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethane such as block type isocyanate of the above polyisocyanate. A cross-linking agent or the like can be given. As the compound having two or more isocyanate groups in one molecule, one kind or a mixture of two or more kinds thereof can be used. Further, at the time of cross-linking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as needed.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzophenone compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenylketone; methylanthraquinone, 2-ethylanthraquinone, 2 -Anthraquinone compounds such as amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenone compounds such as acetophenone dimethylketal; triazine compounds; biimidazole compounds; acylphos Examples thereof include finoxide-based compounds; titanosen-based compounds; oxime ester-based compounds; oximuphenyl acetate-based compounds; hydroxyketone-based compounds; and aminobenzoate-based compounds. As the photopolymerization initiator, one kind or a mixture of two or more kinds of these can be used.

The paint for forming the first hard coat includes, if desired, an antistatic agent, a surfactant, a leveling agent, a thixogenic agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and the like. 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.

Since the first hard coat forming paint is diluted to a concentration that is easy to apply, it may contain a solvent if desired. The solvent is particularly limited as long as it does not react with the components (A) to (C) and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like. As the solvent, one kind or a mixture of two or more kinds of these can be used.

The first hard coat forming paint 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 above 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 to the second hard coat, it is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less.

Second hard coat :
The second hard coat is made of a paint containing inorganic particles. The second hard coat preferably comprises a coating material containing (A) 100 parts by mass of 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.

The (A) polyfunctional (meth) acrylate was described above in the description of the first hard coat forming paint. As the component (A), one kind or a mixture of two or more kinds of these can be used.

(D) Inorganic fine particles with an average particle diameter of 1 to 300 nm:
The above component (D) has a function of dramatically increasing 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; and the like.

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

A silane-based coupling agent such as vinylsilane and aminosilane on the surface of the inorganic fine particles for the purpose of increasing the dispersibility of the inorganic fine particles in the coating material and increasing the surface hardness of the obtained hard coat; a titanate-based coupling agent. Aluminate-based coupling agents; organic compounds having reactive functional groups such as ethylenically unsaturated bonding groups such as (meth) acryloyl groups, vinyl groups, and allyl groups and epoxy groups; and fatty acids, fatty acid metal salts, etc. It is preferable to use one treated with a surface treatment agent or the like.

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

The average particle size of the component (D) is usually 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less from the viewpoint of maintaining the transparency of the hard coat and surely obtaining the hardness improving effect. On the other hand, although there is no particular lower limit on the average particle size, the inorganic fine particles that are usually available are at most about 1 nm.

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

The blending amount of the component (D) is usually 50 parts by mass or more, preferably 80 parts by mass or more, with respect to 100 parts by mass of the component (A) from the viewpoint of surface hardness. 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, and more preferably 160 parts by mass or less.

(E) Leveling agent:
It is preferable that the paint for forming the second hard coat further contains (E) a leveling agent from the viewpoint of smoothing the surface of the second hard coat and facilitating the formation of the first hard coat.

Examples of the leveling agent include an acrylic leveling agent, a silicon-based leveling agent, a fluorine-based leveling agent, a silicon-acrylic copolymer-based leveling agent, a fluorine-modified acrylic-based leveling agent, a fluorine-modified silicon-based leveling agent, and functional groups thereof. Examples include leveling agents into which a group (for example, an alkoxy group such as a methoxy group or an ethoxy group, an acyloxy group, a halogen group, an amino group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an isocyanate group, etc.) has been introduced. Can be done. Among these, as the component (E), a silicon-acrylic copolymer system leveling agent is preferable. As the component (E), one kind or a mixture of two or more kinds of these 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 with respect to 100 parts by mass of the component (A) and facilitating the formation of the first hard coat. It is 0.01 part by mass or more, preferably 0.1 part by mass or more, and more preferably 0.2 part by mass or more. On the other hand, from the viewpoint of enabling the paint for forming the first hard coat to be satisfactorily applied onto the second hard coat without being repelled, it is more than 1 part by mass, preferably 0.6 parts by mass or less. It may be preferably 0.4 parts by mass or less.

From the viewpoint of improving the curability by active energy rays, the second 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 include the 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 kind or a mixture of two or more kinds thereof can be used.

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

The paint for forming the second hard coat includes an antistatic agent, a surfactant, a thixo property-imparting agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light resistance stability, if desired. One or more additives such as an agent, an ultraviolet absorber, a heat stabilizer, a colorant, and organic fine particles can be contained.

Since the second hard coat forming paint is diluted to a concentration that is easy to apply, it may contain a solvent if desired. As long as the solvent does not react with the component (A), the component (D), and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. There are no particular restrictions. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like. Of these, 1-methoxy-2-propanol is preferable. As the solvent, one kind or a mixture of two or more kinds of these can be used.

The second hard coat forming paint 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 above 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, still more 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 further 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 on the second hard coat. The second hard coat may be formed directly on at least one surface of the transparent resin sheet, may be formed via an anchor coat, or may be formed as an arbitrary transparent layer such as a layer of a transparent resin film. It may be formed through. The transparent resin sheet is limited except that it has a thickness within a predetermined range, high transparency, and no coloring for the purpose of using the transparent resin laminate of the present invention as a material instead of glass. However, any transparent resin sheet can be used.

The transparent resin sheet has a total light transmittance (measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd. according to JIS K 7631-1: 1997), preferably 80% or more. , More preferably 85% or more, still more preferably 90% or more. The higher the total light transmittance, the more preferable.

