JP5230313B2 - Laminated plate and front plate for display device - Google Patents

Description

  The present invention relates to a laminated board. More specifically, the present invention relates to a laminate having excellent scratch resistance, optical properties, and surface hardness, and having impact resistance, and a front plate for a display device having an antireflection function made of the laminate.

As a transparent material resin, a polycarbonate plate is generally an effective material from the viewpoint of having good mechanical strength and excellent impact resistance. However, since the surface hardness of the polycarbonate itself is low, it is easily scratched, and a hard coat or acrylic resin having a high hardness is coated on the surface. For example, when the hard coat treatment is performed directly on the polycarbonate, the surface hardness is pencil hardness and HB is the limit, so that an acrylic resin layer provided as an intermediate layer between the polycarbonate and the hard coat has been proposed ( For example, Patent Document 1). However, even in this case, as the surface hardness, a resin plate having a surface hardness as high as about 2 to 3 H in pencil hardness is required, and the surface steel wool property is not sufficient.
Moreover, when it uses for the front plate for display apparatuses, it is used in the environment where external light injects, regardless of indoor or outdoor. External light incident on the display device is reflected, and a virtual image of the external light is reproduced on the display screen of the display device. For this reason, an image due to external light, such as a fluorescent lamp, is displayed on the screen, causing problems such as making the original display image difficult to see. In addition, external light incident on the display device is mixed with the original display light to deteriorate the display quality. Therefore, an antireflection function is required to prevent such external light from entering the display device.
On the other hand, a heat-resistant acrylic resin having a ring structure in the main chain excellent in transparency and hardness is known as an acrylic resin. For example, Patent Document 2 discloses a laminate in which an acrylic resin having a lactone ring structure is laminated on a polycarbonate surface. A board has been proposed. However, since this laminated plate structure did not have sufficient performance with respect to scratch resistance, it was not used for a front panel for a display device that requires scratch resistance and high surface hardness.

JP2003-183577 JP 2002-254544 A

    The present invention is to improve the above-mentioned conventional problems, and to provide a laminate having excellent transparency and scratch resistance and excellent mechanical strength and impact resistance at high productivity and at low cost. It is another object of the present invention to provide a front plate for a display device having an antireflection function made of the laminate.

  In view of the above circumstances, the present inventors have a high-hardness heat-resistant acrylic resin layer on at least one surface of a polycarbonate resin layer excellent in impact resistance, and further, a hard coat layer is disposed on the heat-resistant acrylic resin layer, and a laminate. In addition, by setting the thickness of each layer to a specific range, a laminated board that has excellent transparency and scratch resistance, and has both mechanical strength and impact resistance can be obtained. The inventors have found that a front plate for a display device having a function can be obtained, and completed the present invention.

That is, this invention is a laminated board which has a polycarbonate resin layer (A), a heat-resistant acrylic resin layer (B), and a hard-coat layer (C), Comprising: The laminated board which satisfies the following conditions.
(A) The total thickness of the laminate is 0.5 to 2 mm.
(B) The heat-resistant acrylic resin layer (B) has a thickness of 20 to 200 μm.
(C) The thickness of the hard coat layer (C) is 2 to 10 μm
(D) Further having an antireflection layer (D) The present invention is an invention relating to a front plate for a display device which further has an antireflection function comprising the above laminate and is transparent and has high hardness.

  According to the present invention, the acrylic resin in the laminate is a heat-resistant acrylic resin, and by setting the thickness of the heat-resistant acrylic resin layer, the thickness of the hard coat layer, and the total thickness of the laminate in a specific range, the transparent Laminates suitable as various front materials for display devices having various anti-reflection functions, in particular, a variety of transparent materials having a good balance of properties, surface hardness, and impact resistance.

The present invention is described in detail below. In the present specification, the “main component” is intended to contain 50% by weight or more. In addition, “A to B” indicating a range indicates that the range is A or more and B or less.
The laminate of the present invention is a laminate having a polycarbonate resin layer (A), a heat-resistant acrylic resin layer (B), and a hard coat layer (C), and satisfies the following conditions.
(A) The total thickness of the laminate is 0.5 to 2 mm.
(B) The heat-resistant acrylic resin layer (B) has a thickness of 20 to 200 μm.
(C) The thickness of the hard coat layer (C) is 2 to 10 μm
(D) It further has an antireflection layer (D)

Hereinafter, each layer will be described <polycarbonate resin layer>
The polycarbonate resin used for the polycarbonate resin layer (A) in the present invention contains as a main component a polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melting method. Representative examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxy). Phenyl) cyclohexane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like can be mentioned, and among them, bisphenol A is preferable. These dihydric phenols can be used alone or in admixture of two or more.
As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like. When producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melting method, use catalyst, terminal terminator, dihydric phenol antioxidant, etc. as necessary May be. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
The molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M). A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained and the melt fluidity during molding is good.
The Izod impact strength (measured according to ASTM-D-256, notched, thickness 3.2 mm) of the polycarbonate resin is preferably 10 kJ / m 2 or more, more preferably 20 kJ / m 2 or more, more preferably 30 kJ / m 2. That's it.
When producing such a polycarbonate resin, stabilizers such as phosphites, phosphates and phosphonates, hindered phenols, phosphorus and sulfur antioxidants, tetrabromobisphenol A, Flame retardants such as low molecular weight polycarbonate of bromobisphenol A, decabromodiphenol, tris (dibromopropyl) phosphate, ethylene tetrabromide, antimony oxide, zinc borate, UV absorbers that can be used for heat-resistant acrylic resins described later, coloring An antistatic agent such as a surfactant, an anionic, a cationic, a nonionic or an amphoteric surfactant, a lubricant, an inorganic pigment, an organic pigment, or a dye can be added. What is necessary is just to set suitably the addition time and addition amount of these additives in the range which does not impair the effect of this invention.
<Heat resistant acrylic resin layer>
The thickness of the heat-resistant acrylic resin layer (B) according to the present invention is in the range of 20 to 200 μm, preferably in the range of 20 to 150 μm, and more preferably in the range of 40 to 120 μm. If it is less than 20 μm, the scratch resistance and pencil hardness of the laminate may be lowered, and if it exceeds 200 μm, the impact resistance of the laminate surface may be inferior.

The heat-resistant acrylic resin used for the heat-resistant acrylic resin layer (B) according to the present invention contains a (co) polymer obtained by polymerizing a (meth) acrylate monomer as a main component and a derivative thereof as a main component, and has a glass transition. A resin having a temperature (Tg) of 110 ° C. or higher. The Tg of the heat-resistant acrylic resin is preferably 115 ° C or higher, more preferably 120 ° C or higher, still more preferably 125 ° C or higher, and most preferably 130 ° C or higher.
Specifically, lactone ring structure is formed by intramolecular cyclization reaction of maleic anhydride and (meth) acrylate copolymer, N-substituted maleimide phenylmaleimide and (meth) acrylate copolymer, (meth) acrylate copolymer. Examples of so-called glutaric anhydride polymers and glutarimide polymers in which glutaric anhydride structures and glutarimide structures are introduced into the introduced so-called lactone ring- containing polymers and (meth) acrylate copolymers by intramolecular cyclization reaction are mentioned. It is done.
Here, the glass transition temperature is a temperature at which polymer molecules start micro-Brownian motion, and there are various measurement methods. In the present invention, a differential scanning calorimeter (DSC) is used in accordance with ASTM-D-3418. It is defined as the temperature obtained by the midpoint method. Acrylic resins having a glass transition temperature of 110 ° C. or higher are generally recognized as heat-resistant acrylic resins by those skilled in the art.
By using heat-resistant acrylic resin as the acrylic resin in the laminate in this way, balanced transparency, surface hardness, impact resistance can be obtained, and heat resistance can be improved. However, a laminated board can be used suitably.
Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and t- (meth) acrylate. Butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Examples include 3-hydroxypropyl, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, and 2,3,4,5-tetrahydroxypentyl (meth) acrylate, and one of these. May be included alone, or two or more of them may be present together. Among these, methyl methacrylate is most preferable in that the resin obtained by polymerization is excellent in optical properties and thermal stability.

