JP2017128002A - Molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded body having a three-dimensional shape excellent in surface hardness and scratch resistance.SOLUTION: There is provided a molded body having a resin base, where the base has a part or all of a surface coated with a hard coat, the hard coat has a layer of a first hard coat and a layer of a second hard coat in order from the surface side, the first hard coat contains (A) polyfunctional (meth)acrylate of 100 pts.mass; (B) a water-repellent agent of 0.01-7 pts.mass; and (C) a silane coupling agent of 0.01-10 pts.mass, and is formed from a coating material containing no inorganic particle, and the second hard coat is formed from a coating material that contains (A) polyfunctional (meth)acrylate of 100 pts.mass; and (D) inorganic fine particles having an average particle size of 1-300 nm of 50-300 pts.mass.SELECTED DRAWING: Figure 1

Description

The present invention relates to a molded body. More specifically, the present invention relates to a molded body having excellent surface hardness.

Conventionally, molded products such as housings for home appliances and information electronic devices, and instrument panels of automobiles have been given functions such as surface hardness, scratch resistance, durability, contamination resistance, and design. In order to achieve this, it is often performed that a curable resin paint such as an acrylic resin, a melamine resin, an isocyanate resin, and a urethane resin is applied to the surface of a substrate of an article to form a coating film. Yes. There are many proposals for techniques for improving the scratch resistance by forming a coating film of a curable resin paint (for example, Patent Documents 1 and 2). However, these surface hardness and scratch resistance are still insufficient, and there is a need for a molded product that can maintain surface characteristics even when repeatedly wiped with a dust cloth or the like.

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

The subject of this invention is providing the molded object excellent in surface hardness. The further subject of this invention is providing the molded object which has the three-dimensional shape excellent in surface hardness and scratch resistance.

As a result of intensive studies, the present inventor has found that the above-described problems can be achieved by forming two specific types of hard coats.

That is, the present invention is a molded body having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm;
It is a molded object which consists of a coating material containing.

In a second invention, the (C) silane coupling agent includes 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. It is a molded article according to the invention.

3rd invention is a molded object as described in 1st invention or 2nd invention in which the said (B) water repellent contains a (meth) acryloyl group containing fluoropolyether type water repellent.

4th invention is the molded object of any one of 1st-3rd invention in which the coating material which forms the said 2nd hard coat contains 0.01-1 mass part of (E) leveling agents further. is there.

According to a fifth invention, the coating material forming the first hard coat further comprises (F) 0.1 to 5 parts by mass of resin fine particles having an average particle diameter of 0.5 to 10 μm. It is a molded object of any one.

A sixth invention is the molded article according to any one of the first to fifth inventions, wherein the thickness of the first hard coat is 0.5 to 5 µm.

7th invention is a molded object in any one of 1st-6th invention whose thickness of the said 2nd hard coat is 5-30 micrometers.

The eighth invention is a molded body having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
The molded body satisfies the following (A) and (B).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the first hard coat surface is 5H or more.

The ninth invention is a molded body having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
The molded body satisfies the following (c) and (d).
(C) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(D) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.

A tenth invention is the molded article according to any one of the first to ninth inventions, wherein the substrate has a three-dimensional shape.

An eleventh aspect of the invention is the molded body according to any one of the first to tenth aspects of the invention having a shape with a chamfered end.

A twelfth invention is an article including the molded body according to any one of the first to eleventh inventions.

A thirteenth invention is a method for producing the molded body according to any one of the first to eleventh inventions, wherein (1a) a step of three-dimensionally molding a resin sheet to produce the substrate; (2) Forming the second hard coat on part or all of the surface of the substrate obtained in the step (1a); and (3) the surface of the second hard coat formed in the step (2). Forming the first hard coat on the substrate.

A fourteenth aspect of the invention is a method for producing the molded body according to any one of the first to eleventh aspects of the invention, wherein (1b) a step of molding a thermoplastic resin to produce the substrate; (2) the above Forming the second hard coat on part or all of the surface of the substrate obtained in the step (1b); and (3) the surface of the second hard coat formed in the step (2). And forming the first hard coat on the substrate.

A fifteenth aspect of the invention is a method for producing a molded body according to any one of the first to eleventh aspects of the invention, wherein (1c) a step of molding a curable resin to produce the substrate; (2) the above Forming the second hard coat on part or all of the surface of the substrate obtained in the step (1c); and (3) the surface of the second hard coat formed in the step (2). And forming the first hard coat on the substrate.

A sixteenth aspect of the invention is a method for producing the article according to the twelfth aspect of the invention, the step of producing a molded body by the method according to any one of the thirteenth to fifteenth aspects of the invention; and (4) the above step A step of producing an article using the molded body obtained in (1) above.

The molded product of the present invention is excellent in surface hardness. The preferable molded article of the present invention has an arbitrary three-dimensional shape and is excellent in surface hardness and scratch resistance. Therefore, it can be suitably used as a housing for home appliances such as a television set, a refrigerator, a washing machine, a vacuum cleaner, a microwave oven, and an air conditioner. Therefore, it can be suitably used as a casing of information electronic equipment such as a smartphone, a tablet terminal, a car navigation system, a digital camera, and a personal computer, and a curved display face plate. Therefore, it can be suitably used as an instrument panel, a window, a shift knob, etc. of an automobile.

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

1. Base:
The molded body of the present invention has a resin base. The said base | substrate functions to provide a desired shape to the molded object of this invention. The substrate functions to impart mechanical properties such as impact resistance, strength, and rigidity to the molded article of the present invention.

The shape of the substrate is not particularly limited and may be a desired shape. The shape of the substrate may be planar, but is usually a three-dimensional shape when the molded body of the present invention is used in a housing for home appliances, an instrument panel for automobiles, and the like. It is.

The method for producing the substrate is not particularly limited, and can be produced by molding an arbitrary resin by an arbitrary method.