The transparent resin sheet is preferably 5% or less, more preferably 3) by Haze (measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd. according to JIS K 7136: 2000). % Or less, more preferably 2% or less. The lower the haze, the better.

The transparent resin sheet has a yellowness index (measured using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981), preferably 3 or less, more preferably. It is 2 or less, more preferably 1 or less. The lower the yellowness index, the more preferable.

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 the strength and rigidity required as a member to replace glass and from the viewpoint of imparting a glass-like deep design. , More preferably 0.8 mm or more, still more preferably 1 mm or more. On the other hand, from the viewpoint of meeting the demand for weight reduction of the article, it may be usually 10 mm or less, preferably 6 mm or less, and 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 the strength and rigidity required as a member to replace glass. There is no particular upper limit to the tensile elastic modulus, but since it is a resin sheet, it is at most about 10,000 MPa in the range that is usually available. The tensile elastic modulus was measured according to JIS K7127: 1999 under the conditions of test piece 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 for manufacturing the article and heat resistance required for using the article). , Usually 80 ° C. or higher, preferably 90 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 110 ° C. or higher. When the transparent resin sheet contains two or more kinds of resins as constituent resins, it is preferable that the resin having the lowest glass transition temperature among them satisfies the above 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, still more preferably 140 ° C. or lower, from the viewpoint of processability at the time of manufacturing the article. .. When the transparent resin sheet contains two or more kinds of resins as constituent resins, it is preferable that the resin having the highest glass transition temperature among them satisfies the above range.

In the present specification, the glass transition temperature is measured by using a Diamond DSC type differential scanning calorimeter manufactured by Perkin Elmer Japan Co., Ltd., and raising the sample to 200 ° C. at a heating rate of 50 ° C./min for 10 minutes at 200 ° C. The final heating process in the temperature program: after holding, cooling to 50 ° C. at a temperature lowering rate of 20 ° C./min, holding at 50 ° C. for 10 minutes, and then heating to 200 ° C. at a heating rate of 20 ° C./min It is an intermediate point glass transition temperature calculated by drawing according to FIG. 2 of ASTM D3418 for the glass transition appearing in the curve measured in.

The transparent resin sheet is not particularly limited. Examples of the transparent resin sheet include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; cellophane, triacetyl cellulose and diacetyl. Cellular resins such as cellulose and acetylcellulose butyrate; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene / ethylene / ethylene / propylene / styrene copolymer , Sterium-based resin such as styrene / ethylene / butadiene / styrene copolymer; Polyvinyl chloride-based resin; Polyvinylidene chloride-based resin; Fluoro-containing resin such as polyvinylidene fluoride; Others, Polyvinyl alcohol, Ethylene vinyl alcohol, Polyether Examples thereof include transparent resin sheets such as ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulphon; These sheets include non-stretched sheets, uniaxially stretched sheets, and biaxially stretched sheets. Further, it includes a laminated sheet in which two or more layers of one or more of these are laminated.

When the transparent resin sheet is a laminated sheet, the laminating method is not limited, and laminating can be performed by any method. For example, a method in which each resin sheet is obtained by an arbitrary method and then dry-laminated or heat-laminated; each constituent material is melted by an extruder, and a T-die by a feed block method, a multi-manifold method, or a stack plate method is used. Method obtained by extrusion; Extrusion laminating method in which at least one resin sheet is obtained by an arbitrary method and then another resin sheet is melt-extruded onto the resin sheet; melt-extruded onto an arbitrary film substrate, or with a constituent material. Examples include a method of applying and drying a paint containing a solvent, peeling the formed resin sheet from the film base material, and transferring it onto another resin sheet, and a method of combining two or more of these. it can.

When the transparent resin sheet is a laminated sheet, if desired, embossing may be performed between arbitrary layers in order to enhance the design feeling.

When the transparent resin sheet is a laminated sheet, a printing layer may be provided between arbitrary layers in order to enhance the design feeling, if desired. The print layer can be formed by printing an arbitrary pattern with an arbitrary ink and an arbitrary printing machine. At this time, from the viewpoint of imparting a glass-like deep design, it is preferable that the printing is partially provided or is provided by using transparent ink. Further, the number of print layers is not limited to 1, and may be 2 or more.

Among these, the transparent resin sheet is selected from the viewpoints of mechanical properties, transparency, and non-coloring property.
(A1) Acrylic resin sheet;
(A2) Aromatic polycarbonate resin sheet;
(A3) Polyester resin sheet;
(A4) Any one or more laminated sheets of the transparent resin sheets (a1) to (a3);
Is preferable.

The acrylic resin sheet (a1) mainly contains an acrylic resin such as polymethyl methacrylate and ethyl polymethacrylate (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) polymer, copolymer containing a structural unit derived from (meth) acrylic acid ester, and modified products thereof. In addition, (meth) acrylic means acrylic or methacrylic. Further, the (co) polymer means a polymer or a copolymer.

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

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

Examples of the modified product include a polymer in which a lactone ring structure has been introduced by an intramolecular cyclization reaction; a polymer in which a glutaric anhydride has been introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl). A polymer in which an imide structure is introduced by reacting with an amine, a cyclohexylamine, an ammonia, or the like; can be mentioned.

As the acrylic resin, one kind or a mixture of two or more kinds of these can be used.