The heat-resistant acrylic resin may polymerize monomers other than the (meth) acrylate monomer described above, for example, styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, acetic acid. Other than (meth) acrylate monomers such as vinyl, methallyl alcohol, allyl alcohol, allyl alcohol such as 2-hydroxymethyl-1-butene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, (meth) acrylic acid, etc. Acrylic acid derivatives, 2- (hydroxyalkyl) acrylic acid esters such as 2- (hydroxyethyl) methyl acrylate; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid, and the like. Only one type may be used, or two or more types It may be use.
The heat-resistant acrylic resin according to the present invention preferably has a weight average molecular weight of 1,000 to 300,
000, more preferably 5,000 to 250,000, still more preferably 10,000 to 2
00,000, particularly preferably 50,000 to 200,000.

  The heat-resistant acrylic resin according to the present invention preferably has a 5% weight loss temperature in thermogravimetric analysis (TG) of 280 ° C or higher, more preferably 290 ° C or higher, and further preferably 300 ° C or higher. The 5% weight loss temperature in thermogravimetric analysis (TG) is an index of thermal stability, and if it is less than 280 ° C., sufficient thermal stability may not be exhibited.

The heat-resistant acrylic resin may have an ultraviolet absorbing ability as long as the heat resistance, physical properties, and optical properties are not impaired. Specifically, a method using an ultraviolet-absorbing monomer and / or an ultraviolet-stable monomer as a monomer component when producing a heat-resistant acrylic resin, an ultraviolet absorber and / or an ultraviolet stabilizer are used in the above heat-resistant acrylic resin. There is a method of blending with an acrylic resin. These methods may be used in combination as long as the physical properties of the layer mainly composed of a heat-resistant acrylic resin are not hindered. In order to maintain the ultraviolet absorbing function, it is preferable to use an ultraviolet absorbing monomer and an ultraviolet stabilizing monomer in combination, or to use an ultraviolet absorber and an ultraviolet stabilizer in combination. It is also preferable to use an ultraviolet absorber and / or an ultraviolet stabilizer in combination with the ultraviolet absorbing monomer and / or the ultraviolet stabilizing monomer.
Examples of the ultraviolet absorbing monomer include benzotriazole compounds, benzophenone compounds or triazine compounds and acrylic monomers having a polymerizable unsaturated group. Examples of benzotriazole compounds include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethyl. Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyhexyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′ -(Β- (Meth) acryloyloxyethoxy) -3'-tert-butylphenyl] -5-te rt-butyl-2H-benzotriazole and the like can be used. Examples of the benzophenone compounds include 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, 2,2 ′. -Dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 '-(2-hydroxyethoxy) benzophenone, and the like can be used. . Examples of the triazine compound include 4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methylphenyl) -6- [2-Hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]- An s-triazine or the like can be used. When such an ultraviolet absorbing monomer is used, it is preferably 0.1 to 25% by weight of the total monomer, more preferably 1 to 15% by weight. . If the content is small, the contribution to improving the weather resistance is low, and if the content is too large, the hot water resistance and solvent resistance may decrease or yellowing may occur.
As the UV-stable monomer, a monomer having a polymerizable unsaturated group bonded to a hindered amine compound can be used, and specific examples include 4- (meth) acryloyloxy-2,2,6,6. -Tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- ( (Meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2 , 2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (me ) Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl -4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like. In the case of using such an ultraviolet stable monomer, it is preferably copolymerized in an amount of 0.1 to 25% by weight, more preferably 1 to 15% by weight of all monomers. . If the content is small, the contribution to improving the weather resistance is low, and if the content is too large, the hot water resistance and solvent resistance may decrease or yellowing may occur.
Examples of the ultraviolet absorber include benzophenone compounds, salicinate compounds, benzoate compounds, and triazole compounds. Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 4-n-octyloxy-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-n-octyl. Examples thereof include oxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 1,4-bis (4-benzoyl-3-hydroxyphenone) -butane and the like. Examples of the silicate compound include pt-butylphenyl silicate. Examples of the benzoate compound include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate. Examples of triazole compounds include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (3 , 5-Di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2- [5-chloro (2H) -benzotriazole- 2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-butylphenol Enol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6 -(3,4,5,6-tetrahydrophthalimidylmethyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction products, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 3- (2H-benzo Triazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-C7-9 side chain and straight chain alkyl esters. Further, triazine compounds include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl)- 1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyethoxy) -1,3,5-triazine, 2,4-bis “2-hydroxy-4-butoxyphenyl” And -6- (2,4-dibutoxyphenyl) -1,3-5-triazine. Among them, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-alkyloxy-2) is highly compatible with heat-resistant acrylic resins and has excellent absorption characteristics. -Hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine skeleton (alkyloxy; long-chain alkyloxy groups such as octyloxy, nonyloxy, decyloxy, etc.) is more preferred, and is represented by the following formula (2): An ultraviolet absorber containing as a main component an ultraviolet absorber having the structure represented is particularly preferred. Examples of commercially available products include Tinuvin 477 (manufactured by Ciba Specialty Chemicals Co., Ltd.).

These can be used alone or in combination of two or more. Although the compounding quantity of the said ultraviolet absorber is not specifically limited, It is preferable that it is 0.01-25 weight% in the layer which has a heat-resistant acrylic resin as a main component, More preferably, it is 0.05-10 weight%. If the amount added is too small, the contribution to improving the weather resistance is low, and if it is too large, the mechanical strength may be lowered or yellowing may be caused.
The layer mainly composed of the heat-resistant acrylic resin in the present invention can contain other various additives and other resins as necessary within a range not impairing the effects of the present invention. However, even in that case, the proportion of the heat-resistant acrylic resin in the layer containing the heat-resistant acrylic resin in the present invention is preferably in the range of 50-100% by weight, more preferably in the range of 75-100% by weight, and 90-100% by weight. % Range is more preferred.
Examples of other resin components include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, and poly (4-methyl-1-pentene); halogen-containing polymers such as vinyl chloride and chlorinated vinyl resins; Acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer; polyethylene terephthalate, polybutylene terephthalate, Polyester such as polyethylene naphthalate; biodegradable polyester such as polylactic acid and polybutylene succinate; polyamide such as nylon 6, nylon 66, nylon 610; polyacetal: polycarbonate Polyphenylene oxide; Polyphenylene sulfide: Polyether ether ketone; Polysulfone; Polyether sulfone: Polyoxypentylene; Polyamideimide; Rubber polymer such as ABS resin and ASA resin blended with polybutadiene rubber and acrylic rubber; Can be mentioned. From the viewpoint of compatibility, a styrene-acrylonitrile copolymer is preferable. Further, the rubbery polymer preferably has a graft portion having a composition compatible with the lactone ring- containing polymer of the present invention on the surface, and the average particle diameter of the rubbery polymer is an extruded film. From the viewpoint of improving the transparency, the thickness is preferably 100 nm or less, and more preferably 70 nm or less.

The heat-resistant acrylic resin according to the present invention may contain other additives. The content of other additives in the heat-resistant acrylic resin according to the present invention is preferably 0 to 5% by weight, more preferably 0 to 2% by weight, and still more preferably 0 to 0.5% by weight. Other additives include, for example, hindered phenol-based, phosphorus-based, sulfur-based antioxidants; light stabilizers, weather stabilizers, heat stabilizers, and other stabilizers: reinforcing materials such as glass fibers and carbon fibers. : Near-infrared absorbers; flame retardants such as tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide; antistatic agents such as anionic, cationic and nonionic surfactants; inorganic pigments, organic pigments, dyes, etc. Organic fillers and inorganic fillers: resin modifiers; organic fillers and inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants;
A known antioxidant can be used as the antioxidant. Examples of phenolic antioxidants include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, n-octadecyl-3- (3,5-di-t-butyl). -4-hydroxyphenyl) acetate, n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl-3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, neododecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl-β- (3,5-di- t-butyl-4-hydroxyphenyl) propionate, ethyl-α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate Octadecyl-α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n-octylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (n-octylthio) ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2 -(N-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2-hydroxyethylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5 -Di-t-butyl-4-hydroxy-phenyl) propionate, 2- (n-octadecylthio) ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide-N, N -Bis- [ethylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino-N, N-bis- [ethylene-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2- (2-stearoyloxyethylthio) ethyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl- 7- (3-Methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), glycerin-1-n-octadecanoate- 2,3-bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) Propionate], 1,1,1-trimethylolethanetris- [3- (3,5-di-tert-butyl-4-hydroxypheny ) Propionate], sorbitol hexa- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl-7- (3-methyl-5-tert-butyl-4-hydroxy Phenyl) propionate, 2-stearoyloxyethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol bis-[(3 ', 5'-di- t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis- (3,5-di-t-butyl-4-hydroxyhydrocinnamate), 3,9-bis [1,1-dimethyl-2- [ [beta]-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetrao Saspiro [5,5] -undecane, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and 2-t-butyl -6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.

