JP2017100366A - Resin laminate and method for producing the same - Google Patents

Abstract

A resin laminate having a functional layer such as an antireflection function, an antistatic function, an antiglare function and a dirt prevention function, and having excellent surface hardness, scratch resistance, adhesion and crack resistance, and a method for producing the same provide. A specific cured coating (A) having a pencil hardness of 8H, a repeating unit derived from urethane (meth) acrylate, and a repeating unit derived from (meth) acrylate having an amino group on at least one surface of the resin substrate. The resin laminated body in which the cured film (B) containing at least 1 type of a unit was formed in order. The cured coating (B) of the resin laminate can have at least one function selected from an antireflection function, an antistatic function, an antiglare function, and a stain prevention function. Or the said resin laminated body can further laminate | stack the functional layer (C) which has the function mentioned above on the surface of the said cured film (B). [Selection figure] None

Description

  The present invention relates to a resin laminate and a method for producing the same. More specifically, a resin laminate in which a functional layer having at least one function selected from an antireflection function, an antistatic function, an antiglare function, and an antifouling function is formed on the surface of a cured film having a pencil hardness of 8H, and The present invention relates to a method for producing the resin laminate.

Conventionally, there is a demand for a resin sheet having transparency as a display front plate for protecting displays such as liquid crystal televisions and mobile phones. Highly transparent resin sheets are required to have performances such as scratch resistance and high surface hardness in addition to functions such as an antireflection function, an antistatic function, an antiglare function, and an antifouling function.

  As a technique for improving the surface hardness, scratch resistance, etc. of the resin sheet, for example, Patent Document 1 discloses an active energy containing a specific polyfunctional (meth) acrylate monomer and a specific urethane (meth) acrylate monomer. A cured coating obtained by curing a linear curable composition is disclosed.

  In Patent Document 2, an active energy ray curable resin and light diffusing particles are applied to the surface of a transparent plastic film substrate as a technique for further imparting an antiglare function to a resin sheet having scratch resistance, surface hardness, and antifouling function. An optical film having a light diffusing layer contained therein is disclosed.

  In addition, Patent Document 3 discloses an antistatic technique on the surface of a resin base material, as a technique for laminating various functional layers on the surface of a hard coat layer (cured coating) to achieve both scratch resistance and surface hardness of the resin laminate. A resin laminate in which a layer and a low refractive index layer are sequentially laminated is disclosed.

  Patent Document 4 discloses a resin laminate in which a high refractive index film containing aminosilane and a low refractive index film are laminated in this order on the surface of a resin base material.

  As a technique for satisfying the surface hardness of the resin laminate, Patent Document 5 discloses a resin laminate in which a cured film containing a specific polyfunctional monomer is laminated on the surface of a resin base material.

JP 2009-114,248 A JP 2007-114,760 WO2006 / 132,180 publication WO2012 / 086,749 WO2014 / 184,983 publication

However, with the techniques disclosed in Patent Document 1 and Patent Document 2, the scratch resistance of the resin sheet is improved, but the surface hardness is not sufficient.

  In the technique disclosed in Patent Document 3, the interface strength (interlayer adhesive force) between the base material of the resin laminate and the antistatic layer is not sufficient.

  In the technique disclosed in Patent Document 4, the scratch resistance of the resin laminate and the adhesion between the layers are improved, but the surface hardness is not sufficient.

  In the technique disclosed in Patent Document 5, the surface hardness of the resin laminate is improved, but an antireflection layer, an antistatic layer, an antiglare layer, and an antifouling layer are formed on the surface of the cured film that is the outermost layer of the resin laminate. When a functional layer such as a layer is laminated as it is, the adhesion between the cured film and the functional layer is not sufficient.

  The present invention aims to solve these problems. That is, the present invention provides a resin laminate having functional layers such as an antireflection function, an antistatic function, an antiglare function, and an antifouling function and excellent in surface hardness, scratch resistance, adhesion and crack resistance. The purpose is to do.

  The first gist of the present invention is that a cured coating (A) having a pencil hardness of 8H or more is provided on at least one surface of a resin substrate, and the cured coating (A) is cured on a surface facing the surface in contact with the resin substrate. It is a sheet-like resin laminate provided with a coating (B). The cured coating (B) preferably contains at least one of a repeating unit (b2-1) derived from urethane (meth) acrylate and a repeating unit (b2-2) derived from (meth) acrylate having an amino group. The film thickness of the cured coating (A) is preferably 17 μm or more and 40 μm or less. The cured coating (B) may be a layer having one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer. The pencil hardness of the surface of the resin laminate is preferably 8H or more.

  The second gist of the present invention is that a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antiglare layer are formed on the surface of the cured film (B) of the resin laminate of the first gist. It is a resin laminate provided with a functional layer (C) composed of a layer having at least one function selected from a dirty layer. The pencil hardness of the surface of the resin laminate is preferably 8H or more.

  The third gist of the present invention is a sheet comprising a cured coating on at least one surface of a resin substrate, and a cured coating (B) on the surface facing the surface in contact with the resin substrate in the cured coating (A). It is a resin-like laminated body. The cured coating (A) has a repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule, and a single unit having 2 or less (meth) acryloyloxy groups in the molecule. The repeating unit (a2) derived from a monomer is included. Moreover, the said cured film (B) contains at least 1 sort (s) of the urethane (meth) acrylate unit (b2-1) and the (meth) acrylate unit (b2-2) which has an amino group. The film thickness of the cured coating (A) is preferably 17 μm or more and 40 μm or less. The pencil hardness of the cured coating (A) is preferably 8H or higher, and the pencil hardness of the surface of the resin laminate is preferably 8H or higher.

  The 4th summary of this invention exists in the manufacturing method of the resin laminated body containing the following process (1) and process (2).

Step (1): A repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule on at least one surface of the resin substrate, and 2 or less (meta ) A cured coating (A) containing a repeating unit (a2) derived from a monomer having an acryloyloxy group is formed.

Step (2): A cured film (B) containing at least one kind of urethane (meth) acrylate unit (b2-1) and methacrylate unit (b2-2) having an amino group on the surface of the cured film (A). Form.

  In the step (2), the cured film (B) is formed on the surface of the cured film (A) by the monomer (b1) having 3 or more (meth) acryloyloxy groups in the molecule and urethane (meta ) At least one of acrylate monomer (b2-1) and (meth) acrylate monomer (b2-2) having an amino group (excluding monomer (b1)), and organic solvent (b4) A method of forming a cured coating film (B ′) by forming a coating film of the curable composition (s1) containing, and curing it can be used.

  The fifth gist of the present invention is that the step of forming the cured film (B) in the step (2) of the production method of the fourth gist comprises three or more molecules in the molecule on the surface of the cured film (A). At least one of a monomer (b1) having a (meth) acryloyloxy group, a urethane (meth) acrylate monomer (b2-1), and a (meth) acrylate monomer (b2-2) having an amino group Forming a coating film of the curable composition (s2) containing (except for the monomer (b1)) and curing to form a cured coating film (B ″); ) Is followed by the following steps (3) to (5) in order.

Step (3): a functional layer comprising a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer on the surface of the resin film. (C) is formed.

Step (4): The functional layer (C) of the step (5) is bonded to the surface of the cured film (B ″) obtained in the step (4).

Step (5): A resin in which the resin film is peeled and the cured coating (A), the cured coating (B ″), and the functional layer (C) are sequentially laminated on at least one surface of a resin base material. A laminate is obtained.

  According to the present invention, it has a layer having at least one function selected from an antireflection function, an antistatic function, an antiglare function, and an antifouling function, and has high surface hardness, scratch resistance, adhesion and crack resistance. A resin laminate can be provided. Such a resin laminate is suitable for a front plate or the like for protecting displays such as liquid crystal televisions and mobile phones.

  Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylate” and “(meth) acrylic acid” are each at least one selected from “acrylate” and “methacrylate”, and at least one selected from “acrylic acid” and “methacrylic acid”. I mean.

  “Monomer” means an unpolymerized monomer, and “repeating unit” means a unit derived from the monomer formed by polymerization of the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or may be a part of the unit converted into another structure by treating the polymer.

  Moreover, "mass%" shows content of the predetermined | prescribed component contained in 100 mass% of whole quantity unless there is particular notice.

Further, in the specification, the “first surface” refers to an outer surface in a laminate composed of two or more layers.
For example, a surface that is provided with a cured coating 2 on at least one surface of the resin substrate 1 and faces the surface that contacts the resin substrate 1 in the cured coating 2 is referred to as a “first surface of the cured coating 2”.

<Resin laminate>
The 1st aspect of the resin laminated body of this invention is equipped with the cured film (A) mentioned later on the at least one surface of the resin base material mentioned later, and the surface which opposes the surface which contacts the resin base material in a cured film (A). It is the sheet-like resin laminated body which provided the cured film (B) in order.

  In the resin laminate of the first aspect, it is preferable that the cured film (A) has a pencil hardness of 8H or more. If the lower limit of the pencil hardness is 8H or more, the obtained resin laminate is preferable from the viewpoint of high surface hardness and good scratch resistance, and more preferably 9H or more. On the other hand, the upper limit of pencil hardness is not particularly limited. As will be described later, the value of the pencil hardness of the cured film (A) includes the types and contents of the (a1) and (a2) components constituting the cured film (A), the film thickness of the cured film (A), and the like. It can control by selecting suitably.

  In the resin laminate of the first embodiment, the cured coating (B) is a repeating unit derived from a urethane (meth) acrylate described later (b2-1) and a repeating unit derived from a (meth) acrylate having an amino group described later. At least one type of unit (b2-2) can be included.

  For the cured coating (B), a functional layer comprising a layer having one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer is used. Can do. The specific low refractive index layer, high refractive index layer, hard coat layer, antistatic layer, antiglare layer and antifouling layer are not particularly limited, and a functional layer made of a known resin composition is used. be able to.

  Accordingly, the resin laminate of the first aspect has at least one function selected from an antireflection function, an antistatic function, an antiglare function, and a stain prevention function, and the pencil hardness of the surface of the resin laminate is 8H or more. Therefore, it can have high surface hardness and scratch resistance.