1-1. Substrate formed by three-dimensionally molding a resin sheet:
As a preferable method for producing the substrate, there can be mentioned a so-called three-dimensional molding method such as membrane press molding, pressure press molding, vacuum molding and vacuum / pressure molding.

The thickness of the resin sheet is not particularly limited, but is usually 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, from the viewpoint of maintaining strength and rigidity necessary as a base of the molded body. Preferably it may be 0.8 mm or more, most preferably 1 mm or more. On the other hand, from the viewpoint of meeting the demand for weight reduction of articles and from the viewpoint of three-dimensional formability, it may be usually 10 mm or less, preferably 6 mm or less, more preferably 3 mm or less.

The tensile modulus of elasticity of the resin sheet is not particularly limited, but may be preferably 1500 MPa or more, more preferably 1800 MPa or more, from the viewpoint of maintaining strength and rigidity necessary for the base of the molded body. There is no particular upper limit on the tensile modulus of elasticity, but since it is a resin sheet, it is at most about 10000 MPa within the normally available range. The tensile elastic modulus was measured according to JIS K7127: 1999 under the conditions of specimen type 1B and a tensile speed of 50 mm / min.

The glass transition temperature of the resin constituting the resin sheet is not particularly limited, but includes both heat resistance (heat resistance required at the time of manufacturing the molded body and heat resistance required at the time of using the molded body. ) Is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher. In addition, when the said resin sheet contains 2 or more types of resin as constituent resin, it is preferable that resin with the lowest glass transition temperature among these satisfy | fills the said range.

The glass transition temperature of the resin constituting the resin sheet is preferably 160 ° C. or less, more preferably 150 ° C. or less, and still more preferably 140 ° C. or less, from the viewpoint of workability when three-dimensionally molding to obtain the substrate. It is. In addition, when the said resin sheet contains 2 or more types of resin as constituent resin, it is preferable that resin with the highest glass transition temperature satisfy | fills the said range among these.

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

Examples of the resin sheet include polyester resins such as aromatic polyester and aliphatic polyester; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane / (meth) methyl acrylate copolymer. Poly (meth) acrylimide resins; polycarbonate resins such as aromatic polycarbonates and aliphatic polycarbonates; polyolefin resins such as polyethylene, polypropylene, polybutene-1, and poly-4-methyl-pentene-1; cellophane, tri Cellulosic resins such as acetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer Styrene resin such as resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, and styrene / ethylene / butadiene / styrene copolymer; cyclic hydrocarbon resin such as ethylene norbornene copolymer; nylon 6, Polyamide resins such as nylon 66, nylon 12, and nylon 11; polyvinyl chloride and polyvinyl chloride resins such as vinyl chloride / vinyl acetate copolymer; polyvinylidene chloride resins; fluorine-containing systems such as polyvinylidene fluoride Other resins such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone polyarylate resin, and polymer type urethane acrylate resin It is possible to increase the over door. These sheets include unstretched sheets, uniaxially stretched sheets, and biaxially stretched sheets. Moreover, the laminated sheet which laminated | stacked 1 or more types of these 2 or more layers is included. Furthermore, these resin sheets may be transparent and may be colored with an arbitrary colorant.

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

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

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

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

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

Examples of the copolymer containing the (meth) acrylic acid ester include ethylene / (meth) methyl acrylate copolymer, styrene / (meth) methyl acrylate copolymer, vinylcyclohexane / methyl (meth) acrylate. Examples thereof include a copolymer, maleic anhydride / methyl (meth) acrylate copolymer, and N-substituted maleimide / methyl (meth) acrylate copolymer.

Examples of the modified substance include a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which glutaric anhydride is introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl Amine, cyclohexylamine, ammonia, etc.) and a polymer in which an imide structure has been introduced by reaction (hereinafter sometimes referred to as a poly (meth) acrylimide resin). Can do.

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

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

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include an acid ester graft copolymer, a methacrylic acid ester / acrylic acid ester rubber graft copolymer, and a methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymer. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

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

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

Examples of the aromatic polycarbonate resin include interfacial weight between an aromatic dihydroxy compound such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and phosgene. Polymer obtained by legal method; ester of aromatic dihydroxy compound such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and diester carbonate such as diphenyl carbonate And polymers obtained by an exchange reaction. As said aromatic polycarbonate-type resin, these 1 type, or 2 or more types of mixtures can be used.

As a preferable optional component that can be included in the aromatic polycarbonate-based resin, a core-shell rubber can be exemplified. When the total of the aromatic polycarbonate resin and the core shell rubber is 100 parts by mass, the core shell rubber is 0 to 30 parts by mass (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably 0 to 10 parts by mass. By using it in an amount of 100 parts by weight (100 to 90 parts by mass of the aromatic polycarbonate resin), the cutting resistance and impact resistance of the (a2) aromatic polycarbonate resin sheet can be improved.

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Examples thereof include core-shell rubbers such as acid ester graft copolymers, methacrylic acid ester / acrylic acid ester rubber graft copolymers, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymers. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

The aromatic polycarbonate-based resin may be a thermoplastic resin other than the aromatic polycarbonate-based resin and the core-shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a mold release agent, an antistatic agent, and a surfactant may be further included. The compounding amount of these optional components is usually about 0.01 to 10 parts by mass when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.

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

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

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

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

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

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

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

Examples of the core shell rubber include methacrylic ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic. Mention one or a mixture of two or more core-shell rubbers such as acid ester graft copolymers, methacrylate ester / acrylate rubber graft copolymers, methacrylate ester / acrylonitrile / acrylate rubber graft copolymers Can do. As said core shell rubber, these 1 type, or 2 or more types of mixtures can be used.