  Examples of the thioether-based antioxidant include pentaerythrityl tetrakis (3-laurylthiopropionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl. -3,3'-thiodipropionate.

Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d. , F] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [D, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] ethanamine, diphenyltridecyl phosphite, triphenyl phosphite, 2,2-methylenebis (4,6- Di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite DOO, cyclic neopentanetetraylbis (2,6-di -t- butyl-4-methylphenyl) phosphite and the like.
The heat-resistant acrylic resin according to the present invention is preferably a polymer containing a ring structure in the main chain, and a so-called lactone ring containing a (meth) acrylate copolymer by introducing a lactone ring structure by intramolecular cyclization reaction. The use of a polymer is most effective.
Regarding the lactone ring structure in the main chain, a 4- to 8-membered ring may be used, but a 5- to 6-membered ring is more preferable, and a 6-membered ring is more preferable in terms of stability of the structure. Moreover, when the lactone ring structure in the main chain is a 6-membered ring, examples include the structure represented by the general formula (1) and Japanese Patent Application Laid-Open No. 2004-168882, and the lactone ring structure is introduced into the main chain. In synthesizing the previous polymer, it has a high polymerization yield, a polymer having a high content of lactone ring structure, and a copolymer with (meth) acrylate such as methyl methacrylate. In terms of good points, the structure represented by the general formula (1) is preferable.

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
As a method for producing a heat-resistant acrylic resin containing a lactone ring structure, a known production method can be applied. For example, it can be manufactured by the manufacturing method described in JP-A-2006-96960, JP-A-2006-171464, or JP-A-2007-63541.

  The content of the lactone ring structure in the lactone ring-containing polymer is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, still more preferably 10 to 60% by weight, and particularly preferably 10 to 50% by weight. . If the content of the lactone ring structure represented by the above formula (1) is less than 5% by weight, the heat resistance, solvent resistance and surface hardness may be insufficient, which is not preferable.

  The lactone ring-containing polymer preferably has a weight loss rate of 150 to 300 ° C. in dynamic TG measurement of 1% by weight or less, more preferably 0.5% by weight or more, and still more preferably 0.3% by weight. % Or less.

  Since the lactone ring-containing polymer has a high cyclization condensation reaction rate, it is possible to avoid the disadvantage that bubbles and silver streaks enter the molded product after molding. Furthermore, since the lactone ring structure is sufficiently introduced into the polymer due to a high cyclization condensation reaction rate, the obtained lactone ring-containing polymer has sufficiently high heat resistance.

The glass transition temperature (Tg) of the lactone ring-containing polymer is preferably 110 ° C. or higher, more preferably 115 ° C. or higher, further preferably 120 ° C. or higher, more preferably 125 ° C. or higher, and most preferably 130 ° C. or higher. . Here, the glass transition temperature is as described above.
<Hard coat layer>
In this invention, a hard-coat layer (C) means what shows hardness more than "H" by the pencil hardness test prescribed | regulated by JISK5600-5-4 (1999). In the present invention, the hard coat layer (C) includes any form such as a hard coat film, a hard coat plate, and a hard coat film. The hard coat layer has a thickness (at the time of curing) of 2 to 10 μm, preferably 3 to 8 μm, more preferably 4 to 7 μm. If the thickness is less than 2 μm, the scratch resistance and pencil hardness may not be sufficiently exhibited. If the thickness exceeds 10 μm, the hard coat may have poor crack resistance.
The hard coat layer is a coating solution in which an acrylate such as a silicone-based curable resin, a curable resin containing organic polymer composite inorganic fine particles, urethane acrylate, epoxy acrylate, polyfunctional acrylate, and a photopolymerization initiator are dissolved or dispersed in an organic solvent. It is formed by applying, drying, and photocuring by a conventionally known coating method so that it is preferably positioned on the outermost layer of the optical planar thermoplastic resin molding of the present invention. Silicone-based curable resins are resins with siloxane bonds, for example, hydrolyzing trialkoxysilanes and tetraalkoxysilanes or their partial hydrolysates, methyltrialkoxysilanes and phenyltrialkoxysilanes. And partially hydrolyzed condensates of colloidal silica-filled organotrialkoxysilanes. Examples of commercially available products include “Si Coat 2” (manufactured by Eighth Chemical Co., Ltd.), “Tosguard 510”, “UVHC8553” (manufactured by Toshiba Silicone), “Solgard NP720”, “Solgard NP730” and “Solgard RF0831”. (Above, manufactured by Nippon Dacro Shamrock Co., Ltd.). The organic polymer composite inorganic fine particles mean composite inorganic fine particles in which an organic polymer is fixed on the surface of the inorganic fine particles. By forming a surface protective layer with a curable resin containing the fine particles, the surface hardness is improved. Is planned. The details of the composite inorganic fine particles and the production method thereof are described in, for example, JP-A-7-178335, JP-A-9-302257, JP-A-11-124467. The curable resin containing the composite inorganic fine particles is not particularly limited, and examples thereof include melamine resin, urethane resin, alkyd resin, acrylic resin, and polyfunctional acrylic resin. Examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate. As a commercial item of curable resin containing the said composite inorganic fine particle, "Udable C-3300", "Udable C-3600" (above, Nippon Shokubai Co., Ltd. product) etc. are mentioned, for example.
As an example of a hard coating agent that is cured using active energy rays, a monofunctional or polyfunctional acrylate monomer or oligomer, a trifunctional or higher resin composition such as a urethane acrylate resin, or photopolymerization as a curing catalyst. Examples thereof include a resin composition to which an initiator is added.
Examples of the thermosetting resin include polyorganosiloxane and cross-linked acrylic resins. Some of such resin compositions are commercially available as hard coating agents for acrylic resins, and may be appropriately selected in consideration of suitability with the coating line.
These hard coat agents include various stabilizers such as an appropriate monofunctional polymerizable monomer, ultraviolet absorber, light stabilizer, antioxidant, leveling agent, antifoaming agent, as well as an organic solvent, if necessary. Surfactants such as thickeners, lubricants, antistatic agents, antifouling agents, antifogging agents, and antiglare agents may be added as appropriate. Various coating layers can be provided on the surface of the hard coat layer, and antistatic properties, antifouling properties, slip properties, antiglare properties, and antireflection properties can be imparted.
Addition of the antistatic agent can effectively prevent dust adhesion on the surface of the optical laminate. Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonates, amphoteric compounds such as amino acids and aminosulfate esters, nonionic compounds such as amino alcohols, glycerols and polyethylene glycols, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group, or a metal chelate portion and polymerizable by ionizing radiation, or an organometallic compound such as a coupling agent having a functional group, etc. Polymerizable compounds can also be used as antistatic agents.
Examples of the antistatic agent include conductive fine particles. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The fine particles refer to those having a so-called submicron size of 1 micron or less, and preferably those having an average particle size of 0.1 nm to 0.1 μm.
Examples of the antistatic agent include conductive polymers. Specific examples thereof include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, Examples include atomic conjugated polyaniline and mixed conjugated poly (phenylene vinylene). In addition to these, a double-chain conjugated system having a plurality of conjugated chains in the molecule, the conjugated polymer chain described above Examples thereof include a conductive composite which is a polymer grafted or block co-polymerized on a saturated polymer.
The addition amount of the antistatic agent can be appropriately determined. For example, it is 0.01 part by weight or more and 50 parts by weight or less with respect to the total amount of the hard coat layer composition, and preferably the lower limit is 0.1 part by weight. The upper limit is 25 parts by weight or less.
The antiglare agent includes fine particles, and the shape thereof may be a true sphere or an ellipse, preferably a true sphere. The fine particles include inorganic and organic particles. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include silica beads for inorganic systems, and plastic beads for organic systems, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads.
When the antiglare agent is added, it is preferable to add an antisettling agent. This is because by adding an anti-settling agent, precipitation of the resin beads can be suppressed and the resin beads can be uniformly dispersed in the solvent. Specific examples of the anti-settling agent include silica beads and polyethylene beads having a particle size of 0.5 μm or less, preferably about 0.1 to 0.25 μm.
The addition amount of the antiglare agent can be appropriately determined. For example, it is 0.001 part by weight or more and 75 parts by weight or less, preferably 0.01 part by weight based on the total amount of the composition for hard coat layer. The upper limit is 50 parts by weight or less.
The antifouling agent is mainly intended to prevent the outermost surface of the optical laminate from being stained, and can further impart scratch resistance to the optical laminate. Specific examples of the antifouling agent include a fluorine compound, a silicone compound, or a mixed compound thereof. Moreover, it does not ask | require whether antifouling agent itself has a reactive group.
As the antifouling agent for fluorine-based compounds, monomers such as fluorine-containing silane compounds and fluorine-containing organic acid salts (perfluorosulfonate, perfluorosulfonate, etc.), oligomers, polymers, and the like can be used. As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain {for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.}, even branched structures {eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.}, an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, May be a perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C ₄ F). ₈ H, -CH _{CH 2 OCH 2 CH 2 C 8} F 17, -CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.
Although there is no restriction | limiting in particular in fluorine atom content in a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. . Examples of preferred fluorine-based compounds include R-2020, M-2020, R-3833, M-3833 manufactured by Daikin Industries, Ltd .; Megafac F-171, Megafac manufactured by Dainippon Ink and Chemicals, Inc. Examples include, but are not limited to, F-172, Megafuck F-179A, and Defender MCF-300.

Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of the compound chain, which contains a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.
The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done.
The molecular weight of the silicone compound is not particularly limited, but is preferably 100,000 or less, particularly preferably 50,000 or less, and most preferably 3,000 to 30,000.
Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37. Most preferably, it is 0 mass%.
Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D manufactured by Shin-Etsu Chemical Co., Ltd. X-22-1821; FM-0725, FM-7725, FM-4421, FM-5521, FM-6621, FM-1121 manufactured by Chisso Corporation; DMS-U22, RMS-033, RMS- manufactured by Gelest 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221, and the like, but are not limited thereto.
Furthermore, specific examples of the antifouling agent having no reactive group include Megafac series manufactured by Dainippon Ink, for example, MCF350-5, F445, F455, F178, F470, F475, F479, F477, TF1025, F478, FSFK, etc .; TSF series manufactured by Toshiba Silicone, Inc .; X22 series, KF series manufactured by Shin-Etsu Chemical Co., Ltd., and Silaplane series manufactured by Chisso Corporation, etc. are included.
Specific examples of the antifouling agent having a reactive group include SUA1900L10 (weight average molecular weight 4200; manufactured by Shin-Nakamura Chemical Co., Ltd.), SUA1900L6 (weight average molecular weight 2470; manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel UCB), UT3971 (manufactured by Nihon Gosei Co., Ltd.), Defensor TF3004 (manufactured by Dainippon Ink, Inc.), Defensor TF3000 (manufactured by Dainippon Ink, Inc.), Defensor TF3028 (manufactured by Dainippon Ink, Inc.), KRM7039 (manufactured by Daicel UCB), Light Procoat AFC3000 (manufactured by Kyoeisha Chemical), KNS5300 (manufactured by Shin-Etsu Silicone), UVHC1105 (manufactured by GE Toshiba Silicone), UVHC8550 (manufactured by GE Toshiba Silicone), Ebecryl 350 (manufactured by Daicel UCB), ACS-11 22 (made by Nippon Paint Co., Ltd.).
When the antifouling agent is an organic compound, the number average molecular weight is not limited, but is 500 or more and 100,000 or less, preferably the lower limit is 750 or more, more preferably 1000 or more, and preferably the upper limit is 70,000. Or less, more preferably 50,000 or less.
According to a preferred embodiment of the present invention, the antifouling agent comprises a polyfunctional acrylate having two or more functional groups containing a polyorganosiloxane group, a polyorganosiloxane-containing graft polymer, a polyorganosiloxane-containing block polymer, a fluorinated alkyl group, and the like. Is preferred. As a polyfunctional acrylate, for example, as a bifunctional acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butane Diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, pro Xylated neopentyl glycol di (meth) acrylate, pentaerythritol diacrylate monostearate, isocyanuric acid ethoxy modified di (meth) acrylate (isocyanuric acid EO modified di (meth) acrylate), bifunctional urethane acrylate, bifunctional polyester acrylate, etc. Is mentioned. Trifunctional acrylates include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ethoxylated trimethylolpropane tri Examples include (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, and trifunctional polyester acrylate. Examples of the tetrafunctional acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate. Examples of the pentafunctional or higher acrylate include dipentaerythritol hydroxypenta (meth) acrylate and dipentaerythritol hexaacrylate.
The addition amount of the antifouling agent can be appropriately determined, but is 0.001 part by weight or more and 90 parts by weight or less with respect to the total weight of the composition forming the hard coat layer, and preferably the lower limit is 0.01 part by weight. Part or more, more preferably 0.1 part by weight or more, preferably the upper limit is 70 parts by weight or less, more preferably 50 parts by weight or less. It is preferable that the addition amount of the antifouling agent is within the above range since a sufficient antifouling function is exhibited and the optical laminate has hardness.
<Antireflection layer>
In the present invention, the antireflection layer (D) is for suppressing reflection of the surface and preventing reflection of external light such as a fluorescent lamp on the surface. The antireflection layer has a refractive index different from that of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide, such as an acrylic resin, a fluororesin, or an organosilicon compound. In some cases, the organic material is made of a single layer or multiple layers. Moreover, what laminated | stacked the thin film containing the composite fine particle of an inorganic type compound and an organic type compound as disclosed by Unexamined-Japanese-Patent No. 2003-292805 can also be used. It is also a preferable form to alternately stack low refractive index materials typified by silicon oxide and magnesium fluoride and high refractive index materials such as titanium oxide, acid value zirconium, zinc oxide, yttrium oxide, tin oxide and ITO. One.
The antireflection layer is preferably laminated on the hard coat layer. When the antireflection layer is a single layer, the thickness is preferably 0.005 μm to 1 μm, more preferably 0.01 μm to 0.5 μm. Such a single antireflection layer has a refractive index smaller than that of the hard coat layer, and preferably has a refractive index of 1.30 to 1.45. Moreover, when laminating | stacking in a multilayer, each layer of 0.005 micrometer-1 micrometer, More preferably, 0.01 micrometer-0.5 micrometer thickness can be laminated | stacked to a required number of layers according to an optical characteristic.
If necessary, as in the case of the hard coat layer, an appropriate monofunctional polymerizable monomer, ultraviolet absorber, and light stabilizer in addition to an organic solvent as a coating agent for the antireflection layer (low reflection layer). Add various stabilizers such as antioxidants, leveling agents, antifoaming agents, thickeners, lubricants, antistatic agents, antifouling agents, antifogging agents, antiglare agents and other surfactants as appropriate. Also good. Furthermore, various coating layers can be provided on the surface of the antireflection layer, and antistatic properties, antifouling properties, slip properties, antiglare properties, and scratch resistance can be imparted.
<Laminated plate>
The laminate of the present invention includes a polycarbonate resin layer (A), a heat-resistant acrylic resin layer (B), a hard coat layer (C), and an antireflection layer (D). Originally, for that purpose, it is necessary to arrange the heat-resistant acrylic resin layer (B), the hard coat layer (C) and the antireflection layer (D) in this order on at least one side of the polycarbonate resin (A).
As a specific configuration of the laminated plate, from the surface, (D) / (C) / (B) / (A), (D) / (C) / (B) / (A) / (C), ( D) / (C) / (B) / (A) / (B), (D) / (C) / (B) / (A) / (B) / (C) are listed as typical configurations. . The configuration of (D) / (C) / (B) / (A) is the basic configuration with the least number of layers and thickness, but (D) / (C) / (B) / (A) / ( B), (D) / (C) / (B) / (A) / (B) / (C) has a more symmetric configuration, and therefore occurs during and after molding. It is difficult for the laminate to warp.
The total thickness of the laminated board in this invention is 0.5-2 mm, Preferably it is 0.7-1.7 mm, More preferably, it is 0.8-1.5 mm. If the total thickness is less than 0.5 mm, the impact properties and rigidity as a protective plate may not be maintained, and if it exceeds 2 mm, optical characteristics such as light transmittance may be inferior.
The heat-resistant acrylic resin layer (B) has a thickness in the range of 20 to 200 μm, preferably in the range of 20 to 150 μm, and more preferably in the range of 40 to 120 μm. If it is less than 20 μm, the scratch resistance and pencil hardness of the laminate may be lowered, and if it exceeds 200 μm, the impact resistance of the laminate surface may be inferior.
The thickness of the hard coat layer (C) is 2 to 10 μm, preferably 3 to 8 μm, more preferably 4 to 7 μm. If the thickness is less than 2 μm, the scratch resistance and pencil hardness may not be sufficiently exhibited. If the thickness exceeds 10 μm, the hard coat may have poor crack resistance.
When the antireflection layer is a single layer, the thickness of the antireflection layer (D) is preferably 0.005 μm to 1 μm, and more preferably 0.01 μm to 0.5 μm. Moreover, when laminating | stacking in a multilayer, each layer of 0.005 micrometer-1 micrometer, More preferably, 0.01 micrometer-0.5 micrometer thickness can be laminated | stacked to a required number of layers according to an optical characteristic.
In the laminated board of this invention, it is preferable that the total light transmittance measured by the method according to ASTM-D-1003 is 88% or more, More preferably, it is 90%, Most preferably, it is 92%. The total light transmittance is a measure of transparency, and if it is less than 88%, the transparency is lowered and may not be used for the intended purpose. Furthermore, in the case of making a laminate having the above transparency, the haze value measured by a method according to ASTM-D-1003 is 1.5% or less, preferably 1.0% or less, more preferably 0.5% or less. The haze value is a measure of transparency, and if it exceeds 1.5%, the transparency is lowered and may not be used for the intended purpose.
In order to ensure the optical uniformity of the laminate of the present invention, the arithmetic average roughness Ra of the surface of the substrate laminate (I) obtained by co-extrusion of polycarbonate resin and heat-resistant acrylic resin is 0.5 μm. It is preferable that the thickness be less than 0.3, more preferably 0.3 μm or less, and most preferably 0.2 μm or less.
The laminated board in the present invention has a surface hardness of 4H or more, preferably 5H or more, more preferably 6H or more, as defined by JIS K5600-5-4.
The laminated board in this invention has steel wool resistance. Steel wool resistance means that there is no damage when # 0000 steel wool is rubbed 10 times with a constant load. Preferably, the load is 700 g and there is no damage, more preferably the load is 1000 g and there is no damage, more preferably the load is 1500 g and there is no damage, and most preferably the load is 2000 g and there is no damage. It is.
In the laminate of the present invention, the adhesion between the heat-resistant acrylic resin layer (B) and the hard coat layer (C), or the hard coat layer (C) and the antireflection layer (D) is JIS K5600-5-6 (1999). In the cross-cut method based on the above, it is preferable that, among the 100 squares, the squares that have not been peeled are 95/100 or more, more preferably 97/100 or more, still more preferably 99/100 or more, Preferably it is 100/100 and there is no peeling.
There is no restriction | limiting in particular as a method of laminating | stacking the polycarbonate resin layer (A) in the laminated board of this invention, and a heat-resistant acrylic resin layer (B), A general method is employable. For example, a method in which each layer is separately formed into a sheet or film and then heated and pressure-bonded, a method in which an adhesive resin is applied in advance to at least one of the surfaces and bonded, and the polycarbonate resin and the heat-resistant material in an extruder die Examples include a co-extrusion molding method in which an acrylic resin is laminated to obtain a sheet or a sheet-like material, an in-mold molding method in which a heat-resistant acrylic resin is previously vacuum-formed and then a polycarbonate resin as a base material is injection-molded. . In order to reduce costs and improve productivity, a coextrusion molding method and an in-mold molding method are preferable. In particular, when obtaining a sheet-like or film-like laminate, a coextrusion molding method is preferred from the viewpoint of cost and productivity.
As a method of laminating the hard coat layer, a method of forming a hard coat layer after laminating the polycarbonate resin layer (A) and the heat resistant acrylic resin layer (B), or a hard coat layer on the heat resistant acrylic resin layer (B). After forming, a method of laminating with the polycarbonate resin layer (A) is possible. There are no particular restrictions on the method of laminating the hard coat layer. For example, spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing Method, bead coating method and the like can be used.
<Method of forming laminate>
In the method for producing a laminate according to the present invention, the hard coat layer (C) is formed on at least one surface of the base laminate (I) obtained by co-extrusion of a polycarbonate resin and a heat-resistant acrylic resin, and further the hard coat layer A production method in which the antireflection layer (D) is formed on the surface of (C) is preferred.
The substrate laminate (I) in which the heat-resistant acrylic resin layer (B) is laminated on at least one surface of the polycarbonate resin layer (A) is preferably produced by the following coextrusion. That is, it is constituted by one main extruder for extruding polycarbonate resin and a sub-extruder for extruding acrylic resin constituting the coating layer, and the sub-extruder is usually smaller than the main extruder. The temperature condition of the main extruder is usually 230 to 300 ° C, preferably 250 to 290 ° C, and the temperature condition of the sub-extruder is usually 220 to 290 ° C, preferably 240 to 280 ° C. Moreover, it is preferable to install a mesh, a polymer filter, etc. upstream from the T die of the extruder in order to remove foreign substances in the resin.