  Furthermore, in the resin laminate of the first aspect, the residual ratio of the cured film (B) by the cross-cut peel test in accordance with ISO 2409: 1992 indicates that the resin laminate has good scratch resistance and crack resistance. From this viewpoint, it is preferably 80% or more, more preferably 90% or more, and further preferably 100%. The residual rate of the cured coating (B) here refers to the residual rate of the cured coating (B) that remains on the resin sheet without peeling after the cross-cut peeling test. As will be described later, the value of the residual ratio is the type and content of the (a1) component and (a2) component constituting the cured coating (A), the thickness of the cured coating (A), and the cured coating (B). It is possible to control by appropriately selecting the type and content of the component (b1), the component (b2), and the thickness of the cured coating (B).

  The 2nd aspect of the resin laminated body of this invention is a sheet-like resin laminated body by which the functional layer (C) mentioned later was laminated | stacked on the surface of the cured film (B) of the resin laminated body of a 1st aspect.

  In the resin laminate of the second embodiment, the pencil hardness of the cured film (A) is preferably 8H or more for the same reason as described in the resin laminate of the first embodiment.

  In the second aspect of the resin laminate, the cured coating (B) is one selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer. A functional layer composed of a layer having a function can be used. The specific low refractive index layer, high refractive index layer, hard coat layer, antistatic layer, antiglare layer and antifouling layer are not particularly limited, and a functional layer made of a known resin composition is used. be able to.

  Accordingly, the resin laminate of the second aspect has at least one function selected from an antireflection function, an antistatic function, an antiglare function, and a stain prevention function, and the pencil hardness of the surface of the resin laminate is 8H or more. Therefore, it can have high surface hardness and scratch resistance. The pencil hardness value of the cured coating (A) can be controlled by the method described above.

  In the resin laminate of the second aspect, the residual ratio of the cured film (B) and the functional layer (C) by the cross-cut peel test in accordance with ISO 2409: 1992 is the scratch resistance of the resin laminate. From the viewpoint of good crack resistance, it is preferably 80% or more, more preferably 90% or more, and even more preferably 100%. The residual ratio of the cured film (B) and the functional layer (C) as used herein refers to the cured film (B) and the functional layer (C) remaining on the resin laminate without being peeled after the cross-cut peel test. ). As will be described later, the value of the residual ratio is the type and content of the (a1) component and (a2) component constituting the cured coating (A), the thickness of the cured coating (A), and the cured coating (B). It is possible to control by appropriately selecting the type and content of the component (b1), the component (b2), and the thickness of the cured coating (B).

  The third aspect of the resin laminate of the present invention is provided with the following cured coating (A) on at least one surface of a resin substrate described later, and opposed to the surface in contact with the resin substrate in the cured coating (A). A sheet-like resin laminate comprising the following cured coating (B) on the surface to be coated, and the following functional layers (C) sequentially laminated on the surface facing the cured coating (A) in the cured coating (B) Is the body.

  In the resin laminate according to the third aspect, the cured coating (A) has two or more repeating units (a1) derived from a monomer having three or more (meth) acryloyloxy groups in the molecule and two in the molecule. The repeating unit (a2) derived from a monomer having the following (meth) acryloyloxy group can be included.

  The pencil hardness of the cured coating (A) is preferably 8H or more for the same reason as described in the resin laminate of the first aspect. The pencil hardness of the cured coating (A) can be controlled by appropriately adjusting the contents of the repeating unit (a1) and the repeating unit (a2) contained in the cured coating (A).

  Moreover, in the resin laminated body of the 3rd aspect, a cured film (B) contains at least 1 sort (s) of the urethane (meth) acrylate unit (b2-1) and the (meth) acrylate unit (b2-2) which has an amino group. Can be included. By including the unit (b2-1) and the unit (b2-2), in the resin laminate, adhesion between the cured coating (B) and the cured coating (A), and scratch resistance of the resin laminate. Is good.

  Thereby, since the resin laminated body of the 3rd aspect can make the pencil hardness of the surface of a resin laminated body 8H or more, it can have high surface hardness and scratch resistance. As will be described later, the value of the pencil hardness of the cured coating (A) can be controlled by appropriately selecting the composition and film thickness of the cured coating (A) and the cured coating (B).

  Moreover, the resin laminated body of a 3rd aspect can also laminate | stack the functional layer (C) mentioned above on the surface of the said cured film (B).

<Resin substrate>
Examples of the resin base material used in the resin laminate of the present invention include polyolefin resin, (meth) acrylic resin, epoxy resin, polyimide resin, phenol resin, polyester resin, and polycarbonate resin. A plurality of the above resins may be laminated on the resin base material.

  As the resin base material, the total weight of the resin constituting the resin base material is 100% by mass, and 90 to 100% by mass of (meth) acrylic resin is contained, whereby the transparency of the resin laminate is improved. To preferred.

  The (meth) acrylic resin constituting the resin base material is preferably a polymer having a methyl methacrylate unit as a main component. As the polymer having the methyl methacrylate unit as a main component, a polymer containing 50 to 100% by mass of repeating units derived from methyl methacrylate is preferable, with the total weight of the (meth) acrylic resin being 100% by mass, A polymer containing 80 to 100% by mass is more preferable, and a polymer composed of 100% by mass is more preferable.

  When the (meth) acrylic resin is a polymer having a methyl methacrylate unit as a main component, a monomer copolymerizable with methyl methacrylate constituting the polymer (hereinafter referred to as “other copolymerizable monomer”). For example, the following may be mentioned.

1) Methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (Meth) acrylic acid esters such as methacrylate and benzyl methacrylate;

2) Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and itaconic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride;

3) Maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

4) Hydroxy group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

5) Vinyl esters such as vinyl acetate and vinyl benzoate; vinyl chloride, vinylidene chloride and derivatives thereof; nitrogen-containing vinyl monomers such as (meth) acrylamide and (meth) acrylonitrile; epoxy groups such as glycidyl (meth) acrylate Containing monomer;

6) Aromatic vinyl monomers such as styrene and α-methylstyrene.

  Among these, n-butyl acrylate, tert-butyl methacrylate and isobornyl (meth) acrylate are preferable in terms of reducing the water absorption rate of the resin base material.

  Examples of other copolymerizable monomers include the following in addition to the above monomers.

7) Alkanediol di (meth) acrylate such as ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate (Meth) acrylate;

8) Diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Polyoxyalkylene glycol di (meth) acrylates such as acrylates;

9) A vinyl monomer having two or more ethylenically unsaturated bonds in a molecule such as divinylbenzene;

10) an unsaturated polyester prepolymer obtained from at least one polycarboxylic acid containing ethylenically unsaturated polycarboxylic acid and at least one diol;

11) and a vinyl ester prepolymer obtained by modifying the terminal of the epoxy group with acrylic. Among these, neopentyl glycol dimethacrylate is preferred in terms of improving the heat resistance of the resin laminate.

  A polymer having a methyl methacrylate unit as a main component on the resin base material can be obtained by polymerizing the resin base material.

Examples of the resin base material include (a) to (c) below, but are not limited thereto.
(A) A radical polymerizable monomer mixture containing 50% by mass or more and 100% by mass of methyl methacrylate and 0% by mass or more and 50% by mass of another copolymerizable monomer may be mentioned.
(B) A mixture of a partial polymer and an unpolymerized radical polymerizable monomer obtained by polymerizing a part of the radical polymerizable monomer mixture (hereinafter referred to as “syrup 1”).
(C) A (meth) acrylic resin obtained by dissolving a (meth) acrylic resin obtained from a monomer raw material having the same or different composition as the radical polymerizable monomer mixture in the radical polymerizable monomer mixture. And a radically polymerizable monomer (hereinafter referred to as “syrup 2”).

  Resin base materials include colorants, mold release agents, antioxidants, stabilizers, flame retardants, impact modifiers, light stabilizers, UV absorbers, polymerization inhibitors, chain transfer agents as necessary. Various additives such as can be added.

  A polymerization initiator can be added to the resin base material. As a polymerization initiator, a known organic peroxide or an azo compound, a redox polymerization in which a known organic peroxide is combined with an amine such as N, N-dimethylaniline or N, N-dimethyl-p-toluidine Agents. The addition amount of the polymerization initiator is preferably 0.005 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the radical polymerizable monomer in the resin base material.

  As a polymerization method of the resin base material, for example, a known bulk polymerization method, solution polymerization method, emulsion polymerization method and suspension polymerization method can be used. Among these, the bulk polymerization method is preferable from the viewpoint of excellent production cost of the (meth) acrylic resin composition, environmental load due to the use of a solvent, productivity of the (meth) acrylic resin molded product, and transparency.

  The thickness of the resin base material is not particularly limited, but can be 0.1 mm or more and 10 mm or less. 0.3 mm or more and 3.0 mm or less are more preferable. In addition, in this application, the thickness of a resin base material says the average value which measured the distance from an upper surface to a bottom face using arbitrary calipers five places.

<Hardened film (A)>
As one aspect of the present invention, the cured coating (A) is one of the components constituting the resin laminate of the present invention, and is formed on the first surface of the resin base material. The resin composition constituting the cured coating (A) is composed of a repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule and 2 or less (meth) acryloyl in the molecule. It contains a repeating unit (a2) derived from a monomer having an oxy group.

  In the present specification, the monomer constituting the repeating unit derived from (a1) is referred to as “component (a1)”, and the monomer constituting the repeating unit derived from (a2) is represented by “ (A2) component ".

  The film thickness of the cured coating (A) is not particularly limited, but can be 17 μm or more and 40 μm or less. The lower limit of the film thickness is preferably 17 μm or more, more preferably 20 μm or more, and even more preferably 25 μm or more from the viewpoint of good scratch resistance and surface hardness of the cured film. In addition, the upper limit of the film thickness is preferably 40 μm or less from the viewpoint of being able to suppress cracking during cutting of the resin product, suppressing cracks from occurring in the cured film during handling of the resin product, and improving workability. Is more preferable. That is, the film thickness of the cured coating is more preferably 25 μm or more and 35 μm or less. The film thickness of a cured film (A) here means the film thickness of the cured film (A) in the resin laminate.

