JP5339775B2 - LAMINATED PLATE, MANUFACTURING METHOD FOR LAMINATED PLATE, AND FRONT PLATE FOR DISPLAY DEVICE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated plate which is excellent in scratch resistance, optical characteristics, surface hardness and mechanical strength and is excellent in shock resistance, too, to provide a method of manufacturing the laminated plate and to provide a front plate for a display device comprising the laminated plate. <P>SOLUTION: The laminated plate has a high-hardness heat-resistant acrylic resin layer on at least one surface of a polycarbonate resin layer excellent in shock-resistant property and further has a hardcoat layer disposed on the heat-resistant acrylic resin layer, wherein by setting the thickness of laminated body and respective layers in the specified range, the laminated plate which is excellent in transparency and scuffing resistance and has both of a mechanical strength and a shock resistance is provided. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a laminated board. More specifically, the present invention relates to a laminate having excellent scratch resistance, optical characteristics, and surface hardness and impact resistance, a method for producing the laminate, and a front plate for a display device comprising 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, see Reference 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.
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.

  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 within a specific range, it was found that a laminate having excellent transparency and scratch resistance and also having mechanical strength and impact resistance was obtained, and the present invention was completed.

That is, the present invention provides a hard coat layer (C) on the heat-resistant acrylic resin layer (B) side surface or both surfaces of the substrate laminate (I) comprising the polycarbonate resin layer (A) and the heat-resistant acrylic resin layer (B). It is a laminated board which satisfy | fills 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
The present invention also provides a hard coat layer (C) on at least one side of the substrate laminate (I) in which the heat-resistant acrylic resin layer (B), the polycarbonate resin layer (A), and the heat-resistant acrylic resin layer (B) are arranged in this order. ) And satisfying 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

In the laminated board of this invention, it is desirable to satisfy | fill the conditions of following (1)-(2).
(1) The pencil hardness according to JIS-K5400 is at least 4H on at least one surface.
(2) It has steel wool resistance with no damage when # 0000 steel wool is rubbed 10 times with a load of 500 g.

The heat-resistant acrylic resin layer (B) is preferably made of a resin containing a lactone ring structure represented by the following formula (1).

(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.)
The present invention further relates to a transparent front plate for a display device comprising the above laminate and having a 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, in particular, various 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 has a hard coat layer (C on the surface or both sides of the heat-resistant acrylic resin layer (B) of the substrate laminate (I) comprising the polycarbonate resin layer (A) and the heat-resistant acrylic resin layer (B). ) And satisfying 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
The present invention also provides a hard coat layer (C) on at least one side of the substrate laminate (I) in which the heat-resistant acrylic resin layer (B), the polycarbonate resin layer (A), and the heat-resistant acrylic resin layer (B) are arranged in this order. ) And satisfying 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

In the laminated board of this invention, it is further desirable to satisfy the following conditions (1) to (2).
(1) The pencil hardness according to JIS-K5400 is at least 4H on at least one surface.
(2) It has steel wool resistance with no damage when # 0000 steel wool is rubbed 10 times with a load of 500 g.

Each layer will be described below.

<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 polymers and (meth) acrylate copolymers by intramolecular cyclization reaction are mentioned. .
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. 2- (hydroxyalkyl) such as vinyl, methallyl alcohol, allyl alcohol, allyl alcohol such as 2-hydroxymethyl-1-butene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, methyl 2- (hydroxyethyl) acrylate ) Acrylic acid ester; 2- (hydroxyalkyl) acrylic acid such as 2- (hydroxyethyl) acrylic acid and the like may be used, and these may be used alone or in combination of two or more.
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 to 100% by weight, more preferably in the range of 75 to 100% by weight, and 90 to 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. The rubbery polymer preferably has a graft portion having a composition compatible with the lactone ring polymer of the present invention on the surface, and the average particle size of the rubbery polymer is transparent when formed into an extruded film. From the viewpoint of improving the properties, 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, neo-dodecyl-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) isobuty Rate, 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-hydroxy-benzoate, 2- (n-octylthio) ethyl-3,5-di-t-butyl-4-hydroxy-phenylacetate 2- (n-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxy Benzoate, 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-stearoyloxy) Ethylthio) ethyl-7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate, 1,2-propylene glycol-bis- [ -(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- ln-octadecanoate-2,3-bis- (3,5-di-t-butyl-4-hydroxyphenylacetate), pentaerythritol-tetrakis- [3- (3 ', 5'-di- t-butyl-4'-hydroxyphenyl) propionate], 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl) 4-hydroxyphenyl) propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl-7- (3-methyl-5-t-butyl -4-hydroxyphenyl) 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- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2, , 8,10-tetraoxaspiro [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 view of the 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" in the pencil hardness test prescribed | regulated by JIS5600-5-4 (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.
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, and antifogging 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.