The amount of the core-shell rubber is preferably 0.5 parts by mass or more in order to improve impact resistance when the polyester resin is 100 parts by mass. Moreover, when it is going to produce a transparent base | substrate, in order to maintain transparency, Preferably it is 5 mass parts or less, More preferably, you may be 3 mass parts or less.

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

If desired, the resin sheet may be provided with a printing layer on the second hard coat forming surface in order to enhance the design feeling. When the resin sheet is a transparent resin sheet, the printing layer may be provided on a surface opposite to the second hard coat forming surface. The printed layer is provided for imparting high designability to the molded article of the present invention, and can be formed by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine.

The printed layer can be applied on the desired surface of the resin sheet, either directly or via an anchor coat, either entirely or partially. The printed layer may be formed on the surface of an arbitrary resin film, and may be laminated on the desired surface of the resin sheet directly or via an anchor coat. In this case, the arbitrary resin film may be laminated as it is or may be removed. The patterns include metal-like patterns such as hairlines, wood grain patterns, stone patterns imitating the surface of rocks such as marble, fabric patterns imitating cloth and cloth-like patterns, tiled patterns, brickwork patterns, parquet patterns, And patchwork. As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used. Moreover, in order to give a metallic design, aluminum, tin, titanium, indium, and oxides thereof are directly or partially formed on a desired surface of the resin sheet directly or via an anchor coat. The vapor deposition may be performed by a known method.

A method for producing a substrate by the vacuum forming method using the resin sheet will be described. An example of a substrate produced by a vacuum forming method is shown in FIG. 1 (FIG. 1 (a) is a plan view and FIG. 1 (b) is a side view). An example of the vacuum forming method is shown in FIG. First, the resin sheet 6 is heated and softened using an infrared heater 7 or the like (FIG. 2A). Next, the softened resin sheet 6 is removed from the infrared heater 7 and promptly covered on the mold 8 (FIG. 2B). Subsequently, the space 9 between the resin sheet 6 and the molding die 8 is decompressed, and the resin sheet 6 is brought into close contact with the molding die 8 to obtain the base body 10 (FIG. 2C). The pressure in the space 9 is preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of sufficiently adhering the resin sheet 6 and the mold 8 without leaving any air between them. From the viewpoint of the adhesion force, the pressure of the space 9 is preferably smaller as the adhesion force becomes larger. On the other hand, in consideration of the fact that it takes a high cost to reduce the pressure in the space 9 and the mechanical strength of the resin sheet 6, the lower limit of the pressure in the space 9 is practically 10 ^−. It may be about ⁵ KPa.

1-2. Substrate formed by molding a thermoplastic resin:
As a preferable method for producing the substrate, there can be mentioned methods of injection molding, blow molding and extrusion molding of a thermoplastic resin. Among these, injection molding is preferable from the viewpoint of the degree of freedom of shape. In the present specification, the injection molding includes insert molding. As the resin sheet to be inserted into the mold, those described above can be used.

The thermoplastic resin for constituting the substrate is not particularly limited; preferably, it is not limited except that it can be applied to at least one of injection molding, blow molding, and extrusion molding; more preferably It is not limited except that it can be applied to injection molding; any thermoplastic resin can be used.

Examples of the thermoplastic resins include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylimide resins; polyolefins such as polyethylene, polypropylene, and polymethylpentene. Cellulosic resin; cellulosic resin such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), styrene・ Styrene resins such as ethylene / butadiene / styrene copolymers and styrene / ethylene / butadiene / styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; Fluorine-Motokei resin such Kka vinylidene; and the like; other, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamides, polyurethanes, polyetherimide, polysulfone, polyether sulfone. One or more of these can be used as the thermoplastic resin.

Among these, when the molded body of the present invention is used for housings of home appliances and information electronic devices, and instrument panels of automobiles, mechanical properties such as impact resistance, strength, and rigidity. Resins excellent in the above are preferred. Examples of such thermoplastic resins include acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane / (meth) acrylate methyl copolymer; polystyrene, acrylonitrile / styrene copolymer, And styrene resins such as acrylonitrile / butadiene / styrene copolymer (ABS resin); aromatic polyester resins; aromatic polycarbonate resins; polyolefin resins such as polyethylene and polypropylene;

One or more of these can be used as the thermoplastic resin.

In the above thermoplastic resin, as long as it does not contradict the purpose of the present invention, components other than the thermoplastic resin, for example, antioxidants such as phosphorus, phenol, and sulfur; anti-aging agents, light stability Weathering agents such as chemicals and ultraviolet absorbers; copper damage inhibitors; lubricants such as modified silicone oils, silicone oils, waxes, acid amides, fatty acids, and fatty acid metal salts; aromatic metal phosphates, gelols, etc. Nucleating agent; antistatic agent such as glycerin fatty acid ester; calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, cellulose fiber, glass fiber, and carbon Fillers such as black; organic flame retardants; and inorganic flame retardants;

1-3. Substrate formed by molding a curable resin:
As a preferable method for producing the substrate, a method in which a curable resin is injected into a mold having a desired shape and cured can be exemplified.

The curable resin for constituting the substrate is a resin that can be cured by heat or active energy rays. The curable resin is not particularly limited, and any curable resin can be used. Examples of the curable resin include a resin having two or more reactive functional groups in one molecule; the resin and an isocyanate curing agent (two or more isocyanate groups (—N═C═O) in one molecule). Compound), a photopolymerization initiator, and a resin composition with at least one of organic peroxide and the like. Examples of the reactive functional group include an amino group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, an isocyanate group, an alkoxy group, an acyloxy group, and a halogen group.