  In the present invention, the cured coating (A) preferably has a surface with a pencil hardness of 8H or more from the viewpoint of the surface hardness and scratch resistance of the resin laminate. In the present invention, the pencil hardness is a value obtained according to JISO 2409: 1992.

<(A1) component>
In the present invention, the component (a1) is a monomer constituting a repeating unit derived from a monomer having three or more (meth) acryloyloxy groups in the molecule.

  When the cured coating (A) contains the component (a1), the scratch resistance and surface hardness of the resin laminate are improved, the crack resistance of the cured coating (A) is improved, and the cured coating on the resin substrate. The adhesion of (A) can be improved.

  (A1) As a component, the monomer which has a (meth) acryloyloxy group is mentioned, For example, the monomer which has 3 or more and 20 or less (meth) acryloyloxy groups is mentioned.

  Specific examples of the component (a1) include monomers in which the residue bonded to each (meth) acryloyloxy group is a hydrocarbon group or a derivative thereof, and in the molecule, an ether bond, a thioether bond, an ester A bond such as a bond, an amide bond, and a urethane bond can be included.

  Specific examples of the component (a1) include an esterified product and a polyhydric alcohol obtained from 1 mol of a polyhydric alcohol and 3 mol or more of (meth) acrylic acid or a derivative thereof, and a polyvalent carboxylic acid or an anhydride thereof. And a linear esterified product obtained from (meth) acrylic acid or a derivative thereof.

  As used herein, “polyhydric alcohol” refers to an alcohol having two or more hydroxyl groups in the molecule. “Polyvalent carboxylic acid” refers to a carboxylic acid having two or more carboxyl groups in the molecule. The “derivative of (meth) acrylic acid” refers to a compound in which a hydrogen atom of (meth) acrylic acid is substituted with another functional group. “Linear” means linear and branched.

  Examples of esterified products obtained from 1 mol of polyhydric alcohol and 3 mol or more of (meth) acrylic acid or derivatives thereof include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ethylene oxide Adduct trimethylolpropane tri (meth) acrylate, propylene oxide adduct trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate , Tripentaerythritol tetra (meth) acrylate, ethylene oxide adduct pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone adduct dipentaerythritol penta (meth) acrylate And caprolactone adduct dipentaerythritol hexa (meth) acrylate.

  In a linear esterified product obtained from a polyhydric alcohol, a polyhydric carboxylic acid or an anhydride thereof, and (meth) acrylic acid or a derivative thereof, the polyhydric alcohol, the polyhydric carboxylic acid or an anhydride thereof, Preferred examples of combinations of (meth) acrylic acid include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / Pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, sebacine Acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolethane Emissions / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, maleic acid / trimethylolpropane / (meth) acrylic anhydride. These may be used alone or in combination of two or more.

  As the component (a1), one type of monomer can be used alone, or two or more types of monomers can be used in combination.

  As the component (a1), pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipenta are used in terms of scratch resistance and surface hardness of the cured coating (A). Erythritol hexa (meth) acrylate is more preferred.

  The content of the component (a1) is not particularly limited, but 55% by mass or more and 90% by mass with respect to 100% by mass of the total weight of the curable composition containing the component (a1) and the component (a2) described later. % Or less. The lower limit of the content of the component (a1) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% by mass or more from the viewpoint of improving the scratch resistance and surface hardness of the cured coating (A). preferable. The upper limit of the content of the component (a1) is that the curing shrinkage rate when the curable composition containing the component (a1) and the component (a2) described later is cured is reduced, and the crack resistance of the cured film (A) is reduced. From the viewpoint of improving the adhesion of the cured film (A) to the resin base material, is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 75% by mass or less.

<(A2) component>
In the present invention, the component (a2) is a monomer constituting a repeating unit derived from a monomer having 2 or less (meth) acryloyloxy groups in the molecule.

  When the cured coating (A) contains the component (a2), the adhesion between the cured coating (A) and the resin substrate is improved, the crack resistance of the cured coating (A) is improved, and the cured coating (A ) Can be prevented from warping.

  Examples of the component (a2) include the following.

  As a (meth) acrylate monomer having two (meth) acryloyl groups in the molecule, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol Di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, 1,10-decandiol di (meth) acrylate and hydroxy Examples include pivalate neopentyl glycol di (meth) acrylate.

  As a monomer having one (meth) acryloyl group in the molecule, for example, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate , Lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, polyethylene Glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-ethylhexyl polyoxy (meth) acrylate, benzyl (meth) acrylate, tri Cyclodecane mono (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, ethoxydiethylene glycol Call (meth) acrylate, methoxy triethylene glycol (meth) acrylate and 2-methacryloyloxyethyl-2-hydroxyethyl phthalate.

  The component (a2) described above may be used alone or in combination of two or more. Among these, 1,6-hexanediol di (meth) acrylate is preferable in terms of enhancing the adhesion between the cured coating (A) and the resin substrate.

  The content of the component (a2) is not particularly limited, but is 10% by mass to 50% by mass with respect to 100% by mass of the total weight of the curable composition containing the component (a1) and the component (a2). can do. The lower limit of the content of the component (a2) is that the curing shrinkage rate when the curable composition containing the component (a1) and the component (a2) is cured decreases, and the crack resistance of the cured film (A) is good. From the viewpoint of improving the adhesion of the cured coating (A) to the resin substrate and suppressing the warpage of the resin laminate in which the cured coating (A) is laminated on the surface of the resin substrate. % Or more is preferable, 15 mass% or more is more preferable, and 25 mass% or more is more preferable. The upper limit of the content of the component (a2) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less from the viewpoint of improving the scratch resistance and surface hardness of the cured film (A). preferable.

<Other additives>
The said curable composition used for manufacture of a cured film (A), or the curable composition (s1) and curable composition (s2) used for manufacture of the cured film (B) mentioned later are as needed. Organic solvents, mold release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers, UV absorbers, flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane couplings Various additives such as an agent, a leveling agent, an antifoaming agent, a fluorescent agent, and a chain transfer agent can be contained.

<Polymerization initiator>
The curable composition used for the production of the cured film (A), or the curable composition (s1) and the curable composition (s2) used for the production of the cured film (B) described below, are known polymerization initiations. An agent can be contained.

  Examples of the polymerization initiator include benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2 Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzene such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Inethers; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; methylbenzoylformate; 1 , 7-bisacridinyl heptane; and 9-phenylacridine. These can be used alone or in combination of two or more.

  The addition amount of the polymerization initiator is not particularly limited, but the total weight of the curable composition is 100 parts by mass (excluding the polymerization initiator) in terms of promoting the curability of the curable composition. Is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5.0 parts by mass or less.

<Method for forming cured coating (A)>
As a method for forming the cured film (A), for example, after applying a curable composition as a raw material of the cured film (A) to the surface of the resin substrate, the coating film of the curable composition is heated or The method of irradiating an active energy ray to a coating film is mentioned.

  The cured coating (A) of this invention can be laminated | stacked on the 1st surface of a resin base material, or a 1st surface and a 2nd surface, and can be selected according to the objective. The 2nd surface of a resin base material means the surface which opposes the 1st surface of a resin base material in a resin base material.

  Examples of the method for applying the curable composition to the surface of the resin substrate include a casting method, a roller coating method, a bar coating method, a spray coating method, and an air knife coating method.

  Examples of the method for laminating the cured coating (A) on the surface of the resin substrate include the following two methods.

(1) A method of curing a coating film of the curable composition after forming a coating film of the curable composition on the surface of the resin substrate.

(2) A mold (1) in which a coating film of a curable composition is formed on the surface of a mold, and then a coating film of the curable composition is cured, and a cured film (A) is laminated on the surface of the mold Get. Next, the mold (1) and another mold (mold (2)) are arranged so as to face each other so that the cured coating (A) is on the inside, thereby forming a laminated mold. Next, a method of removing the two molds after pouring a resin base material into the space of the laminated mold, cast polymerizing the resin base material

  Among the above methods, the method (2) is preferable from the viewpoint of obtaining a cured film (A) having high pencil hardness.

  When the curable composition is cured by the methods (1) and (2), the surface of the coating film of the curable composition is obtained in order to obtain a cured film (A) having a good appearance free from defects due to foreign matters and the like. It can coat | cover with the resin film mentioned later. Moreover, after covering the surface of the curable composition with a resin film, the resin film surface can be smoothed using a roll such as a rubber roll having a hardness of 40 ° in accordance with JIS K 6253. By the smoothing treatment with a roll, a cured film (A) having a more uniform film thickness can be obtained, and a cured film having high smoothness and a desired film thickness tends to be obtained. Moreover, when using an active energy ray curable composition as a curable composition, the crosslinking reaction of a curable composition is enough by irradiating an active energy ray after coat | covering the surface of a curable composition with a resin film. The cured film having a good curing degree tends to be obtained, and the scratch resistance and surface hardness of the cured film (A) tend to be good.

<Resin film>
As a resin film used for manufacture of a cured film (A), a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, and a polyvinylidene fluoride (PVDF) film are mentioned, for example. Among these, a PET film is preferable in terms of cost and curability of the curable composition.

  The thickness of the resin film is preferably 8 μm or more and 125 μm or less in terms of the strength, handleability and cost of the resin film.

<Active energy rays>
When the curable composition is cured with an active energy ray, examples of the active energy ray include an electron beam, an ultraviolet ray and a visible ray, and an ultraviolet ray is preferable from the viewpoint of apparatus cost and productivity.

Examples of the active energy ray light source include a fluorescent ultraviolet lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an Ar laser, a He-Cd laser, a solid laser, a xenon lamp, and a high frequency. Examples include induction mercury lamps and sunlight. Among these, a fluorescent ultraviolet lamp and a high-pressure mercury lamp are preferable from the viewpoint of the curing rate of the curable composition (a). The integrated light quantity of the active energy ray, 5 mJ / cm ² or more 2,000 mJ / cm ² or less.