<Laminated plate>
The laminate of the present invention comprises a polycarbonate resin layer (A), has a heat-resistant acrylic resin layer (B) on one or both sides, and a hard coat layer (C) on one or both sides of the outermost surface. For that purpose, the heat-resistant acrylic resin layer (B) and the hard coat layer (C) need to be arranged in this order on at least one side of the polycarbonate resin (A).
As a specific configuration of the laminated plate, from the surface, (C) / (B) / (A), (C) / (B) / (A) / (C), (C) / (B) / ( A) / (B), (C) / (B) / (A) / (B) / (C). The configuration of (C) / (B) / (A) is the basic configuration with the fewest number of layers and thickness, but (C) / (B) / (A) / (B), (C) / ( In the case of the configuration of B) / (A) / (B) / (C), the configuration becomes more symmetrical, and thus the warping of the laminate that occurs at the time of molding and after molding is less likely to occur.
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.
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.
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) is preferably 0.5 μm or less, and more preferably It is 0.3 μm or less, 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-K5400.
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 adhesiveness between the heat-resistant acrylic resin layer (B) and the hard coat layer (C) is 95/100 or more in the 100 cells in the cross cut method based on JIS K5600. It is preferably 97/100 or more, more preferably 99/100 or more, and most preferably 100/100 and 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>
The manufacturing method of the laminated body concerning this invention is a manufacturing method formed by forming this hard-coat layer (C) in the at least single side | surface of this base-material laminated board (I) obtained by coextrusion of a polycarbonate resin and a heat-resistant acrylic resin. preferable.
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, a method of applying a hard coat agent to a resin layer or a substrate laminate and drying and curing as necessary is preferable. There are no particular restrictions on the method of applying the hard coating agent. For example, spin coating method, dipping method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen A 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 a sandblast method, a solvent treatment method, a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, an ozone / ultraviolet treatment, a primer treatment with a resin composition, etc. Each material of A), the heat-resistant acrylic resin layer (B), and the hard coat layer (C) is preferably filtered and purified by a filter treatment. 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 K5400, measurement was performed on a sample (surface on the hard coat layer side when the hard coat layer was laminated) with a load of 750 g.
<Abrasion resistance>
Press # 0000 steel wool with a constant load against the sample (if the hard coat layer is laminated, the surface on the hard coat layer side), 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 of hard coat layer>
In accordance with JIS K5600, the number of squares that did not peel was counted.
<Surface roughness>
Arithmetic average roughness Ra prescribed | regulated to JISK5400 was calculated | required. The measurement was performed using a laser microscope (VK-9700 manufactured by Keyence Corporation) from an area of 50 μm square or more. When the hard coat layer was laminated, the measurement was performed on the surface on the hard coat layer side.
<Total light transmittance>
It measured by the method according to ASTM-D-1003.
<Cloudiness value>
It measured by the method according to ASTM-D-1003.
<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.
<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 1 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 Chemical Industry Co., Ltd.) is used as a foam inhibitor (deactivator) between the third and fourth forvents. The toluene solution was injected so that zinc octylate was 700 ppm by weight with respect to the obtained thermoplastic resin composition.

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 6/100 g. Moreover, the amount of methyl methacrylate (residual volatile matter) contained in the heat-resistant acrylic resin (b-1) was 930 ppm (weight conversion), and the mass reduction by dynamic TG measurement was 0.17% by mass.

[Production Example 2] (Production of heat-resistant acrylic resin 2)
When the polymer solution (a-1) of Production Example 1 is subjected to devolatilization treatment and polymer filter treatment at the same time, an ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd.) is interposed between the third forevent and the fourth forvent. ), Manufactured by Tinuvin 477) in the same manner as in Production Example 1 except that the weight ratio of the obtained thermoplastic resin composition was 1.6% by weight. A heat-resistant acrylic resin (b-2) pellet containing was obtained. The obtained heat-resistant acrylic resin (b-2) had a glass transition temperature of 128 ° C., and the number of foreign matters was 4/100 g. Moreover, the amount of methyl methacrylate (residual volatile matter) contained in the heat-resistant acrylic resin (b-2) was 980 ppm (weight conversion), and the mass reduction by dynamic TG measurement was 0.19% by mass.