As a method for laminating the polycarbonate resin layer (A) and the heat-resistant acrylic resin layer (B), a known method such as a feed block method or a multi-manifold method can be used. In this case, each resin introduced by the extruder is introduced into the feed block and laminated, then guided to a sheet forming die such as a T die, and formed into a sheet shape, and then the surface is subjected to mirror finishing. A bank is formed by flowing into a roll (polishing roll). This sheet-like molded product is mirror-finished and cooled while passing through the molding roll, thereby forming a laminate. In the case of a multi-manifold die, after being formed into a sheet shape inside the die, surface finishing and cooling are performed with a forming roll to form a laminated plate.
A multi-manifold die is more preferable in consideration of the appearance of the laminate, particularly the smoothness of the interface between the polycarbonate resin layer (A) and the heat-resistant acrylic resin layer (B).
The forming roll is composed of three pieces, and the sheet-like molded product coextruded from the T-die is first guided to the gap between the first roll and the second roll, and then guided to the third roll while contacting the surface of the second roll. It is burned. Subsequently, after the sheet-like molded article passes through the gap between the second roll and the third roll, the sheet-like molded article proceeds while contacting the surface of the third roll, and molding is performed. As the roll, a vertical roll or a horizontal roll can be appropriately used.
The temperature of these rolls is usually 80 to 190 ° C, preferably 90 to 180 ° C. The first roll is more preferably an elastic roll. This is because the surface smoothness and thickness unevenness of the laminate (I) are improved by using the first roll as an elastic roll.
Moreover, it is preferable to control the contact time with the third roll to be shorter than the contact time with the second roll by changing the contact time of the sheet-like molded product with the second roll and the third roll.
When Tg of heat-resistant acrylic resin is low compared to polycarbonate resin and due to differences in melt viscosity, it is possible to achieve both molding stability and appearance of laminated board (I) such as warp and swell only by controlling the temperature of each roll. This is because it may be difficult. That is, in the process where the sheet-like molded product is cooled as it passes through each roll, if the heat-resistant acrylic resin as the surface layer resin is not sufficiently cooled, the roll may be wound and cannot be produced. If it is too large, warping and undulation of the obtained laminate may occur.
The obtained base laminate (I) can be increased in strength by stretching. The process and timing of stretching are not particularly limited, but it is preferable to perform the stretching process after the formation of the laminated sheet-shaped product in the coextrusion molding process, and to control the temperature of the substrate and the productivity. Excellent.
As a method for laminating the hard coat layer (C) in the present invention, the hard coat layer (C) is formed on at least one surface of the base laminate (I) obtained by co-extrusion of a polycarbonate resin and a heat-resistant acrylic resin. A lamination method is preferred.
As a method for laminating the hard coat layer (C), a method of applying a hard coat agent to a resin layer or a substrate laminate, and drying and curing as required is preferable. There are no particular restrictions on the method of applying the hard coating agent. For example, spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, flow coating, meniscus coating, flexo A printing method, a screen printing method, a bead coating method, or the like can be used.
Before applying the hard coating agent for the purpose of improving adhesion, surface treatment may be applied to one or both sides of the base material (I) on which the polycarbonate resin layer (A) and the heat-resistant acrylic resin layer (B) are laminated. it can. Specific examples of the surface treatment include sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment, primer treatment with a resin composition, etc. As a lamination method of D), the antireflection layer (C) is formed on the surface of the hard coat layer (C) formed on at least one surface of the base laminate (I) obtained by coextrusion of a polycarbonate resin and a heat-resistant acrylic resin. The production method obtained by forming D) is preferred.
Examples of the method for forming the antireflection layer include a method of wet coating or dry coating (evaporation or sputtering) and a method of laminating an antireflection film.
The wet coat is used when organic materials such as a fluorine resin having a low refractive index, an organic silicon compound, and an acrylic resin are mainly laminated in a single layer or multiple layers. It is also possible to form a film by a paint or sol-gel method in which a metal oxide is made into fine particles and dispersed in a binder. Similar to the method of laminating the hard coat layer (C), a method of applying a coating agent, and drying and curing as necessary is preferable. There are no particular restrictions on the coating method, for example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, flow coating method, meniscus coating method, flexographic printing method, screen The organic material that can be used for printing, bead coating, and the like is usually applied after being diluted in a volatile solvent. In consideration of stability of the composition, wettability to the hard coat layer (4), volatility, etc., alcohols such as methanol, ethanol, isopropanol, butanol, 2-methoxyethanol, acetone , Ketones such as methyl ethyl ketone and methyl isobutyl, esters such as methyl acetate, ethyl acetate and butyl acetate, ethers such as diisopropyl ether, glycols such as ethylene glycol, propylene glycol and hexylene glycol, ethyl cellosolve, butyl cellosolve, ethyl Glycol ethers such as carbitol and butyl carbitol, aliphatic hydrocarbons such as hexane, heptane and octane, halogenated hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, N-methylpyrrolidone Dimethylformamide and the like. You may use these individually or in combination of 2 or more types.
Dry coating is mainly made of inorganic materials such as low refractive index materials such as silicon oxide and magnesium fluoride, and high refractive index materials such as titanium oxide, acid value zirconium, zinc oxide, yttrium oxide, tin oxide and ITO. Used in the case of laminating a single layer or multiple layers, examples include vapor deposition methods such as vacuum deposition, reactive deposition, ion beam deposition, sputtering, ion plating, and plasma CVD.
Each material of the polycarbonate resin layer (A), the heat-resistant acrylic resin layer (B), the hard coat layer (C), and the antireflection layer (D) in the present invention may be filtered and purified by filtering as necessary. preferable. By forming and further laminating each layer using the filtered and refined material, a laminate with few foreign matters and defects can be obtained. The filtration method is not particularly limited, and melt filtration, solution filtration, or a combination thereof can be used.
The filter to be used is not particularly limited, and known filters can be used, and are appropriately selected depending on the use temperature, viscosity, and filtration accuracy of each material. The filter material of the filter is not particularly limited, but polypropylene, cotton, polyester, viscose rayon, non-woven fabric such as glass fiber or roving yarn roll, phenol resin impregnated cellulose, metal fiber nonwoven fabric sintered body, metal powder sintered body Any of a type in which a plurality of wire meshes are laminated or a hybrid type in which they are combined can be used. Among these, a type in which a metal fiber nonwoven fabric is sintered is preferable from the viewpoints of heat resistance, durability, and pressure resistance.
Filtration accuracy is 50 μm or less, preferably 30 μm or less, more preferably 10 μm or less, and most preferably 5 μm or less for the polycarbonate resin and heat-resistant acrylic resin used. The filtration accuracy of the hard coat agent is 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less, and most preferably 3 μm or less because it comes to the outermost surface of the laminate.
About filtration of each material of a polycarbonate resin layer (A) and a heat-resistant acrylic resin layer (B), it is preferable to process with the polymer filter currently used for the melt filtration of a thermoplastic resin, for example. The polymer filter can be classified into a leaf disk filter, a candle filter, a pack disk filter, a cylindrical filter, and the like depending on its structure. Among them, a leaf disk filter having a high effective filtration area is preferable.
<Application>
Since the laminate of the present invention combines optical properties, high surface hardness (scratch resistance), mechanical strength and impact resistance, covers such as vending machine covers and lighting covers, signboards, roads Civil engineering and building materials such as translucent plates, sound barriers, daylighting plates, road shelters, carports, architectural glazing materials, various vehicle glazing materials, bathtub materials, automotive interior parts, vehicle exteriors such as garnish, various types It can be suitably used for household goods sheets, packaging materials for foods and pharmaceuticals, and the like. Moreover, it can be used as a front plate for a display device of a liquid crystal display, an organic EL display, or a plasma display, and is particularly suitable for a liquid crystal display or an organic EL display used for a personal computer, a game machine, a PDA, or a portable terminal device. be able to.

