JP2010260224A - Acrylic resin laminate, method for producing the same, and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin laminate which has a surface layer excellent in scratch resistance and transparency and a low water absorption rate, is restrained from being deformed owing to the absorbed moisture and is excellent in adhesiveness between the layers thereof and to provide a method for producing the acrylic resin laminate, and a display device having a display part which is excellent in scratch resistance and transparency and is restrained from be deformed owing to the absorbed moisture. <P>SOLUTION: The acrylic resin laminate is produced by layering a cured layer (A), which is obtained by curing a monomer mixture (a) containing a monomer having at least two (meth)acryloyloxy groups in one molecule thereof, a low moisture-permeable layer (B) containing a polymer comprising halogenated vinylidene units, and another cured layer (C) which is obtained by curing another monomer mixture (c) containing another monomer having at least two (meth)acryloyloxy groups in one molecule thereof, successively on at least one surface of an acrylic resin base material. There are also provided the method for producing the acrylic resin laminate and the display device having the acrylic resin laminate as the protective member of the display part. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an acrylic resin laminate, a method for producing an acrylic resin laminate, and a display device.

  Acrylic resin is excellent in transparency and superior in impact resistance compared to glass. Therefore, it is used for the front plate of various displays such as CRT and liquid crystal televisions, and is widely used as industrial materials and building materials. in use. However, like other resins, acrylic resin is more flexible than glass, and scratches due to scratching or the like may easily occur. In addition, the acrylic resin has high water absorption, and particularly when applied to a display front plate, there is a difference in moisture absorption behavior between the front and back surfaces, and there is a problem that shape change such as warpage due to moisture absorption is likely to occur.

  As a method for improving the scratch resistance of an acrylic resin molded article, a crosslinked cured layer obtained by curing a monomer composition containing a polyfunctional monomer such as polyfunctional (meth) acrylate is molded with acrylic resin. Methods for forming on the surface of the body are known. However, although the scratch resistance of the surface of the obtained laminate is sufficient, the problem of shape change due to moisture absorption is not improved.

  As a method for reducing deformation due to moisture absorption of an acrylic resin base material, for example, Patent Document 1 discloses a resin containing a methyl methacrylate resin and a vinylidene fluoride resin on at least one surface of a base material layer made of a methyl methacrylate polymer. A resin plate on which a surface layer of the composition is laminated has been proposed. However, although the resulting laminate has reduced shape change due to moisture absorption, it has a room for improvement because of its high water absorption rate.

  Patent Document 2 discloses an optical material that is close to glass in terms of rigidity, heat resistance, air resistance, moisture resistance, and optical isotropy, has other properties, and is advantageous in terms of cost. In order to provide a laminated sheet for use, a laminated sheet in which an inner side curable resin cured layer, an air permeable resin layer, and an outer side heat resistant solvent resistant layer are sequentially laminated on both sides of an active energy ray curable resin cured layer Has been proposed. Patent Document 2 discloses that surface hardness is imparted by providing a curable resin cured product layer on an air-permeable resin layer. However, a polyvinyl alcohol-based resin layer is used as the air-resistant resin layer, and sufficient interlayer adhesion cannot be obtained when an acrylic resin is used as the base material.

JP 2004-306601 A JP-A-9-96803

  An object of the present invention is to provide a resin laminate having a surface layer excellent in scratch resistance and transparency, having a low water absorption rate, suppressing deformation due to moisture absorption, and having excellent adhesion between layers, and a method for producing the same It is another object of the present invention to provide a display device having a display portion that is excellent in scratch resistance and transparency and in which deformation due to moisture absorption is suppressed.

  The gist of the present invention is that a monomer mixture (a) containing a monomer having at least two (meth) acryloyloxy groups in a molecule is cured on at least one surface of an acrylic resin substrate. Monomer containing a cured layer (A) to be obtained, a low moisture-permeable layer (B) containing a polymer containing a vinylidene halide unit, and a monomer having at least two (meth) acryloyloxy groups in the molecule An acrylic resin laminate in which cured layers (C) obtained by curing the body mixture (c) are sequentially laminated is defined as a first invention.

  The gist of the present invention is that a monomer mixture (a) containing a monomer having at least two (meth) acryloyloxy groups in the molecule is cured on at least one surface of the base film. The low moisture permeable layer (B) of the transfer film having the cured layer (A) obtained in this manner, and the low moisture permeable layer (B) containing a polymer containing a vinylidene halide unit on the cured layer (A). The transfer film is attached to the mold with a coating layer of a monomer mixture (c) containing a monomer having at least two (meth) acryloyloxy groups in the molecule. A first step of applying; a second step of curing the coating layer to form a cured layer (C); a cured layer (C) laminated on the mold, a low moisture permeable layer (B), a cured layer ( A) and a third step of peeling only the base film from the base film; A fourth step of forming a mold using the mold in which the hardened layer (C), the low moisture permeable layer (B) and the hardened layer (A) are laminated; the raw material of the acrylic resin base material is injected into the mold An acrylic resin in which a cured layer (A), a low moisture-permeable layer (B), and a cured layer (C) are sequentially laminated on an acrylic resin substrate formed after the fifth step of casting polymerization and casting polymerization. The manufacturing method of the acrylic resin laminate including the sixth step of peeling the laminate from the mold is a second invention.

  Furthermore, a display device having the acrylic resin laminate as a protective member for the display portion is a third invention.

  The resin laminate of the present invention has a surface layer excellent in scratch resistance and transparency, has a low water absorption rate, suppresses deformation due to moisture absorption, and has excellent adhesion between layers. It is suitable for various uses such as the front plate of various displays.

Acrylic resin base material The acrylic resin base material used in the present invention is, for example, an acrylic resin obtained by polymerizing monomers such as (meth) acrylic acid ester, acrylamide, acrylonitrile, (meth) acrylic acid or its derivatives. The base material formed from resin is mentioned. Among these, in terms of transparency and weather resistance, polymethyl methacrylate, a copolymer having a methyl methacrylate unit as a main constituent, and a styrene-methyl methacrylate copolymer substrate are preferable.