[Production Example 3] (Production of UV curable resin paint)
In a mixing dissolution vessel equipped with a stirring blade and a temperature control jacket, 60 parts of tris (acryloxyethyl) isocyanurate (Daiichi Kogyo Seiyaku Co., Ltd., GX8430), neopentyl glycol oligoacrylate (Osaka Organic Chemical Co., Ltd.) 215D) 40 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan, APO) 1 part, 1-hydroxy-cyclohexyl phenyl ketone (Ciba Specialty Chemicals) Co., Ltd., I-184) 0.3 part and 2- (hydroxy-5-tert-butylphenyl) benzotriazole (Ciba Specialty Chemicals Co., Ltd., Tinuvin-PS) 1 part were introduced, and 40 ° C. The mixture was stirred for 1 hour to prepare an ultraviolet curable paint (c-3).

[Production Example 4] (Production of thermosetting resin paint)
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 was added to 100 parts of the resin content in the paint to complete the thermosetting resin paint (c-4).

Example 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 substrate laminate (I-1) in which a heat resistant acrylic resin layer (B-1) is laminated on both sides of a polycarbonate resin layer (A-1) by simultaneously melt coextruding two types of resins using a multi-manifold die. ) Was manufactured. 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 ultraviolet curable resin paint (c-3) of Production Example 3 was applied to one side of the substrate laminate (I-1) cut to a length of 300 mm and a width of 200 mm using a bar coater. The ultraviolet curable resin paint was cured by irradiating with 250 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp to obtain a laminate (D-1) with a hard coat. The total thickness of the obtained laminate (D-1) was 0.81 mm, the heat-resistant acrylic resin layers (B-1) on both surfaces were 52 μm and 49 μm, and the hard coat layer (C-1) was 6 μm. there were. The evaluation results of the manufactured laminate are shown in Table 1.

(Example 2)
A heat-resistant acrylic resin layer (B) is formed on both sides of the polycarbonate resin layer (A-2) in the same manner as in Example 1 except that the discharge amount ratio of the main extruder and the sub-extruder is adjusted to main / sub = 6/2. -2) was laminated to form a substrate laminate (I-2). The thermosetting resin paint (c-4) of Production Example 4 was applied to one side of the base laminate (I-2) cut to a length of 300 mm and a width of 200 mm using a bar coater. After air-drying at room temperature for 15 minutes, it was cured for 120 minutes in a hot air dryer at 125 ° C. to obtain a laminate with hard coat (D-2). The obtained laminate (D-2) has a total thickness of 0.79 mm, the heat-resistant acrylic resin layers (B-1) on both surfaces have a thickness of 102 μm and 96 μm, and the hard coat layer (C-2) has a thickness of 5 μm. there were. The evaluation results of the manufactured laminate are shown in Table 1.

(Example 3)
The same operation as in Example 1 was performed except that the heat-resistant acrylic resin (b-2) obtained in Production Example 2 was used, and the heat-resistant acrylic resin layer (B-3) was formed on both sides of the polycarbonate resin layer (A-3). The base material laminated board (I-3) which laminated | stacked this was shape | molded. The ultraviolet curable resin coating material (c-3) of Production Example 3 was applied to one side of the base laminate (I-3) cut to a length of 300 mm and a width of 200 mm using a bar coater. The ultraviolet curable resin paint was cured by irradiating with an ultraviolet ray of 250 mJ / cm 2 with a high pressure mercury lamp to obtain a laminate (D-3) with a hard coat. The resulting laminate (D-3) had a total thickness of 0.78 mm, the heat-resistant acrylic resin layers (B-3) on both surfaces had a thickness of 51 μm and 47 μm, and the hard coat layer (C-3) had a thickness of 7 μm. Was there. The evaluation results of the manufactured 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. The base material which laminated | stacked the acrylic resin layer (B-4) on both surfaces of the polycarbonate resin layer (A-4) like Example 1 except having set to 2nd roll temperature 95 degreeC and 3rd roll temperature 100 degreeC. A laminate (I-4) was molded. The ultraviolet curable resin paint (c-3) of Production Example 3 was applied to one side of the base laminate (I-4) cut to a length of 300 mm and a width of 200 mm using a bar coater. The ultraviolet curable resin paint was cured by irradiating with 250 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp to obtain a laminate (D-4) with hard coat. The resulting laminate (D-4) had a total thickness of 0.82 mm, the acrylic resin layers (B-4) on both surfaces had a thickness of 54 μm and 50 μm, and the hard coat layer (C-4) had a thickness of 6 μm. It was. The evaluation results of the manufactured laminate are shown in Table 1.

