JP6420925B1 - Curved resin laminate - Google Patents

Abstract

A curved resin laminate having excellent shape stability is provided.
A curved surface including a resin layer having a dielectric constant of 3.5 or more, a hard coat layer 8 laminated on the surface of the resin layer 4 and a hard coat layer 9 laminated on the back surface, curved in the direction of the back surface. The curved surface resin laminate 1 includes a curved portion, the curvature radius R of the curved portion is 0.1 mm ≦ R ≦ 30 mm, and the following formulas 180 ≦ UH _f ≦ 300, 120 ≦ UH _b ≦ 300,. Curved resin laminate 1 satisfying the relationship of 1 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 8.0. [Wherein, UHF and UHb each represent a universal hardness (N / mm ²⁾ of the universal hardness of the hard coat layer ^{(1) (N / mm 2} ) and a hard coat layer (2), Df and Db respectively hardcoat The thickness of the layer (1) and the thickness of the hard coat layer (2) are shown]
[Selection] Figure 2

Description

  The present invention relates to a curved resin laminate used for a front plate of an image display device or the like.

  In recent years, development of smart phones, portable game machines, audio players, tablet terminals, etc. that are characterized by design has been actively carried out, and it has been considered to give curved surfaces to flat display devices so far . A glass sheet is usually used for the front plate of such a display device. However, a resin sheet that is a substitute for the glass sheet has been studied due to problems such as poor yield (for example, Patent Document 1).

JP 2014-688 A

  However, depending on the type of resin used for the resin laminate, when it is molded into a shape with a large curvature, appearance defects such as cracks, wrinkles, and cloudiness may occur, and a resin laminate having a desired shape may not be obtained. . Furthermore, since the resin laminate processed into a curved shape may be deformed when placed in a severe environment such as high temperature or high temperature and high humidity, the present inventor cannot use it as a front plate of a display device. I found it.

  Accordingly, an object of the present invention is to provide a curved resin laminate excellent in shape stability.

  In order to solve the above-mentioned problems, the present inventor has studied in detail a curved resin laminate suitably used as a front plate of a display device, and has completed the present invention.

That is, the present invention includes the following preferred embodiments.
[1] including a resin layer having a dielectric constant of 3.5 or more, a hard coat layer (1) laminated on the surface of the resin layer, and a hard coat layer (2) laminated on the back surface, and curved in the back surface direction A curved surface-shaped resin laminate including a curved surface portion,
The curvature radius R of the curved surface portion is 0.1 mm ≦ R ≦ 30 mm, and the following formula 180 ≦ UH _f ≦ 300
120 ≦ UH _b ≦ 300
0.1 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 8.0
Wherein, UH _f and UH _b each represent a universal hardness of the universal hardness of the hard coat layer ^{(1) (N / mm 2} ) and a hard coat layer ^{(2) (N / mm 2} ), D f and _{D b} Indicates the thickness of the hard coat layer (1) and the thickness of the hard coat layer (2), respectively]
Curved resin laminate that satisfies the above relationship.
[2] The curved resin laminate according to [1], wherein the resin layer has a main layer (A) and one or more thermoplastic resin layers (B) on at least one surface of the main layer (A). .
[3] Of the main layer (A) and the one or more thermoplastic resin layers (B), the difference between the layer having the highest glass transition temperature and the layer having the lowest glass transition temperature is 0 to 80 ° C., [2 ] The curved-surface-shaped resin laminate described in the above.
[4] The curved resin laminate according to any one of [1] to [3], wherein the pencil hardness of the surface is 4H or more.
[5] The resin layer includes a main layer (A) containing a (meth) acrylic resin, and thermoplastic resin layers (B-1) and (B-2) laminated on both surfaces of the main layer (A). The curved-surface-shaped resin laminate according to any one of [1] to [4].
[6] The curved resin laminate according to any one of [2] to [5], wherein the main layer (A) includes a (meth) acrylic resin and a vinylidene fluoride resin.

  The curved resin laminate of the present invention has excellent shape stability.

It is a schematic sectional drawing which shows an example of the curved-surface-shaped resin laminated body of this invention. It is a schematic sectional drawing which shows an example of the layer structure in the curved-surface-shaped resin laminated body of this invention. It is a figure which shows the inscribed circle which a curved surface part forms in the cross section of the curved-surface-shaped resin laminated body of this invention. It is the schematic which shows an example of the apparatus for manufacturing the resin layer of the curved-surface-shaped resin laminated body of this invention. In an Example and a comparative example, it is a figure which shows the curved resin laminated body and distance (A) before a durability test, and the curved resin laminated body and distance (B) after a durability test.

  The curved resin laminate of the present invention comprises a resin layer having a dielectric constant of 3.5 or more, a hard coat layer (1) laminated on the surface of the resin layer, and a hard coat layer (2) laminated on the back surface. And a curved surface portion curved in the back surface direction. In the present specification, the surface of the resin layer means the viewing side of the image display device. Further, the curved surface portion means a portion that curves toward the back surface (opposite side to the viewing side). The shape of the curved resin laminate of the present invention is not particularly limited as long as it includes at least a curved surface portion.