Examples of the curable resin include an active energy ray curable resin; an isocyanate-based curing agent (a compound having two or more isocyanate groups (—N═C═O) in one molecule) and / or photopolymerization. The composition containing with an initiator can be mention | raise | lifted. The active energy ray-curable resin is a resin that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate Phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Methoxy) acryloyl group-containing bifunctional reactive monomers such as 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexaacrylate (Meth) acryloyl group-containing hexafunctional reactive monomer such as (meth) acryloyl group-containing octafunctional reactive monomer such as tripentaerythritol acrylate; and polymers having one or more of these as constituent monomers (oligomers) -And prepolymers). As said active energy ray curable resin, these 1 type, or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the isocyanate curing agent include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Polyisocyanates such as isocyanurates, isocyanurates of hexamethylene diisocyanate, isocyanurates of isophorone diisocyanate, biurets of hexamethylene diisocyanate; and urethane crosslinking agents such as block isocyanates of the above polyisocyanates. . These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

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

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

Since the active energy ray-curable resin composition is diluted to a concentration that facilitates molding, it may contain a solvent as desired. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including degradation reaction) of these components. . Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

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

2. Hard coat:
In the molded article of the present invention, part or all of the surface of the substrate is coated with a hard coat. The hard coat functions to improve the surface hardness and scratch resistance of the molded article of the present invention. The hard coat may have high transparency from the viewpoint of design. It is preferable that the hard coat itself is not colored so that it can be easily colored in a desired color from the viewpoint of design. The hard coat may cover a part of the surface of the substrate, or may cover the whole, depending on the shape, application, and usage of the molded article of the present invention.

The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side.

2-1. First hard coat:
The first hard coat includes (A) 100 parts by mass of a polyfunctional (meth) acrylate; (B) 0.01 to 7 parts by mass of a water repellent; and (C) 0.01 to 10 parts by mass of a silane coupling agent; And a coating material that does not contain inorganic particles.

The first hard coat forms the surface of the molded article of the present invention. The first hard coat forms the surface of the article when the article is produced using the molded article of the present invention. The first hard coat exhibits good scratch resistance and functions to maintain surface characteristics such as water repellency even when repeatedly wiped with a handkerchief or the like.

Inorganic particles (for example, silica (silicon dioxide); metal oxide particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide; fluorination Metal fluoride particles such as magnesium and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes insufficient scratch resistance. Therefore, in the present invention, the first hard coat forming the outermost surface is kept free of inorganic particles so as to retain the scratch resistance, while the second hard coat contains a large amount of specific inorganic fine particles. This problem is solved by increasing the hardness.

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

(A) Polyfunctional (meth) acrylate:
The component (A) is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule, and has two or more (meth) acryloyl groups in one molecule. Polymerizes and cures with active energy rays to form a hard coat.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, (Meth) acryloyl group-containing bifunctional reaction such as 2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane -Functional monomers; (meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythritol (Meth) acryloyl group-containing tetrafunctional reactive monomers such as tetral (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomers such as dipentaerythritol hexaacrylate; (meth) acryloyl group containing tripentaerythritol acrylate Examples thereof include octafunctional reactive monomers and polymers (oligomers and prepolymers) containing one or more of these as constituent monomers. As said component (A), these 1 type, or 2 or more types of mixtures can be used. In the present specification, (meth) acrylate means acrylate or methacrylate.

(B) Water repellent:
The component (B) functions to increase water repellency.

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

Among these, as the component (B), a fluoropolyether water repellent is preferable from the viewpoint of water repellent performance. From the viewpoint of preventing troubles such as a chemical bond or strong interaction between the component (A) and the component (B) and bleeding out of the component (B), the component (B) includes A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter abbreviated as a (meth) acryloyl group-containing fluoropolyether water repellent) is more preferable. More preferable as the component (B) is to appropriately adjust the chemical bond or interaction between the component (A) and the component (B), from the viewpoint of expressing good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether water repellent and a methacryloyl group-containing fluoropolyether water repellent.

The (meth) acryloyl group-containing fluoropolyether water repellent is clearly distinguished from the component (A) in that it contains a fluoropolyether group in the molecule. The compound having two or more (meth) acryloyl groups in one molecule and having a fluoropolyether group is a (meth) acryloyl group-containing fluoropolyether water repellent, which is the component (B). .

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

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

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

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

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

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

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

(F) Resin fine particles having an average particle size of 0.5 to 10 μm:
When it is going to give anti-glare property to the molded object of this invention, the coating material which forms the said 1st hard coat can further contain (F) resin fine particles with an average particle diameter of 0.5-10 micrometers. The component (F) can strongly interact with a resin component such as the component (A).

Examples of the resin fine particles include resin fine particles such as a silicon resin, a styrene resin, an acrylic resin, a fluorine resin, a polycarbonate resin, an ethylene resin, and a cured resin of an amino compound and formaldehyde. . Among these, from the viewpoint of low specific gravity, lubricity, dispersibility, and solvent resistance, fine particles of silicon resin, acrylic resin, and fluorine resin are preferable. From the viewpoint of improving light diffusibility, a spherical shape is preferable. As the resin fine particles, one or a mixture of two or more of these can be used.

The average particle size of the component (F) is usually 0.5 μm or more, preferably 1 μm or more from the viewpoint of reliably obtaining antiglare properties. On the other hand, when it is intended to maintain the transparency of the hard coat, it may be usually 10 μm or less, preferably 6 μm or less.

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

The compounding amount of the component (F) is usually 0.01 to 15 parts by mass, preferably 0.1 to 100 parts by mass of the component (A), although it depends on the antiglare level to be imparted. -10 mass parts, More preferably, it may be 0.2-5 mass parts, More preferably, it may be 0.3-3 mass parts. Moreover, from a viewpoint of abrasion resistance, it may be preferably 0.5 to 3 parts by mass.

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

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

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

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

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

The said 1st hard-coat formation coating material can be obtained by mixing and stirring these components.

The method for forming the first hard coat using the first hard coat forming paint is not particularly limited, and a known coating method can be used. Examples of the method include methods such as dip coating, spray coating, spin coating, and air knife coating. Further, the coating is not limited to once, and may be repeated twice or more. Furthermore, when the hard coat forming part of the molded product of the present invention is planar, methods such as roll coating, gravure coating, reverse coating, and die coating may be applied.