  In the present invention, “(meth) acryl” means at least one selected from “methacryl” and “acryl”.

  In the present invention, the acrylic resin base material may contain a colorant, a light diffusing agent, and various additives as necessary.

  Examples of the shape of the acrylic resin substrate include a film shape and a plate shape.

As thickness of an acrylic resin base material, the thing of about 0.1-10 mm is mentioned, for example.
Monomer mixture (a)
In the present invention, the monomer mixture (a) is a raw material for forming the cured layer (A) described later.

  The monomer mixture (a) contains a monomer having at least two (meth) acryloyloxy groups in the molecule.

  Examples of the monomer having at least two (meth) acryloyloxy groups in the molecule include esters obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof, polyvalent The ester obtained from carboxylic acid or its anhydride, a polyhydric alcohol, and (meth) acrylic acid or its derivative (s) is mentioned.

  Specific examples of esters obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di Polyethylene glycol di (meth) acrylate such as (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, etc. Alkyl diol di (meth) acrylates; and trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Taerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, etc., and at least three (meth) acryloyloxy Examples thereof include polyol poly (meth) acrylate having a group.

  Ester obtained from polyhydric carboxylic acid or its anhydride, polyhydric alcohol and (meth) acrylic acid or its derivative (polyhydric carboxylic acid or its anhydride / polyhydric alcohol / (meth) acrylic acid or its derivative) Specific examples include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meta ) Acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) Acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / Limethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / tri Methylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylol Propane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (Meth) acrylic acid, fluorine Luric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic Acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, Mention may be made of maleic anhydride / glycerin / (meth) acrylic acid and maleic anhydride / pentaerythritol / (meth) acrylic acid.

  In addition to the above, other examples of the monomer having at least two (meth) acryloyloxy groups in the molecule include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) per mole of polyisocyanate obtained by trimerization of diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate Acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) ) (Meth) acryloyloxy group-containing single amount having active hydrogen such as acrylamide, 1,2,3-propanetriol-1,3-di (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate Urethane (meth) acrylate obtained by reacting 3 mol or more of the body; poly [(meth) acryloyloxyethylene] isocyanurate such as di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid Epoxy poly (meth) acrylates and urethane poly (meth) acrylates.

A monomer mixture (a) can be used individually or in combination of 2 or more types.
Hardened layer (A)
In the present invention, the cured layer (A) is formed by curing the monomer mixture (a).

  The cured layer (A) is laminated on at least one surface of the acrylic resin base material, and is positioned between the low moisture-permeable layer (B) described later and the acrylic resin base material. It has a function of protecting the low moisture permeable layer (B) from penetration of the raw material monomer into the low moisture permeable layer (B).

  The thickness of the cured layer (A) is preferably 2 to 50 μm and more preferably 5 to 20 μm from the viewpoint of transparency and the protective function of the low moisture permeable layer (B).

  As a formation method of a hardened layer (A), the method of hardening a monomer mixture (a) after forming the thin film of a monomer mixture (a) on the surface of an acrylic resin base material or the transfer film mentioned later, for example. Can be mentioned.

  Examples of the method for forming a thin film of the monomer mixture (a) include a coating method, a spray method, and an immersion method.

  Examples of the curing method of the monomer mixture (a) include a thermosetting method and a photocuring method. Here, light refers to active energy rays such as electron beams, radiation, and ultraviolet rays. From the viewpoint of productivity, the photocuring method is preferable, and the ultraviolet curing method is more preferable.

  When the monomer mixture (a) is cured by a photocuring method, it is preferable to add a photoinitiator to the monomer mixture (a).

  Examples of the photoinitiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α , Α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one Carbonyl compounds such as tetramethylthiuram monosulfide, sulfur compounds such as tetramethylthiuram disulfide; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Examples thereof include phosphorus compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and benzoyldiethoxyphosphine oxide. These can be used alone or in combination of two or more.

As addition amount of a photoinitiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of monomer mixtures (a). When the addition amount of the photoinitiator is 0.1 parts by mass or more, good polymerizability tends to be obtained, and when it is 10 parts by mass or less, coloring of the cured layer (A) tends to be suppressed.
Low moisture permeability layer (B)
In the present invention, the low moisture-permeable layer (B) contains a polymer containing a vinylidene halide unit.

  The low moisture-permeable layer (B) is laminated on the cured layer (A), and has a function of suppressing deformation due to water absorption speed and moisture absorption of the acrylic resin base material. Moreover, a low moisture-permeable layer (B) can express a sufficient water absorption rate reduction effect by providing a hardened layer (A) between an acrylic resin base material and a low moisture-permeable layer (B).

  Examples of the vinylidene halide which is a raw material for constituting the vinylidene halide unit include vinylidene chloride and vinylidene fluoride. These can be used alone or in combination of two or more.

  When the polymer containing a vinylidene halide unit is contained in the low moisture-permeable layer (B), the adhesion between the cured layer (A) and the cured layer (C) described later is improved.

  Polymers containing vinylidene chloride units (hereinafter referred to as “vinylidene chloride polymers”) include vinylidene chloride, (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate. A copolymer with at least one monomer selected from monomers copolymerizable with vinylidene chloride such as vinyl chloride and acrylonitrile is preferred. As content of the vinylidene chloride unit in a vinylidene chloride polymer, 50-99 mass% is preferable.

  Polymers containing vinylidene fluoride units (hereinafter referred to as “vinylidene fluoride polymers”) include vinylidene fluoride homopolymers and vinylidene fluorides and vinylidene fluorides such as hexafluoropropylene and tetrafluoroethylene. Examples thereof include a copolymer with a polymerizable monomer. As content of the vinylidene fluoride unit in a vinylidene fluoride polymer, 50-99 mass% is preferable.