[Resin layer]
The resin layer has a relatively high dielectric constant, preferably 3.5 or more, more preferably 3.6 or more, and still more preferably 3.7 or more, from the viewpoint of obtaining a function sufficient for use in a display device such as a touch panel. Has a dielectric constant of The upper limit value of the dielectric constant is not particularly limited, but is usually 20. The dielectric constant is based on JIS K 6911: 1995. The curved resin laminate of the present invention is allowed to stand for 24 hours in an environment of 50% relative humidity at 23 ° C. It is a value measured at 3 V and 100 kHz. For the measurement, commercially available equipment may be used, for example, “precision LCR meter HP4284A” manufactured by Agilent Technologies, Inc. may be used.

  The resin contained in the resin layer is not particularly limited as long as it can form a resin layer having a dielectric constant of 3.5 or more. Examples thereof include (meth) acrylic resin, vinylidene fluoride resin, and polycarbonate resin. , Polyamide resin, polystyrene resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, polyethylene terephthalate, polyethersulfone, and cycloolefin resin. Among these, (meth) acrylic resins and vinylidene fluoride resins are preferable. These resins can be used alone or in combination of two or more. When two or more kinds of resins are used, the amounts of the resin having a high dielectric constant and the resin having a low dielectric constant may be appropriately adjusted, and the dielectric constant may be adjusted to 3.5 or more.

  Examples of the (meth) acrylic resin [sometimes referred to as (meth) acrylic resin (M)] contained in the resin layer include, for example, a single weight of a (meth) acrylic monomer such as (meth) acrylic acid ester and (meth) acrylonitrile And a copolymer of two or more (meth) acrylic monomers, a copolymer of (meth) acrylic monomers and monomers other than (meth) acrylic monomers, and the like. In the present specification, the term “(meth) acryl” means “acryl” or “methacryl”.

  The (meth) acrylic resin is preferably a methacrylic resin from the viewpoint of easily improving the shape stability, hardness, weather resistance, transparency and the like of the curved resin laminate. A methacrylic resin is a polymer of a monomer mainly composed of a methacrylic acid ester (alkyl methacrylate). For example, a homopolymer of a methacrylic acid ester (polyalkyl methacrylate), a copolymer of two or more methacrylic acid esters And a copolymer of a monomer other than 50% by mass of a methacrylic acid ester and a monomer other than 50% by mass of a methacrylic acid ester. As a copolymer of a methacrylic acid ester and a monomer other than the methacrylic acid ester, from the viewpoint of easily improving optical properties and weather resistance, 70% by mass or more of the methacrylic acid ester and 30% relative to the total amount of the monomers. Copolymers with other monomers of less than or equal to mass% are preferred, and copolymers of more than 90 mass% of methacrylic acid esters with other monomers of less than or equal to 10 mass% are more preferred.

  Examples of monomers other than methacrylic acid esters include acrylic acid esters and monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule.

  Monofunctional monomers include, for example, styrene monomers such as styrene, α-methylstyrene and vinyltoluene; alkenyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; N-substituted And maleimide.

  From the viewpoint of heat resistance, the (meth) acrylic resin may be copolymerized with N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide, or in the molecular chain (in the main skeleton in the polymer or A lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced into the main chain).

［式中、Ｒ_１は水素原子又はメチル基を表し、Ｒ_１が水素原子のときＲ_２は炭素数１〜８のアルキル基を表し、Ｒ_１がメチル基のときＲ_２は炭素数２〜８のアルキル基を表す］
で示される（メタ）アクリル酸エステルに由来する少なくとも１つの構造単位を含む共重合体、
若しくは
（ａ１）及び（ａ２）の混合物
であることが好ましい。ここで、各構造単位の含有量は、得られた重合体を熱分解ガスクロマトグラフィーにより分析し、各単量体に対応するピーク面積を測定することにより算出できる。 From the viewpoint of easily improving the shape stability, hardness, weather resistance, transparency and the like of the (meth) acrylic resin,
(A1) Methyl methacrylate homopolymer, or (a2) 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, more preferably based on all structural units constituting the copolymer. 80.0-99.7% by weight of structural units derived from methyl methacrylate, and 0.1-50% by weight, preferably 0.2-30% by weight, more preferably 0.3-20% by weight. Formula (1):

[Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 1 to 8 carbon atoms when R ₁ is a hydrogen atom, and R ₂ represents _{2 to 2} carbon atoms when R ₁ is a methyl group. Represents an alkyl group of 8]
A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by:
Or it is preferable that it is a mixture of (a1) and (a2). Here, the content of each structural unit can be calculated by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.