<Hardened film (B)>
The cured coating (B) is one of the components constituting the resin laminate of the present invention, and faces the surface in contact with the resin substrate in the cured coating (A) laminated on the first surface of the resin substrate. It is formed on the surface.

  In the present invention, when the cured coating (A) is laminated on the first surface and the second surface of the resin substrate, the cured coating (B) is a cured coating (A) laminated on the first surface of the resin substrate. Even if it is laminated | stacked only on it, it may be laminated | stacked on both of the cured film (A) laminated | stacked on the 1st surface and 2nd surface of the resin base material, and it can select according to the objective.

  In the resin laminate of the present invention, the cured film (B) has a pencil hardness of 8H or more, and the residual rate of the cured film (B) by a cross-cut peel test in accordance with ISO 2409: 1992 is 80% or more. Further, by setting the pencil hardness of the surface of the cured coating (B) to 8H or more, it is possible to suppress the occurrence of scratches caused by finger nails on the surface of the resin laminate, and to obtain a resin laminate having good scratch resistance. be able to.

  In the resin laminate of the present invention, the cured coating (B) is a functional layer having one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer. Is a cured film (B ′), or a cured film (B ″) of an adhesive layer that bonds the cured film (A) and a functional layer (C) described later.

  The film thickness of the cured coating (B ′) is not particularly limited, but is preferably 0.6 μm or more and 3 μm or less. The lower limit of the film thickness of the cured film (B ′) is preferably 0.6 μm or more and more preferably 1 μm or more from the viewpoint of good scratch resistance and surface hardness of the cured film. Further, the upper limit of the film thickness is preferably 3 μm or less, more preferably 2 μm or less, from the viewpoint of improving the adhesion with the cured coating (A). That is, the film thickness of the cured coating (B) is preferably 1 μm or more and 2 μm or less.

  The film thickness of the cured coating (B ″) is not particularly limited, but is preferably 3 μm or more and 7 μm or less. The lower limit of the film thickness of the cured film (B ′) is preferably 3 μm or more, and more preferably 4 μm or more, from the viewpoint of improving the appearance of the cured film. Further, the upper limit of the film thickness is preferably 7 μm or less, and more preferably 6.5 μm or less from the viewpoint of improving the adhesion between the cured film (A) and the functional layer (C) described later. That is, the thickness of the cured coating (B) is more preferably 4 μm or more and 6.5 μm or less.

  The film thickness of the cured film (B) here refers to the film thickness of the cured film (B) in the resin laminate. Regarding the thickness of the cured coating (B), a sample having a width of 100 nm was cut out with a microtome in the thickness direction, and a cross section of the resin laminate was observed with a transmission electron microscope (JEM-1010 (trade name) manufactured by JEOL Ltd.).

<Curable composition (s1)>
In this invention, a curable composition (s1) is a raw material used in order to obtain the said cured film (B ').

  Examples of the curable composition (s1) include at least one of a component (b1) described later, a component (b2-1) described later, and a component (b2-2) described later, an organic solvent (b4) described later, And a composition containing a polymerization initiator.

  Furthermore, for the purpose of lowering the viscosity of the curable composition (s1), at least one monomer selected from monomers having one or two (meth) acryloyloxy groups in the molecule is added. be able to. Specifically, the same thing as the component (a2) mentioned above is mentioned. These can be used alone or in combination of two or more.

<Curable composition (s2)>
In the present invention, the curable composition (s2) is a raw material used for obtaining the cured film (B ″).

  Examples of the curable composition (s2) include at least one of a component (b1) described later, a component (b2-1) described later, and a component (b2-2) described later, inorganic fine particles (b3) described later, And a composition containing a polymerization initiator.

  Furthermore, for the purpose of lowering the viscosity of the curable composition (s2), at least one monomer selected from monomers having one or two (meth) acryloyloxy groups in the molecule is added. be able to. Specifically, the same thing as the component (a2) mentioned above is mentioned. These can be used alone or in combination of two or more.

<(B1) component>
In the present invention, the component (b1) refers to a monomer constituting a repeating unit derived from a monomer having three or more (meth) acryloyloxy groups in the molecule. The component (b1) has the effect of improving the scratch resistance and surface hardness of the resin laminate by improving the hardness of the cured coating (B).

  Examples of the component (b1) include the same monomers as those described in the component (a1). For example, a monomer having 3 to 20 (meth) acryloyloxy groups in one molecule. Can be mentioned. These can be used alone or in combination of two or more.

  As component (b1), trimethylolpropane triacrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate is preferred.

<(B2-1) component>
In the present invention, the component (b2-1) refers to a monomer that constitutes a repeating unit derived from urethane (meth) acrylate. The component (b2-1) has an effect of improving the adhesion between the cured film (B) and the cured film (A) and improving the scratch resistance and surface hardness of the resin laminate.

  Examples of the component (b2-1) include 1,5-diisocyanatopentane, 1,6-diisocyanatohexane, 1,4-diisocyanatopentane, 1,6-diisocyanato-3,5,5- Trimethylhexane, 1,6-diisocyanato-3,3,5-trimethylhexane, 1,12-diisocyanatododecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane 1,6,11-triisocyanatoundecane, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,2-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,2-hydrogenated xylylene diisocyanate, 1, , 4-Hydrogenated xylylene diisocyanate, tetramethyloxy Isocyanate compounds such as diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate, polyethylene glycol (repeating unit = 6-20), polypropylene glycol (repeating unit = 6-20), polybutylene glycol (repeating unit) = 6-20) 1-methylbutylene glycol (repeating unit = 6-20), polytetramethylene glycol (repeating unit = 6-20), polycaprolactone diol, caprolactone addition of alkylene (2-10 carbon atoms) diol (repeating) Unit = 2 to 10) Diol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, phthalic acid and alkylenediode Polyol compounds such as polyester diols and polycarbonate diols (aliphatic skeleton having 4 to 6 carbon atoms) derived from ruthenium, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Having a hydroxyl group such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-hydroxyethyl-N ′, N ″ -di ((meth) acryloxyethoxyethyl) isocyanurate (meta ) Urethane (meth) acrylate reacted with acrylate; hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,2-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1 , 2-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate -Urethane poly (meth) acrylate added with (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and their caprolactone adducts; 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,4-diisocyanatopentane, 1,6-diisocyanato-3,5, -Trimethylhexane, 1,6-diisocyanato-3,3,5-trimethylhexane, 1,12-diisocyanatododecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanato Hexane, 1,6,11-triisocyanatoundecane hexane, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate , A monomer or multimer of an isocyanate compound such as decalin diisocyanate, lysine diisocyanate, lysine triisocyanate, Examples include urethane (meth) acrylate added with (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and caprolactone adducts thereof. It is done.

  Other examples of the component (b1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3 with respect to 1 mol of the polyisocyanate represented by the following formula (I). -Urethane (meth) acrylate obtained by reacting 3 mol or more of an acrylic monomer having active hydrogen such as methoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, etc .; Tris (2- And poly [(meth) acryloyloxyethyl] isocyanurate such as tri (meth) acrylate of hydroxyethyl) isocyanuric acid; epoxy poly (meth) acrylate; and urethane poly (meth) acrylate.

(I)
(In formula (I), R represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may contain a substituent.)

  Examples of the polyisocyanate represented by the formula (I) include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene. Polyisocyanates obtained by trimerization of isocyanate compounds such as diisocyanate are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  As the component (b2-1), a urethane (meth) acrylate having 3 or more (meth) acryloyloxy groups is preferable, and a urethane (meth) acrylate having 6 or more (meth) acryloyloxy groups is more preferable.

<(B2-2) component>
In the present invention, the component (b2-2) refers to a monomer constituting a repeating unit derived from a (meth) acrylate having an amino group. The component (b2-2) has an effect of improving the adhesion between the cured coating (B) and the cured coating (A) and improving the scratch resistance and surface hardness of the resin laminate.

  Examples of the component (b2-2) include acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate, tetrachlorophenyl (meth) acrylate, N-vinylformamide, Nn-butoxymethyl (meth) acrylamide N-isobutoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide and (meth) acryloylmorpholine. These can be used alone or in combination of two or more.

  The total content of the component (b2-1) and the component (b2-2) described above is not particularly limited, but the solid content of the curable composition (s1) or the curable composition (s2) is 100 masses. % (However, excluding the polymerization initiator) can be 1.0% by mass or more and 15% by mass or less. The lower limit of the content is preferably 1.0% or more and more preferably 2.2% by mass or more from the viewpoint of good adhesion of the cured film (B) to the cured film (A). The upper limit of the content is preferably 15% by mass or less and more preferably 10% by mass or less from the viewpoint of improving the scratch resistance and surface hardness of the cured coating (B).

<(B3) component>
In the present invention, the component (b3) refers to inorganic fine particles. When the curable composition (s2) contains the inorganic fine particles (b3), the adhesion of the cured coating (B ″) to the cured coating (A) is improved, and the scratch resistance of the cured coating (B). Can be improved.

  Examples of the component (b3) include inorganic particles such as amorphous silica, crystalline silica, silica-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, vaterite type), zeolite, alumina, hydroxyapatite, Heat-resistant polymer particles such as crosslinked acrylic particles, crosslinked PMMA particles, crosslinked polystyrene particles, nylon particles, polyester particles, benzoguanamine / formalin condensate particles, benzoguanamine / melamine / formaldehyde condensate particles, melamine / formaldehyde condensate particles, and silica / acrylic Organic / inorganic hybrid fine particles such as composite compounds are exemplified.

  Examples of the shape of the inorganic fine particles (b3) include a spherical shape, a block shape, a plate shape, a fiber shape, and a flake shape. Among these, the dispersibility and the falling off of the particles when coming into contact with other members are included. From the viewpoint of difficulty, spherical particles are preferred.

  The average particle size of the inorganic fine particles (b3) is not particularly limited, but for example, from the viewpoint of good dispersibility of the inorganic fine particles in the cured film, the average particle size is preferably 1 nm to 300 nm, 3 nm or more and 100 nm or less are more preferable.