  In the present invention, in the low moisture permeable layer (B), if necessary, other thermoplastic resins such as acrylic resins, various fillers, pigments or dyes for color tone adjustment, antistatic agents, leveling agents. Various additives such as conductive inorganic fine particles, non-conductive inorganic fine particles, ultraviolet absorbers, and light stabilizers can be contained.

  The addition amount of the thermoplastic resin and various additives is preferably 10% by mass or less in the low moisture permeable layer (B) in terms of transparency of the low moisture permeable layer (B). Moreover, in the case of the low moisture-permeable layer (B) containing a vinylidene fluoride polymer, it is preferable to contain thermoplastic resins, such as an acrylic resin, in a low moisture-permeable layer (B) at the point of film forming property. As content of a thermoplastic resin, 5-50 mass% is preferable in a low moisture-permeable layer (B).

  In the case of the low moisture-permeable layer (B) containing a vinylidene chloride polymer, the thickness of the low moisture-permeable layer (B) is preferably 1 to 50 μm, and more preferably 2 to 30 μm. Moreover, in the case of the low moisture-permeable layer (B) containing a vinylidene fluoride polymer, the thickness of the low moisture-permeable layer (B) is preferably 2 to 200 μm, and more preferably 5 to 50 μm. By setting the thickness of the low moisture permeable layer (B) within the above range, a sufficient effect of reducing the water absorption rate tends to be obtained, and a decrease in transparency tends to be suppressed.

As a method for forming the low moisture permeable layer (B), for example, a solution or emulsion of a polymer containing vinylidene halide units by solution polymerization or emulsion polymerization is coated on the cured layer (A) and dried to form a thin film. The method of doing is mentioned. Among these, a method using an emulsion is preferable from the viewpoint of handleability.
Monomer mixture (c)
In the present invention, the monomer mixture (c) is a raw material for forming the cured layer (C) described later.

  The monomer mixture (c) contains a monomer having at least two (meth) acryloyloxy groups in the molecule.

  Examples of the monomer mixture (c) include those similar to the monomer mixture (a). Further, the monomer mixture (c) may contain a monomer having at least three (meth) acryloyloxy groups in the molecule from the viewpoint of scratch resistance of the obtained cured layer (C). preferable.

  As content of the monomer which has at least 3 (meth) acryloyloxy group in the molecule | numerator in a monomer mixture (c), it is 20-99 mass from a viewpoint of the abrasion resistance of the acrylic resin laminated body obtained. % Is preferred.

In the present invention, the monomer mixture (c) contains various additives such as a leveling agent, conductive inorganic fine particles, non-conductive inorganic fine particles, an ultraviolet absorber, a light stabilizer, and a resin as necessary. Can be made. As content of these additives, 10 mass% or less is preferable at the transparency point of the hardened layer (C) obtained.
Hardened layer (C)
In the present invention, the cured layer (C) is formed by curing the monomer mixture (c). Examples of the method for curing the monomer mixture (c) include a thermosetting method and a photocuring method as in the case of the monomer (a). From the viewpoint of productivity, the photocuring method is preferable, and the ultraviolet curing method is more preferable.

  The hardened layer (C) is laminated on the low moisture permeable layer (B) and has a function of imparting scratch resistance to the surface of the acrylic resin laminate described later.

  In the present invention, the cured layer (C) can be directly laminated on one side of the acrylic resin substrate.

  The surface state of the surface of the cured layer (C) that is not laminated on the low moisture permeable layer (B) may be flat or matt.

The thickness of the cured layer (C) is preferably 1 to 100 μm and more preferably 1 to 30 μm from the viewpoint of the transparency and scratch resistance of the cured layer (C).
Acrylic resin laminate The acrylic resin laminate of the present invention is obtained by sequentially laminating the cured layer (A), the low moisture permeable layer (B) and the cured layer (C) on at least one surface of an acrylic resin substrate.

  In the present invention, a cured layer (C) / low moisture permeable layer (B) in which a cured layer (A), a low moisture permeable layer (B), and a cured layer (C) are sequentially laminated on one side of an acrylic resin substrate. / Hardened layer (A) / Acrylic resin base material in a four-layer structure; a hardened layer (A), a low moisture permeable layer (B) and a hardened layer (C) are sequentially laminated on one side of the acrylic resin base material, Cured layer (C) / low moisture-permeable layer (B) / cured layer (A) / acrylic resin, in which a cured layer (A) and a low moisture-permeable layer (B) are sequentially laminated on another side of the acrylic resin substrate Laminate having a 6-layer structure of substrate / cured layer (A) / low moisture-permeable layer (B); cured layer (A), low moisture-permeable layer (B) and cured layer (C) on one side of the acrylic resin substrate Are sequentially laminated, and the cured layer (C) is laminated on the other surface of the acrylic resin substrate, the cured layer (C) / the low moisture permeable layer (B) / the cured layer (A) / the acrylic resin substrate / the cured layer. (C) Layered laminate; and cured layer (C) / low moisture permeable layer (a cured layer (A), low moisture permeable layer (B), and cured layer (C) sequentially laminated on both sides of the acrylic resin substrate) B) / hardened layer (A) / acrylic resin substrate / cured layer (A) / low moisture-permeable layer (B) / hardened layer (C) can be used as a laminate having a seven-layer structure.

  In the present invention, if necessary, on the acrylic resin substrate, between the acrylic resin substrate and the cured layer (A), between the cured layer (A) and the low moisture permeable layer (B), low Another functional layer may be provided between the moisture permeable layer (B) and the cured layer (C) or on the cured layer (C).

  Examples of other functional layers include an antireflection layer, an antifouling layer and an antistatic layer provided on the surface of the cured layer (C). Moreover, as another functional layer, the intermediate | middle layer which has the antistatic performance, scattering prevention performance, etc. which are provided between each layer is mentioned, for example.