In formula (1), R ₁ represents a hydrogen atom or a methyl group, when R ₁ is a hydrogen atom R ₂ represents an alkyl group having 1 to 8 carbon atoms, when R ₁ is a methyl group R ₂ represents the number of carbon atoms Represents 2 to 8 alkyl groups. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group. R ₂ is preferably an alkyl group having 2 to 4 carbon atoms and more preferably an ethyl group from the viewpoint of heat resistance.

  The weight average molecular weight of the (meth) acrylic resin contained in the resin layer (hereinafter sometimes referred to as Mw) is 50,000 to 300,000. When Mw is lower than the above lower limit, transparency when exposed to high temperature or high temperature and high humidity environment is not sufficient, and when Mw is higher than the above upper limit, film formability when producing a resin layer is obtained. Absent. The Mw of the (meth) acrylic resin is preferably 100,000 or more, more preferably 120,000 or more, from the viewpoint of easily increasing transparency when exposed to a high temperature or high temperature and high humidity environment. More preferably, it is 150,000 or more. The Mw of the (meth) acrylic resin is preferably 250,000 or less, and more preferably 200,000 or less, from the viewpoint of film formability when producing the resin layer. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

  The (meth) acrylic resin is usually 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, more preferably 0.5 to 3 g / 10, as measured at a load of 3.8 kg and 230 ° C. Minute melt mass flow rate (hereinafter sometimes referred to as MFR). The MFR is preferably not more than the above upper limit because it is easy to increase the strength of the obtained film, and is preferably not less than the above lower limit from the viewpoint of the film formability of the resin layer. The MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”. This JIS stipulates that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C. and a load of 3.80 kg (37.3 N).

From the viewpoint of heat resistance, the (meth) acrylic resin preferably has a glass transition temperature (Tmg) of 90 ° C. or higher, more preferably 95 ° C. or higher, and even more preferably 100 ° C. or higher.
The glass transition temperature can be obtained by using a differential scanning calorimeter (DSC) “EXSTAR DSC6100” manufactured by SII NanoTechnology Co., Ltd., under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. In addition, in this specification, a glass transition temperature means a midpoint glass transition temperature (Tmg).

  The (meth) acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization or the like. In that case, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent. As the chain transfer agent, an appropriate commercial product can be used. What is necessary is just to determine the addition amount of a chain transfer agent suitably according to the kind of monomer, its ratio, the characteristic to obtain | require, etc.

  Examples of the vinylidene fluoride resin contained in the resin layer [sometimes referred to as vinylidene fluoride resin (F)] include homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and other monomers. . The vinylidene fluoride resin is selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene from the viewpoint of easily improving the transparency of the curved resin laminate. It is preferably a copolymer of at least one monomer and vinylidene fluoride and / or a homopolymer of polyvinylidene fluoride (polyvinylidene fluoride), more preferably polyvinylidene fluoride.

  The weight average molecular weight (Mw) of the vinylidene fluoride resin is preferably 100,000 to 500,000, more preferably 130,000 to 450,000, still more preferably 150,000 to 450,000, particularly preferably 170. 1 million to 400,000. It is preferable that Mw is equal to or more than the above lower limit since the transparency of the curved resin laminate is easily increased when the curved resin laminate is exposed to a high temperature or high temperature and high humidity environment. Further, it is preferable that Mw is not more than the above upper limit because the film forming property is easily improved. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

The vinylidene fluoride resin has a melt of 3.8 kg, measured at 230 ° C., preferably 0.1 to 50 g / 10 minutes, more preferably 1 to 50 g / 10 minutes, still more preferably 5 to 45 g / 10 minutes. It has a mass flow rate (MFR). It is preferable that MFR is not more than the above upper limit because it is easy to suppress a decrease in transparency when the curved resin laminate is used for a long period of time.
It is preferable that the MFR is not less than the above lower limit because the film formability is easily improved. The MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”.

The vinylidene fluoride resin is industrially produced by a suspension polymerization method or an emulsion polymerization method.
The suspension polymerization method is carried out by using water as a medium, dispersing the monomer as droplets in the medium with a dispersant, and polymerizing an organic peroxide dissolved in the monomer as a polymerization initiator, A granular polymer of 100 to 300 μm is obtained. Suspension polymers are preferred because they have a simpler manufacturing process than powdered emulsions, have excellent powder handling properties, and do not contain an emulsifier or salting-out agent containing an alkali metal unlike emulsion polymers.

  A commercially available product may be used as the vinylidene fluoride resin. Examples of preferable commercially available products include “KF Polymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300 from Kureha Corporation. "SOLEF (registered trademark) 6012, 6010 and 6008" manufactured by Solvay.

  The resin layer may have a single layer or a multilayer structure, and a multilayer structure is preferable from the viewpoint of multifunctionalization.

  In a preferred embodiment, the resin layer has a main layer (A) and one or more thermoplastic resin layers (B) on at least one surface of the main layer (A). The main layer (A) preferably contains the (meth) acrylic resin (M) and the vinylidene fluoride resin (F).

