JP6625885B2 - Molded body - Google Patents

Description

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

Conventionally, molded products such as housings of home electric appliances and information electronic devices, and instrument panels of automobiles have been given functions such as surface hardness, scratch resistance, durability, stain resistance, and design. In order to apply a curable resin paint such as an acrylic resin, a melamine resin, an isocyanate resin, and a urethane resin on the surface of a substrate of an article, a coating film is often formed. I have. There are many proposals for a technique for improving the scratch resistance by forming a coating film of a curable resin paint (for example, Patent Documents 1 and 2). However, their surface hardness and abrasion resistance are still inadequate, and there is a need for a molded article that can maintain its surface characteristics even if it is repeatedly wiped with a rag or the like.

JP 2014-043101 A JP 2014-040017 A

An object of the present invention is to provide a molded article having excellent surface hardness. A further object of the present invention is to provide a molded article having a three-dimensional shape excellent in surface hardness and scratch resistance.

As a result of earnest research, the present inventor has found that the above-mentioned object can be achieved by forming two specific types of hard coats.

That is, the present invention is a molded article having a resin base;
A part or all of the surface of the substrate is 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,
(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;
Comprising a paint containing no inorganic particles;
The second hard coat,
(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;
It is a molded object which consists of a paint containing.

In the 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 object according to the invention.

A third invention is the molded article according to the first invention or the second invention, wherein the (B) water repellent includes a (meth) acryloyl group-containing fluoropolyether-based water repellent.

A fourth invention is the molded article according to any one of the first to third inventions, wherein the coating material forming the second hard coat further comprises (E) 0.01 to 1 part by mass of a leveling agent. is there.

According to a fifth aspect of the present invention, the paint for forming the first hard coat further comprises (F) 0.1 to 5 parts by mass of resin fine particles having an average particle size of 0.5 to 10 μm. A molded article according to any one of the above.

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.

A seventh invention is the molded article according to any one of the first to sixth inventions, wherein the thickness of the second hard coat is 5 to 30 μm.

An eighth invention is a molded article having a resin base;
A part or all of the surface of the substrate is 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 comprises a paint free of inorganic particles;
The second hard coat comprises a paint containing inorganic particles;
The molded article satisfies the following (a) and (b).
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the surface of the first hard coat is 5H or more.

A ninth invention is a molded article having a resin base;
A part or all of the surface of the substrate is 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 comprises a paint free of inorganic particles;
The second hard coat comprises a paint containing inorganic particles;
The molded article satisfies the following (c) and (d).
(C) The first hard coat surface has a water contact angle of 100 degrees or more.
(D) The water contact angle after reciprocating 20,000 times of cotton on the surface of the first hard coat 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 invention is the molded article according to any one of the first to tenth inventions, which has a shape with a chamfered end.

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

A thirteenth invention is a method for producing the molded article according to any one of the first to eleventh inventions, wherein (1a) a step of three-dimensionally molding a resin sheet to produce the base; (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 first hard coat.

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

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

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

The molded article of the present invention has excellent surface hardness. The preferred 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 of home electric appliances such as a television, a refrigerator, a washing machine, a vacuum cleaner, a microwave oven, and an air conditioner. Therefore, it can be suitably used as a housing of an information electronic device 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, and the like of an automobile.

In this 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 the resin. The term “sheet” is used as a term including a film and a plate.

1. Substrate:
The molded article of the present invention has a resin base. The above-mentioned substrate functions to give a desired shape to the molded article of the present 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 base is not particularly limited, and may be a desired shape. The shape of the base may be planar, but when the molded article of the present invention is used for a housing of a home electric appliance or the like, and an instrument panel of an automobile or the like, it usually has a three-dimensional shape. It is.

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

1-1. Substrate formed by three-dimensional molding of resin sheet:
As a preferable method of producing the above-mentioned substrate, there can be mentioned a method of so-called three-dimensional molding such as membrane press molding, air pressure press molding, vacuum molding, and vacuum air 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 the strength and rigidity required as a base of the molded article. Preferably it may be 0.8 mm or more, most preferably 1 mm or more. On the other hand, it may be usually 10 mm or less, preferably 6 mm or less, more preferably 3 mm or less, from the viewpoint of meeting the demand for weight reduction of the article and the viewpoint of three-dimensional formability.

The tensile modulus 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 the strength and rigidity required as a base of the molded article. Although there is no particular upper limit for the tensile modulus, it is at most about 10,000 MPa in a normally available range because it is a resin sheet. The tensile modulus was measured in accordance with JIS K7127: 1999 under the conditions of test piece type 1B and a tensile speed of 50 mm / min.

Although the glass transition temperature of the resin constituting the resin sheet is not particularly limited, it includes heat resistance (both heat resistance required at the time of manufacturing a molded article and heat resistance required at the time of using the molded article). From the viewpoint of maintaining the above condition, the temperature may be preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher. When the resin sheet contains two or more kinds of resins as constituent resins, it is preferable that the resin having the lowest glass transition temperature among these satisfy the above 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 performing three-dimensional molding to obtain the substrate. It is. When the resin sheet contains two or more resins as constituent resins, the resin having the highest glass transition temperature among these resins preferably satisfies the above range.

In the present specification, the glass transition temperature is measured by using a Diamond DSC differential scanning calorimeter manufactured by Perkin Elmer Japan Co., Ltd., and heating the sample to 200 ° C. at a heating rate of 50 ° C./min. After holding, cool down to 50 ° C. at a cooling rate of 20 ° C./min, hold at 50 ° C. for 10 minutes, and then heat up to 200 ° C. at a heating rate of 20 ° C./min. Is the midpoint glass transition temperature calculated by plotting according to FIG. 2 of ASTM D3418 for the glass transition appearing in the curve measured in FIG.