  In the case of forming the antireflection layer, for example, it is formed by a method of applying and drying a commercially available antireflection coating (wet method) and a physical vapor deposition method (dry method) such as a vapor deposition method or a sputtering method. can do.

  As a manufacturing method of an acrylic resin laminated body, for example, (1) A method in which a cured layer (A), a low moisture-permeable layer (B), and a cured layer (C) are sequentially laminated on the surface of an acrylic resin substrate; ) Using the laminated transfer film in which the cured layer (C), the low moisture permeable layer (B) and the cured layer (A) are sequentially laminated on the surface of the base film, the surface of the cured layer (A) of the laminated transfer film is A method of peeling a substrate film after laminating on an acrylic resin substrate through an adhesive layer; and (3) laminating a cured layer (C), a low moisture permeable layer (B) and a cured layer (A) sequentially After forming a mold by previously laminating the low moisture-permeable laminated film on the mold surface, the raw material of the acrylic resin base material is injected into the mold to perform casting polymerization, and after the polymerization is finished, the acrylic resin laminate is peeled off from the mold A method is mentioned.

  In the present invention, the above method (3) is preferable, and among these, a method through the following steps is more preferable.

  First, in the first step, the low moisture permeable layer of the transfer film having the cured layer (A) on at least one surface of the base film and the low moisture permeable layer (B) laminated on the cured layer (A). The surface of (B) is the mold side, and the transfer film is attached to the mold with the coating layer of the monomer mixture (c) interposed.

  Next, in the second step, the coating layer is cured to form a cured layer (C).

  Thereafter, only the base film is peeled off from the cured layer (C), the low moisture permeable layer (B), the cured layer (A) and the base film laminated on the mold in the third step.

  Furthermore, a mold is formed using the mold in which the cured layer (C), the low moisture permeability layer (B), and the cured layer (A) are laminated in the fourth step.

Thereafter, in the fifth step, the raw material of the acrylic resin base material is injected into the mold and cast polymerization is performed.
Next, an acrylic resin laminate in which a cured layer (A), a low moisture-permeable layer (B), and a cured layer (C) are sequentially laminated on the acrylic resin base material formed after cast polymerization in the sixth step. By peeling from the mold, an acrylic resin laminate is obtained.
Base film As the base film used in the present invention, for example, it transmits ultraviolet rays used for curing the monomer mixture (c) and is dissolved by the monomer mixture (a) and the monomer mixture (c). Or the thing which has the solvent resistance which does not swell, and the oxygen permeability is low is mentioned. Specific examples of the base film include a biaxially stretched film of polyethylene terephthalate (PET).

  The thickness of the base film is preferably 1 μm or more from the viewpoint of maintaining the film strength, and is preferably 200 μm or less from the viewpoints of handleability and cost.

  In this invention, the film which has a peeling layer on the surface as needed can be used as a base film.

  As the base film having a release layer, a film obtained by applying a release agent to the surface of the base film or a commercially available film with a release layer can be used. Those in which the release layer remains are preferred.

  Examples of the material for forming the release layer include a paraffin release agent, a silicone resin release agent, a cellulose derivative release agent, a melamine resin release agent, a polyolefin resin release agent, a fluororesin release agent, and a urea resin release agent. Agents and mixtures thereof.

Examples of the method for applying the release agent to the base film include a brush coating method, a bar coating method, a flow coating method, a spray coating method, a knife coating method, a roll coating method, and a die coating method.
In the transfer film present invention, as the transfer film, for example, hardened layer on the surface of the base film (C), those low permeable Shimeso (B) and curing layer (A) are sequentially laminated, the surface of the substrate film The cured layer (A) and the low moisture-permeable layer (B) are sequentially laminated, and the cured layer (A), the low moisture-permeable layer (B) and the cured layer (C) are sequentially laminated on the surface of the base film. A transfer film having an appropriate structure can be used according to the method for producing the acrylic resin laminate. Among these transfer films, as described in the section of the acrylic resin laminate, those in which the cured layer (A) and the low moisture permeable layer (B) are sequentially laminated on the surface of the base film are preferable.
The types used in the type the present invention, for example, stainless steel plate and a glass plate. Examples of the surface shape of the mold include a mirror surface shape and an uneven shape.
Mold In the present invention, as the mold, for example, a stainless steel plate in which a hardened layer (C), a low moisture-permeable layer (B), and a hardened layer (A) are sequentially laminated, and a stainless steel plate in which nothing is laminated are each 1 Casting polymerization molds prepared one by one, with two stainless steel plates facing each other with the hardened layer (A) side of one stainless steel plate facing inward, and sealed with a soft polyvinyl chloride gasket And an injection mold in which a cured layer (C), a low moisture permeable layer (B), and a cured layer (A) are sequentially laminated on the surface of the injection mold.
Display device The display device of the present invention has the acrylic resin laminate of the present invention as a protective member (front plate) of a display unit of the display device.
The resin laminate is excellent in transparency and scratch resistance, and is suitable for the above-mentioned use because it has a small shape change due to moisture absorption.

  Examples of the display device of the present invention include various displays such as a CRT, a liquid crystal display, an organic EL display, a plasma display, and a projection television having an information display unit, and information terminals such as a mobile phone, a portable music player, and a mobile personal computer. It is done.