In a more preferred embodiment, the resin layer contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the main layer (A).
When the amount of (meth) acrylic resin is lower than the above lower limit, sufficient transparency cannot be obtained, and when the amount of (meth) acrylic resin is higher than the above upper limit, sufficient dielectric constant cannot be obtained. When the amount of the vinylidene fluoride resin is lower than the above lower limit, a sufficient dielectric constant cannot be obtained, and when the amount of the vinylidene fluoride resin is higher than the above upper limit, durability and sufficient transparency cannot be obtained.

  The main layer (A) has a dielectric constant of 30 to 60% by weight (meta) based on the total resin contained in the main layer (A) from the viewpoint of easily increasing the dielectric constant and enhancing the transparency of the curved resin laminate. It preferably contains an acrylic resin and 70 to 40% by weight of vinylidene fluoride resin, more preferably contains 35 to 45% by weight of (meth) acrylic resin and 65 to 55% by weight of vinylidene fluoride resin, 37 to It is more preferable that 45 mass% (meth) acrylic resin and 63-55 mass% vinylidene fluoride resin are included, 38-45 mass% (meth) acrylic resin and 62-55 mass% vinylidene fluoride resin are included. It is particularly preferable to include 38 to 43% by mass of (meth) acrylic resin and 62 to 57% by mass of vinylidene fluoride resin.

  The main layer (A) may further contain another resin different from the (meth) acrylic resin and the vinylidene fluoride resin. When it contains other resin, the kind is not specifically limited unless the transparency of a curved-surface-shaped resin laminated body is impaired remarkably. From the viewpoint of the hardness and weather resistance of the curved resin laminate, the amount of the other resin is preferably 15% by mass or less based on the total resin contained in the main layer (A), and is preferably 10% by mass or less. It is more preferable that it is 5% by mass or less. Examples of other resins include polycarbonate resin, polyamide resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, and polyethylene terephthalate. The main layer (A) may further contain another resin, but from the viewpoint of transparency, the amount of the other resin is preferably 1% by mass or less, and the resin contained in the main layer (A) is ( More preferably, it is only a (meth) acrylic resin and a vinylidene fluoride resin.

  The content of alkali metal in the main layer (A) is preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, particularly preferably 1 ppm or less, based on the total resin contained in the main layer (A). It is. It is preferable that the content of the alkali metal in the main layer (A) is not more than the above upper limit because it is easy to suppress a decrease in transparency when the curved resin laminate is used for a long time at high temperature or high temperature and high humidity. . The lower limit value of the content of alkali metal in the main layer (A) is 0, and it is extremely preferable that the content is not substantially contained from the viewpoint of easily suppressing a decrease in the transparency of the curved resin laminate. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the main layer (A), a trace amount of emulsifier used in the production process remains. Therefore, the alkali metal such as sodium and potassium is derived from the remaining emulsifier and is contained in the main layer (A) at 0.05 ppm or more, for example. In particular, when the (meth) acrylic resin and / or vinylidene fluoride resin contained in the main layer (A) is obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases, and the main layer (A) The alkali metal content is also increased. From the viewpoint of easily suppressing a decrease in the transparency of the curved resin laminate, a resin having a low alkali metal content should be used as the (meth) acrylic resin and vinylidene fluoride resin contained in the main layer (A). Is preferred.

  In order to make the content of the alkali metal in the resin within the above range, the amount of the compound containing the alkali metal is reduced during the polymerization of the resin, or the compound containing the alkali metal is increased by increasing the washing step after the polymerization. Remove it. The alkali metal content can be determined by, for example, inductively coupled plasma mass spectrometry (ICP / MS). Examples of inductively coupled plasma mass spectrometry include sample pellets to be measured such as a high temperature ashing melting method, a high temperature ashing acid dissolution method, a Ca-added ashing acid dissolution method, a combustion absorption method, and a low temperature ashing acid dissolution method. The sample may be ashed by an appropriate method, dissolved in an acid, and the volume of the dissolved solution may be determined, and the content of alkali metal may be measured by inductively coupled plasma mass spectrometry.

  The glass transition temperature (Tmg) of the main layer (A) is preferably 50 to 100 ° C, more preferably 55 to 80 ° C, and further preferably 55 to 70 ° C. The Tmg of the main layer (A) can be obtained by measurement using a differential scanning calorimeter (DSC) “EXSTAR DSC6100” manufactured by SII Nanotechnology, under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. In addition, when the main layer (A) contains one kind of resin, it is the glass transition temperature of the resin, and when the main layer (A) contains two or more kinds of resins, the glass transition of a mixture of a plurality of resins. Temperature.

  The thermoplastic resin layer (B) is laminated at least one layer, preferably one layer, on at least one surface (one surface or both surfaces) of the main layer (A).