  The average particle diameter is a value measured according to JIS Z 8825-1 using a particle size distribution analyzer SALD-7100 (product name, manufactured by Shimadzu Corporation).

  The content of the component (b3) is not particularly limited, but is 1.0 mass when the total weight of the solid content of the curable composition (s2) is 100 mass% (excluding the polymerization initiator). % To 10% by mass. The lower limit of the content of the component (b3) is preferably 1.0% by mass or more, and more preferably 2.0% by mass or more from the viewpoint of good adhesion of the cured film (B) to the cured film (A). The upper limit of the content of the component (b3) is preferably 10% by mass or less and more preferably 7.5% by mass or less from the viewpoint of improving the scratch resistance of the cured coating (B).

<(B4) component>
In the present invention, the component (b4) improves the coating property by reducing the viscosity of the curable composition (s1) and improves the adhesion between the cured coating (B ′) and the cured coating (A). For the purpose and the purpose of improving the appearance of the cured coating (B ′), it means at least one organic solvent in the curable composition (s1).

  Examples of the component (b4) include non-fluorine solvents such as hydrocarbon solvents and fluorine-containing solvents.

  Specific examples of the non-fluorine solvent include ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone; monohydric alcohols such as ethanol, 1-propanol, 2-propanol, butanol and 1-methoxy-2propanol, ethylene glycol, diethylene glycol, Alcohols such as polyhydric alcohols such as propylene glycol; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; ethers such as diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, tetrahydrofuran and 1,4-dioxane; toluene, xylene And aromatic amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Specific examples of the fluorine-containing solvent include fluorine-containing alcohols, fluorine-containing ethers, hydrofluorocarbons, and ditrifluoromethylbenzene.

Specific examples of the fluorinated alcohol include H (CF ₂ ) _m (CH ₂ ) _n —OH, F (CF ₂ ) _o (CH ₂ ) _p —OH, F (CF ₂ ) _q CH═CHCH ₂ OH and F _{(CF 2)} a compound represented by _{r CH 2 CH (I) CH} 2 OH and the like. In the above formula, m, n, o, p, q and r each independently represent an integer of 1 to 8.

Specific examples of the fluorine-containing ether include compounds represented by R ²¹ —O—R ²² . In the above formula, R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, and at least one of R ²¹ and R ²² contains a fluorine atom.

  Examples of the fluorinated ether include hydrofluoroalkyl ether. Moreover, as a commercial item of fluorine-containing ether, Sumitomo 3M Co., Ltd. product "HE-7100" (brand name) and "HFE-7200" (brand name) are mentioned, for example.

  Specific examples of the hydrofluorocarbon include a hydrofluorocarbon having a chain structure and a cyclic structure.

  Examples of commercially available hydrofluorocarbons include “Bertrel HFC43-10mee” (trade name) manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and “Zeorolla H” (trade name) manufactured by Nippon Zeon Co., Ltd.

  Specific examples of ditrifluoromethylbenzene include o-ditrifluoromethylbenzene, m-ditrifluoromethylbenzene, p-ditrifluoromethylbenzene, and mixtures thereof.

  The organic solvent (b4) can be used alone or in combination of two or more. As the organic solvent, ethanol, 2-propanol, ethyl acetate, and toluene are preferable, and ethyl acetate is preferable in terms of improving the adhesion with the cured film (A) and improving the appearance of the cured film (B). Particularly preferred.

<Method for forming cured coating (B ')>
As a method for forming the cured coating (B ′), for example, after applying the curable composition (s1) to the surface of the cured coating (A), the coating of the curable composition (s1) is heated or activated energy rays. Is a method of curing the curable composition (s1) to form a cured coating (B).

  Examples of the method for applying the curable composition (s1) to the surface of the cured film (A) include the same method as the method for applying the curable composition for forming the cured film (A).

<Hardened film (B ')>
The cured coating (B ′) is a functional layer composed of a layer having one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer.

  The low refractive index layer refers to a layer having a refractive index of 1.3 to 1.5. In order to lower the refractive index, the curable composition (s1) may contain colloidal silica as necessary. As the colloidal silica, a colloidal solution obtained by dispersing at least one kind of fine particles selected from porous silica and non-porous silica in a dispersion medium can be used. Here, the porous silica is low-density silica in which the inside of the particle is porous or hollow and contains air inside. Examples of the refractive index of porous silica include 1.20 to 1.40, which is lower than the refractive index of 1.45 to 1.47 of ordinary silica. Moreover, in this invention, the colloidal silica by which the surface was processed with the silane coupling agent can be used as needed.

  The high refractive index layer refers to a layer having a refractive index of 1.3 to 1.5. . In order to increase the refractive index, metal oxide fine particles having a high refractive index can be dispersed in the curable composition (s1). Examples of the metal oxide fine particles include metal oxides obtained by condensing metal alkoxide after hydrolysis.

Examples of the metal alkoxide include those represented by the following formula (II).

M (OR) _m (II)
(In formula (II), M represents a metal atom, R represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents the valence (3 or 4) of the metal atom M.)

  As the metal atom M, titanium, aluminum, zirconium and tin are preferable, and titanium is more preferable in view of the refractive index of the high refractive index layer.

  Specific examples of the metal alkoxide include titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide and aluminum. Examples include t-butoxide, tin t-butoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide and zirconium n-butoxide.

In the present invention, from the viewpoint of achieving a higher refractive index of the metal oxide film, a high refractive index metal oxide, ZrO ₂ , TiO ₂ , NbO, _{ITO, ATO, SbO 2, in} 2 O 3, those obtained by dispersing at least one kind of fine particles selected from SnO ₂ and ZnO are preferable.

  The lower limit of the film thickness of the low refractive index layer and the high refractive index layer is preferably 50 nm or more, and more preferably 70 nm or more. Moreover, the upper limit of the film thickness of the low refractive index layer and the high refractive index layer is preferably 200 nm or less, and more preferably 150 nm or less. The film thicknesses of the low refractive index layer and the high refractive index layer are each preferably 50 nm to 200 nm, and more preferably 70 nm to 150 nm. When the film thickness is within this range, reflected light having a visible wavelength tends to be sufficiently suppressed.

  Examples of the antireflection layer include a low refractive index layer having a refractive index lower than that of the cured coating (A), a laminated structure having a two-layer structure in which a low refractive index layer is laminated on a high refractive index layer, or a high refractive index. A layered structure having a three-layer structure in which a middle refractive index layer and a low refractive index layer are sequentially laminated on the refractive index layer can be mentioned. The antireflection layer is preferably such that the amount of reflected light of light incident in the direction toward the inside of the resin laminate on the surface of the resin laminate is 0% or more and 20% or less of the amount of incident light. What becomes 10% or less is more preferable, and what becomes 0% or more and 5% or less is still more preferable.

  When the antireflection layer has a two-layer structure in which a low refractive index layer is laminated on a high refractive index layer, for example, the refractive index of the low refractive index layer is 1.3 to 1.5, and a high refractive index The refractive index of the refractive index layer is preferably in the range of 1.6 to 2.0. If it is this range, reflection of incident light can be sufficiently suppressed.

  When the cured coating (B ′) is used as an antistatic layer, a known antistatic component may be added to the curable composition (s1). Examples of the antistatic component include an electron conductive organic compound, conductive particles, and an ion conductive organic compound.

  Examples of the π-conjugated conductive organic compound include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), and heterocyclic conjugated polypyrrole.

  Examples of the conductive fine particles include carbon-based, metal oxide-based, and conductive coating-based fine particles.

  Examples of the carbon-based fine particles include carbon powders such as carbon black, ketjen black, and acetylene black, and carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers.

  Metal oxide fine particles include tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO), zinc oxide, aluminum-doped zinc oxide, zinc antimonate, pentoxide And antimony.

  Examples of the conductive coated fine particles include conductive particles in which various fine particle surfaces such as titanium oxide (spherical, needle-shaped), potassium titanate, barium sulfate, mica, silica, etc. are coated with antistatic components such as tin oxide, ATO, and ITO. Resin beads such as polystyrene, acrylic resin, epoxy resin, polyamide resin, and polyurethane resin, which are surface-treated with a metal such as conductive fine particles, gold and / or nickel, are preferable. Examples of the ion conductive organic compound include compounds having a quaternary ammonium base, polystyrene sulfonic acid, and the like.

  As the antiglare layer, when the cured coating (B ′) is an antiglare layer, a method for forming fine irregularities on the surface of the antiglare layer, and light scattering particles are added to the inside of the string prevention layer to cause internal scattering. Thus, reflection of external light can be suppressed by at least one method of irregularly reflecting external light. As the light diffusing fine particles, organic fine particles or inorganic fine particles can be used. As the organic fine particles, for example, acrylic resin (PMMA), polystyrene (PS), acrylic-styrene copolymer, melamine resin, polycarbonate (PC) and the like can be used. The organic fine particles are not particularly limited in properties such as crosslinking and non-crosslinking, and can be arbitrarily selected. Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin and calcium sulfate. These inorganic fine particles are preferably subjected to an organic treatment such as a silane coupling treatment so that the fine particles are easily dispersed in the organic matter.

  The size of the inorganic fine particles can be appropriately selected. As the shape of the fine irregularities on the surface of the resin laminate, the surface center line average roughness is preferably 0.05 μm or more and 0.3 μm or less, and the pitch of the fine irregularities is preferably 30 μm or more and 200 μm or less. Fine particles will be used.

  The antifouling layer preferably has water repellency or oil repellency, or has hydrophilicity or lipophilicity. When dirt such as fingerprints, sebum, sweat, cosmetics, etc. adheres, it is preferable to have water repellency and oil repellency from the viewpoint of easily removing the dirt. Examples of a method for imparting water repellency and oil repellency to the antifouling layer include a method of adding a (meth) acrylate monomer having a fluorine atom to the curable composition (s1). The (meth) acrylate monomer having a fluorine atom is not particularly limited, and a known compound can be used.