Hereinafter, the present invention will be described by way of examples. In addition, the symbol of the compound used by the Example and the comparative example is as follows. In the following, “part” means “part by mass”.
MMA: Methyl methacrylate AIBN: 2,2′-azobis (isobutyronitrile)
C6DA: 1,6-hexanediol diacrylate TAS: succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4 condensation mixture DPHA: dipentaerythritol hexaacrylate A200: tetraethylene glycol diacrylate BAPO: bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide The total light transmittance, haze, scratch resistance, adhesion, water absorption after 2 hours and moisture absorption warpage of the obtained acrylic resin laminate were as follows. evaluated.
(1) Total light transmittance and haze The total light transmittance and haze value were measured based on the measurement method shown by JIS K7136 using HAZE METER NDH2000 (trade name) manufactured by Nippon Denshoku Industries Co., Ltd. .
(2) Scratch resistance A circular pad with a diameter of 25.4 mm, equipped with # 000 steel wool, is placed on the surface of the acrylic resin laminate, and scratched by reciprocating a distance of 20 mm 100 times under a load of 9.8 N. The difference between the haze values before and after scratching (Δhaze) was determined from the following formula (α), and scratch resistance was evaluated.

[Δhaze (%)] = [haze value after abrasion (%)] − [haze value before abrasion (%)] (α)
(3) Adhesiveness Based on the observation by the cross-cut test (JIS K5600-5-6) of the surface of an acrylic resin laminated body, adhesiveness was evaluated by the following references | standards.
○: No peeling from the interface between the cured layer (C) and the low moisture permeable layer (B) or from the interface between the low moisture permeable layer (B) and the cured layer (A).
X: There is peeling from the interface between the cured layer (C) and the low moisture permeable layer (B) or from the interface between the low moisture permeable layer (B) and the cured layer (A).
(4) Water Absorption After 2 Hours A test piece obtained by cutting a 100 mm × 100 mm section from the acrylic resin laminate was vacuum-dried at 60 ° C. for 48 hours. Next, the test piece was held for 2 hours under the conditions of 60 ° C. and 95% relative humidity, the change in mass of the test piece before and after the test was measured, and the water absorption after 2 hours was calculated.
(5) Moisture absorption warp After a test piece obtained by cutting out a 100 mm × 100 mm section from the acrylic resin laminate was vacuum-dried at 60 ° C. for 24 hours, an aluminum film was deposited on one side as a moisture-proof layer with a vacuum deposition apparatus, A test piece having a moisture-proof layer was prepared. In addition, when the low moisture-permeable laminated film was laminated | stacked only on the single side | surface of the acrylic resin base material, the vapor deposition process of the aluminum film was implemented on the side without the low moisture-permeable layer (B) of an acrylic resin laminated body.

Subsequently, the test piece which has a moisture-proof layer was hold | maintained on the conditions of 60 degreeC and 95% relative humidity for 100 hours, and was then hold | maintained on the conditions of 23 degreeC and 50% relative humidity for 100 hours. The maximum amount of warpage of the central portion with respect to the four corners of the test piece having the moisture-proof layer during the holding period was measured, and moisture absorption warpage was evaluated according to the following criteria.
○: Warpage of the central portion is 2 mm or less.
X: Warpage at the center exceeds 2 mm.
[Example 1]
(1) Production of transfer film in which cured layer (A) and low moisture-permeable layer (B) were sequentially laminated 25 μm thick polyethylene terephthalate (PET) film with release layer (manufactured by Toyobo Co., Ltd., trade name: TN100) A monomer mixture (a) containing 50 parts of TAS, 50 parts of C6DA and 2 parts of BAPO is applied by a bar coater on the release layer so that ultraviolet rays are irradiated from the coating layer side of the monomer mixture (a). The coating layer of the monomer mixture (a) is cured by passing a position 20 cm under a high-pressure mercury lamp with an output of 30 W / cm at a speed of 0.3 m / min, and a cured layer (A) having a thickness of 10 μm is cured. A transfer film (A) having the above was obtained.

  Next, an emulsion containing vinylidene chloride copolymer (manufactured by Asahi Kasei Chemicals Corporation, trade name: Saran Latex L536B) is applied onto the cured layer (A) by a bar coater so that the film thickness after drying is 12 μm. Then, by drying at 80 ° C. for 10 minutes, a low moisture-permeable layer (B) was formed, and a transfer film (B) in which the cured layer (A) and the low moisture-permeable layer (B) were sequentially laminated was obtained.

The thickness of the low moisture permeable layer (B) is a value calculated by measuring the thickness of the coating solution before drying and multiplying by the solid content concentration of the coating solution.
(2) Production of a mold in which a hardened layer (C), a low moisture permeable layer (B), and a hardened layer (A) are laminated on a stainless steel (SUS304) plate as a mold, containing 50 parts of TAS, 50 parts of C6DA, and 2 parts of BAPO The monomer mixture (c) to be applied was applied.

  Next, a transfer film (b) in which a hardened layer (A) and a low moisture-permeable layer (B) are sequentially laminated on the coated surface of the stainless steel plate monomer mixture (c) is used as a stainless steel plate monomer mixture ( c) The coated surface of the transfer film (b) and the low moisture permeable layer (B) of the transfer film (b) are stacked so that they face each other, and a cured layer after curing of the monomer mixture (c) using a rubber roll having a JIS hardness of 40 °. The excess monomer mixture (c) was squeezed out so that the thickness of (C) was 15 μm, and pressure-bonded so as not to contain bubbles.

  The thickness of the cured layer (C) was calculated from the supply amount of the monomer mixture (c), the development area, and the shrinkage rate at the time of curing.

  Thereafter, the stainless steel plate in which the coating layer of the monomer mixture (c), the low moisture permeable layer (B), the hardened layer (A), and the PET film are sequentially laminated is applied to the coating layer side of the monomer mixture (c). The monomer mixture (by passing through a position 20 cm below a fluorescent ultraviolet lamp (trade name: FL40BL, manufactured by Toshiba Corporation) with an output of 40 W at a speed of 0.3 m / min so that ultraviolet rays are irradiated from The coating layer of c) was cured to obtain a stainless steel plate in which the cured layer (C), the low moisture permeable layer (B), the cured layer (A), and the PET film were sequentially laminated.