  The thermoplastic resin layer (B) contains at least one thermoplastic resin. The thermoplastic resin layer (B) is preferably 60% by mass or more, more preferably 70% by mass or more based on the total resin contained in each thermoplastic resin layer from the viewpoint of maintaining transparency and molding processability. Even more preferably, 80% by mass or more of the thermoplastic resin is included. The upper limit of the amount of the thermoplastic resin is 100% by mass.

  If the absolute value of the difference in glass transition temperature (Tmg) between the main layer (A) and the thermoplastic resin layer (B) is too large, cracks, wrinkles, cloudiness, etc. will occur between the layers when the curved shape is imparted to the resin layer. May cause poor appearance. In particular, when molding into a shape with a large curvature (a shape with a small radius of curvature of the curved surface portion), the above-mentioned appearance defect between layers appears remarkably. In a preferred embodiment of the present invention, in the resin layer, the difference between the layer having the highest glass transition temperature and the layer having the lowest glass transition temperature among the main layer (A) and the one or more thermoplastic resin layers (B), Since it is preferably 0 to 80 ° C., more preferably 20 to 80 ° C., and further preferably 40 to 75 ° C., it effectively suppresses appearance defects such as cracks, wrinkles, and cloudiness between layers, and has a shape with a large curvature. Even if it exists, it can shape | mold. In a preferred embodiment, the thickness of the main layer (A) is larger than the thickness of the thermoplastic resin layer (B). In this case, if the Tmg of the main layer (A) is larger than the Tmg of the thermoplastic resin layer (B), the flexibility of the main layer (A) having a large thickness with respect to the molding temperature becomes better, and the resin layer Is preferable because it is easy to form a curved surface.

  Examples of the thermoplastic resin contained in the thermoplastic resin layer (B) include the (meth) acrylic resin (M), polycarbonate resin, and cycloolefin resin. These thermoplastic resins can be used alone or in combination of two or more. When the (meth) acrylic resin (M) is contained in the thermoplastic resin layer (B), the difference in glass transition temperature from the main layer (A) is small, and the main layer (A) has good adhesiveness. preferable. Further, the polycarbonate resin has a high Tmg, and the difference in Tmg from the main layer (A) may be large. Therefore, when a polycarbonate resin is used, a polymer alloy (hereinafter referred to as a PC alloy) of a resin capable of reducing Tmg and a polycarbonate resin (hereinafter referred to as a PC alloy), for example, an alloy of a polycarbonate resin and a (meth) acrylic resin, a polystyrene resin or the like is used. It is preferable.

  Examples of the polycarbonate resin include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. Specifically, a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) can be mentioned.

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  Examples of polycarbonate resins other than the above polycarbonate resins include polycarbonates synthesized from isosorbite and aromatic diols. An example of the polycarbonate is “DURABIO (registered trademark)” manufactured by Mitsubishi Chemical Corporation.

  Commercially available products may be used as the polycarbonate resin. For example, “Caliver (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301-40” manufactured by Sumika Stylon Polycarbonate Co., Ltd. SD2221W, SD2201W, TR2201 ”and the like.

  A PC alloy can be formed from such a polycarbonate resin and a resin compatible with the polycarbonate resin.

  As a preferred commercial product of PC alloy, for example, SD Polyca (registered trademark) “PCX-6648”, “PCX-6630”, “PCX-6684”, “PCX-6680”, manufactured by Sumika Stylon Polycarbonate Co., Ltd., Mitsubishi Engineered plastics Iupilon (registered trademark) “KH4210UR”, “KH3310UR”, “KH3410UR”, “KH3520UR”, “KS3410UR”, “KS2410UR”, and the like can be given.

  The glass transition temperature of the thermoplastic resin layer (B) is preferably 80 to 180 ° C, more preferably 90 to 150 ° C, and still more preferably 100 to 140 ° C. In addition, when the thermoplastic resin layer (B) contains one kind of thermoplastic resin, it is the glass transition temperature of the resin, and when the thermoplastic resin layer (B) contains two or more kinds of thermoplastic resins, It is a glass transition temperature of a mixture of a plurality of resins.

  The thermoplastic resin layer (B) may further contain other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin for the purpose of increasing the strength and elasticity of the thermoplastic resin layer. In this case, the amount of the other resin is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total resin contained in each thermoplastic resin layer. . The lower limit of the amount of other resins is 0% by mass.

  In a more preferred embodiment, from the viewpoint of shape stability of the curved resin laminate, the resin layer includes a main layer containing a (meth) acrylic resin, and a thermoplastic resin layer (B-) laminated on both sides of the main layer. 1) and (B-2). The thermoplastic resin layers (B-1) and (B-2) may contain the same thermoplastic resin or may contain different thermoplastic resins. The thermoplastic resin layers (B-1) and (B-2) preferably contain the same thermoplastic resin from the viewpoint of the shape stability of the curved resin laminate.

  The thermoplastic resin layers (B-1) and (B-2) are preferable from the viewpoint that the transparency, surface hardness, and molding processability of the resin layer are good, and it is easy to mold a curved resin laminate having a large curvature. Is a (meth) acrylic resin layer or a PC alloy layer.