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

2-2. Second hard coat:
The second hard coat is made of a paint containing (A) 100 parts by mass of a polyfunctional (meth) acrylate; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm.

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

(D) Inorganic fine particles having an average particle size of 1 to 300 nm:
The component (D) serves to dramatically increase the surface hardness of the molded article of the present invention.

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

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

For the purpose of increasing the dispersibility of the inorganic fine particles in the paint or increasing the surface hardness of the obtained hard coat, the surface of the inorganic fine particles is treated with a silane coupling agent such as vinylsilane or aminosilane; a titanate coupling agent. An aluminate coupling agent; an organic compound having a reactive functional group such as an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group; and an epoxy group; and a fatty acid, a fatty acid metal salt, etc. It is preferable to use a material treated with a surface treatment agent or the like.

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

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

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

The compounding amount of the component (D) is 50 parts by mass or more, preferably 80 parts by mass or more from the viewpoint of surface hardness with respect to 100 parts by mass of the component (A). On the other hand, from the viewpoint of transparency, it may be usually 300 parts by mass or less, preferably 200 parts by mass or less, more preferably 160 parts by mass or less.

(E) Leveling agent:
The second hard coat forming coating material preferably further includes (E) a leveling agent from the viewpoint of improving the surface of the second hard coat and facilitating the formation of the first hard coat.

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

The blending amount of the component (E) is usually 0 from the viewpoint of improving the surface of the second hard coat and facilitating the formation of the first hard coat with respect to 100 parts by mass of the component (A). 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of allowing the first hard coat-forming coating material to be satisfactorily applied without being repelled on the second hard coat, it is usually 1 part by mass or less, preferably 0.6 parts by mass or less, More preferably, it may be 0.4 parts by mass or less.

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

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

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

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

The second hard coat-forming coating material may contain a solvent as desired in order to dilute to a concentration that facilitates coating. If the said solvent does not react with the said component (A), the said component (D), and other arbitrary components, or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components, There is no particular limitation. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Of these, 1-methoxy-2-propanol is preferred. As said solvent, these 1 type, or 2 or more types of mixtures can be used.

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

The method for forming the second hard coat using the second hard coat forming paint is not particularly limited, and a known coating method can be used. Examples of the method include methods such as dip coating, spray coating, spin coating, and air knife coating. Further, the coating is not limited to once, and may be repeated twice or more. Furthermore, when the hard coat forming part of the molded product of the present invention is planar, methods such as roll coating, gravure coating, reverse coating, and die coating may be applied.

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

3. End face machining:
The molded body of the present invention is subjected to cutting, for example, so-called R surface cutting (FIG. 3A) or so-called C surface cutting (FIG. 3B), and the end is chamfered. It may have a shape. As a method for producing a molded body having a shape with chamfered ends, for example, the end of the base is first cut and then the second hard is formed on the surface of the base that has been cut. A method of forming a coat and subsequently forming a first hard coat on the surface of the second hard coat formed; first, forming a second hard coat on the surface of the substrate; (2) A method of cutting an end portion of a hard coat forming body and subsequently forming a first hard coat on the surface of the obtained cutting body; and first forming a second hard coat on the surface of the substrate. And the method of forming a 1st hard coat on the surface of the 2nd hard coat formed next, and cutting the edge part of the obtained molded object etc. can be mention | raise | lifted. In the case of the third method, after cutting the end portion of the molded body, a coating film may be formed on the cut surface using a method such as dip coating using an arbitrary paint. Since the first hard coat forming the surface of the molded article of the present invention has good water repellency, it is easy to form the coating film only on the cut surface. That is, after the end portion of the molded body is cut, even if dip coating is performed using any of the above-described paints without particularly masking, the coating film can be expected to be formed only on the cut surface. . Examples of the optional paint include the above-mentioned first hard coat forming paint and second hard coat forming paint.

4). Articles containing the molded article of the present invention:
Although it does not restrict | limit especially as articles | goods containing the molded object of this invention, For example, the housing | casing of household appliances, such as a television, a refrigerator, a washing machine, a vacuum cleaner, a microwave oven, and an air conditioner; Refrigerator, a washing machine, a cupboard, and Panels that make up the front of the door that opens and closes the opening on the front of the main body of articles such as clothes racks, and panels that make up the plane of the lid that opens and closes the opening on the main body; smartphones, tablet devices, car navigation systems, digital cameras, And a case of an information electronic device such as a personal computer and a curved display face plate; an instrument panel of a car, a shift knob, and the like.

When the molded product of the present invention is used for applications requiring transparency such as curved display face plates such as smartphones, tablet terminals, car navigation systems, and personal computers, the total light transmittance (JIS K) of the molded product of the present invention. 7361-1: 1997, measured with a turbidimeter “NDH2000 (trade name)” by Nippon Denshoku Industries Co., Ltd.) is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. It is. When the total light transmittance is 85% or more, the molded article of the present invention can be suitably used as a curved display face plate or the like. A higher total light transmittance is preferable.

The molded body of the present invention was measured using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under a load of 750 g in accordance with JIS K 5600-5-4 in accordance with JIS K 5600-5-4. ) Is preferably 5H or more, more preferably 6H or more, and even more preferably 7H or more. Higher pencil hardness is preferable.

In the molded article of the present invention, the water contact angle on the surface of the first hard coat is preferably 100 degrees or more, more preferably 105 degrees or more. When the water contact angle on the surface of the first hard coat is 100 degrees or more, water repellency, fingerprint resistance and antifouling properties are improved. There is no particular upper limit for the water contact angle, but about 120 degrees is usually sufficient. Here, the water contact angle is a value measured according to the test (c) of the following example.