  Next, the cured film (C), the low moisture permeable layer (B), the cured layer (A), and the PET film are peeled from the stainless steel plate in which the PET film is laminated in order, thereby the cured layer (C) and the low moisture permeable layer. A stainless plate in which (B) and a hardened layer (A) were sequentially laminated was obtained.

  Furthermore, the stainless steel plate in which the hardened layer (C), the low moisture permeable layer (B), and the hardened layer (A) are sequentially laminated is irradiated with ultraviolet rays from the hardened layer (C) side with an output of 30 W / cm. The cured layer (C) is further cured by passing a position 20 cm under the high-pressure mercury lamp at a speed of 0.3 m / min, and the cured layer (C), the low moisture permeable layer (B), and the cured layer (A) A sequentially laminated stainless steel plate (hereinafter referred to as “laminated stainless steel plate”) was obtained. The film thickness of the three layers laminated on this stainless steel plate was 37 μm.

In addition, the film thickness of the low moisture-permeable laminated film was calculated | required from the differential interference microscope photograph of the cross section of the acrylic resin laminated body finally obtained.
[Production of acrylic resin laminate]
Prepare one each of the laminated stainless steel plate and the stainless steel plate on which nothing is laminated, with the two stainless steel plates facing each other so that the low moisture-permeable laminated film of one stainless steel plate is on the inside, and the surroundings are soft Sealed with a polyvinyl chloride gasket to prepare a casting polymerization mold.

  In this mold, an acrylic resin substrate containing 100 parts of a mixture of 20 parts of polymethyl methacrylate having a mass average molecular weight of 220,000 and 80 parts of MMA, 0.05 parts of AIBN, and 0.005 part of sodium salt of dioctylsulfosuccinate The spacing between the opposing stainless steel plates was 1.6 mm. Next, the mold into which the acrylic resin base material was injected was polymerized in an 80 ° C. water bath for 1 hour, and further in an air furnace at 130 ° C. for 1 hour, and then cooled.

  After that, by peeling the acrylic resin laminate obtained by polymerization from both stainless steel plates, a cured layer (A), a low moisture permeable layer (B) and a cured layer (C ) Were sequentially laminated to obtain an acrylic resin laminate having a plate thickness of 1 mm. The evaluation results are shown in Table 1.

[Example 2]
In the production of the transfer film, the thickness of the low moisture permeability layer (B) was 6 μm, and in the production of the acrylic resin laminate, two laminated stainless steel plates were used. Otherwise, in the same manner as in Example 1, an acrylic resin laminate in which the cured layer (A), the low moisture permeable layer (B), and the cured layer (C) were sequentially laminated on both sides of the acrylic resin base material was prepared and carried out. Evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1. In addition, evaluation of adhesiveness was implemented only about one side of the acrylic resin laminated body.
[Example 3]
In the production of the transfer film, the thickness of the low moisture permeable layer (B) was 11 μm. Otherwise, in the same manner as in Example 2, an acrylic resin laminate in which the cured layer (A), the low moisture-permeable layer (B), and the cured layer (C) were sequentially laminated on both sides of the acrylic resin base material was prepared and carried out. Evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1.
[Example 4]
In the production of the transfer film, the thickness of the cured layer (A) was 6 μm. Otherwise, in the same manner as in Example 1, an acrylic resin laminate in which the cured layer (A), the low moisture-permeable layer (B), and the cured layer (C) were sequentially laminated on one side of the acrylic resin base material was prepared and carried out. Evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1.
[Example 5]
A mixture of 50 parts of DPHA, 50 parts of A200 and 2 parts of BAPO was used as the monomer mixture (a) in the production of the transfer film and the monomer mixture (c) in the production of the laminated stainless steel plate. Otherwise, in the same manner as in Example 1, an acrylic resin laminate in which the cured layer (A), the low moisture-permeable layer (B), and the cured layer (C) were sequentially laminated on one side of the acrylic resin base material was prepared and carried out. Evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1.
[Comparative Example 1]
A monomer mixture (c) containing 50 parts of TAS, 50 parts of C6DA, and 2 parts of BAPO is applied on a stainless steel plate (SUS304) as a mold so that the thickness after curing is 15 μm, and the monomer mixture (c) A stainless steel plate having a coating layer was obtained.

  Next, a fluorescent ultraviolet lamp (Co., Ltd.) with an output of 40 W is applied so that the active energy ray is irradiated on the stainless steel plate having the coating layer of the monomer mixture (c) from the coating layer side of the monomer mixture (c). The coating layer of the monomer mixture (c) is cured by passing a position 20 cm below the product made by Toshiba, trade name: FL40BL) at a speed of 0.3 m / min. C) The cured layer (C) is further cured by passing a position 20 cm below the high-pressure mercury lamp with an output of 30 W / cm at a speed of 0.3 m / min so that the active energy rays are irradiated from the C side. A stainless steel plate on which a cured layer (C) having a thickness of 15 μm was laminated was obtained.

  Prepare one each of the stainless steel plate on which the hardened layer (C) is laminated and the stainless steel plate on which nothing is laminated, so that the hardened layer (C) of one stainless steel plate is inside. A stainless steel plate was made to face and the periphery was sealed with a gasket made of soft polyvinyl chloride to prepare a casting polymerization mold.

  In this mold, an acrylic resin substrate containing 100 parts of a mixture of 20 parts of polymethyl methacrylate having a mass average molecular weight of 220,000 and 80 parts of MMA, 0.05 parts of AIBN, and 0.005 part of sodium salt of dioctylsulfosuccinate The spacing between the opposing stainless steel plates was 1.6 mm. Next, the mold into which the acrylic resin base material was injected was polymerized in an 80 ° C. water bath for 1 hour, and further in an air furnace at 130 ° C. for 1 hour, and then cooled.