EXAMPLES The present invention will be described in further detail below with reference to examples, but the present invention is not limited thereto. The measurement and evaluation of various physical properties in Examples and Comparative Examples were performed by the following methods.
<Pencil hardness>
In accordance with JIS K5600-5-4, measurement was performed on a sample (surface on the antireflection layer side when the antireflection layer was laminated) with a load of 750 g.
<Abrasion resistance>
Press # 0000 steel wool with a constant load against the sample (the surface on the side of the anti-reflection layer when an anti-reflection layer is laminated), and visually observe the surface after reciprocating a predetermined number of times with a stroke width of 25 mm and 30 mm / sec. A was classified into 0 scratches, B was 1 to 10 scratches, and C was 11 or more scratches. Steel wool was gathered to a diameter of about 10 mm, and was cut and rubbed so as to have a uniform surface.
<Adhesion>
In accordance with JIS K5600-5-6, a sample (surface on the side of the antireflection layer when the antireflection layer is laminated) was tested, and the hard coat layer and the antireflection layer were not peeled off. I counted the number.
<Glass transition temperature>
The thermal analysis of the resin was performed using DSC (manufactured by Rigaku Corporation, apparatus name: DSC-8230) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min and a nitrogen flow of 50 cc / min. The glass transition temperature (Tg) was determined by the midpoint method according to ASTM-D-3418.
<Antireflection>
A laminated plate is installed in front of the liquid crystal display device. The liquid crystal display has good visibility without the influence of external light reflection, and the liquid crystal display has poor visibility due to the reflection of external light. Was visually evaluated as x.
<Dynamic TG>
The resin (or polymer solution or pellet) is once dissolved or diluted in tetrahydrofuran, poured into excess hexane or methanol for reprecipitation, and the taken out precipitate is vacuum dried (1 mmHg (1.33 hPa), 80 ° C., Volatile components and the like were removed by conducting the reaction for 3 hours or more, and the obtained white solid resin was analyzed by the following method (dynamic TG method).
Measuring apparatus: Thermo Plus2 TG-8120 Dynamic TG (manufactured by Rigaku Corporation)
Measurement conditions: Sample amount 5 to 10 mg
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen flow 200ml / min
Method: Step-like isothermal control method (controlled at a weight reduction rate value of 0.005% / sec or less between 60 ° C and 500 ° C)
<Measurement of volatile content in polymer>
The amount of residual volatile components contained in the resin was measured using gas chromatography (manufactured by Shimadzu Corporation, apparatus name: GC-14A).
<Measurement of the number of foreign objects>
The molded product was dissolved in a chloroform solution purified to 20 wt%, suctioned with a Teflon filter having a diameter of 47 mm and a filtration accuracy of 1 μm, and foreign matters remaining on the Teflon filter were visually measured under a microscope. The foreign matter of 20 μm or more means a foreign matter having the largest foreign matter diameter of 20 μm or more.
[Production Example 1] (Production of heat-resistant acrylic resin)
In a 30 L capacity reactor equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introduction pipe, 8,000 g of methyl methacrylate (MMA) and 2,000 g of methyl 2- (hydroxymethyl) methyl acrylate (MHMA) were added. ) 10,000 g of toluene was charged, and the temperature was raised to 105 ° C. while refluxing nitrogen. When refluxed, 10.0 g of t-amylperoxyisononanoate (Lupazole 570, Atofina Yoshitomi ( At the same time, a solution consisting of 20.0 g of t-amylperoxyisononanoate and 100 g of toluene was added dropwise over 2 hours while solution polymerization was carried out at about 105 to 110 ° C. under reflux. Aged for another 4 hours.