  Specifically, “Biscoat 17F” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is heptadecane fluorodecyl acrylate, “Light acrylate FA-108” (trade name, Kyoeisha), which is perfluorooctylethyl acrylate. Chemical Co., Ltd.), 1,10-bis (meth) acryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- “16-FDA” (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), which is hexadecafluorodecane. In order to improve the water repellency or oil repellency of the water repellent layer, a (meth) acrylate having a perfluoropolyether group is preferred. Specific examples include “OPTOOL DAC” (trade name) manufactured by Daikin Industries, Ltd., “EXP RS-503” and “EXP RS-751-k” manufactured by DIC Corporation.

The (meth) acrylate monomer which has a fluorine atom can be used 1 type or in combination of 2 or more types. <Hardened film (B ')>
The cured film (B ″) is an adhesive layer that adheres the cured film (A) and a functional layer (C) described later.

<Method for forming cured coating (B ″)>
The following method is mentioned as a preferable example of the formation method of a cured film (B '').

  A functional layer (C) on the surface of the resin film on which a functional layer (C) described later is formed and a resin laminate on which the cured coating (A) is laminated are laminated via the curable composition (s2). This curable composition (s2) can form a coating layer by coating using a roll coat, a bar coat, a slit die or the like.

  A functional layer (C), which will be described later, is formed on the surface of the resin film, and further, a coating layer is formed on the surface of the functional layer (C) by using a roll coat, a bar coat, a slit die or the like.

  Examples of a method for attaching the resin film surface on which the functional layer (C) on which the coating layer has been formed to the resin base material include a method of pressure bonding with a rubber roll. At this time, the surface temperature of the resin base material is preferably set to 40 ° C to 100 ° C. When the temperature is within such a range, the adhesion can be improved, a decrease in hardness due to excessive dissolution of the substrate can be suppressed, and yellowing of the coating film can be reduced. The surface temperature of the resin substrate can be adjusted by the set temperature of the heating unit, the heating time, and the like. As a method for measuring the temperature of the resin substrate, a known method such as a non-contact type surface thermometer can be used.

  The active energy ray is irradiated through the transfer film to cure the curable composition (s2) to form a cured coating (B ″). As the active energy ray, ultraviolet rays are preferable. The resin film is peeled, and a resin laminate in which a cured coating (B ″) and a functional layer (C) are sequentially laminated on the cured coating (A) can be obtained.

<Functional layer (C)>
The functional layer (C) is one of the components constituting the resin laminate of the present invention, and is formed on the surface of the cured film (B) formed on the first surface of the cured film (A). It is.

  The functional layer (C) is a functional layer having one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer, and an antifouling layer. The cured coating described in B ′) can be used.

  The film thickness of the functional layer (C) is not particularly limited, but is preferably 0.05 μm or more and 5.0 μm or less. The lower limit of the film thickness of the functional layer (C) is preferably 0.05 μm or more from the viewpoint of improving the appearance of the resin laminate. Moreover, the upper limit of the film thickness of the functional layer (C) is preferably 5.0 μm or less from the viewpoint of improving the adhesion between the cured film (B) and the functional layer (C). The lower limit of the film thickness of the functional layer (C) is more preferably 0.1 μm or more, and the upper limit of the film thickness is more preferably 3.0 μm or less. That is, the thickness of the functional layer (C) is more preferably 0.1 μm or more and 3.0 μm or less.

<Method for forming functional layer (C)>
The functional layer (C) is formed by forming a functional layer (C) as a transfer layer once on the surface of a resin film, which will be described later, and then providing a cured film provided as an adhesive layer on the first surface of the cured film (A). The method of transferring to the surface of (B) and forming a resin laminated body is mentioned.

  As a specific method for forming the functional layer (C) as a transfer layer on the surface of the resin film, after adding the components for forming each functional layer to the curable composition (s1), the curable composition ( A method of forming the functional layer (C) by applying s1) to the surface of the resin film and then curing the coating film of the curable composition (s1) by heating or irradiating active energy rays. It is done.

  Examples of the method for applying the curable composition (s1) to the surface of the resin film include the methods described in the method for applying the curable composition for forming the cured film (A) described above.

<Resin film>
As a resin film used for manufacture of a cured film (B), what is excellent in active energy ray permeability | transmittance and solvent resistance, and a low oxygen permeability is mentioned, for example.

  Specific examples of the resin film include polyethylene terephthalate film (hereinafter referred to as “PET film”); nylon film; polycarbonate film; acrylic film; polyolefin film such as polypropylene and polyethylene; and cellulose film such as diacetyl cellulose and triacetyl cellulose. Examples thereof include a film and a polyvinylidene chloride film. Among these, a PET film is preferable because it has transparency and solvent resistance and has a low oxygen permeability.

  Moreover, the commercially available film in which the mold release process layer is formed can be used.

  The thickness of the resin film is not particularly limited, but is preferably 5.0 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less. If the minimum of the thickness of a resin film is 5.0 micrometers or more, the external appearance fall of the cured film by the wave | undulation and bending of a film can be suppressed. Moreover, if the upper limit of the thickness of a resin film is 200 micrometers or less, adjustment of the film thickness of a functional layer (C) will become easy.

<Method for producing resin laminate>
As one embodiment which manufactures the resin laminated body of this invention, the method containing the following process (1) and process (2) is mentioned, for example.

Step (1): A repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule on at least one surface of the resin substrate, and 2 or less (meta ) A cured coating (A) containing a repeating unit (a2) derived from a monomer having an acryloyloxy group is formed.

Step (2): The surface of the cured film (A) contains at least one of a repeating unit (b2-1) derived from urethane (meth) acrylate and a repeating unit (b2-2) derived from a methacrylate having an amino group. A cured coating (B) is formed.

  As said process (1), after forming the coating film of the curable resin composition containing the said (a1) component and the said (a2) component on at least one surface of a resin base material, it hardens | cures, for example. And a method of forming a laminated resin body in which the cured coating (A) is formed on at least one surface of the resin base material.

  In the step (1), the cured film (A) preferably has a pencil hardness of 8H or more. By setting the pencil hardness of the surface of the cured coating (A) to 8H or more, it is possible to suppress the occurrence of scratches caused by fingernails on the surface of the resin laminate, so that a resin laminate having good scratch resistance can be obtained. Can be obtained.

  The process for forming the cured coating (B) in the step (2) can include the following steps (2-1) to (2-3).

Step (2-1): Monomer (b1) having three or more (meth) acryloyloxy groups in the molecule on the surface of the cured film (A) in step (1), urethane (meth) acrylate monomer A curable composition comprising at least one of (b2-1) and (meth) acrylate monomer (b2-2) having an amino group (excluding monomer (b1)) and organic solvent (b4) A coating film of the object (s1) is formed.

Step (2-2): The coating film of the curable composition (s1) is dried.

Step (2-3): The coating film of the curable composition (s1) after drying is cured to form a cured film (B).

  Examples of the method for forming a coating film of the curable composition in the step (2-1) include a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, and a flow coating. Method, curtain coating method, film cover method and dipping method.

  Examples of the method of curing the coating film of the curable resin composition include a method of heating the coating film or a method of irradiating the coating film with active energy rays as described above.

  As a method of drying in step (2-2) and a method of heating in step (2-3), for example, a method of heat treatment under a condition of 90 to 150 ° C. using a heat source such as a far infrared heater in an air atmosphere. Can be mentioned. Moreover, in order to raise the polymerization rate of the resin composition which comprises the resin laminated body in a lamination mold, a lamination mold can be heated with heat sources, such as 30-98 ° C warm water, as needed. Further, after the heat treatment, a cooling treatment such as blowing can be performed as necessary.

  Moreover, as another embodiment which manufactures the resin laminated body of this invention, the process of forming the cured film (B) of the said process (2) is carried out in the molecule | numerator on the surface of the said cured film (A). Of a monomer (b1) having three or more (meth) acryloyloxy groups, a urethane (meth) acrylate monomer (b2-1), and a (meth) acrylate monomer (b2-2) having an amino group Forming a cured film of the curable composition (s2) containing at least one type (excluding the monomer (b1)) and curing to form a cured film (B ″); The method including performing following process (3)-(5) after process (2) is mentioned. .

Step (3): a function comprising a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer on the surface of the resin film Layer (C) is formed.

Step (4): The functional layer (C) of the step (3) is bonded to the surface of the cured film (B ″) obtained in the step (2).

Step (5): The resin film is peeled off to obtain a resin laminate in which the cured coating (A), the cured coating (B ″), and the functional layer (C) are sequentially laminated on at least one surface of the resin base material. .

  In the step (5), specific examples in the case of forming an antireflection layer or an antiglare layer as the functional layer (C) on the surface of the resin film are shown below. Examples of the method for forming the antireflection layer include a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method, a film cover method, and a dipping method. Is mentioned.

  As a method for forming an antiglare layer, for example, when laminating an antiglare layer on the surface of a resin film, a method of forming fine irregularities on the surface of the antiglare layer, and adding light diffusing fine particles in the stringproof layer Thus, reflection of external light can be suppressed by at least one method of irregularly reflecting external light by internal scattering. Specifically, there are the following two methods.

  In the first method, after forming a fine uneven shape on the surface of the active energy ray transmissive film by a known method, a coating film of the composition for forming an antiglare layer is formed on the surface on which the fine uneven shape is formed. Then, it is cured to obtain an active energy ray transparent film on which an antiglare layer is laminated. Then, the surface of the antiglare layer of the active energy ray-transmitting film in which the antiglare layer is laminated is in contact with the surface of the coating film of the curable composition (s2) obtained in the step (4). After the lamination, the active energy ray-permeable film is peeled off to obtain a laminate in which an antiglare layer having a fine uneven surface is laminated on the surface of the resin laminate.

  The second method is a method in which the surface of the active energy ray permeable film itself has an uneven shape, for example, a method of kneading particles for forming an active energy ray permeable film into a resin, or And a method for transferring the fine irregularities on the surface of the mold by bringing the resin for forming the active energy ray transmissive film into contact with a mold having fine irregularities in a state where the resin is heated to a glass transition temperature or higher.

  In the step (5), the thickness of the functional layer (C) is not particularly limited, but the appearance of the resin laminate can be improved, the uneven thickness of the resin laminate can be suppressed, and curing. From the viewpoint of improving the adhesion between the coating (B) and the functional layer (C), it is preferably 0.05 μm or more and 5.0 μm or less.