As a preferable optional component that can be contained in the acrylic resin, core-shell rubber can be mentioned. 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 (acrylic). By using the amount of the based resin (100 to 70 parts by mass), the cutting workability and impact resistance of the acrylic resin sheet (a1) can be improved.

Examples of the core-shell rubber include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. As the core-shell rubber, one kind or a mixture of two or more kinds of these can be used.

In addition, other optional components that can be contained 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. Additives such as stabilizers, heat stabilizers, mold release agents, antistatic agents, nucleating agents, and surfactants; and the like can be mentioned. The blending 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-based resin sheet is a sheet made of a resin mainly containing an aromatic polycarbonate-based 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-based resin include the interfacial weight of an aromatic dihydroxy compound such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and phosgen. Polymers obtained by law; esters of aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and carbonate diesters such as diphenyl carbonate. Polymers obtained by the exchange reaction; and the like can be mentioned. As the aromatic polycarbonate-based resin, one kind or a mixture of two or more kinds of these can be used.

As a preferable optional component that can be contained in the aromatic polycarbonate-based resin, core-shell rubber can be mentioned. 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 the amount of parts (100 to 90 parts by mass of the aromatic polycarbonate resin), the cutting workability and impact resistance of the (a2) aromatic polycarbonate resin sheet can be enhanced.

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

Further, the above aromatic polycarbonate resin may be a thermoplastic resin other than the aromatic polycarbonate resin and the core shell rubber, if desired, to the extent not contrary to the object of the present invention; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, Additives such as antioxidants, weather-resistant stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants; and the like can be further included. The blending amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

The polyester-based resin sheet (a3) is a sheet made of a resin mainly containing a polyester-based 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 non-stretched sheets, uniaxially stretched sheets, and biaxially stretched sheets. It also includes one or more of these laminated sheets.

The polyester-based resin sheet (a3) is preferably mainly amorphous or low-crystalline aromatic polyester-based resin (usually 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more). It is a sheet made of a resin containing.

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

Examples of the amorphous or low crystalline aromatic polyester resin include 50 mol% of terephthalic acid, 30 to 40 mol% of ethylene glycol, and 1,4-cyclohexanedimethanol 10 to 100 mol% in total of the monomers. Glycol-modified polyethylene terephthalate (PETG) containing 20 mol%; glycol-modified polycyclohexylene methylene terephthalate containing 50 mol% terephthalic acid, 16-21 mol% ethylene glycol and 29-34 mol% 1,4-cyclohexanedimethanol ( PCTG); acid-modified polycyclohexylene dimethylene terephthalate (PCTA) containing 25-49.5 mol% terephthalic acid, 0.5-25 mol% isophthalic acid and 50 mol% 1,4-cyclohexanedimethanol; terephthalic acid 30 Acid-modified and glycol-modified polyethylene terephthalates containing ~ 45 mol%, isophthalic acid 5-20 mol%, ethylene glycol 35-48 mol%, neopentyl glycol 2-15 mol%, diethylene glycol less than 1 mol%, bisphenol A less than 1 mol% And 45-50 mol% of terephthalic acid, 5-0 mol% of isophthalic acid, 25-45 mol% of 1,4-cyclohexanedimethanol, and 2,2,4,4-tetramethyl-1,3-cyclobutane. One or a mixture of two or more, such as acid-modified and glycol-modified polyethylene terephthalates containing 25 to 5 mol% of diol, can be mentioned.

In the present specification, using a Diamond DSC type differential scanning calorimeter of Perkin Elmer Japan Co., Ltd., the sample is held at 320 ° C. for 5 minutes, cooled to −50 ° C. at a temperature lowering rate of 20 ° C./min, and -50 ° C. The amount of heat of fusion of the second melting curve (melting curve measured in the final heating process) measured by the temperature program of heating to 320 ° C at a heating rate of 20 ° C / min after holding at ° C for 5 minutes A polyester of 10 J / g or less was defined as non-crystalline, and a polyester of more than 10 J / g and 60 J / g or less was defined as low crystallinity.

The polyester resin may contain other components, if desired, to the extent that it does not contradict the object of the present invention. Optional components that can be included include thermoplastic resins other than polyester resins; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weather-resistant stabilizers, heat stabilizers, mold release agents, antistatic agents, etc. In addition, additives such as surfactants; and the like can be mentioned. The blending 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.

As a preferable optional component that can be contained in the polyester resin, core-shell rubber can be mentioned. By using the core-shell rubber, the impact resistance of the polyester-based resin sheet (a3) can be improved.

Examples of the core-shell rubber include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. List one or a mixture of two or more core-shell rubbers such as acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. Can be done. As the core-shell rubber, one kind or a mixture of two or more kinds of these can be used.

The blending 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.

(A4) Any one or more laminated sheets of the transparent resin sheets (a1) to (a3) can be used in any coextrusion apparatus such as a feed block method, a multi-manifold method, and a stack plate method. By co-extruding a film so as to have a desired layer structure; using an arbitrary film forming device, any one or more of the above transparent resin sheets (a1) to (a3) can be produced. After obtaining them, they are heat-laminated or dry-laminated so as to have a desired layer structure; any one of the above transparent resin sheets (a1) to (a3) is obtained using an arbitrary film forming apparatus. After that, it can be obtained by extruding and laminating the sheet as a base material so as to have a desired layer structure.