Examples of the resin sheet include polyester resins such as aromatic polyesters and aliphatic polyesters; and acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane / methyl (meth) 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; Cellulose resins such as acetylcellulose, diacetylcellulose, and acetylcellulose butyrate; polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer Resin (ABS resin), styrene-based resin such as styrene-ethylene-butadiene-styrene copolymer, and styrene-ethylene-butadiene-styrene copolymer; cyclic hydrocarbon-based resin such as ethylene norbornene copolymer; nylon 6, Polyamide resins such as nylon 66, nylon 12 and nylon 11; polyvinyl chloride resins such as polyvinyl chloride and vinyl chloride / vinyl acetate copolymer; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride Resins; Other resins such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, polyimide, polyurethane, polyetherimide, polysulfone, polyethersulfone 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. Also, a laminated sheet in which one or more of these are laminated in two or more layers is included. Further, these resin sheets may be transparent or may be colored with an arbitrary coloring agent.

When the resin sheet is a laminated sheet, the laminating method is not limited, and can be laminated by any method. For example, a method in which each resin sheet is obtained by an arbitrary method and then dry-laminated or heat-laminated; each constituent material is melted by an extruder, and the T-die is formed by a feed block method or a multi-manifold method or a stack plate method. A method of obtaining by extrusion; an extrusion laminating method of obtaining at least one resin sheet by an arbitrary method and then melt-extruding another resin sheet on the resin sheet; A method of applying and drying a paint containing a solvent, peeling the formed resin sheet from the film substrate, transferring the resin sheet to 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) an acrylic resin sheet;
(A2) an aromatic polycarbonate resin sheet;
(A3) a polyester resin sheet;
(A4) any one or two or more laminated sheets of the above resin sheets (a1) to (a3);
Is preferred.

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

Examples of the acrylic resin include a (meth) acrylate (co) polymer, a copolymer containing a (meth) acrylate, and modified products thereof. In addition, (meth) acryl means acryl or methacryl. Further, the (co) polymer means a polymer or a copolymer.

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

Examples of the copolymer containing the (meth) acrylic ester include ethylene / methyl (meth) acrylate, styrene / methyl (meth) acrylate, and vinylcyclohexane / methyl (meth) acrylate Copolymers, maleic anhydride / methyl (meth) acrylate copolymer, N-substituted maleimide / methyl (meth) acrylate copolymer, and the like can be given.

Examples of the modified product 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 A polymer in which an imide structure is introduced by reacting with an amine, cyclohexylamine, and ammonia (hereinafter, may be referred to as a poly (meth) acrylimide resin). Can be.

One or a mixture of two or more of these acrylic resins can be used.

Preferred optional components that can be included in the acrylic resin include core-shell rubber. 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 resin is 100 parts by mass). (100-70 parts by mass of the base resin) can improve the cutting resistance and impact resistance of the (a1) acrylic resin sheet.

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

Other optional components that may 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 a stabilizer, a heat stabilizer, a release agent, an antistatic agent, a nucleating agent, and a surfactant. The mixing amount of these optional components is usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass, when the total of the acrylic resin and the core shell rubber is 100 parts by mass.

The (a2) aromatic polycarbonate-based resin sheet is a sheet mainly composed of an aromatic polycarbonate-based resin (normally 70% by mass or more, preferably 90% by mass or more).

Examples of the aromatic polycarbonate resin include an interface weight between an aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and phosgene. Polymer obtained by a synthetic method: Ester of aromatic dihydroxy compound such as bisphenol A, dimethyl bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and diester carbonate such as diphenyl carbonate And a polymer obtained by an exchange reaction. One or a mixture of two or more of these aromatic polycarbonate resins can be used.

Preferred optional components that can be included in the aromatic polycarbonate-based resin include a core-shell rubber. 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 an amount of 100 parts by mass (100 to 90 parts by mass of the aromatic polycarbonate-based resin), the cutting resistance and impact resistance of the (a2) aromatic polycarbonate-based resin sheet can be improved.

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

In addition, the aromatic polycarbonate-based resin may include, if desired, 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; a lubricant; An additive such as an antioxidant, a weather resistance stabilizer, a heat stabilizer, a release agent, an antistatic agent, and a surfactant can be further included. The mixing 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 mainly composed of a polyester-based resin such as polyethylene terephthalate (usually 80% by mass or more, preferably 90% by mass or more). And a biaxially stretched sheet. Further, one or two or more of these laminated sheets are included.

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

Examples of the amorphous or low-crystalline aromatic polyester resin include aromatic polycarboxylic acid components such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid, and ethylene glycol, diethylene glycol, neopentyl glycol, and the like. , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, And polyester-based copolymers with polyhydric alcohol components such as 1,4-cyclohexanedimethanol.

Examples of the amorphous or low-crystalline aromatic polyester resin include 50 mol% of terephthalic acid and 30 to 40 mol% of ethylene glycol and 1,4-cyclohexane dimethanol 10 to 100 mol% of the total of monomers. Glycol-modified polyethylene terephthalate (PETG) containing 20 mol%; glycol-modified polycyclohexylene dimethylene terephthalate containing 50 mol% of terephthalic acid, 16 to 21 mol% of ethylene glycol and 29 to 34 mol% of 1,4-cyclohexanedimethanol ( PCTG); acid-modified polycyclohexylene dimethylene terephthalate (PCTA) containing 25 to 49.5 mol% of terephthalic acid, 0.5 to 25 mol% of isophthalic acid and 50 mol% of 1,4-cyclohexanedimethanol; terephthalic acid 30 ~ 45 Acid-modified and glycol-modified polyethylene terephthalate containing 5% to 20% by mole of isophthalic acid, 35 to 48% by mole of ethylene glycol, 2 to 15% by mole of neopentyl glycol, less than 1% by mole of diethylene glycol, and less than 1% by mole of bisphenol A; 45-50 mol% of terephthalic acid, 5-0 mol% of isophthalic acid, 25-45 mol% of 1,4-cyclohexanedimethanol, and 2,2,4,4, -tetramethyl-1,3-cyclobutanediol 25 Acid-modified and glycol-modified polyethylene terephthalate containing up to 5 mol%, or a mixture of two or more thereof.