Thereafter, an acrylic resin laminate having a thickness of 1 mm in which a cured layer (C) is laminated on one surface of the acrylic resin base material by peeling the acrylic resin laminate obtained by polymerization from the stainless steel plate. The same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.
[Comparative Example 2]
In the same manner as in Comparative Example 1 except that two stainless steel plates on which the hardened layer (C) was laminated were prepared and the two stainless steel plates were opposed so that the hardened layer (C) of the stainless steel plate was inside. An acrylic resin laminate was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Comparative Example 3]
25 μm thick polyethylene terephthalate (PET) film with release layer (trade name: TN100, manufactured by Toyobo Co., Ltd.) emulsion containing vinylidene chloride copolymer on the release layer (trade name, manufactured by Asahi Kasei Chemicals Corporation) : Saran Latex L536B) was applied by a bar coater so that the film thickness after drying was 13 μm, and dried at 80 ° C. for 10 minutes to form a low moisture permeable layer (B). Was obtained.

  A monomer mixture (c) containing 50 parts of TAS, 50 parts of C6DA and 2 parts of BAPO was applied onto a stainless (SUS304) plate as a mold.

  Next, the transfer film in which the low moisture permeability layer (B) is laminated on the surface of the stainless steel plate monomer mixture (c) is applied to the surface of the stainless steel plate monomer mixture (c). Overlap so that the application surface of the monomer mixture (c) faces each other, and using a rubber roll having a JIS hardness of 40 °, the thickness of the cured layer (C) after curing of the monomer mixture (c) is 15 μm. While squeezing out the monomer mixture (c), it was pressure-bonded so as not to contain bubbles.

  Thereafter, the stainless steel plate on which the coating layer of the monomer mixture (c), the low moisture permeable layer (B), and the PET film are sequentially laminated is irradiated with ultraviolet rays from the coating layer side of the monomer mixture (c). As described above, the coating layer of the monomer mixture (c) was passed through a position 20 cm below the fluorescent ultraviolet lamp (product name: FL40BL, manufactured by Toshiba Corporation) with an output of 40 W at a speed of 0.3 m / min. It was cured to obtain a stainless steel plate in which a cured layer (C), a low moisture permeability layer (B), and a PET film were sequentially laminated.

  Next, the cured layer (C), the low moisture permeable layer (B), and the PET film are peeled from the stainless steel plate on which the PET film is sequentially laminated, whereby the cured layer (C) and the low moisture permeable layer (B) are sequentially laminated. A stainless plate was obtained.

  Furthermore, the stainless steel plate on which the hardened layer (C) and the low moisture permeable layer (B) are sequentially laminated is irradiated with ultraviolet rays from the hardened layer (C) side at 20 cm under a high pressure mercury lamp with an output of 30 W / cm. The cured layer (C) is further cured by passing the position at a speed of 0.3 m / min, and a laminated film having a thickness of 28 μm is formed by laminating the cured layer (C) and the low moisture permeable layer (B) sequentially. Got the mold.

  Prepare one stainless steel plate with the laminated film and one stainless steel plate with nothing laminated, with the two stainless steel plates facing each other so that the laminated film of one stainless steel plate is on the inside. Was sealed with a soft polyvinyl chloride gasket to prepare a casting polymerization mold.

  In this mold, an acrylic resin substrate containing 100 parts of a mixture of 20 parts of polymethyl methacrylate having a mass average molecular weight of 220,000 and 80 parts of MMA, 0.05 parts of AIBN, and 0.005 part of sodium salt of dioctylsulfosuccinate The spacing between the opposing stainless steel plates was 1.6 mm. Next, the mold into which the acrylic resin base material was injected was polymerized in an 80 ° C. water bath for 1 hour, and further in an air furnace at 130 ° C. for 1 hour, and then cooled.

Then, the low moisture-permeable layer (B) and the hardened layer (C) were sequentially laminated on one side of the acrylic resin base material by peeling off the acrylic resin laminate obtained by polymerization from the stainless steel plate. An acrylic resin laminate with a plate thickness of 1 mm was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Comparative Example 4]
Instead of the emulsion containing the vinylidene chloride copolymer, a 5% solution of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., polymerization degree 400 to 600) was used, and the film thickness after drying was set to 10 μm. Otherwise, an attempt was made to produce an acrylic resin laminate in the same manner as in Example 1, but the adhesion between the low moisture permeable layer (B) and the cured layer (C) was poor, and an acrylic resin laminate could not be obtained. It was.
[Comparative Example 5]
An emulsion containing vinylidene chloride copolymer (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Saran Latex L536B) is applied on a stainless steel (SUS304) plate as a mold by a bar coater so that the film thickness after drying is 15 μm. And it dried at 80 degreeC for 10 minutes, the low moisture-permeable layer (B) was formed, and the stainless steel board by which the low moisture-permeable layer (B) was laminated | stacked was obtained.

  Prepare one stainless steel plate with low moisture permeability layer (B) and one stainless steel plate without low moisture permeability layer (B), with the low moisture permeability layer (B) of one stainless steel plate inside The two stainless steel plates were made to face each other, and the periphery was sealed with a gasket made of soft polyvinyl chloride to prepare a casting polymerization mold.

  In this mold, an acrylic resin substrate containing 100 parts of a mixture of 20 parts of polymethyl methacrylate having a mass average molecular weight of 220,000 and 80 parts of MMA, 0.05 parts of AIBN, and 0.005 part of sodium salt of dioctylsulfosuccinate The spacing between the opposing stainless steel plates was 1.6 mm. Next, the mold into which the acrylic resin base material was injected was polymerized in an 80 ° C. water bath for 1 hour, and further in an air furnace at 130 ° C. for 1 hour, and then cooled.

Thereafter, the acrylic resin laminate obtained by superposing the acrylic resin laminate obtained by polymerization from the stainless steel plate is laminated with the low moisture permeable layer (B) on one surface of the acrylic resin base material, and the acrylic resin laminate having a plate thickness of 1 mm. A body was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Comparative Example 6]
An emulsion containing vinylidene chloride copolymer (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Saran Latex L536B) is applied on a stainless steel (SUS304) plate as a mold by a bar coater so that the film thickness after drying is 15 μm. And it dried at 80 degreeC for 10 minutes, the low moisture-permeable layer (B) was formed, and the stainless steel board by which the low moisture-permeable layer (B) was laminated | stacked was obtained.