If desired, the transparent resin sheet may be provided with a printing layer on the surface on which the second hard coat is formed or on the surface opposite to the surface on which the second hard coat is formed, in order to enhance the design feeling. The printing layer is provided to impart high designability to an article produced by 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 by The detailed method will be described later. From the viewpoint of imparting a glass-like deep design, when the printing layer is provided on the second hard coat forming surface, it is preferable that the printing is partially provided or the printing is provided using transparent ink.

The transparent resin laminate of the present invention may have the first hard coat, the second hard coat, the transparent resin film layer, and the third hard coat in order from the surface side. By forming the third hard coat, it becomes easy to impart suitable characteristics as the back surface. FIG. 1 is a conceptual diagram of a cross section 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 this order from the surface side.

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

As the anchor coating agent for forming the anchor coating, for example, known agents such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used.

The method of forming the anchor coat using the anchor coat agent is not particularly limited, and a known web coating method can be used. Specific examples thereof include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating and die coating.

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 turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.). It is 80% or more, more preferably 85% or more, still more preferably 90% or more. The higher the total light transmittance, the more preferable.

The transparent resin laminate of the present invention has a haze (measured using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7136: 2000), preferably 5% or less. It is preferably 3% or less, more preferably 2% or less. The lower the haze, the better.

The transparent resin laminate of the present invention has a yellowness index (measured using a colorimeter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981), preferably 3 or less. It is more preferably 2 or less, still more preferably 1 or less. The lower the yellowness index, the more preferable.

The transparent resin laminate of the present invention has a water contact angle of the surface of the first hard coat 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 of the surface of the first hard coat is 100 degrees or more, the fingerprint resistance (difficulty of attaching stains such as fingerprints and ease of wiping off stains such as fingerprints) is improved. The water contact angle is preferably high, and there is no particular upper limit on the water contact angle. However, from the viewpoint of fingerprint resistance, about 120 degrees is usually sufficient. 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 wiping the surface of the first hard coat 20,000 times in a reciprocating manner. More preferably, the water contact angle after wiping the cotton 25,000 times back and forth is 100 degrees or more. Since the water contact angle after wiping with cotton 20,000 times reciprocating is 100 degrees or more, surface characteristics such as fingerprint resistance can be maintained even if the product is repeatedly wiped with a handkerchief or the like. It is preferable that the number of cotton wipes that can maintain a water contact angle of 100 degrees or more is large. Here, the water contact angle after wiping with cotton is a value measured according to the test (e) of the following example.

The transparent resin laminate of the present invention uses the pencil "Uni (trade name)" of Mitsubishi Pencil Co., Ltd. under the condition of a load of 750 g according to the pencil hardness of the surface of the first hard coat (JIS K 5600-5-4). Measurement) is preferably 5H or more, more preferably 6H or more, still more preferably 7H or more. When the pencil hardness is 5H or more, the scratch resistance becomes particularly good. The higher the pencil hardness, the more preferable.

Production method:
The method for producing the transparent resin laminate of the present invention is not particularly limited, and the transparent resin laminate can be produced by any method. As a preferable manufacturing method, for example, from the viewpoint of adhesion between the first hard coat and the second hard coat, for example.
(1) A step of forming a wet coating film made of the second hard coat forming paint on the transparent resin sheet;
(2) The integrated light amount of active energy rays is 1 to 230 mJ / cm ² , preferably 5 to 200 mJ / cm ² , more preferably 10 to 160 mJ / cm on the wet coating material composed of the second hard coat forming paint. ² , more preferably 20 to 120 mJ / cm ² , and most preferably 30 to 100 mJ / cm ^2, and the wet coating material made of the second hard coat forming paint is applied in a dry state to the touch. The process of making a film;
(3) A step of forming a wet coating film made of the first hard coat forming paint on the coating material in a dry state to the touch made of the second hard coat forming paint; and (4) the first The wet coating material made of the paint for forming a hard coat is preheated to a temperature of 30 to 100 ° C., preferably a temperature of 40 to 85 ° C., more preferably a temperature of 50 to 75 ° C., and the active energy rays are integrated to 240 to 10,000 mJ / cm. ^2. A method including a step of irradiating to a temperature of 320 to 5000 mJ / cm ² , more preferably 360 to 2000 mJ / cm ² , can be mentioned.

In the step (1), the method for forming the wet coating film made of the second hard coat forming paint is not particularly limited, and a known web coating method can be used. Examples of the above 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 a dry state to the touch or a non-tacky state in the step (2), and directly touches the web device. However, it will not cause handling problems such as sticking. Therefore, in the next step (3), a wet coating film made of the first hard coat forming paint is formed on the touch-dried coating film made of the second hard coat forming paint. Will be able to.

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

The irradiation of the 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 in a dry state 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.

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

When irradiating the active energy rays in the step (2), the wet coating film made of the second hard coat forming paint may be preheated to a temperature of 40 to 120 ° C., preferably a temperature of 70 to 100 ° C. The coating film can be reliably dried to the touch. 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 the following step (4).

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 above method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, dip coating and die coating.

The wet coating film composed 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 paint is also completely cured.

Although it is 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 above method by irradiating the irradiation with active energy rays in the above step (2). Is sufficient for the coating film to be dry to the touch, but the integrated light intensity is insufficient for complete curing, and the integrated light intensity is sufficient for the coating film to be completely cured for the first time in the above step (4). It is presumed that this is because the complete curing of both hard coats is achieved at the same time.