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

The polyester-based resin may contain other components, if 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, weather resistance stabilizers, heat stabilizers, release agents, antistatic agents, And additives such as surfactants; and the like. The mixing amount of these optional components is usually 25 parts by mass or less, preferably about 0.01 to 10 parts by mass, based on 100 parts by mass of the polyester resin.

Preferred optional components that can be included in the polyester-based resin include a 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 acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acryl One or a mixture of two or more core-shell rubbers such as an acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, and a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer. Can be. As the core-shell rubber, one or a mixture of two or more of these can be used.

The amount of the core-shell rubber is preferably at least 0.5 part by mass when the polyester resin is 100 parts by mass to improve the impact resistance. When a transparent substrate is to be produced, the amount may preferably be 5 parts by mass or less, more preferably 3 parts by mass or less, in order to maintain transparency.

(A4) Any one or two or more of the transparent resin sheets (a1) to (a3) of the above-mentioned laminated sheet may be any co-extrusion device such as a feed block system, a multi-manifold system, and a stack plate system. To form a desired layer structure by co-extrusion film formation; using any film forming apparatus, any one or more of the transparent resin sheets (a1) to (a3) After being obtained, these are subjected to heat lamination or dry lamination to obtain a desired layer constitution; and any one of the transparent resin sheets (a1) to (a3) is obtained using an arbitrary film forming apparatus. After that, the sheet is extruded and laminated as a base material so as to have a desired layer constitution;

In the resin sheet, a print layer may be provided on the second hard coat forming surface, if desired, to enhance the design feeling. When the resin sheet is a transparent resin sheet, the print layer may be provided on a surface opposite to the surface on which the second hard coat is formed. The printing layer is provided to impart high designability to the molded article of the present invention, and can be formed by printing an arbitrary pattern with an arbitrary ink and an arbitrary printing machine.

The printing layer can be applied entirely or partially on the desired surface of the resin sheet directly or via an anchor coat. The printing layer may be formed on an arbitrary resin film surface, and may be laminated on a 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. As the pattern, metal tone pattern such as hairline, wood grain pattern, stone pattern that imitates the surface of rock such as marble, cloth pattern that imitates grain and cloth-like pattern, tile pasting pattern, brickwork pattern, parquet pattern, And patchwork. As the printing ink, those obtained by appropriately mixing a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like with a binder can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and their resin compositions can be used. Further, in order to give a metallic design, on the desired surface of the resin sheet, directly or via an anchor coat, entirely or partially, aluminum, tin, titanium, indium and their oxides and the like It may be deposited by a known method.

A method for producing a substrate by a 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. 1A is a plan view, and FIG. 1B is a side view). FIG. 2 shows an example of the vacuum forming method. First, the resin sheet 6 is heated using an infrared heater 7 or the like to be softened (FIG. 2A). Next, the softened resin sheet 6 is removed from the infrared heater 7, and is quickly coated on the mold 8 (FIG. 2B). Subsequently, the space 9 between the resin sheet 6 and the molding die 8 is depressurized, and the resin sheet 6 is brought into close contact with the molding die 8 to obtain the base 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 molding die 8 without leaving air therebetween. From the viewpoint of the adhesion, the pressure of the space 9 is preferably smaller as the adhesion becomes larger. On the other hand, considering that the cost of accelerating the reduction of the pressure in the space 9 and the mechanical strength of the resin sheet 6 are taken into account, 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:
Preferred methods for producing the above-mentioned substrate include injection molding, blow molding, and extrusion molding of a thermoplastic resin. Of these, injection molding is preferred from the viewpoint of the degree of freedom in shape. In the present specification, the injection molding includes insert molding. The above-described resin sheet can be used as the resin sheet to be inserted into the molding die.

The thermoplastic resin for forming the base is not particularly limited; preferably, it is not limited except that it can be applied to at least any one of injection molding, blow molding, and extrusion molding; more preferably There is no limitation except that it is applicable to injection molding; any thermoplastic resin can be used.

Examples of the thermoplastic resin 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 resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), styrene・ Styrene resins such as ethylene / butadiene / styrene copolymer and styrene / ethylene / butadiene / styrene copolymer; polyvinyl chloride resin; polyvinylidene chloride resin; 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 article of the present invention is used for housings of home electric appliances and information electronic devices, and instrument panels of automobiles, mechanical properties such as impact resistance, strength, and rigidity are used. A resin excellent in quality is preferred. Examples of such thermoplastic resins include, for example, acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, and vinylcyclohexane / methyl (meth) acrylate 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.

The thermoplastic resin may contain, if desired, components other than the thermoplastic resin, for example, antioxidants such as phosphorus-based, phenol-based, and sulfur-based; Agents, weathering agents such as ultraviolet absorbers; copper damage inhibitors; modified silicone oils, silicone oils, waxes, lubricants such as acid amides, fatty acids, and fatty acid metal salts; aromatic metal phosphates and gerols 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. Substrates formed by molding a curable resin:
As a preferable method of producing the above-mentioned substrate, a method of injecting a curable resin into a mold having a desired shape and curing the resin can be given.

The curable resin for forming the base 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; a resin and an isocyanate-based curing agent (two or more isocyanate groups (-N = C = O) in one molecule). Compounds), a photopolymerization initiator, and a resin composition with at least one of organic peroxides 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. Mention may be made of compositions that are included with the initiator. The active energy ray-curable resin is a resin that can be polymerized and cured by an active energy ray such as an ultraviolet ray or an electron beam.

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) acrylates and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acrylo (Meth) acryloyl group-containing bifunctional reactive monomers such as ruoxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) (Meth) acryloyl group-containing trifunctional reactive monomers such as acrylate and trimethylolethanetri (meth) acrylate; and (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; dipentaerythritol hexaacrylate (Meth) acryloyl group-containing 6-functional reactive monomers such as tripentaerythritol acrylate; etc .; and polymers (oligomers) comprising at least one of these as a constituent monomer And prepolymers). As the active energy ray-curable resin, one or a mixture of two or more of these can be used. In this specification, (meth) acrylate means acrylate or methacrylate.