  One embodiment of the present invention in which the thermoplastic resin layers (B-1) and (B-2) are (meth) acrylic resin layers will be described below. In this embodiment, the thermoplastic resin layers (B-1) and (B-2) contain one or more (meth) acrylic resins. The thermoplastic resin layers (B-1) and (B-2) are preferably 50% by mass or more, more preferably 60% by mass based on the total resin contained in each thermoplastic resin layer from the viewpoint of surface hardness. As mentioned above, 70 mass% or more (meth) acrylic resin is included further more preferably.

  Examples of the (meth) acrylic resin include the (meth) acrylic resin (M). The (meth) acrylic resin contained in the thermoplastic resin layers (B-1) and (B-2) and the (meth) acrylic resin contained in the main layer (A) may be the same or different. May be.

  The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, more preferably 70,000 to 250, from the viewpoint of good moldability and easy enhancement of mechanical strength. 1,000. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

  In this embodiment, the thermoplastic resin layers (B-1) and (B-2) may further contain a thermoplastic resin other than one or more (meth) acrylic resins. As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. Specific examples include a methyl methacrylate-styrene-maleic anhydride copolymer (for example, “Regisphi” manufactured by Denki Kagaku Kogyo) and a methyl methacrylate-methacrylic acid copolymer (for example, “Altglass HT121” manufactured by Arkema). . The glass transition temperature of the thermoplastic resin other than the (meth) acrylic resin is preferably 80 to 180 ° C, more preferably 90 to 150 ° C, and still more preferably 100 to 140 ° C, from the viewpoint of heat resistance. From the viewpoint of heat resistance, it is preferable that the thermoplastic resin layers (B-1) and (B-2) contain substantially no vinylidene fluoride resin.

  Next, another embodiment of the present invention in which the thermoplastic resin layers (B-1) and (B-2) are PC alloy layers will be described below. In this embodiment, the thermoplastic resin layers (B-1) and (B-2) contain one or more kinds of PC alloys. From the viewpoint of impact resistance, the thermoplastic resin layers (B-1) and (B-2) are preferably 60% by mass or more, more preferably 70% by mass based on the total resin contained in each thermoplastic resin layer. % Or more, still more preferably 80% by mass or more of PC alloy.

  In this embodiment, the weight average molecular weight (Mw) of the PC alloy is preferably 25,000 to 60,000, more preferably 30,000 to 50,000, from the viewpoint of easily improving impact resistance and molding processability. It is. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

In this embodiment, PC alloy contained in the thermoplastic resin layer (B-1) and (B-2), measured at a temperature of 275 ° C. and a load 1.2 kg, preferably 1 to 100 cm ^3/10 min has more preferably 2~80cm ^3/10 min, even more preferably 3~40cm ^3/10 min, particularly preferably 4~20cm ^3/10 min melt volume rate (hereinafter, also referred to as a MVR.). It is preferable that the MVR is equal to or more than the above lower limit because the fluidity is sufficiently high, the molding process is easy in melt coextrusion molding and the like, and the appearance defect hardly occurs. It is preferable that MVR is not more than the above upper limit because mechanical properties such as strength of the PC alloy layer can be easily improved.
MVR can be measured under the condition of 275 ° C. under a load of 1.2 kg in accordance with JIS K 7210.

  In this embodiment, the thermoplastic resin layers (B-1) and (B-2) may further contain one or more thermoplastic resins other than the PC alloy. As the thermoplastic resin other than the PC alloy, a thermoplastic resin compatible with the resin contained in the PC alloy is preferable.

  At least one of the main layer (A) and the thermoplastic resin layer (B) in the curved resin laminate of the present invention may further contain various commonly used additives as long as the effects of the present invention are not impaired. May be included. Examples of additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, and flame retardant aids. And coloring agents such as reinforcing agents, nucleating agents, and bluing agents.

  Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phthalocyanine skeleton. Among these, a compound having an anthraquinone skeleton is preferable from the viewpoint of heat resistance.

When at least one of the main layer (A) and the thermoplastic resin layer (B) further contains a colorant, the content of the colorant in each layer may be appropriately selected according to the purpose, the type of the colorant, and the like. it can. When using a bluing agent as a coloring agent, the content can be made into about 0.01-10 ppm based on the total resin contained in each layer containing a bluing agent.
This content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, further preferably 0.1 ppm or more, preferably 7 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, particularly preferably. Is 3 ppm or less. Known bluing agents can be used as appropriate. For example, Macrolex (registered trademark) Blue RR (manufactured by Bayer), Macrolex (registered trademark) Blue 3R (manufactured by Bayer), respectively, under the trade name, Sumiplast (registered trademark) Viloet B (manufactured by Sumika Chemtex Co., Ltd.) and Polycinslen (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G, Diaresin Blue N (above, Mitsubishi Chemical Corporation) It is done.