  Next, a monomer mixture (a) containing 50 parts of TAS, 50 parts of C6DA and 2 parts of BAPO is applied by a bar coater on the low moisture permeability layer (B) of the stainless steel plate on which the low moisture permeability layer (B) is laminated, The monomer mixture (a) is passed through a position 20 cm below a high-pressure mercury lamp with an output of 30 W / cm at a speed of 0.3 m / min so that active energy rays are irradiated from the coating layer side of the monomer mixture (a). The coating layer of the mixture (a) was cured to obtain a stainless steel plate in which a cured layer (A) having a thickness of 10 μm was laminated on the low moisture permeable layer (B).

  Prepare one by one a stainless steel plate in which the low moisture-permeable layer (B) and the hardened layer (A) are sequentially laminated and a stainless steel plate in which nothing is laminated, and the hardened layer (A) of one stainless steel plate Two stainless steel plates were opposed so as to be inside, and the periphery was sealed with a gasket made of soft polyvinyl chloride to prepare a casting polymerization mold.

  In this mold, an acrylic resin substrate containing 100 parts of a mixture of 20 parts of polymethyl methacrylate having a mass average molecular weight of 220,000 and 80 parts of MMA, 0.05 parts of AIBN, and 0.005 part of sodium salt of dioctylsulfosuccinate The spacing between the opposing stainless steel plates was 1.6 mm. Next, the mold into which the acrylic resin base material was injected was polymerized in an 80 ° C. water bath for 1 hour, and further in an air furnace at 130 ° C. for 1 hour, and then cooled.

  After this, by peeling the acrylic resin laminate obtained by polymerization from the stainless steel plate, the cured layer (A) and the low moisture permeable layer (B) were sequentially laminated on one side of the acrylic resin substrate. An acrylic resin laminate with a plate thickness of 1 mm was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  From the above evaluation results, in Examples 1 to 5, the obtained acrylic resin laminate had high total light transmittance and low haze, and was excellent in transparency. The acrylic resin laminate had a good appearance without appearance defects and interference patterns due to foreign matters. Furthermore, the warpage after the hygroscopic warpage test was small, no haze increment was observed after scratching, the shape change due to moisture absorption was small, and the scratch resistance was excellent. Moreover, the adhesiveness of the interface of a cured layer (C) and a low moisture-permeable layer (B) and the interface of a low moisture-permeable layer (B) and a cured layer (A) was also favorable.

  On the other hand, in Comparative Examples 1 and 2, the obtained acrylic resin laminate had good transparency, appearance, and scratch resistance, but the cured layer (A) and the low moisture permeable layer (B). Therefore, the moisture absorption warpage of the acrylic resin laminate was large. In Comparative Example 3, the acrylic resin laminate had good transparency, appearance, and scratch resistance, and had a small hygroscopic warpage, but had no cured layer (A), so the water absorption rate was high. Furthermore, in Comparative Example 4, since a polymer containing a vinylidene halide unit is not used in the low moisture permeable layer (B), the interface between the cured layer (C) of the acrylic resin laminate and the low moisture permeable layer (B). Peeling from the interface between the low moisture permeable layer (B) and the cured layer (A) was observed. Moreover, in Comparative Example 5, since it does not have a cured layer (A) and a cured layer (C), a poor appearance occurs in the low moisture permeable layer (B) of the acrylic resin laminate, and the points of scratch resistance and moisture absorption warpage. It was inferior. Furthermore, in Comparative Example 6, the water absorption rate of the acrylic resin laminate was low and the moisture absorption warpage was excellent, but the cured layer (C) was not provided, so that the scratch resistance was poor.

  The acrylic resin laminate obtained by the present invention can be used for various applications such as front plates of various displays.

Claims (4)

  A cured layer (A) obtained by curing a monomer mixture (a) containing a monomer having at least two (meth) acryloyloxy groups in the molecule on at least one surface of an acrylic resin substrate, halogen A low moisture-permeable layer (B) containing a polymer containing vinylidene fluoride units and a monomer mixture (c) containing a monomer having at least two (meth) acryloyloxy groups in the molecule; An acrylic resin laminate in which the resulting cured layers (C) are sequentially laminated.   The acrylic resin laminate according to claim 1, wherein the cured layer (A) and the cured layer (C) are ultraviolet cured layers.   At least one surface of the substrate film has a cured layer (A) obtained by curing a monomer mixture (a) containing a monomer having at least two (meth) acryloyloxy groups in the molecule. The surface of the low moisture permeable layer (B) of the transfer film in which the low moisture permeable layer (B) containing a polymer containing a vinylidene halide unit is laminated on the cured layer (A) is the mold side, A first step of attaching the transfer film to a mold with a coating layer of a monomer mixture (c) containing a monomer having at least two (meth) acryloyloxy groups; curing the coating layer A second step of forming a cured layer (C); only the substrate film from the cured layer (C), the low moisture permeable layer (B), the cured layer (A) and the substrate film laminated on the mold A third step of peeling off the cured layer (C), low moisture-permeable layer (B) and A fourth step of forming a mold using the mold on which the hardened layer (A) is laminated; a fifth step of injecting a raw material of an acrylic resin base material into the mold and performing casting polymerization; and forming after casting polymerization An acrylic resin including a sixth step of peeling from the mold an acrylic resin laminate in which the cured layer (A), the low moisture-permeable layer (B), and the cured layer (C) are sequentially laminated on the acrylic resin base material formed A manufacturing method of a layered product.   The display apparatus which has the acrylic resin laminated body of Claim 1 or 2 as a protection member of a display part.