(Comparative Example 2)
A heat-resistant acrylic resin (Production Example 1, b-1) was laminated on both sides of a polycarbonate resin in the same manner as in Example 1 except that a feed block was used to melt-extrude and laminate two types of resins simultaneously. The obtained base laminate (I-5) had a total thickness of 0.82 mm, and the heat-resistant acrylic resin layers (B-5) on both surfaces had a thickness of 50 μm and 44 μm. When observed with reflected light, an unfavorable wave pattern was observed in appearance. Such a wave pattern was not observed on the base material laminate (I-1) produced in Example 1 laminated using a multi-manifold die. In the observation of the outermost surface with a laser microscope, the difference between the substrate laminate (I-1) and the substrate laminate (I-5) could not be confirmed, so the wave pattern is between the polycarbonate layer and the heat-resistant acrylic layer. It was thought to have occurred.

(Comparative Example 3)
In Example 3, the base laminate (I-3) having no hard coat layer was evaluated. The evaluation results are shown in Table 1.

Example 4
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. Thereby, the base-material laminated body (I-6) which laminated | stacked the heat-resistant acrylic resin layer (B-1) on the single side | surface of the polycarbonate resin layer (A-1) was manufactured. 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 ultraviolet curable resin paint (c-3) of Production Example 3 was applied to one side of the substrate laminate (I-6) cut to 300 mm length and 200 mm width using a bar coater. The ultraviolet curable resin paint was cured by irradiating with 250 mJ / cm 2 of ultraviolet light with a high-pressure mercury lamp to obtain a laminate (D-1) with a hard coat. The total thickness of the obtained laminate (D-6) was 0.81 mm, the thickness of the heat-resistant acrylic resin layer (B-1) on the surface was 94 μm, and the thickness of the hard coat layer (C-6) was 7 μm. The evaluation results of the manufactured laminate are shown in Table 1.

  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 (5)

A laminate having a hard coat layer (C) on the heat-resistant acrylic resin layer (B) side or both sides of a substrate laminate (I) comprising a polycarbonate resin layer (A) and a heat-resistant acrylic resin layer (B). A laminated board that 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) The heat-resistant acrylic resin is a resin having a glass transition temperature (Tg) of 110 ° C. or higher. (E) The heat-resistant acrylic resin is a polymer containing a ring structure in the main chain. (F) At least one side The surface of the steel has a pencil hardness according to JIS-K5400 of 5H or more. (G) It has steel wool resistance that is not damaged when # 0000 steel wool is rubbed 10 times with a load of 2000 g. but (meth) lactone ring polymer obtained by introducing a lactone ring structure by intramolecular cyclization reaction acrylate copolymer, (meth) glutaric anhydride by intramolecular cyclization reaction acrylate copolymer structure or a glutarimide structure Is either a glutaric anhydride polymer or a glutarimide polymer Laminate having a hard coat layer (C) on at least one side of the substrate laminate (I) in which the heat-resistant acrylic resin layer (B), the polycarbonate resin layer (A), and the heat-resistant acrylic resin layer (B) are arranged in this order. And 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) The heat-resistant acrylic resin is a resin having a glass transition temperature (Tg) of 110 ° C. or higher. (E) The heat-resistant acrylic resin is a polymer containing a ring structure in the main chain. (F) At least one side The surface of the steel has a pencil hardness according to JIS-K5400 of 5H or more. (G) It has steel wool resistance that is not damaged when # 0000 steel wool is rubbed 10 times with a load of 2000 g. but (meth) lactone ring polymer obtained by introducing a lactone ring structure by intramolecular cyclization reaction acrylate copolymer, (meth) glutaric anhydride by intramolecular cyclization reaction acrylate copolymer structure or a glutarimide structure Is either a glutaric anhydride polymer or a glutarimide polymer The laminate according to any one of claims 1 and 2, wherein the heat-resistant acrylic resin layer (B) is made of a resin containing a lactone ring structure represented by the following formula (1).

(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.)   It is a method of manufacturing the laminated board of any one of Claims 1-3, Comprising: At least one surface of this base-material laminated board (I) obtained by coextrusion of a polycarbonate resin and a heat-resistant acrylic resin WHEREIN: This hard coat The manufacturing method of the laminated board formed by forming a layer (C). The front board for display apparatuses which consists of a laminated board of any one of Claims 1-3.