  It does not specifically limit as a ultraviolet absorber, You may use a conventionally well-known various ultraviolet absorber. For example, the ultraviolet absorber which has an absorption maximum in 200-320 nm or 320-400 nm is mentioned. Specific examples include triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. As an ultraviolet absorber, you may use 1 type of these ultraviolet absorbers individually or in combination of 2 or more types. The viewpoint that the combination of at least one ultraviolet absorber having an absorption maximum at 200 to 320 nm and at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm can also more effectively prevent damage from ultraviolet rays. To preferred. Commercially available products may be used as the UV absorber, such as “Kemisorb 102” (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-N-octyl) manufactured by Chemipro Kasei Co., Ltd. Oxyphenyl) -1,3,5-triazine) (absorbance 0.1), “ADEKA STAB LA-F70” (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methyl) manufactured by ADEKA Corporation Phenyl) -1,3,5-triazine) (absorbance 0.6), “Adekastab LA-31, LA-31RG, LA-31G” (2,2′-methylenebis (4- (1,1,3,3) -Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) (absorbance 0.2), "ADEKA STAB LA-46" (2- (4,6) manufactured by ADEKA Corporation. Diphenyl-1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or “TINUVIN 1577” manufactured by BASF Japan Ltd. ( 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine) (absorbance 0.1), etc. The absorbance of the exemplified ultraviolet absorber is 380 nm. This is absorbance, which can be measured using a spectrophotometer (for example, a spectrophotometer U-4100 manufactured by HITACHI) after dissolving an ultraviolet absorber in chloroform at a concentration of 10 mg / L.

  When at least one of the main layer (A) and the thermoplastic resin layer (B) further contains a UV absorber, the content of the UV absorber in each layer is appropriately selected according to the purpose, the type of the UV absorber, etc. You can do it. For example, the content of the ultraviolet absorber can be about 0.005 to 2.0 mass% based on the total resin contained in each layer containing the ultraviolet absorber. The content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.03% by mass or more. Further, the content of the ultraviolet absorber is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. The content of the ultraviolet absorber is preferably not less than the above lower limit from the viewpoint of easily enhancing the ultraviolet absorption effect, and being not more than the above upper limit is a change in the color (for example, yellowness YI) of the curved resin laminate. It is preferable because it is easy to prevent. For example, it is preferable to use the above-mentioned commercially available “ADK STAB LA-31, LA-31RG, LA-31G” in the above amounts.

  In another aspect of the present invention, the thermoplastic resin layers (B-1) and (B-2) are PC alloy layers, and 0.005 to 2 based on the total resin contained in each thermoplastic resin layer. It is preferable to contain 0.0% by mass of an ultraviolet absorber because it is easy to obtain a curved resin laminate having excellent light resistance.

  The thickness of the resin layer is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more, from the viewpoint of shape stability of the curved resin laminate. Moreover, from a viewpoint of transparency and a moldability, Preferably it is 2000 micrometers or less, More preferably, it is 1500 micrometers or less, More preferably, it is 1000 micrometers or less. The thickness of the curved resin laminate can be measured with a digital micrometer.

  The thickness of the main layer (A) is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more, from the viewpoints of shape stability and dielectric constant of the curved resin laminate. Moreover, from a viewpoint of transparency and a moldability, Preferably it is 1500 micrometers or less, More preferably, it is 1200 micrometers or less, More preferably, it is 1000 micrometers or less. The thickness of the main layer (A) can be measured with a digital microscope.

  The thickness of the thermoplastic resin layer (B) is preferably 10 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more, from the viewpoint of shape stability of the curved resin laminate. From the viewpoint of moldability and dielectric constant, each is preferably 200 μm or less, more preferably 175 μm or less, and even more preferably 150 μm or less. The thickness of the thermoplastic resin layer (B) can be measured with a digital microscope.

  The resin layer can be produced by a conventional method. For example, a main layer (A) containing a (meth) acrylic resin and a vinylidene fluoride resin, which is a preferred embodiment of the present invention, is laminated on both surfaces of the main layer (A). The resin layer having the thermoplastic resin layers (B-1) and (B-2) can be produced by the following method.

  The main layer (A) can be produced from a resin composition (A) containing a (meth) acrylic resin and a vinylidene fluoride resin, and the thermoplastic resin layers (B-1) and (B-2) are respectively resin compositions. It can manufacture from (B-1) and (B-2). The resin compositions (B-1) and (B-2) may contain at least a resin that gives the thermoplastic resin layers (B-1) and (B-2). A composition containing two or more components may be used, or a single resin may be used.

  The resin composition (A) is usually obtained by kneading (meth) acrylic resin, vinylidene fluoride resin and the like. The kneading can be performed, for example, by a method including a step of melt-kneading at a shear rate of 10 to 1000 / second at a temperature of 150 to 350 ° C.