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

It is preferable to pre-dry the wet coating film composed of the first hard coat forming paint before irradiating the active energy rays in the step (4). In the pre-drying, for example, it takes about 0.5 to 10 minutes to pass the web from the inlet to the outlet in a drying furnace set to a temperature of about 23 to 150 ° C., preferably a temperature of about 50 to 120 ° C. This can be done by passing at a line speed of preferably 1 to 5 minutes.

When irradiating the active energy rays in the step (4), the wet coating material composed of the first hard coat forming paint has the characteristics of the first hard coat forming paint and the second hard coat forming paint. From the viewpoint of obtaining good interlayer adhesion strength, the temperature is preheated to a temperature of 30 to 100 ° C., preferably a temperature of 40 to 85 ° C., and more preferably a temperature of 50 to 75 ° C. The method of preheating is not particularly limited, and any method can be used. 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 in a roll opposite to the active energy ray irradiator; the periphery of the active energy ray irradiator is surrounded as an irradiation furnace, and the inside of the irradiation furnace. A method of controlling the temperature of the above to a predetermined temperature; and a combination thereof can be mentioned.

After the above 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:
The article containing the transparent resin laminate of the present invention is not particularly limited, but for example, windows and doors of buildings; TVs, personal computers, tablet-type information devices, smartphones, and their housings and display face plates; refrigerators, Washing machines, cupboards, clothes racks, and the panels that make them up; vehicles, vehicle windows, windshields, roof windows, instrument panels, etc .; electronic signs and protective plates for them; and show windows, etc. it can.

When producing an article using the transparent resin laminate of the present invention, in order to impart high designability to the obtained article, the surface of the transparent resin sheet opposite to the first hard coat and the second hard coat forming surface. A decorative sheet may be laminated on top of it. In such an embodiment, the transparent resin laminate of the present invention is used as a panel constituting the front surface of a door body for opening and closing an opening on the front surface of a main body of an article such as a refrigerator, a washing machine, a cupboard, and a clothes rack, or a main body. It is particularly effective when used as a panel constituting the flat surface of a lid that opens and closes a flat surface 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) acrylicimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Based resin; Cellulosic resin such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / propylene / styrene copolymer, styrene -Sterene resins such as ethylene / ethylene / propylene / styrene copolymers and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; fluororesins such as vinylidene fluoride In addition, colored resin sheets such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulphon, and polyethersulphon; can be mentioned. These sheets include non-stretched sheets, uniaxially stretched sheets, and biaxially stretched sheets. Further, it includes a laminated sheet in which two or more layers of one or more of these are laminated.

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

If desired, a printing layer may be provided on the front surface of the colored resin sheet in order to enhance the design feeling. The printing layer is provided to impart high designability, and can be formed by printing an arbitrary pattern with an arbitrary ink and an arbitrary printing machine.

Printing is performed directly or via an anchor coat on the surface of the transparent resin sheet opposite to the hard coat forming surface and / and on the front surface of the colored resin sheet, entirely or partially. Can be applied. The patterns include metallic patterns such as hairlines, wood grain patterns, stone grain patterns that imitate the surface of rocks such as marble, fabric patterns that imitate cloth texture and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, etc. And patchwork etc. can be mentioned. As the printing ink, a binder in which a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed 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, and polyamides. Resins such as based resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins, and resin compositions thereof can be used. Further, in order to give a metallic design, aluminum, tin, titanium, indium, oxides thereof, etc. are applied directly or via an anchor coat on the surface of the transparent resin sheet opposite to the hard coat forming surface. Alternatively, the colored resin sheet may be entirely or partially deposited on the front surface of the colored resin sheet by a known method.

The laminating of the transparent resin sheet and the decorative sheet is not particularly limited, and can be performed by any method. Examples of the above method include a method of dry laminating using a known adhesive; and a method of forming a layer made of a known adhesive and then superimposing and pressing the two.

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

Measurement method (a) Total light transmittance:
Measurement was performed using a turbidity meter "NDH2000 (trade name)" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7361-1: 1997.

(B) Haze:
According to JIS K 7136: 2000, the measurement was performed using a turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Industries Co., Ltd.

(C) Yellowness index (YI):
The measurement was performed using a chromaticity meter "SolidSpec-3700 (trade name)" manufactured by Shimadzu Corporation in accordance with JIS K 7105: 1981.

(D) Water contact angle:
A method of calculating the first hard-coated 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 KRUSS (see JIS R 3257: 1999). Measured at.

(E) Scratch resistance 1 (water contact angle after cotton wiping):
A test piece having a size of 150 mm in length and 50 mm in width and collected so that the machine direction of the transparent resin laminate is the vertical direction of the test piece is JIS L so that the first hard coat of the transparent resin laminate is on the surface. A stainless steel plate (length 10 mm, width 10 mm) placed on the Gakushin type tester at 0849: 2013 and covered with four layers of gauze (Medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) on the friction terminals of the Gakushin type tester. , Thickness 1 mm), set so that the vertical and horizontal surfaces of the stainless steel plate are in contact with the test piece, load 350 g, and place the first hard coat surface of the test piece on the first hard coat surface of the test piece with a friction terminal movement distance of 60 mm and a speed of 1 reciprocation / After rubbing 10,000 times back and forth under the condition of seconds, the water contact angle of the cotton wiping portion was measured according to the method (d) above. When the water contact angle is 100 degrees or more, after rubbing it back and forth 5,000 times, the work of measuring the water contact angle of the cotton-wiping part is repeated according to the method (d) above, and the evaluation is made according to the following criteria. ..
A: The water contact angle is 100 degrees or more even after 25,000 round trips.
B: The water contact angle is 100 degrees or more after 20,000 round trips, but less than 100 degrees after 25,000 round trips.
C: The water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 times.
D: The water contact angle is 100 degrees or more after 10,000 round trips, but less than 100 degrees after 15,000 round trips.
E: Water contact angle is less than 100 degrees after 10,000 round trips.