  To the obtained polymer solution, 10 g of stearyl phosphate / distearyl phosphate mixture (Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) was added and cyclized at about 90-110 ° C. for 5 hours under reflux. A condensation reaction was performed to produce a polymer solution (a-1).

  Next, in a vent type screw twin screw extruder equipped with a leaf disk type polymer filter (5 inches, 5 sheets, manufactured by Nagase Sangyo) with a filtration accuracy of 5 μm and a gear pump, with a rear vent number of 1 and a fore vent number of 4, The polymer (thermoplastic resin) solution (a-1) was introduced at a treatment rate of 2.0 kg / h in terms of the amount of resin, and devolatilization treatment and polymer filter treatment were performed simultaneously. In the above treatment, zinc octylate (18% Nikka octix zinc, manufactured by Nippon Kagaku Sangyo Co., Ltd.) is used as a foaming inhibitor (deactivator) between the third and fourth forvents. And an antioxidant, Irganox 1010 (manufactured by Ciba Specialty Chemicals) and an ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd., Tinuvin 477) are octyl bonded to the resulting thermoplastic resin composition. Zinc acid and antioxidant were injected in a weight ratio of 700 ppm each and an ultraviolet absorber in a weight ratio of 1.6 wt%.

After passing through a die provided at the tip of the twin screw extruder, the strand is cooled with cooling water and introduced into a cutting machine (pelletizer), whereby a heat-resistant acrylic resin (b-1) containing a lactone ring structure in the main chain ) Was obtained. The obtained heat-resistant acrylic resin (b-1) had a glass transition temperature of 130 ° C., and the number of foreign substances was 5/100 g. Moreover, the amount of methyl methacrylate (residual volatile matter) contained in the heat-resistant acrylic resin (b-1) was 970 ppm (weight conversion), and the mass reduction by dynamic TG measurement was 0.19% by mass.
[Production Example 2] (Production of substrate laminate 1)
For extrusion of polycarbonate resin (manufactured by Teijin Chemicals Ltd., Panlite L1225Z100), a single-screw extruder (main extruder) with a barrel diameter of 65 mm and screw L / D = 32 was used, and the cylinder temperature was set to 270 ° C. did. In addition, a single-screw extruder (sub-extruder) having a barrel diameter of 32 mm and a screw L / D = 32 was used to extrude the heat-resistant acrylic resin (Production Example 1, b-1) forming the coating layer, and the cylinder The temperature was set at 270 ° C. The discharge ratio between the main extruder and the sub-extruder was set so that main / sub = 7/1. A multi-manifold die was used to produce a substrate laminate (I-1) in which two types of resins were simultaneously melt coextruded to laminate a heat-resistant acrylic resin layer (B) on both sides of a polycarbonate resin layer (A). . The resin laminated and integrated in the die was cooled by three polishing rolls having a mirror-finished horizontal arrangement. The roll temperature was set at a first roll temperature of 105 ° C, a second roll temperature of 95 ° C, and a third roll temperature of 120 ° C. First, a bank was formed with a gap between the first roll and the second roll, and then passed through the second and third rolls, and a take-up laminate was formed at a speed of 4 m / min. The total thickness of the obtained substrate laminate (I-1) was 0.82 mm, and the heat-resistant acrylic resin layers (B) on both surfaces were 50 μm in both layers.
[Production Example 3] (Production of substrate laminate 2)
The discharge ratio of the main extruder and sub-extruder is set so that main / sub = 7/1, the multi-manifold die configuration is changed to two layers, and two types of resins are simultaneously melt co-extruded. A substrate laminate (I-2) was produced in the same manner as in Production Example 1 except that a heat-resistant acrylic resin layer (B-1) was laminated on one side of the polycarbonate resin layer (A-1). The resin laminated and integrated in the die was cooled by three polishing rolls having a mirror-finished horizontal arrangement. First, a bank was formed with a gap between the first roll and the second roll, and then passed through the second and third rolls, and a take-up laminate was formed at a speed of 4 m / min. The total thickness of the obtained substrate laminate (I-2) was 0.80 mm, and the thickness of the heat-resistant acrylic resin layer (B) on the surface was 95 μm.
[Production Example 4] (Production of hard coat composition 1)
85 parts by weight of dipentaerythritol hexaacrylate, 3 parts by weight of acryloyloxyethyltrimethylammonium chloride, 3 parts by weight of tricyclodecanyl acrylate, 10 parts by weight of spherical acrylic particles having a refractive index of 1.49 and an average particle size of 3.0 μm And 3 parts by weight of a fluorine-based antifouling agent (Defenser TF3004; manufactured by Dainippon Ink) and 1 part by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photoinitiator, It was mixed and dissolved in methyl ethyl ketone so as to have a concentration of 70%, followed by filtration with a filter having an accuracy of 20 μm to produce a hard coat composition (c-1).
[Production Example 5] (Production of hard coat composition 2)
85 parts by weight of dipentaerythritol hexaacrylate, 3 parts by weight of acryloyloxyethyltrimethylammonium chloride, 3 parts by weight of tricyclodecanyl acrylate, 10 parts by weight of silicon dioxide fine particles having a refractive index of 1.49 and an average particle size of 1.3 μm And 3 parts by weight of a silicone-based antifouling agent (SUA1900L6; manufactured by Shin-Nakamura Chemical) and 1 part by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photoinitiator using a homomixer Then, it was mixed and dissolved in methyl ethyl ketone so as to have a concentration of 70%, followed by filtration with a filter having an accuracy of 20 μm to produce a hard coat composition (c-2).
[Production Example 6] (Production 3 of hard coat composition)
After mixing 1 part of acetic acid with 100 parts by weight of methyltrimethoxysilane, the temperature was maintained at 0 to 10 ° C. while stirring and cooling in an ice bath, and then Snowtex 30 (trade name: Nissan Chemical Industries, Ltd.) (Manufactured, colloidal silica 30 wt%, average particle size 10-20 nm) was added dropwise. After dropping, the temperature was kept at 10 ° C. and stirred for 4 hours, and then Snowtex IBA-ST (trade name: manufactured by Nissan Chemical Industries, colloidal silica 25-26 wt%, average particle size 10-20 nm) 84 parts were dropped, and the mixture was aged by continuing stirring at 20 ° C. for 50 hours. Next, 45 parts of cellosolve acetate, 50 parts of isobutyl alcohol and 0.02 part of KP-341 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., polyoxyalkylene glycol dimethylsiloxane copolymer) are taken at room temperature for 1 hour. Further, 0.02 part of tetramethylammonium acetate as a curing catalyst was dropped and mixed at room temperature over 1 hour to prepare a coating material. After the preparation, 10 parts of 2,4-dihydroxybenzophenone as an ultraviolet absorber is added to 100 parts of the resin content in the paint, followed by filtration with a filter having an accuracy of 1 μm, and a hard coat composition (c-3) Was completed.
[Production Example 7] (Production of low refractive index coating agent)
In a 300 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser tube, 144.5 g of tetramethoxysilane, 23.6 g of γ-methacryloxypropyltrimethoxysilane, 19.0 g of water, 30.0 g of methanol, Amberlyst 15 (organo cation exchange resin) 5.0 g was added and stirred at 65 ° C. for 2 hours to be reacted. After the reaction mixture is cooled to room temperature, a distillation column, a cooling tube connected to the distillation tube, and an outlet are provided in place of the cooling tube, and the temperature inside the flask is increased to about 80 ° C. over 2 hours under normal pressure. It was kept at the same temperature until it did not flow out. Further, the reaction was further proceeded by maintaining at a temperature of 90 ° C. under a pressure of 2.67 × 10 kPa until methanol no longer flows out. After cooling to room temperature again, Amberlyst 15 was filtered off to obtain polymerizable polysiloxane (M-1) having a number average molecular weight of 1800.