The molded product of the present invention preferably has a water contact angle of 100 degrees or more after 20,000 cotton swabs on the surface of the first hard coat. More preferably, the water contact angle after reciprocating 25,000 cotton swabs is 100 degrees or more. Since the water contact angle after 20,000 cotton swabs is 100 degrees or more, even if it is repeatedly wiped with a handkerchief or the like, it can maintain surface properties such as water repellency, fingerprint resistance, and antifouling properties. it can. The larger the number of cotton wipes that can maintain a water contact angle of 100 degrees or more, the better. Here, the water contact angle after cotton wiping is a value measured according to the test (d) of the following examples.

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

Measurement method In any of the following tests (a) to (l), a test piece was cut out from the flat part of the zenith of the molded body and measured, unless otherwise specified.

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

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

(C) Water contact angle:
The first hard coat surface of the molded body is measured by a method of calculating 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). did.

(D) 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 taken from the flat part of the zenith of the molded body is placed on a JIS L 0849: 2013 Gakushin type tester so that the first hard coat is the surface. A stainless steel plate (10 mm long, 10 mm wide, 1 mm thick) covered with four layers of gauze (Kawamoto Sangyo Co., Ltd. medical type 1 gauze) is attached to the friction terminal of the vibration tester. Is set so as to come into contact with the test piece, a 350 g load is applied, and the first hard coat surface of the test piece is rubbed 10,000 times back and forth under the conditions of a moving distance of the friction terminal of 60 mm and a speed of 1 reciprocation / second. According to the method (c), the water contact angle of the cotton swab was measured. When the water contact angle is 100 degrees or more, after reciprocating 5,000 times, according to the method of (c) above, the operation of measuring the water contact angle of the cotton wiping location was repeated and evaluated according to the following criteria: .
A: Water contact angle of 100 degrees or more even after 25,000 round trips.
B: Water contact angle is 100 degrees or more after 20,000 round trips, but less than 100 degrees after 25,000 rounds.
C: Water contact angle is 100 degrees or more after 15,000 round trips, but less than 100 degrees after 20,000 rounds.
D: Water contact angle is 100 degrees or more after 10,000 round trips, but less than 100 degrees after 15,000 rounds.
E: Water contact angle less than 100 degrees after 10,000 round trips.

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

(F) Cross cut test (adhesion):
In accordance with JIS K 5600-5-6: 1999, after making 100 square cuts (1 square = 1 mm × 1 mm) from the first hard coat surface side of the molded product, a tape for adhesion test is applied to the grid. I peeled it off with my finger and peeled it off. Evaluation criteria were in accordance with Table 1 of the above JIS standard.
Classification 0: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
Classification 1: Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
Classification 2: The coating film is peeled along the edge of the cut and / or at the intersection. The cross-cut portion is clearly affected by more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
Category 5: When the degree of peeling exceeds Category 4.

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

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

(R) Y value of XYZ display system based on 2 degree visual field:
Using a spectrophotometer “SolidSpec-3700 (trade name)” of Shimadzu Corporation and a reflection unit “absolute reflectance measuring device, incident angle 5 ° (trade name)”, according to the spectrophotometer instructions above, 5 degrees Measurement was performed under the conditions of regular reflection (a reflection unit was installed in front of the integrating sphere).

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

(B) Water repellent:
(B-1) An acryloyl group-containing fluoropolyether water repellent “KY-1203 (trade name)” from Shin-Etsu Chemical Co., Ltd. Solid content 20% by weight.
(B-2) Solvay's methacryloyl group-containing fluoropolyether water repellent “FOMBLIN MT70 (trade name)”. Solid content 70% by weight.

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

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

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

(F) Fine resin particles having an average particle size of 0.5 to 10 μm:
(F-1) Spherical silicon resin fine particles “Tospearl 120 (trade name)” by Momentive Performance Materials. Average particle size 2 μm.
(F-2) Spherical silicon resin fine particles “Tospearl 130 (trade name)” by Momentive Performance Materials. Average particle size 3 μm.
(F-3) Acrylic resin fine particles “MA-180TA (trade name)” by Soken Chemical Co., Ltd. Average particle size 1.8 μm.
(F-4) Acrylic resin fine particles “MX-80H3wT (trade name)” manufactured by Soken Chemical Co., Ltd. Average particle size 0.5 μm.
(F-5) Toyobo Co., Ltd. acrylic resin fine particles “FH-S010 (trade name)”. Average particle size 10 μm.

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

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

(H1-2-2) A paint was obtained in the same manner as (H1-1) except that the formulation was changed as shown in any one of Tables 1 to 3.

(H1 ′) Reference first hard coat forming paint:
A paint was obtained in the same manner as in the above (H1-1) except that the formulation (H1′-1 to 4) was changed as shown in Table 1.

(H2) Second hard coat forming paint:
(H2-1) 100 parts by mass of (A-2), 140 parts by mass of (D-1), 2 parts by mass of (E-1) (0.2 parts by mass in terms of solid content), (F-1) ) A paint obtained by mixing and stirring 17 parts by mass and 200 parts by mass of the above (F-2). Table 4 shows the recipe. In addition, about said (E-1) and said (E-2), the value of solid content conversion is described in the table | surface.

(H2-2 to 12) A paint was obtained in the same manner as in the above (H2-1) except that the formulation was changed as shown in Table 4 or Table 5.

(H2 ′) Reference second hard coat forming paint:
A coating material was obtained in the same manner as in the above (H2-1) except that the formulation of (H2′-1, 2) was changed as shown in Table 5.