Examples of the isocyanate-based curing agent include, for example, 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, and biurets of hexamethylene diisocyanate; and urethane crosslinking agents such as blocked 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, and 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin 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 and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Triazine-based compound; biimidazole compound; acylphosphine oxide-based compound; titanocene-based compound; oxime ester-based compound; oxime phenylacetate-based compound; hydroxyketone-based compound; and aminobenzoate-based compound. it can. These can be used alone or in combination of two or more.

The active energy ray-curable resin composition may contain, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropy-imparting agent, a stain inhibitor, a printability improver, an antioxidant, and a weathering stabilizer. And one or more additives such as a light resistance stabilizer, a UV absorber, a heat stabilizer, a colorant, and a filler.

The active energy ray-curable resin composition may contain a solvent, if desired, in order to dilute it to a concentration that facilitates molding. 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 catalyze (promote) the self-reaction (including the degradation reaction) of these components. . Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone.

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 covered with a hard coat. The hard coat functions to improve the surface hardness and abrasion 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 has no coloring so that it can be easily colored into 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 entire surface, depending on the shape, application, and use mode of the molded article of the present invention.

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

2-1. First hard court:
The first hard coat comprises (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 paint containing no inorganic particles.

The first hard coat forms the surface of the molded article of the present invention. The first hard coat forms a surface of an article when an article is produced using the molded article of the present invention. The first hard coat exhibits good abrasion 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; fluoride) Metal fluoride particles such as magnesium and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles; etc.) are highly effective in increasing the hardness of the hard coat. On the other hand, the interaction with the resin component such as the component (A) is weak, which causes the scratch resistance to be insufficient. Therefore, in the present invention, the first hard coat forming the outermost surface does not contain inorganic particles to maintain abrasion resistance, while the second hard coat contains a large amount of specific inorganic fine particles. This problem has been solved by increasing the hardness.

Here, “does not include” inorganic particles means that it does not include a significant amount of inorganic particles. In the field of coatings for forming a hard coat, a significant amount of the inorganic particles is usually about 1 part by mass or more based on 100 parts by mass of the component (A). Therefore, the phrase "free of inorganic particles" means that the amount of the inorganic particles is usually less than 1 part by mass, preferably 0.1 part by mass or less, more preferably 0.01 part by mass, based on 100 parts by mass of the component (A). It can be paraphrased as a mass part 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. It acts to form a hard coat by polymerization and curing by active energy rays.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Bifunctional reaction containing a (meth) acryloyl group such as 2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane and 2,2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane (Meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate; pentaerythri (Meth) acryloyl group-containing tetrafunctional reactive monomer such as allyl tetra (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group containing tripentaerythritol acrylate Examples thereof include an octafunctional reactive monomer and a polymer (oligomer or prepolymer) containing at least one of these as a constituent monomer. As the component (A), one or a mixture of two or more of these can be used. In this 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 silicone oil, silicone resin, polydimethylsiloxane, and alkylalkoxysilane. Agents; fluorine-containing water repellents such as fluoropolyether water repellents and fluoropolyalkyl water repellents; and the like. As the component (B), one or a mixture of two or more of these can be used.

Among them, the component (B) is preferably a fluoropolyether-based water repellent from the viewpoint of water repellency. The component (A) and the component (B) are chemically bonded or strongly interacted with each other, and from the viewpoint of preventing a trouble such as bleeding out of the component (B), the component (B) is in the molecule. A water repellent containing a compound containing a (meth) acryloyl group and a fluoropolyether group (hereinafter abbreviated as a (meth) acryloyl group-containing fluoropolyether-based water repellent) is more preferable. More preferred as the component (B) is that the component (A) and the component (B) are appropriately adjusted for chemical bonding or interaction, and from the viewpoint of exhibiting good water repellency while maintaining high transparency. It is a mixture of an acryloyl group-containing fluoropolyether-based water repellent and a methacryloyl group-containing fluoropolyether-based water-repellent.

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

The amount of the component (B) is usually 7 parts by mass or less, preferably 4 parts by mass, based on 100 parts by mass of the component (A), from the viewpoint of preventing trouble such as bleeding out of the component (B). Parts by weight, 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 at least 0.01 part by mass, preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass.

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

The silane coupling agent includes a hydrolyzable group (for example, an alkoxy group such as a methoxy group or an ethoxy group; an acyloxy group such as an acetoxy group; a halogen group such as a chloro group; etc.); and an organic functional group (for example, an amino group, A silane compound having at least two different reactive groups such as a mercapto group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group. Among these, as the component (C), from the viewpoint of adhesion, a silane coupling agent having an amino group (a silane compound having an amino group and a hydrolyzable group) and a silane coupling agent having a mercapto group ( Silane compounds having a mercapto group and a hydrolyzable group) are 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, N-2 -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane.

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

One or a mixture of two or more of these components can be used as the component (C).

The amount of the component (C) to be added is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, based on 100 parts by mass of the component (A), from the viewpoint of ensuring the effect of improving adhesion. It is more preferably at least 0.1 part by mass. On the other hand, from the viewpoint of the pot life of the coating material, it may be usually at most 10 parts by mass, preferably at most 5 parts by mass, more preferably at most 1 part by mass.

(F) Resin fine particles having an average particle diameter of 0.5 to 10 μm:
When imparting anti-glare properties to the molded article of the present invention, (F) resin fine particles having an average particle diameter of 0.5 to 10 μm can be further contained in the coating material for forming the first hard coat. 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 silicone 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, silicon-based resin, acrylic-based resin, and fluorine-based resin fine particles are preferable from the viewpoints of low specific gravity, lubricity, dispersibility, and solvent resistance. Further, from the viewpoint of improving the light diffusivity, a spherical shape is preferable. As the resin fine particles, one or a mixture of two or more of these can be used.