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

(G) Scratch resistance:
The transparent resin laminate was placed on a JIS L 0849: 2013 Gakushin type tester 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 tester, a load of 500 g was applied, the surface of the test piece was rubbed 100 times, and then the work of visually observing the friction point was repeated. It was evaluated according to the criteria of.
A: No scratches are found even after 500 round trips.
B: No scratches are observed after 400 round trips, but scratches can be observed after 500 round trips.
C: No scratches are observed after 300 round trips, but scratches can be observed after 400 round trips.
D: No scratches are observed after 200 round trips, but scratches can be observed after 300 round trips.
E: No scratches are found after 100 round trips, but scratches can be seen after 200 round trips.
F: Scratches can be recognized after 100 round trips.

(H) Surface smoothness (surface appearance):
The surface of the transparent resin laminate on the first hard coat side was visually observed while being exposed to various angles of incidence of the light of the fluorescent lamp, and evaluated according to the following criteria.
⊚: There are no waviness or scratches on the surface. Even if you look through the light up close, there is no cloudiness.
◯: When looking through the light up close, there is a slight cloudiness.
Δ: When viewed up close, slight waviness and scratches are observed on the surface. There is also a feeling of cloudiness.
X: Many undulations and scratches can be observed on the surface. There is also a clear cloudiness.

(I) Grid test (adhesion):
According to JIS K 5600-5-6: 1999, make 100 squares (1 square = 1 mm x 1 mm) in the transparent resin laminate from the first hard coat surface side, and then apply the adhesion test tape to the grid. After pasting and squeezing with fingers, it was peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standards.
Category 0: The edges of the cut are perfectly smooth and there is no peeling on any grid.
Category 1: Small peeling of the coating at the intersection of cuts. The cross-cut portion is clearly not affected by more than 5%.
Category 2: The coating is peeling off along the edges of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5% but not more than 15%.
Category 3: The coating film is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Category 4: The coating film is partially or wholly peeled along the edge of the cut, and / or some eyes are partially or wholly peeled. 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.

(N) Weather resistance:
Using a sunshine carbon arc lamp type weather resistance tester specified in JIS B7753: 2007, the conditions shown in Table 10 of JIS A5759: 2008 (however, the test piece has a size of 125 mm in length and 50 mm in width and is laminated with transparent resin. The sample was collected so that the machine direction of the body was the vertical direction of the test piece, and the sample was used as it was and was not attached to the glass.) The accelerated weather resistance test was conducted for 300 hours. The N number of the test was set to 3, and in all the tests, if there was no change in appearance such as swelling, cracking, and peeling of the transparent resin laminate, it passed (marked with ◎ in the table), otherwise it failed (it was rejected). In the table, it is marked with x).

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

(W) Cutting workability (state of curved cutting line):
Using a router processing machine that is automatically controlled by a computer, a perfect circular cutting hole with a diameter of 2 mm was provided in the transparent resin laminate. The mill used at this time was a four-blade made of cemented carbide with a cylindrical round tip shape and a nick, and the blade diameter was appropriately selected according to the machining location. Subsequently, the cut end face of the cutting hole was visually or observed with a microscope (100 times) and evaluated according to the following criteria.
⊚: No cracks or whiskers were observed under a microscope ○: No cracks were observed under a microscope. However, beard is recognized.
Δ: No crack was visually observed. However, cracks are observed under a microscope.
X: Cracks are also visually observed.

Raw materials used (A) Polyfunctional (meth) acrylate:
(A-1) Dipentaerythritol hexaacrylate. 6 sensuality.
(A-2) Pentaerythritol triacrylate. 3 sensuality.

(B) Water repellent:
(B-1) Acryloyl group-containing fluoropolyether-based water repellent agent "KY-1203 (trade name)" of Shin-Etsu Chemical Co., Ltd. Solid content 20% by mass.
(B-2) Solvay's methacryloyl group-containing fluoropolyether-based water repellent "FOMBLIN MT70 (trade name)". Solid content 70% by mass.

(C) Silane coupling agent:
(C-1) N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane "KBM-602 (trade name)" of Shin-Etsu Chemical Co., Ltd.
(C-2) N-2- (aminoethyl) -3-aminopropyltrimethoxysilane "KBM-603 (trade name)" of 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)" of Shin-Etsu Chemical Co., Ltd.

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

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

(F) Optional component:
(F-1) Phenylketon-based photopolymerization initiator (1-hydroxycyclohexylphenylketon) "SB-PI714 (trade name)" of Soho Kogyo 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) above (converted to solid content) 0.042 parts by mass), 0.5 parts by mass of (C-1), 4 parts by mass of (F-1), and 100 parts by mass of (F-2) are mixed and stirred. Table 1 shows the formulation table. For the above (B-1) and the above component (B-2), the solid content conversion values are shown in the table.