(A) Substrate:
(A1-1) Substrate formed by vacuum forming an acrylic resin sheet 1:
Using an acrylic resin “Optimas 6000 (trade name), glass transition temperature 119 ° C.” manufactured by Mitsubishi Gas Chemical Co., Ltd., using an apparatus (see FIG. 4) equipped with an extruder and a T die, Between the first mirror surface roll that continuously extrudes and rotates the molten sheet (the roll on the side that holds the molten sheet and feeds it to the next transfer roll; the same applies hereinafter) and the second mirror surface roll that rotates. The sheet was supplied and pressed to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 120 ° C., a second mirror surface roll setting temperature of 110 ° C., and a T die outlet resin temperature of 300 ° C. The obtained resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness index of 0.3, and a tensile modulus of 3400 MPa. Subsequently, using the obtained resin sheet and using the vacuum forming method, as described above, FIG. 1 (FIG. 1A is a plan view, FIG. 1B is a side view. The long axis length 1 of the zenith flat part is 20 cm, the long axis length 2 of the end part having an elliptical shape is 30 cm, the short axis length 3 of the elliptical flat part is 10 cm, and the end part having an elliptical shape The short axis length 4 was 20 cm, and the height 5 from the end to the zenith was 5 cm. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A1-2) Substrate 2 formed by vacuum forming an acrylic resin sheet:
Using a poly (meth) acrylimide resin “PLEXIMID TT50 (trade name), glass transition temperature 154 ° C.” manufactured by Evonik Co., Ltd., using an apparatus equipped with an extruder and a T die, a molten sheet of the above resin from the T die Was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll, and pressed to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 140 ° C., a second mirror surface roll setting temperature of 120 ° C., and a T-die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 92%, a haze of 0.5%, a yellowness index of 0.3, and a tensile modulus of 4300 MPa. Subsequently, using the obtained resin sheet, a substrate having the shape shown in FIG. 1 was formed using a vacuum forming method as described above. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A2-1) Aromatic polycarbonate resin sheet:
Using the aromatic polycarbonate “Caliver 301-4 (trade name), glass transition temperature 151 ° C.” of Sumika Stylon Polycarbonate Co., Ltd. and using an apparatus equipped with an extruder and a T die, the above resin is melted from the T die. The sheet was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror surface roll setting temperature of 140 ° C., a second mirror surface roll setting temperature of 120 ° C., and a T-die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 0.6%, a yellowness index of 0.5, and a tensile modulus of 2300 MPa. Subsequently, using the obtained resin sheet, a substrate having the shape shown in FIG. 1 was formed using a vacuum forming method as described above. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A3-1) Polyester resin sheet 1:
Eastman Chemical Company's non-crystalline polyester resin (PETG resin) “Cadence GS1 (trade name), glass transition temperature 81 ° C.”, using an apparatus equipped with an extruder and a T die, from the T die The molten sheet of the resin is continuously extruded, and the molten sheet is supplied and pressed between the rotating first mirror roll and the rotating second mirror roll, and a transparent resin sheet having a thickness of 1 mm is obtained. Obtained. The setting conditions at this time were a first mirror surface roll setting temperature of 80 ° C., a second mirror surface roll setting temperature of 40 ° C., and a T die outlet resin temperature of 200 ° C. The obtained transparent resin sheet had a total light transmittance of 89%, a haze of 1.3%, a yellowness index of 0.4, and a tensile elastic modulus of 1500 MPa. Subsequently, using the obtained resin sheet, a substrate having the shape shown in FIG. 1 was formed using a vacuum forming method as described above. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A3-2) Polyester resin sheet 2:
Using Easton Chemical Company's non-crystalline polyester resin “Tritan FX200 (trade name), glass transition temperature 119 ° C.” and using an apparatus equipped with an extruder and a T die, the above resin is melted from the T die. The sheet was continuously extruded, and the molten sheet was supplied and pressed between a rotating first mirror roll and a rotating second mirror roll to obtain a transparent resin sheet having a thickness of 1 mm. The setting conditions at this time were a first mirror roll setting temperature of 80 ° C., a second mirror roll setting temperature of 40 ° C., and a T-die outlet resin temperature of 230 ° C. The obtained transparent resin sheet had a total light transmittance of 90%, a haze of 1.2%, a yellowness index of 0.4, and a tensile modulus of 1500 MPa. Subsequently, using the obtained resin sheet, a substrate having the shape shown in FIG. 1 was formed using a vacuum forming method as described above. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A4-1) Laminated sheet 1:
Using two types and three-layer multi-manifold type co-extrusion film forming equipment equipped with an extruder and T-die, Mitsubishi Gas Chemical Co., Ltd. acrylic resin “Optimas 7500 (trade name), glass transition temperature 119 ° C.” on both outer layers First, the first mirror surface is rotated by continuously extruding a melt-laminated sheet with an intermediate layer of aromatic polycarbonate “Caliver 301-4 (trade name), glass transition temperature 151 ° C.” from Sumika Stylon Polycarbonate Co., Ltd. from a T-die. A transparent resin sheet having a total thickness of 1 mm, a thickness of both outer layers of 0.1 mm, and a thickness of the intermediate layer of 0.8 mm is supplied and pressed between the roll and the rotating second mirror roll. Got. The setting conditions at this time were a first mirror surface roll setting temperature of 120 ° C., a second mirror surface roll setting temperature of 110 ° C., and a T die outlet resin temperature of 300 ° C. The obtained transparent resin sheet had a total light transmittance of 91%, a haze of 0.6%, a yellowness index of 0.5, and a tensile elastic modulus of 2600 MPa. Subsequently, using the obtained resin sheet, a substrate having the shape shown in FIG. 1 was formed using a vacuum forming method as described above. At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A5-1) Substrate formed by injection molding of ABS / PC alloy resin:
Using an ABS / PC alloy resin “Exceloy CK50 (trade name)” manufactured by Technopolymer Co., Ltd., using a 100-ton injection molding machine, cylinder temperature 260 ° C., mold temperature 70 ° C., injection speed 250 mm / sec, and holding A thermoplastic resin substrate was injection molded under a pressure of 50 MPa.