The component (F) may have an average particle size of usually 0.5 μm or more, preferably 1 μm or more, from the viewpoint of ensuring anti-glare properties. On the other hand, when the transparency of the hard coat is to be maintained, 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 determined from the smaller particle size in a particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. Is 50% by mass.

The amount of the component (F) is usually 0.01 to 15 parts by mass, and preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the component (A), depending on the antiglare level to be imparted. It may be from 10 to 10 parts by mass, more preferably from 0.2 to 5 parts by mass, still more preferably from 0.3 to 3 parts by mass. In addition, from the viewpoint of scratch resistance, the amount 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 paint has a compound having two or more isocyanate groups (-N = C = O) in one molecule and / or a photopolymerization start. It is preferable to further include 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, and trimethylol of isophorone diisocyanate Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and biuret of hexamethylene diisocyanate; and urethanes such as blocked isocyanates of the above polyisocyanates Crosslinking agents and the like can be mentioned. 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, and 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin 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 and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Triazine-based compound; biimidazole compound; acylphosphine oxide-based compound; titanocene-based compound; oxime ester-based compound; oxime phenylacetate-based compound; hydroxyketone-based compound; and aminobenzoate-based compound. it can. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

In the first hard coat forming paint, if desired, an antistatic agent, a surfactant, a leveling agent, a thixotropy-imparting agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, One or two or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, and an organic colorant can be contained.

The first hard coat forming paint may contain a solvent, if desired, in order to dilute the paint to a concentration that facilitates application. The solvent is not particularly limited as long as it does not react with the components (A) to (C) and other optional components and does not catalyze (promote) the self-reaction (including the degradation reaction) of these components. Not done. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. One or a mixture of two or more of these solvents can be used as the solvent.

The first hard coat forming paint can be obtained by mixing and stirring these components.

The method of 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 dip coating, spray coating, spin coating, and air knife coating. The coating is not limited to one time, and may be repeated two or more times. Further, when the hard coat forming portion of the molded article of the present invention is planar, a method 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 abrasion resistance and hardness. On the other hand, from the viewpoints of hardness and adhesion to the second hard coat, the thickness is preferably 5 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less.

2-2. Second hard court:
The second hard coat is composed 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.

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

(D) Inorganic fine particles having an average particle size of 1 to 300 nm:
The component (D) functions to dramatically increase the surface hardness of the 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; Fine particles of metal fluoride such as magnesium fluoride and sodium fluoride; fine particles of metal sulfide; fine particles of metal nitride; and fine particles of metal.

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

In order to enhance the dispersibility of the inorganic fine particles in the paint and to increase the surface hardness of the obtained hard coat, the surface of the inorganic fine particles is subjected to a silane coupling agent such as vinylsilane and aminosilane; a titanate coupling agent An aluminate-based 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, or an allyl group or an epoxy group; and a fatty acid, a fatty acid metal salt, or the like. It is preferable to use one treated with a surface treatment agent or the like.

One or a mixture of two or more of these components can be used as the component (D).

The average particle diameter of the component (D) is 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of ensuring the effect of improving the hardness of the hard coat. On the other hand, the lower limit of the average particle diameter is not particularly limited, but usually available inorganic fine particles are at most about 1 nm at most.

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

The 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, based on 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:
It is preferable that the coating material for forming the second hard coat further contains (E) a leveling agent from the viewpoint of making the surface of the second hard coat good and facilitating the formation of the first hard coat.

Examples of the leveling agent include an acrylic leveling agent, a silicon-based leveling agent, a fluorine-based leveling agent, a silicon-acrylic copolymer-based leveling agent, a fluorine-modified acrylic-based leveling agent, a fluorine-modified silicon-based leveling agent, and a functional group. A leveling agent into which a group (for example, an alkoxy group such as a methoxy group or an ethoxy group, an acyloxy group, a halogen group, an amino group, a vinyl group, an epoxy group, a methacryloxy group, an acryloxy group, and an isocyanate group) is introduced. Can be. Among them, the component (E) is preferably a silicon / acrylic copolymer-based leveling agent. As the component (E), one or a mixture of two or more of these can be used.

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

From the viewpoint of improving curability by active energy rays, the second hard coat-forming coating material has a compound having two or more isocyanate groups (-N = C = O) in one molecule and / or a photopolymerization start. It is preferable to further include 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 paint. 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 has been described above in the description of the first hard coat forming paint. As the photopolymerization initiator, one or a mixture of two or more of these can be used.

The coating material for forming the second hard coat may include, if desired, an antistatic agent, a surfactant, a thixotropy-imparting agent, a stain inhibitor, a printability improver, an antioxidant, a weather resistance stabilizer, and a light stability. One, two 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 paint may contain a solvent, if desired, in order to dilute it to a concentration that facilitates application. As long as the solvent does not react with the component (A), the component (D), and other optional components, or catalyze (promote) a self-reaction (including a deterioration reaction) of these components, There is no particular limitation. Examples of the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, and acetone. Of these, 1-methoxy-2-propanol is preferred. One or a mixture of two or more of these solvents can be used as the solvent.

The second hard coat forming paint can be obtained by mixing and stirring these components.

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

The thickness of the second hard coat is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 18 μm or more, from the viewpoint of surface hardness. 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 still more preferably 25 μm or less.

3. End face cutting:
The molded body of the present invention was subjected to a cutting process, for example, a so-called R-surface cutting process (FIG. 3A) or a so-called C-plane cutting process (FIG. 3B), and the end portion was chamfered. It may have a shape. As a method of producing a molded body having a shape in which the end is chamfered, for example, first, the end of the base is cut, and then the second hard material is placed on the surface of the base whose end is 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, and then forming the second hard coat (2) A method of cutting the end of the hard coat formed body, followed by forming a first hard coat on the surface of the obtained cut body; and first forming a second hard coat on the surface of the substrate Then, a method of forming the first hard coat on the surface of the second hard coat formed next, and subsequently cutting the end of the obtained molded body can be used. 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 by using a method such as dip coating using an arbitrary paint. Since the first hard coat that forms 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 cutting the end portion of the molded body, it is expected that the coating film is formed only on the cut surface even if dip coating is performed using any of the above-described paints without performing masking or the like. . Examples of the optional paint include the above-described paint for forming the first hard coat and the paint for forming the second hard coat.