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

(H2) Paint for forming the second hard coat:
(H2-1) 100 parts by mass of (A-2), 140 parts by mass of (D-1), 2 parts by mass of (E-1) (0.2 parts by mass in terms of solid content), (F-1) ) 17 parts by mass and 200 parts by mass of (F-2) above were mixed and stirred to obtain a coating material. Table 3 shows the formulation table. For the above (E-1), the solid content conversion value is shown in the table.

A paint was obtained in the same manner as in (H2-1) above, except that the formulation (H2-2 to 15) 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." of Mitsubishi Gas Chemical Company, Inc., a molten sheet of the above resin is continuously formed from the T die using an apparatus equipped with an extruder and a T die. The molten sheet is supplied and charged between the rotating first mirror surface roll (the roll that holds the molten sheet and sends it to the next transfer roll; the same applies hereinafter) and the rotating second mirror surface roll. , Pressing to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a set temperature of the first mirror surface roll of 120 ° C., a set temperature of the second mirror surface roll of 110 ° C., and a resin temperature of the T-die outlet of 300 ° C. The total light transmittance of the obtained transparent resin sheet was 92%, the haze was 0.5%, the yellowness index was 0.3, and the tensile elastic modulus was 3400 MPa.

(A1-2) Acrylic resin sheet 2:
Using Ebonic's poly (meth) acrylicimide resin "PLEXIMID TT50 (trade name), glass transition temperature 154 ° C.", a molten sheet of the above resin from the T die using an apparatus equipped with an extruder and a T die. The molten sheet was supplied and charged between the rotating first mirror surface roll and the rotating second mirror surface roll, and pressed to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a set temperature of the first mirror surface roll of 140 ° C., a set temperature of the second mirror surface roll of 120 ° C., and a resin temperature of the T-die outlet of 300 ° C. The total light transmittance of the obtained transparent resin sheet was 92%, the haze was 0.5%, the yellowness index was 0.3, and the tensile elastic modulus was 4300 MPa.

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

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

(A3-1) Polyester resin sheet 1:
Using a non-crystalline polyester resin (PETG resin) "Cadence GS1 (trade name), glass transition temperature 81 ° C." from Eastman Chemical Company, using a device 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 charged between the rotating first mirror surface roll and the rotating second mirror surface roll, and pressed to obtain a transparent resin sheet having a thickness of 1 mm. Obtained. The setting conditions at this time were a set temperature of the first mirror surface roll of 80 ° C., a set temperature of the second mirror surface roll of 40 ° C., and a resin temperature of the T die outlet of 200 ° C. The total light transmittance of the obtained transparent resin sheet was 89%, the haze was 1.3%, the yellowness index was 0.4, and the tensile elastic modulus was 1500 MPa.

(A3-2) Polyester resin sheet 2:
Using a non-crystalline polyester resin "Tritan FX200 (trade name), glass transition temperature 119 ° C." from Eastman Chemical Company, melting of the above resin from the T die using an apparatus equipped with an extruder and a T die. The sheet was continuously extruded, and the molten sheet was supplied and charged between the rotating first mirror surface roll and the rotating second mirror surface roll, and pressed to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a set temperature of the first mirror surface roll of 80 ° C., a set temperature of the second mirror surface roll of 40 ° C., and a resin temperature of the T-die outlet of 230 ° C. The total light transmittance of the obtained transparent resin sheet was 90%, the haze was 1.2%, the yellowness index was 0.4, and the tensile elastic modulus was 1500 MPa.

(A4-1) Laminated sheet 1:
Using a two-kind, three-layer multi-manifold co-extrusion film forming device equipped with an extruder and a T-die, the acrylic resin "Optimas 7500 (trade name), glass transition temperature 119 ° C." A molten laminated sheet having the aromatic polycarbonate "Calibre 301-4 (trade name), glass transition temperature 151 ° C." of Sumika Stylon Polycarbonate Co., Ltd. as an intermediate layer is continuously extruded from the T-die and rotated. The above-mentioned molten laminated sheet is supplied and charged between the roll and the rotating second mirror surface roll, and pressed to obtain a transparent resin sheet having a total thickness of 1 mm, both outer layers having a thickness of 0.1 mm, and an intermediate layer having a thickness of 0.8 mm. Got The setting conditions at this time were a set temperature of the first mirror surface roll of 120 ° C., a set temperature of the second mirror surface roll of 110 ° C., and a resin temperature of the T-die outlet of 300 ° C. The total light transmittance of the obtained transparent resin sheet was 91%, the haze was 0.6%, the yellowness index was 0.5, and the tensile elastic modulus was 2600 MPa.

Example 1
Corona discharge treatment was performed on both sides of the above (a1-1). The wettability 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 (thickness after curing 22 μm) using a die-type coating device. Next, a drying furnace set to an internal temperature of 90 ° C. was passed at a line speed at which the time required to pass from the inlet to the outlet was 1 minute, and then a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm were used. Using a curing device opposed to the mirror surface metal roll (see FIG. 3), the treatment was performed under the conditions that the temperature of the mirror surface metal roll was 90 ° C. and the integrated light amount was 80 mJ / cm ² . The wet coating film of the above (H2-1) became a coating film in a dry state to the touch. Next, a die-type coating device is used on the coating film in the dry state to the touch of (H2-1) so that the wet thickness of (H1-1) is 4 μm (thickness after curing is 2 μm). It was applied. Next, a drying furnace set to an internal temperature of 80 ° C. was passed at a line speed at which the time required to pass from the inlet to the outlet was 1 minute, and then a high-pressure mercury lamp type ultraviolet irradiation device and a diameter of 25.4 cm were used. Using a curing device opposite to the mirror surface metal roll (see FIG. 3), the mirror surface metal roll is processed under the conditions of a temperature of 60 ° C. and an integrated light amount of 480 mJ / cm ² to form a first hard coat and a second hard coat. did. Subsequently, a third hard coat was applied onto the other surface of the above (a1-1), and the same paint used for forming the second hard coat (Example 1 is the above (H2-1)) was used. Using a die-type coating device, it was formed so as to have a thickness of 22 μm after curing to obtain a transparent resin laminate. The above tests (a) to (wo) were performed. The results are shown in Table 5.