  Hereinafter, the present invention will be described in detail by way of examples. In addition, various evaluation in an Example was implemented with the following method.

(1) Film thickness of cured coating A sample having a width of 100 nm was cut out with a microtome in the thickness direction of the resin laminate, and a cross section of the resin laminate was observed with a transmission electron microscope (JEM-1010 (trade name) manufactured by JEOL Ltd.). The film thicknesses of the cured film (A), the cured film (B ′), and the cured film (B ″) were measured.
The film thickness of was measured.

(2) Total light transmittance and haze value
Based on the measurement method shown in ISO 13468-1: 1996 using HAZE METER (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH4000), the total light transmittance of the resin laminate is measured and ISO 14782 is obtained. : Based on the measurement method shown in 1999, the haze value of the resin laminate was measured.

(3) Pencil hardness The surface hardness of the resin laminate was evaluated by pencil hardness. About the resin laminated body before laminating | stacking a cured film (B), and the resin laminated body after laminating | stacking a cured film (B), the pencil hardness of the outermost layer was measured based on ISO2409: 1992.

(4) The scratch resistance of the outermost layer of the scratch-resistant resin laminate was evaluated from the number of scratches on the sample after the scratch test. In the abrasion test, a round pad with a diameter of 24 mm on which # 000 steel wool (manufactured by Nippon Steel Wool Co., Ltd., trade name: Bonster No. 000) was placed was placed on the outermost layer of the resin laminate, and the load was 1,000 g. The distance of 20 mm was reciprocated 100 times.

(5) Crack resistance The crack resistance of the surface of the resin laminate was evaluated by observing the occurrence of cracks when the resin laminate was bent to a radius of curvature of 100 mm, 80 mm, 60 mm and 40 mm. Evaluation of crack resistance was performed according to the following procedure. A resin laminate having a width of 30 mm, a length of 120 mm and a thickness of 1 mm is a semi-cylindrical mold, and the cross-section arc radius of curvature R is 100 mm, 80 mm, 60 mm and 40 mm, and the base length is 100 mm. The resin laminate was placed on the mold so that the outermost layer of the cured film of the resin laminate was on the upper side in the vertical direction. The entire resin laminate was bent along the arc of the mold and held for 30 seconds. Thereafter, the resin laminate was visually observed, and the smallest radius of curvature at which no crack was generated was measured.

(6) Residual rate of cured coating When the cross-cut peel test is performed according to ISO 2409: 1992, the residual rate of the cured coating (B) remaining on the surface of the resin laminate, or the cured coating (B ) And the residual ratio of the functional layer (C).

(7) Residual rate of cured film after environmental test The resin laminate is left to stand for 100 hours in a constant temperature and humidity machine at a temperature of 60 ° C. and a relative humidity of 95%, and is taken out and cured film (B) or cured by the method of (6) The residual rate of the coating (B) and the functional layer (C) was evaluated.

In the following, abbreviations indicate the following monomers or compounds.
Polyacrylate 1: A mixture of dipentaerythritol hexaacrylate (60 to 70% by mass) and dipentaerythritol pentaacrylate (40 to 30% by mass).
Polyacrylate 2: Mixture of pentaerythritol triacrylate (50 to 70% by mass) and pentaerythritol tetraacrylate (50 to 30% by mass) Diacrylate 1: 1,6-hexanediol diacrylate BEE: Benzoin ethyl ether urethane acrylate 1: Urethane compound DEMA obtained by reacting 3 mol of 3-acryloyloxy-2-hydroxypropyl methacrylate with 1 mol of triisocyanate obtained by trimerization of hexamethylene diisocyanate 1: Silica fine particles (silica fine particles ( (Average particle size 10 nm)
IPA: isopropyl alcohol PGM: propylene glycol monomethyl ether crosslinked acrylic-styrene particles: average particle size 3.5 μm, 30 wt% toluene dispersion (manufactured by Soken Chemical Co., Ltd., trade name: SX-350HL)

Initiator 1: 2-Hydroxy 1-1 {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one
Initiator 2: Diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide Initiator 3: Benzoin ethyl ether BYK-UV 3505: Dimethylpolysiloxane having an acrylic group (manufactured by Big Chemie Japan Co., Ltd., trade name: BYK-UV 3505)

Transfer film 1: Transfer film laminated with antistatic layer Transfer film 2: Antireflection transfer film (Oike Industry Co., Ltd., trade name: STEP PAR-1) (PET film, release layer, antireflection layer, cured coating) (Laminated film laminated in order of film layer and adhesive layer)

[Production Example 1] Preparation of curable composition (a) A curable composition (a) for forming a cured film (A) was prepared by the following procedure. 20 parts by mass of polyacrylate 1, 45 parts by mass of polyacrylate 2, 35 parts by mass of diacrylate 1 and 1.5 parts by mass of initiator 3 were mixed to obtain a curable composition (a).

[Production Example 2] Synthesis of antistatic compound A glass flask equipped with stirring blades was charged with 188 parts by mass of dimethylaminopropylmethacrylamide and 228 parts by mass of methanol, and 136 parts by mass of dimethyl sulfate and 41.3 parts by mass of methanol while stirring. Was added dropwise while controlling so that the temperature of the reaction solution in the flask was maintained at 15 ° C. or lower. After completion of the dropwise addition, stirring was further continued for 30 minutes to obtain a compound solution having a quaternary ammonium base.

  In this compound solution, 2.4 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile), 2.4 parts by mass of n-octyl mercaptan, 384 parts by mass of methanol, polyethylene glycol (23) monomethacrylate monomethyl ether (parentheses) The inside was 485 parts by mass of the number of polyethylene glycol units) and polymerized at 60 ° C. for 6 hours in a nitrogen atmosphere. Subsequently, the obtained compound was taken out and vacuum-dried at 50 ° C. for 3 days to obtain an antistatic compound imparting antistatic properties.

[Production Example 3] Production of transfer film 1 with an antistatic layer laminated A transfer film with an antistatic layer laminated was prepared by the following procedure. The film thickness after drying ELCOM MR1008SBC (manufactured by JGC Catalysts & Chemicals Co., Ltd., trade name) on a highly smooth surface of a PET film “OX-50” (trade name, manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 50 μm After coating with a bar coater so as to have a thickness of 1.2 μm, the film was dried at 100 ° C. for 5 minutes to form an antistatic layer on the surface of the PET film.

[Production Example 4] 100 parts by weight of a mixture containing 20 parts by weight of polymethyl methacrylate and 80 parts by weight of methyl methacrylate having an adjusted weight average molecular weight of 220,000 of the resin base material (Z), 2- (5-methyl- After adjusting a mixed solution containing 0.01 part by mass of 2-hydroxyphenyl) -benzotriazole, 0.05 part by mass of azobisdimethylvaleronitrile, and 0.005 part by mass of sodium salt of dioctylsulfosuccinate, The dissolved air was removed and used as a raw material (Z) for the resin base material.

[Example 1]
A SUS304 plate having a mirror surface was used as a mold. On the mirror surface of this mold, the curable composition (a) prepared in Production Example 1 was applied and covered with a PET film having a thickness of 12 μm. The coating film of the applied curable composition (a) is referred to as a pre-curing film (A-1).

  A rubber roll having a JIS hardness of 40 ° is pressure-bonded to the surface of the PET film of the pre-curing coating (A-1), and the excess curable composition (a) is squeezed out so as not to contain air bubbles. A film of the pre-curing coating (A-2) was formed. Next, the mold on which the pre-curing coating (A-2) was formed was placed on the fluorescent UV lamp (trade name: FL40BL, manufactured by Toshiba Corporation) with an output of 40 W with the PET film on the upper side. A position 20 cm below is passed through at a speed of 2 m / min, and the film before curing (A-2) is irradiated with the light of the fluorescent ultraviolet lamp through the PET film to be cured, and the film after curing (A- 3) was obtained. Next, the PET film was peeled from the coated film (A-3) after curing to obtain a mold on which the cured film (A-4) was laminated.

Next, with the cured coating portion of the mold on which the cured coating (A-4) was laminated facing upward, a position 20 cm below the high-pressure mercury lamp with an output of 30 W / cm ² was passed at a speed of 3 m / min, and the cured coating ( A-4) was further cured by irradiating with ultraviolet rays to obtain a laminated mold (X) in which a cured film (A-4) having a film thickness of 30 μm was laminated on the mold surface. The pencil hardness of the cured coating (A-4) was 8H.

  Next, the laminated mold (X) and another SUS304 plate not formed with the cured film (A-4) are opposed to each other so that the cured film (A-4) of the laminated mold (X) is on the inside. Then, the peripheral portions of these two SUS304 plates were sealed with a gasket made of soft polyvinyl chloride to produce a laminated mold (Y).

  The resin base material (Z) prepared in Production Example 4 was injected into the laminated mold (Y) and completely sealed with a soft polyvinyl chloride gasket, and then 1 in an 80 ° C. water bath. Polymerization was carried out by heating for 1 hour in an air furnace at 130 ° C. for 1 hour. Next, after cooling the laminated mold (Y) to room temperature, the two SUS304 plates on both sides were peeled off, and a 1 mm thick resin laminate in which a cured coating (A-4) was formed on one surface of the resin substrate (C-1) was obtained.

  42.5 parts by mass of polyacrylate 1, 42.5 parts by mass of polyacrylate 2, 5 parts by mass of DEMA, 474 parts by mass of toluene, 237 parts by mass of ethyl acetate, 237 parts by mass of IPA, crosslinked acrylic-styrene particles 10 parts by mass (solid content), 5 parts by mass of initiator 1 and BYK-UV 3505 were mixed to obtain a curable composition (s1). The said curable composition (s1) is apply | coated to the surface in which the cured film (A-4) of the said resin laminated body (C-1) was formed using a bar-coater, This is resin laminated body (C-2) ).