Example 1
On the convex side surface of (a1-1), a dip coating method was used, and a hard coat composed of (H2-1) was formed to a thickness of 22 μm after curing. Next, a dip coat method was used on the surface of the hard coat formed as described above, and a hard coat composed of (H1-1) was formed to a thickness of 2 μm after curing. The above tests (A) to (G) were performed on the obtained molded body. The results are shown in Table 6.

Examples 2-12, Examples 1C-4C
The same procedure as in Example 1 was performed except that the paint shown in any one of Tables 6 to 8 was used instead of (H1-1). The results are shown in any one of Tables 6-8.

Examples 13-23, Examples 5C, 6C
The same procedure as in Example 1 was performed except that the paint shown in any one of Tables 8 to 10 was used instead of (H2-1). The results are shown in any one of Tables 8-10.

Examples 24-28
All operations were performed in the same manner as in Example 1 except that the substrate shown in Table 10 was used instead of (a1-1). The results are shown in Table 10.

Example 29
The same procedure as in Example 1 was carried out except that the substrate shown in Table 10 (the above (a5-1)) was used instead of the above (a1-1). The results are shown in Table 10. Since the above (a5-1) is an opaque substrate, the above test (A) and the above test (H) were omitted.

Examples 30-33
Except that the thickness after curing of the first hard coat was changed as shown in Table 11, everything was carried out in the same manner as in Example 1. The results are shown in Table 11.

Examples 34-37
Except that the thickness after curing of the second hard coat was changed as shown in Table 11 or Table 12, everything was performed in the same manner as in Example 1. The results are shown in Table 11 or Table 12.

Examples 38-47
The same procedure as in Example 1 was conducted except that the paint shown in Table 12 or 13 was used instead of (H1-1). The results are shown in Table 12 or Table 13.

Preferred molded articles of the present invention are excellent in surface hardness and scratch resistance. Moreover, the weather resistance and the adhesion of the hard coat are also good.

It is the top view and side view which show the base | substrate produced in the Example. It is a figure explaining a vacuum forming method. It is sectional drawing which shows the example of end surface processing. It is a conceptual diagram of the apparatus used for manufacture of the resin sheet in an Example.

1: Long axis length of the zenith flat portion having an elliptical shape 2: Long axis length of the end portion having the elliptical shape 3: Short axis length of the zenith flat portion having the elliptical shape 4: of the end portion having the elliptical shape Short axis length 5: Height from end to zenith 6: Resin sheet 7: Infrared heater 8: Mold 9: Space between resin sheet 6 and mold 10 10: Substrate 11: Molten resin sheet 12 : T die 13: First mirror roll 14: Second mirror roll

Claims (16)

A molded body,
Having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass;
(B) Water repellent 0.01 to 7 parts by mass; and (C) Silane coupling agent 0.01 to 10 parts by mass;
Consisting of a paint containing no inorganic particles;
The second hard coat is
(A) Polyfunctional (meth) acrylate 100 parts by mass; and (D) 50 to 300 parts by mass of inorganic fine particles having an average particle diameter of 1 to 300 nm;
A molded article made of a paint containing
The molded product according to claim 1, wherein the (C) silane coupling agent includes one or more selected from the group consisting of a silane coupling agent having an amino group and a silane coupling agent having a mercapto group.
The molded article according to claim 1 or 2, wherein the (B) water repellent comprises a (meth) acryloyl group-containing fluoropolyether water repellent.
The molded object according to any one of claims 1 to 3, wherein the coating material forming the second hard coat further comprises (E) a leveling agent in an amount of 0.01 to 1 part by mass.
The coating material which forms the said 1st hard coat contains (F) 0.1-5 mass parts of resin fine particles with an average particle diameter of 0.5-10 micrometers further; Molded body.
The molded body according to any one of claims 1 to 5, wherein the first hard coat has a thickness of 0.5 to 5 µm.
The molded body according to any one of claims 1 to 6, wherein the second hard coat has a thickness of 5 to 30 µm.
A molded body,
Having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
Molded articles satisfying the following (A) and (B).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the first hard coat surface is 5H or more.
A molded body,
Having a resin base;
The substrate is partially or entirely coated with a hard coat;
The hard coat has a first hard coat layer and a second hard coat layer in order from the surface side;
The first hard coat is made of a coating containing no inorganic particles;
The second hard coat is made of a coating containing inorganic particles;
A molded article satisfying the following (c) and (d).
(C) The water contact angle on the surface of the first hard coat is 100 degrees or more.
(D) The water contact angle after 20,000 cotton swabs on the first hard coat surface is 100 degrees or more.
The molded body according to any one of claims 1 to 9, wherein the substrate has a three-dimensional shape.
The molded body according to any one of claims 1 to 10, which has a shape with a chamfered end.
An article comprising the molded article according to any one of claims 1 to 11.
A method for producing the molded body according to any one of claims 1 to 11,
(1a) three-dimensionally molding a resin sheet to produce the substrate;
(2) forming the second hard coat on a part or all of the surface of the substrate obtained in the step (1a); and
(3) forming the first hard coat on the surface of the second hard coat formed in the step (2);
Including methods.
A method for producing the molded body according to any one of claims 1 to 11,
(1b) A step of forming a thermoplastic resin and producing the substrate;
(2) forming the second hard coat on part or all of the surface of the substrate obtained in the step (1b); and
(3) forming the first hard coat on the surface of the second hard coat formed in the step (2);
Including methods.
A method for producing the molded body according to any one of claims 1 to 11,
(1c) A step of producing a substrate by molding a curable resin;
(2) forming the second hard coat on part or all of the surface of the substrate obtained in the step (1c); and
(3) forming the first hard coat on the surface of the second hard coat formed in the step (2);
Including methods.
A method for producing the article of claim 12, comprising:
The process of producing a molded object by the method of any one of Claims 13-15; and (4) The process of producing articles | goods using the molded object obtained at the said process;
Including methods.