Examples 2-16
All were carried out in the same manner as in Example 1 except that the paint shown in any one of Tables 5 to 7 was used instead of the above (H1-1). The results are shown in any one of Tables 5-7.

Examples 17-30
All were carried out in the same manner as in Example 1 except that the paint shown in any one of Tables 7 to 9 was used instead of the above (H2-1). The results are shown in any one of Tables 7-9.

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

Example 37-40
The post-curing thickness of the first hard coat was changed as shown in Table 10, but all the same was performed 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 examples except that the post-curing thickness of the second hard coat was changed as shown in Table 10 or 11, and the post-cured thickness of the third hard coat was changed to the same as the post-cured thickness of the second hard coat. The same procedure as in 1 was performed. The results are shown in Table 10 or Table 11.

Examples 45-59
The same procedure as in Example 1 was carried out except that the production conditions of the transparent resin laminate were changed as shown in any one of Tables 11 to 13. The results are shown in any one of Tables 11 to 13.

The preferable 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 machinability, and is a wiper. The initial characteristics can be maintained even if it is repeatedly squeezed with a cloth or wiped with a wiper. Therefore, windows and windshields of vehicles, windows and doors of buildings, protective plates for electronic signs, front panels of home appliances such as refrigerators, doors of furniture such as cupboards, TVs, personal computers, tablet-type information devices, etc. , And 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 laminate of this invention. It is a conceptual diagram of the apparatus used for forming a film of a transparent resin sheet in an Example. It is a conceptual diagram of the ultraviolet irradiation apparatus used for curing a hard coat in an Example.

1: 1st hard coat 2: 2nd hard coat 3: Transparent resin sheet 4: 3rd hard coat 5: T die 6: Molten sheet 7: 1st mirror surface roll 8: 2nd mirror surface roll 9: Ultraviolet irradiation device 10: Mirror metal roll 11: Web 12: Hugging angle

Claims (14)

It has layers of a first hard coat, a second hard coat, and a transparent resin sheet in order from the surface side.
The first hard coat is
(A) 100 parts by mass of polyfunctional (meth) acrylate;
(B) Water repellent agent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consists of a paint that contains and does not contain inorganic particles;
The second hard coat is
(A) 100 parts by mass of 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;
Consists 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 silane coupling agent (C) comprises at least one 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 or 2, wherein the (B) water repellent agent contains a (meth) acryloyl group-containing fluoropolyether-based water repellent agent.
The transparent resin laminate according to any one of claims 1 to 3, wherein the coating material forming the second hard coat further contains (E) 0.01 to 1 part by mass of a leveling agent.
The transparent resin laminate according to any one of claims 1 to 4, wherein the inorganic fine particles (D) having an average particle diameter of 1 to 300 nm contain silica fine particles.
It has layers of a first hard coat, a second hard coat, and a transparent resin sheet in order from the surface side.
The first hard coat consists of a paint that does not contain inorganic particles;
The second hard coat consists of a paint 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) and (f).
(B) Total light transmittance of 85% or more.
(B) Haze 5% or less.
(C) Yellowness index 3 or less.
(F) The pencil hardness on the surface of the first hard coat is 6H or more.
It has layers of a first hard coat, a second hard coat, and a transparent resin sheet in order from the surface side.
The first hard coat consists of a paint that does not contain inorganic particles;
The second hard coat consists of a paint containing inorganic particles;
The transparent resin sheet has a thickness of 0.2 mm or more;
A transparent resin laminate satisfying the following (a), (d), (e), and (f).
(B) Total light transmittance of 85% or more.
(D) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(E) The water contact angle after wiping the surface of the first hard coat 20,000 times back and forth is 100 degrees or more.
(F) The pencil hardness on the surface of the first hard coat is 6H or more.
The transparent resin laminate according to claim 6 or 7, wherein the first hard coat comprises a paint containing a water repellent and not containing inorganic particles.
The transparent resin laminate according to any one of claims 6 to 8, wherein the first hard coat comprises a paint containing a silane coupling agent and no inorganic particles.
The transparent resin laminate according to any one of claims 6 to 9, wherein the pencil hardness of the surface of the first hard coat is 7H or more.
The transparent resin laminate according to any one of claims 1 to 10, wherein the thickness of the first hard coat is 0.5 to 5 μm.
The transparent resin laminate according to any one of claims 1 to 11, wherein the thickness of the second hard coat is 5 to 30 μm .
An article containing the transparent resin laminate according to any one of claims 1 to 12.
An article containing the transparent resin laminate according to any one of claims 1 to 12 and a decorative sheet.
Here, the decorative sheet is the article laminated on a surface of the transparent resin laminated body opposite to the first hard coat and the second hard coat forming surface.