4. Articles containing the molded article of the present invention:
Examples of the article containing the molded article of the present invention are not particularly limited, and include, for example, housings of home electric appliances such as a television, a refrigerator, a washing machine, a vacuum cleaner, a microwave oven, and an air conditioner; a refrigerator, a washing machine, a cupboard, and Panels that make up the front of the door that opens and closes the front opening of the main body, and panels that make up the plane of the lid that opens and closes the opening of the main body plane; such as smartphones, tablet terminals, car navigation systems, digital cameras, And a housing of an information electronic device such as a personal computer, and a curved display surface plate; an instrument panel of an automobile, a shift knob, and the like.

When the molded article of the present invention is used for applications requiring transparency, such as a curved display surface plate of a smartphone, a tablet terminal, a car navigation system, a personal computer, or the like, the total light transmittance (JIS K) of the molded article of the present invention is used. 7361-1: 1997, using a turbidimeter “NDH2000 (trade name)” manufactured 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. The higher the total light transmittance, the better.

The molded product of the present invention was measured using a pencil “Uni (trade name)” manufactured by Mitsubishi Pencil Co., Ltd. under the condition of a 750 g load according to the pencil hardness of the surface of the first hard coat (JIS K 5600-5-4). ) Is preferably 5H or more, more preferably 6H or more, and still more preferably 7H or more. The higher the pencil hardness, the better.

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

The molded article of the present invention preferably has a water contact angle of 100 degrees or more after the reciprocating 20,000 times of cotton on the surface of the first hard coat. More preferably, the water contact angle after reciprocating 25,000 times of cotton is 100 degrees or more. With a water contact angle of 100 degrees or more after 20,000 reciprocations of cotton, surface properties such as water repellency, fingerprint resistance, and stain resistance can be maintained even when repeatedly wiped with a handkerchief or the like. it can. The larger the number of times of cotton wiping that can maintain a water contact angle of 100 degrees or more, the more preferable. Here, the water contact angle after cotton wiping is a value measured according to the test (d) of the following example.

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

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

(A) Total light transmittance:
According to JIS K 7361-1: 1997, it was measured using a turbidity meter “NDH2000 (trade name)” of Nippon Denshoku Industries Co., Ltd.

(B) Pencil hardness:
According to JIS K 5600-5-4, the first hard coat surface of the molded product 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 a water droplet using an automatic contact angle meter “DSA20 (trade name)” manufactured by KRUSS (refer to JIS R 3257: 1999). did.

(D) Scratch resistance 1 (water contact angle after wiping cotton):
A test piece having a size of 150 mm in length and 50 mm in width and collected from the flat part of the zenith of the molded body is placed on a Gakushin-shape tester of JIS L 0849: 2013 so that the first hard coat is on the surface. A stainless steel plate (length 10 mm, width 10 mm, thickness 1 mm) covered with four layers of gauze (medical type 1 gauze of Kawamoto Sangyo Co., Ltd.) was attached to the friction terminal of the vibration tester, and the length and width of the stainless plate Was set so as to be in contact with the test piece, a 350 g load was placed thereon, and the first hard coat surface of the test piece was rubbed 10,000 times in a reciprocating manner at a friction terminal moving distance of 60 mm and a speed of 1 reciprocation / sec. According to the method of (c), the water contact angle of the cotton swab was measured. When the water contact angle is 100 degrees or more, after rubbing 5,000 more times, the operation of measuring the water contact angle of the cotton wiping point was repeated according to the method (c) above, and evaluated according to the following criteria. .
A: Water contact angle is 100 degrees or more even after 25,000 reciprocations.
B: Water contact angle is 100 degrees or more after 20,000 reciprocations, but less than 100 degrees after 25,000 times.
C: Water contact angle is 100 degrees or more after 15,000 reciprocations, but less than 100 degrees after 20,000 reciprocations.
D: Water contact angle is 100 ° or more after 10,000 reciprocations, but less than 100 ° after 15,000 reciprocations.
E: Water contact angle is less than 100 degrees after 10,000 reciprocations.

(E) Scratch resistance 2 (steel wool resistance):
A test piece collected from the flat part of the zenith of the molded body was placed on a Gakushin test machine of JIS L 0849: 2013 so that the first hard coat was on the surface. Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type testing machine, a load of 500 g was placed thereon, and the surface of the test piece was rubbed 100 times in a reciprocating manner. If no scratches were observed, rubbing was further repeated 100 times, and the operation of visually observing the frictional portion was repeated, and evaluated according to the following criteria.
A: No scratch is observed even after 500 reciprocations.
B: No scratch is observed after 400 reciprocations, but scratch can be recognized after 500 reciprocations.
C: No scratch is observed after 300 reciprocations, but scratch can be recognized after 400 reciprocations.
D: No scratch is observed after 200 reciprocations, but scratch can be recognized after 300 reciprocations.
E: No scratch is observed after 100 reciprocations, but scratch 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, 100 squares (1 square = 1 mm x 1 mm) are cut from the first hard coat side of the molded body, and then a tape for adhesion test is attached to the square. And then peeled off. Evaluation criteria were in accordance with Table 1 of the above-mentioned standard of JIS.
Category 0: The edges of the cut are completely smooth, and there is no peeling of any grid.
Category 1: Small peeling of the coating film at the intersection of cuts. The effect on the crosscuts is not clearly more than 5%.
Category 2: The coating peels off along the edges of the cut and / or at intersections. Affected in the crosscut section is clearly more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled off along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. Affected in the crosscut portion is clearly more than 15% but not more than 35%.
Classification 4: The coating film is partially or completely peeled off along the edge of the cut, and / or several eyes are partially or completely peeled off. Affected in the crosscut section is clearly over 35% but never over 65%.
Category 5: When the degree of peeling exceeds category 4.