  Next, 260 g of n-butyl acetate as an organic solvent was put into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and an N2 gas inlet, and N2 gas was introduced into the flask while stirring. The temperature was heated to 110 ° C. Then, 12 g of polymerizable polysiloxane (M-1), 19 g of tert-butyl methacrylate, 94 g of butyl acrylate, 67 g of 2-hydroxyethyl methacrylate, 48 g of perfluorooctylethyl methacrylate (Light Ester FM-108, manufactured by Kyoeisha Chemical Co., Ltd.), A solution in which 2.5 g of 2,2′-azobis- (2-methylbutyronitrile) was mixed was dropped from the dropping port over 3 hours. After the dropwise addition, stirring was continued for 1 hour at the same temperature, and then 0.1 g of tert-butylperoxy-2-ethylhexanoate was added twice every 30 minutes, and further copolymerization was performed by heating for 2 hours. A solution in which an organic polymer (P-1) having a number average molecular weight of 12,000 and a weight average molecular weight of 27000 was dissolved in n-butyl acetate was obtained. The solid content of the obtained solution was 48.2%.

  Next, 200 g of n-butyl acetate and 50 g of methanol were placed in a 500 ml four-necked flask equipped with a stirrer, two dropping ports (i and b), and a thermometer, and the internal temperature was adjusted to 40 ° C. Then, while stirring the inside of the flask, a mixed solution (raw material liquid (A)) of 10 g of an organic polymer (P-1) n-butyl acetate solution, 30 g of tetramethoxysilane, and 5 g of n-butyl acetate was added from the dropping port i. A mixed solution (raw material liquid (B)) of 5 g of 25% ammonia water, 10 g of deionized water, and 15 g of methanol was dropped from the dropping port over 2 hours. After dropping, a distillation column, a cooling tube connected to the distillation column, and an outlet are provided instead of the cooling tube, and the temperature inside the flask is raised to 100 ° C. under a pressure of 40 kPa, and ammonia, methanol, and n-butyl acetate are added. Then, it was distilled off until the solid content became 30% to obtain a coating agent (S-1) having a ratio of inorganic fine particles to organic polymer of 70/30. The average particle diameter of the inorganic fine particles in the coating agent (S-1) was 23.9 nm.

Next, 9 g of coating agent (S-1), 0.3 g of Desmodur N3200 (isocyanate curing agent manufactured by Sumika Bayer Urethane Co., Ltd.), 0.003 g of di-n-butyltin dilaurate, and 110 g of methyl isobutyl ketone are mixed. Then, filtration treatment was performed with a filter having an accuracy of 1 μm to prepare a low refractive index coating agent (d-1).
Example 1
The hard coat composition c-1 obtained in Production Example 4 was applied to the base material laminate I-1 obtained in Production Example 2 with a bar coater, and then in an oven at 70 ° C. for 1 minute. After removing the solvent, it was cured by irradiating with ultraviolet rays under the condition of 1000 mJ / cm 2 to prepare a hard coat layer. Further, the opposite surface was treated in the same manner to obtain a laminate having a hard coat on both surfaces. The thickness of the obtained hard coat layer was 8 μm in both layers.
Next, the low refractive index coating agent (d-1) described in Production Example 7 is applied to one side of the laminate having a hard coat on both sides, and cured at 100 ° C. for 1 hour to obtain a film thickness of 0. An antireflection layer (D-1) having a low refractive index of 1 μm was formed, and a laminate having an antireflection layer was obtained. The evaluation results of this laminate are shown in Table-1.
(Example 2)
A laminated body having hard coats on both sides was prepared in the same manner as in Example 1. Next, silicon dioxide, titanium oxide, silicon dioxide was formed on one side of the laminated body having hard coats on both sides from the hard coat layer side by vacuum deposition. Each of the thin films was laminated in three layers (D-2) so that each thickness was 140 nm to obtain a laminate having an antireflection layer. The evaluation results of this laminate are shown in Table-1.
(Examples 3 and 4)
A laminate having an antireflection layer was obtained in the same manner as in Example 1 or 2 except that the hard coat composition was changed to the hard coat composition c-2 obtained in Production Example 5. The evaluation results of this laminate are shown in Table-1.
(Examples 5-6)
The hard coat composition was changed to the hard coat composition c-3 obtained in Production Example 6 and the curing conditions were changed (after application, air-dried at room temperature for 15 minutes, and then in a hot air dryer at 125 ° C. for 120 minutes. A laminated board having an antireflection layer was obtained in the same manner as in Example 1 or 2 except that it was cured. The evaluation results of this laminate are shown in Table-1.
(Comparative Example 1)
A general acrylic resin (Sumipex EX, manufactured by Sumitomo Chemical Co., Ltd., Tg: 108 ° C.) is used as the resin for forming the coating layer, the barrel temperature of the sub-extruder is 260 ° C., and the temperature of the polishing roll is 105 ° C. of the first roll. A base laminate (I-3) in which an acrylic resin layer was laminated on both sides of a polycarbonate resin layer was molded in the same manner as in Example 1 except that the second roll temperature was 95 ° C and the third roll temperature was 100 ° C. . The hard coat composition c-1 obtained in Production Example 4 was applied with a bar coater, the solvent was removed in an oven at 70 ° C. for 1 minute, and then cured by irradiation with ultraviolet rays at 1000 mJ / cm 2. To prepare a hard coat layer. Further, the opposite surface was treated in the same manner to obtain a laminate having a hard coat on both surfaces. The thickness of the obtained hard coat layer was 8 μm and 7 μm.
Next, the low refractive index coating agent (d-1) described in Production Example 7 is applied to one side of the laminate having a hard coat on both sides, and cured at 100 ° C. for 1 hour to obtain a film thickness of 0. An antireflection layer (D-1) having a low refractive index of 1 μm was formed, and a laminate having an antireflection layer was obtained. The evaluation results of this laminate are shown in Table-1.

(Comparative Example 2)
A laminate was prepared and evaluated in the same manner as in Example 1 except that no hard coat layer was formed. The evaluation results are shown in Table 1.
(Comparative Example 3)
A laminate was prepared and evaluated in the same manner as in Example 1 except that no antireflection layer was prepared. The evaluation results are shown in Table 1.
(Examples 7 to 12)
Except having changed the base-material laminated body into the base-material laminated body I-2 obtained by manufacture example 2, the laminated board which has an antireflection layer similarly to Examples 1-6 was obtained. The antireflection layer was formed only on the hard coat layer surface having a heat-resistant acrylic layer as a lower layer. The evaluation results of this laminated board are shown in Table-2.

  Since the laminate of the present invention has excellent scratch resistance, optical properties, surface hardness, mechanical strength, and excellent impact resistance, covers, civil engineering and building materials, various glazing materials, bathtub materials It can be widely used for vehicle exteriors, sheets for various household goods, packaging materials for foods and pharmaceuticals, and the like. Further, it is particularly preferably used as a front plate for a display device of a liquid crystal display, an organic EL display, or a plasma display.

Claims (3)

A laminate having a polycarbonate resin layer (A), a heat-resistant acrylic resin layer (B) in which a lactone ring structure is introduced by an intramolecular cyclization reaction of a (meth) acrylate copolymer, and a hard coat layer (C), A laminated board that satisfies the above conditions.
(A) The total thickness of the laminate is 0.5 to 2 mm.
(B) The heat-resistant acrylic resin layer (B) has a thickness of 20 to 200 μm.
(C) The thickness of the hard coat layer (C) is 2 to 10 μm
(D) having an antireflection layer (D)
(E) The outermost layer is (D), and ( F ) # 0000 steel wool loaded in the order of (D) / (C) / (B) / (A) from the outermost layer is loaded with 2000 g No scratch when rubbed 10 times Furthermore, the laminated board of Claim 1 which satisfies the following conditions.
( G ) At least one surface has a pencil hardness defined by JIS K5600-5-4 of 5H or more. Display device for a front plate made of a laminated plate according to claim 1 or 2.