Subsequently, after drying the said resin laminated body (C-2) for 10 minutes with a 70 degreeC hot air drying furnace, it irradiates the ultraviolet-ray of the integrated light quantity 600mJ / cm < ² > (wavelength energy amount of 320-380 nm) using a high pressure mercury lamp. And the resin laminated body (C-3) which has a cured film with a film thickness of 1.3 micrometers was obtained.

  About the obtained resin laminated body (C-3), the total light transmittance, the haze value, pencil hardness, the contact angle, the residual rate of the cured film, and antifouling durability were evaluated. The evaluation results are shown in Table 3.

  The obtained resin laminate (C-3) had a surface pencil hardness of 8H, and was excellent in transparency, surface hardness, and adhesion between the cured coating (A) and the cured coating (B). Further, the scratch resistance and crack resistance were good.

[Examples 2 to 9]
The composition (1-7) of Table 1 was used as a curable composition (s1). A resin laminate was obtained in the same manner as in Example 1 except that the film thickness of the cured film (A), the composition of the cured film (B ′), or the film thickness was as described in Table 3. The evaluation results are shown in Table 3.

[Comparative Example 1]
The same method as in Example 1 except that the type of composition of the curable composition (s1), the film thickness of the cured film (A), and the composition and film thickness of the cured film (B) were as shown in Table 3. A resin laminate was obtained. The evaluation results are shown in Table 3. In the resin laminate of Comparative Example 1, the organic solvent (b4) contained in the curable composition (s1) is PGM, and the curable composition (s1) is the components (b2-1) and (b2-2). Thus, the pencil hardness, scratch resistance, crack resistance, and the residual rate of the cured film were insufficient.

[Example 10]
A resin laminate was obtained in the same manner as in Example 1 except that the thickness of the cured coating (A) was as shown in Table 1. The evaluation results are shown in Table 3. The residual rate and crack resistance of the cured film after the environmental test were insufficient.

[Comparative Example 2]
A resin laminate was obtained in the same manner as in Example 1 except that the cured film (A) was not formed. The evaluation results are shown in Table 3. Since the resin laminate of Comparative Example 3 had no cured coating (A), the scratch resistance and pencil hardness were insufficient.

[Example 11]
The composition 9 shown in Table 2 was applied as a curable composition (s2) to the surface on which the cured film (A) of the resin laminate (C-1) prepared in Example 1 was formed.

  Next, the surface on which the antistatic layer of the transfer film 1 prepared in Production Example 3 was formed was bonded to the application surface of the composition 9 of the resin laminate (C-1) so as to be in contact with the press roll. By passing through the bottom at a speed of 2.5 m / min and laminating while adjusting the film thickness of the pre-curing coating (B-1) as shown in Table 4, the resin laminate (D- 1) A resin laminate (D-2) in which the pre-curing coating (B-1) and the antistatic layer of the transfer film 1 were sequentially laminated was obtained. After the obtained resin laminate (D-2) is held for 1 minute, the resin laminate (D-2) is passed through a position 24 cm below the metal halide lamp with an output of 120 W / cm at a speed of 2.5 m / min. The cured film (B ″) is formed by irradiating the cured film (B-1) with light from the metal halide lamp through the transfer film 1 and curing it, and the resin laminate (D− 3) was obtained.

  Thereafter, the PET film of the transfer film 1 was peeled from the resin laminate (D-3) to obtain a resin laminate (D-4). Table 4 shows the evaluation results of the obtained resin laminate (D-4).

[Examples 12 to 16]
The composition (10-12) of Table 2 was used as a curable composition (s2). A resin laminate was obtained in the same manner as in Example 10, except that the type of transfer film or the film thickness of the cured coating (B ″) was as shown in Table 4. Table 4 shows the evaluation results of the obtained resin laminate.

[Comparative Examples 3 and 4]
Implemented except that the composition (13, 14) in Table 2 was used as the curable composition (s2), and the type of transfer film or the film thickness of the cured coating (B ″) was as described in Table 4. A resin laminate was obtained in the same manner as in Example 12. When the transfer film 2 was used, the transfer film 2 was laminated so that the adhesive layer of the transfer film 2 was in contact with the cured film (B). Table 4 shows the evaluation results of the obtained resin laminate. Since the curable composition (s2) does not contain the component (b2-1) and the component (b2-2), the pencil hardness, the scratch resistance, and the residual ratio of the cured film were insufficient. Moreover, since the comparative example 4 had a large film thickness of the cured coating (B ″), the adhesion with the functional layer (C) was insufficient.

Claims (22)

A sheet-like resin laminate comprising a cured coating (A) on at least one surface of a resin substrate, and a cured coating (B) on the surface facing the resin substrate in the cured coating (A). There,
The cured coating (A) has a pencil hardness of 8H or more,
The resin laminated body in which the said cured film (B) contains at least 1 type of the repeating unit (b2-2) derived from the repeating unit (b2-1) derived from urethane (meth) acrylate and the (meth) acrylate which has an amino group.   The resin laminate according to claim 1, wherein the thickness of the cured coating (A) is 17 µm or more and 40 µm or less.   The resin laminate according to claim 1 or 2, wherein the surface of the resin laminate has a pencil hardness of 8H or more.   The resin laminate according to any one of claims 1 to 3, wherein in the resin laminate, a residual ratio of the cured film (B) by a cross-cut peel test based on ISO 2409: 1992 is 80% or more.   The cured film (B) is composed of a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer. 4. The resin laminate according to any one of 4 above. A sheet-like resin laminate in which the functional layer (C) is laminated on the surface of the cured coating (B) of the resin laminate according to claim 1 or 2,
A resin laminate comprising the functional layer (C) comprising a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer.   The resin laminate according to claim 6, wherein the surface of the resin laminate has a pencil hardness of 8H or more.   The resin according to claim 6 or 7, wherein in the resin laminate, a residual ratio of the cured film (B) and the functional layer (C) by a cross-cut peel test in conformity with ISO 2409: 1992 is 80% or more. Laminated body. A sheet-like resin laminate comprising a cured coating (A) on at least one surface of a resin substrate, and a cured coating (B) on the surface facing the resin substrate in the cured coating (A). And
The cured film (A) has a repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule, and a single amount having 2 or less (meth) acryloyloxy groups in the molecule Including a repeating unit (a2) derived from a body,
The resin laminate, wherein the cured coating (B) includes at least one of a repeating unit (b2-1) derived from urethane (meth) acrylate and a repeating unit (b2-2) derived from (meth) acrylate having an amino group.   The resin laminate according to claim 9, wherein the cured film (A) has a pencil hardness of 8H or more.   The resin laminated body of Claim 9 or 10 whose film thickness of the said cured film (A) is 17 micrometers or more and 40 micrometers or less.   The resin laminate according to any one of claims 9 to 11, wherein the surface of the resin laminate has a pencil hardness of 8H or more. The resin laminate according to any one of claims 9 to 12,
The cured coating (B) contains a repeating unit (b1) derived from a monomer having three or more (meth) acryloyloxy groups in the molecule, and a low refractive index layer, a high refractive index layer, a hard coat A resin laminate which is a cured coating (B ′) comprising a layer having at least one function selected from a layer, an antistatic layer, an antiglare layer and an antifouling layer.   The resin laminated body of Claim 13 whose film thickness of the said cured film (B ') is 0.6 micrometer or more and 3 micrometers or less. A resin laminate comprising a functional layer (C) on the surface of the cured coating (B) of the resin laminate according to any one of claims 9 to 11,
The cured coating (B) is a cured coating (B ″) made of a resin composition containing a repeating unit (b1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule,
A resin laminate comprising the functional layer (C) comprising a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer.   The resin laminate according to claim 15, wherein the cured coating (B ″) contains inorganic fine particles (b3).   The resin laminate according to claim 15, wherein a film thickness of the cured coating (B ″) is 3 μm or more and 7 μm or less.   The resin laminate according to claim 15, wherein the functional layer (C) has a thickness of 0.05 μm or more and 5.0 μm or less. The manufacturing method of the resin laminated body containing following process (1) and (2).
Step (1): on at least one surface of the resin base material,
Repeating unit (a1) derived from a monomer having 3 or more (meth) acryloyloxy groups in the molecule, repeating unit (a2) derived from a monomer having 2 or less (meth) acryloyloxy groups in the molecule ) Is formed.
Step (2): A cured film (B) containing at least one kind of urethane (meth) acrylate unit (b2-1) and methacrylate unit (b2-2) having an amino group on the surface of the cured film (A). Form. The step of forming the cured coating (B) in the step (2) is performed on the surface of the cured coating (A).
A monomer (b1) having 3 or more (meth) acryloyloxy groups in the molecule;
At least one of the urethane (meth) acrylate monomer (b2-1) and the (meth) acrylate monomer (b2-2) having an amino group (excluding the monomer (b1));
・ Organic solvent (b4)
The manufacturing method of the resin laminated body of Claim 19 including forming the coating film of the curable composition (s1) containing this, hardening, and forming a cured coating film (B '). The step of forming the cured coating (B) in the step (2) is performed on the surface of the cured coating (A).
A monomer (b1) having 3 or more (meth) acryloyloxy groups in the molecule, and a urethane (meth) acrylate monomer (b2-1) and a (meth) acrylate monomer having an amino group At least one type of (b2-2) (excluding the monomer (b1))
Forming a cured coating film of the curable composition (s2) containing, and curing to form a cured coating film (B ″), and further after the step (2), the following steps (3) to (5) The manufacturing method of the resin laminated body of Claim 19 including performing this.
Step (3): a function comprising a layer having at least one function selected from a low refractive index layer, a high refractive index layer, a hard coat layer, an antistatic layer, an antiglare layer and an antifouling layer on the surface of the resin film Layer (C) is formed.
Step (4): The functional layer (C) of the step (3) is bonded to the surface of the cured film (B ″) obtained in the step (2).
Step (5): A resin in which the resin film is peeled and the cured coating (A), the cured coating (B ″), and the functional layer (C) are sequentially laminated on at least one surface of a resin base material. A laminate is obtained. The method for producing a resin laminate according to claim 21, wherein in the step (3), the functional layer (C) is formed so that the film thickness of the functional layer (C) is 0.05 µm or more and 5.0 µm or less. .