(G) Weather resistance:
Using a sunshine carbon arc lamp type weather resistance tester specified in JIS B7753: 2007, the conditions of Table 10 of JIS A5759: 2008 (however, the test piece is 125 mm long and 50 mm wide, The collected sample was used as it was, and was not attached to glass.), And an accelerated weather resistance test for 300 hours was performed. The N number of the test was set to 3, and in all tests, the case where there was no change in appearance such as swelling, cracking, and peeling of the transparent resin laminate was passed (indicated by に は in the table), and otherwise failed ( In the table, it was described as x).

(H) Haze:
According to JIS K 7136: 2000, it was measured using a turbidity meter “NDH2000 (trade name)” of Nippon Denshoku Industries Co., Ltd.

(I) Y value of XYZ display system based on 2 degree field of view:
Using a spectrophotometer “SolidSpec-3700 (trade name)” and a reflection unit “absolute reflectance measuring device, incident angle 5 ° (trade name)” manufactured by Shimadzu Corporation, and following the instruction of the spectrophotometer, 5 degrees The measurement was performed under the condition of specular reflection (a reflection unit was installed before the integrating sphere).

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

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

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

(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 which have been surface-treated with a silane coupling agent having a vinyl group.

(E) Leveling agent:
(E-1) Kusumoto Kasei Co., Ltd. silicone-acrylic copolymer system leveling agent “Dispalon NSH-8430HF (trade name)”. Solid content 10% by mass.
(E-2) BYK-3550 (trade name) silicone-acrylic copolymer-based leveling agent from BYK Japan KK. Solid content 52% by mass.
(E-3) Acrylic polymer leveling agent “BYK-399 (trade name)” from BYK Japan KK. Solid content 100% by mass.
(E-4) A silicon-based leveling agent “Dispalon LS-480 (trade name)” manufactured by Kusumoto Kasei. Solid content 100% by mass.

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

(G) Optional components:
(G-1) A phenyl ketone-based photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone) “SB-PI714 (trade name)” manufactured by Sangbang Industrial Co., Ltd.
(G-2) 1-methoxy-2-propanol.

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

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

(H1 ′) Reference first hard coat forming paint:
A coating material was obtained in the same manner as in the above (H1-1), except that the composition of (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), and (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 composition table. In addition, about the said (E-1) and the said (E-2), the value of solid content conversion is described in the table | surface.

(H2-1) A coating material was obtained in the same manner as in (H2-1), except that the composition 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 (H2-1), except that the composition of (H2′-1,2) was changed as shown in Table 5.

(A) Substrate:
(A1-1) Substrate 1 obtained by vacuum forming an acrylic resin sheet 1:
Using an acrylic resin “Optimas6000 (trade name), glass transition temperature 119 ° C.” manufactured by Mitsubishi Gas Chemical Company, Inc., an extruder and a device equipped with a T-die (see FIG. 4) were used. The melted sheet is continuously extruded and the above-mentioned melting is carried out between a rotating first mirror roll (a roll holding the molten sheet and sending it to the next transfer roll; the same applies hereinafter) and a rotating second mirror roll. The sheet was supplied and pressed, and a transparent resin sheet having a thickness of 1 mm was obtained. The set conditions at this time were: a set temperature of the first mirror roll of 120 ° C., a set temperature of the second mirror roll of 110 ° C., and a resin temperature of 300 ° C. at the exit of the T-die. 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 3,400 MPa. Subsequently, using the obtained resin sheet and the vacuum forming method, as described above, FIG. 1 (FIG. 1 (a) is a plan view, FIG. 1 (b) is a side view, The major axis length 1 of the zenith flat portion is 20 cm, the major axis length 2 of the end portion having an elliptical shape is 30 cm, the minor axis length 3 of the zenith flat portion having an elliptical shape is 10 cm, and the end portion having an elliptical shape. Has a minor axis length 4 of 20 cm and a height 5 from the end to the zenith of 5 cm. The same applies hereinafter.). At this time, the pressure in the space 9 was 1.0 × 10 ⁻³ KPa.

(A1-2) Base 2 obtained 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. 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 set conditions at this time were: a set temperature of the first mirror roll of 140 ° C., a set temperature of the second mirror roll of 120 ° C., and a resin temperature of 300 ° C. at the exit of the T-die. 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 4,300 MPa. Subsequently, using the obtained resin sheet, a base having the shape shown in FIG. 1 was formed by the 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 an aromatic polycarbonate “Calibur 301-4 (trade name), glass transition temperature 151 ° C.” manufactured by Sumika Styron Polycarbonate Co., Ltd., the above resin was melted from the T-die using an apparatus equipped with an extruder and a T-die. The sheet was continuously extruded, and the molten sheet was supplied and 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 set conditions at this time were: a set temperature of the first mirror roll of 140 ° C., a set temperature of the second mirror roll of 120 ° C., and a resin temperature of 300 ° C. at the exit of the T-die. The resulting 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 base having the shape shown in FIG. 1 was formed by the 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:
Using a non-crystalline polyester resin (PETG resin) “Cadence GS1 (trade name), glass transition temperature 81 ° C.” manufactured by Eastman Chemical Company, using an apparatus equipped with an extruder and a T-die, The molten sheet of the resin is continuously extruded, and the molten sheet is supplied and pressed between the rotating first mirror surface roll and the rotating second mirror surface roll, and pressed to form a transparent resin sheet having a thickness of 1 mm. Obtained. The set conditions at this time were a set temperature of the first mirror surface roll of 80 ° C., a set temperature of the second mirror surface roll of 40 ° C., and a resin temperature of 200 ° C. at the exit of the T-die. The resulting transparent resin sheet had a total light transmittance of 89%, a haze of 1.3%, a yellowness index of 0.4, and a tensile modulus of 1500 MPa. Subsequently, using the obtained resin sheet, a base having the shape shown in FIG. 1 was formed by the 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 Eastman Chemical Company's non-crystalline polyester resin “Tritan FX200 (trade name), glass transition temperature 119 ° C.”, melting of the resin from the T-die using an apparatus equipped with an extruder and a T-die The sheet was continuously extruded, and the molten sheet was supplied and 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 set conditions at this time were a set temperature of the first mirror roll of 80 ° C., a set temperature of the second mirror roll of 40 ° C., and a resin temperature of 230 ° C. at the outlet of the T-die. The resulting 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 base having the shape shown in FIG. 1 was formed by the 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 an extruder and a T-die, a two-layer, three-layer multi-manifold co-extrusion film forming apparatus, an acrylic resin “Optimas 7500 (trade name), glass transition temperature 119 ° C.” manufactured by Mitsubishi Gas Chemical Co., Ltd. Then, a molten laminated sheet having an intermediate layer of aromatic polycarbonate “Calibur 301-4 (trade name), glass transition temperature 151 ° C.” of Sumika Stylon Polycarbonate Co., Ltd. is continuously extruded from a T-die, and the rotating first mirror surface. The above-mentioned molten laminated sheet is supplied and supplied between the roll and the rotating second mirror roll, and is pressed so that 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 provided. Got. The set conditions at this time were: a set temperature of the first mirror roll of 120 ° C., a set temperature of the second mirror roll of 110 ° C., and a resin temperature of 300 ° C. at the exit of the T-die. The resulting transparent resin sheet had a total light transmittance of 91%, a haze of 0.6%, a yellowness index of 0.5, and a tensile modulus of 2600 MPa. Subsequently, using the obtained resin sheet, a base having the shape shown in FIG. 1 was formed by the 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 ABS / PC alloy resin:
Using ABS / PC alloy resin "Exceloy CK50 (trade name)" manufactured by Techno Polymer Co., Ltd., using a 100-ton injection molding machine, cylinder temperature 260 ° C, mold temperature 70 ° C, injection speed 250mm / sec, and holding Under a pressure of 50 MPa, a substrate made of a thermoplastic resin was injection molded.

Example 1
On the convex side of the above (a1-1), a hard coat composed of the above (H2-1) was formed to have a thickness of 22 μm after curing by using a dip coating method. Next, on the surface of the hard coat formed above, a hard coat composed of the above (H1-1) was formed to have a thickness of 2 μm after curing by using a dip coating method. The above tests (a) to (g) were performed on the obtained molded body. Table 6 shows the results.

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

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

Examples 24-28
All of the procedures were performed in the same manner as in Example 1, except that the substrates shown in Table 10 were used instead of the above (a1-1). Table 10 shows the results.

Example 29
All of the procedures were performed in the same manner as in Example 1 except that the bases shown in Table 10 (the above (a5-1)) were used instead of the above (a1-1). Table 10 shows the results. Since the above (a5-1) is an opaque substrate, the above test (a) and the above test (h) are omitted.

Examples 30 to 33
Except that the thickness of the first hard coat after curing was changed as shown in Table 11, the same procedure was performed as in Example 1. Table 11 shows the results.

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

Examples 38-47
All of the procedures were performed in the same manner as in Example 1 except that the paints shown in Table 12 or Table 13 were used instead of the above (H1-1). The results are shown in Table 12 or Table 13.

The preferred molded article of the present invention is excellent in surface hardness and scratch resistance. Also, the weather resistance and the adhesion of the hard coat are 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 elliptical zenith flat part 2: Long axis length of the elliptical end part 3: Short axis length of the elliptical zenith flat part 4: of the elliptical end part 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 8 10: Base 11: Molten resin sheet 12 : T die 13: First mirror roll 14: Second mirror roll

Claims (18)

A molded article,
Having a resin substrate;
A part or all of the surface of the substrate is 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,
(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;
Comprising a paint containing no inorganic particles;
The second hard coat,
(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;
A molded article comprising a paint containing:
The molded article according to claim 1, wherein 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.
The molded article according to claim 1 or 2, wherein the (B) water repellent comprises a (meth) acryloyl group-containing fluoropolyether-based water repellent.
The molded article 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 according to any one of claims 1 to 4, wherein the coating material forming the first hard coat further comprises (F) 0.01 to 15 parts by mass of resin fine particles having an average particle size of 0.5 to 10 µm. Molded body.
The molded product according to any one of claims 1 to 5, wherein the thickness of the first hard coat is 0.5 to 5 µm.
The molded product according to any one of claims 1 to 6, wherein the thickness of the second hard coat is 5 to 30 µm.
The molded article according to any one of claims 1 to 7, which satisfies (a) and (b) below.
(A) The total light transmittance is 85% or more.
(B) The pencil hardness of the surface of the first hard coat is 5H or more.
The molded article according to any one of claims 1 to 8, which satisfies the following (c) and (d).
(C) The first hard coat surface has a water contact angle of 100 degrees or more.
(D) The water contact angle after reciprocating 20,000 times of cotton on the surface of the first hard coat is 100 degrees or more.
The molded article according to any one of claims 1 to 9 , wherein the substrate has a three-dimensional shape.
The molded article according to any one of claims 1 to 10 , wherein the molded article has a chamfered end.
An article comprising the molded article according to any one of claims 1 to 11 .
A method for producing a molded article according to any one of claims 1 to 11 ,
(1a) a step of three-dimensionally forming a resin sheet to produce the base;
(2) forming the second hard coat on 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);
A method that includes
The method according to claim 13, wherein the resin sheet has a layer for imparting design property on the entire surface or partially on the surface.
The method according to claim 13, wherein the resin sheet has a printed layer on the entire surface or partially on the surface.
A method for producing a molded article according to any one of claims 1 to 11 ,
(1b) a step of molding a thermoplastic resin to produce 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);
A method that includes
A method for producing a molded article according to any one of claims 1 to 11 ,
(1c) molding a curable resin to produce the substrate;
(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);
A method that includes
A method for producing an article according to claim 12 , wherein
A step of producing a molded article by the method according to any one of claims 13 to 17; and (4) a step of producing an article using the molded article obtained in the above step;
A method that includes