  The temperature at the time of melt kneading is preferably 150 ° C. or higher because the resin can be sufficiently melted, and is preferably 350 ° C. or lower because it is easy to suppress thermal decomposition of the resin. Furthermore, it is preferable that the shear rate at the time of melt-kneading is 10 / second or more because the resin can be sufficiently kneaded, and it is preferably 1000 / second or less because the decomposition of the resin is easily suppressed.

  In order to obtain a resin composition in which each component is more uniformly mixed, the melt-kneading is preferably performed at a temperature of 180 to 300 ° C, more preferably 200 to 300 ° C, preferably 20 to 700 / second, and more. Preferably, it is carried out at a shear rate of 30 to 500 / sec.

  As an apparatus used for melt kneading, a normal mixer or kneader can be used. Specific examples include a single-screw kneader, a twin-screw kneader, another-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. Further, when the shear rate is increased within the above range, a high shearing device or the like may be used.

  Resin compositions (B-1) and (B-2) can also be produced in the same manner as resin composition (A), for example, by melt kneading under the above temperature and shear rate. Further, for example, when the thermoplastic resin layers (B-1) and (B-2) contain one kind of thermoplastic resin, the resin layer may be obtained by performing melt extrusion described later without melt-kneading in advance. .

The resin layer having the main layer (A) which is a preferred embodiment of the present invention and the thermoplastic resin layers (B-1) and (B-2) respectively present on both sides of the main layer (A) is, for example, melt extrusion Each layer (A), (B-1) and (B) is formed from the resin composition (A), (B-1) and (B-2) by a molding method, a solution casting film forming method, a hot press method, an injection molding method or the like. B-2) may be prepared separately, and these may be produced, for example, by bonding via a pressure-sensitive adhesive or an adhesive, or resin compositions (A), (B-1) and (B-2). ) May be laminated and integrated by melt coextrusion.
When producing a resin layer by bonding, it is preferable to use an injection molding method and a melt extrusion molding method for the production of each layer, and it is more preferable to use a melt extrusion molding method.

  In melt coextrusion molding, for example, the resin composition (A) and the resin compositions (B-1) and (B-2) are separately fed into two or three uniaxial or biaxial extruders. Then, after each melt-kneading, the main layer (A) and the thermoplastic resin layers (B-1) and (B-2) formed from the resin composition (A) through a feed block die, a multi-manifold die or the like. ) Are laminated and integrated and extruded. When the resin compositions (B-1) and (B-2) are the same composition, one composition melt-kneaded in one extruder is divided into two via a feed block die or the like, The thermoplastic resin layers (B-1) and (B-2) may be formed. The obtained resin layer is preferably cooled and solidified by, for example, a roll unit.

  The curved resin laminate of the present invention is manufactured by laminating the hard coat layers (1) and (2) described later on the resin layer (for example, a flat resin layer) obtained by the above method, and then bending it. However, in a preferred embodiment, the resin layer obtained by the above method is such that the curvature radius R of the curved portion of the curved resin laminate after laminating the hard coat layer is 0.1 mm ≦ R ≦ 30 mm. After bending, it is preferable to laminate hard coat layers (1) and (2) described later.

  Examples of the method of bending the resin layer include a method of hot press molding using a three-dimensional bending mold having a predetermined radius of curvature, a heat bending method, a vacuum molding method, and the like.

The molding processing temperature may be a temperature equal to or higher than Tmg of the layer having the highest Tmg among the layers constituting the resin layer. In a preferred embodiment, molding temperature (T) is the glass transition temperature of the main layer (A) Tmg _A, the thermoplastic resin layer a glass transition temperature of (B) when the Tmg _B, the following equation _Tmg A +40 <T <Tmg _A +90
Tmg _B <T
Satisfy the relationship. For example, the molding processing temperature may be 90 to 170 ° C, more preferably 100 to 150 ° C. The glass transition temperature can be measured by, for example, a differential scanning calorimeter (DSC).

[Hard coat layer]
The curved resin laminate of the present invention includes hard coat layers (1) and (2) laminated on the front and back surfaces of the resin layer, respectively. The hard coat layers (1) and (2) satisfy the relationship of the following formula.
180 ≦ UH _f ≦ 300
120 ≦ UH _b ≦ 300
0.1 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 8.0
Wherein, UH _f and UH _b each represent a universal hardness of the universal hardness of the hard coat layer ^{(1) (N / mm 2} ) and a hard coat layer ^{(2) (N / mm 2} ), D f and _{D b} Indicates the thickness of the hard coat layer (1) and the thickness of the hard coat layer (2), respectively]
In this specification, (D _f × UH _f ) is the rigidity of the front surface side hard coat layer (1), (D _b × UH _b ) is the rigidity of the back surface side hard coat layer (2), and (D _f × UH _{f f} ) / (D _b × UH _b ) is referred to as the rigidity ratio of the hard coat layers (1) and (2).

  The curved resin laminate of the present invention is excellent in shape stability because the hard coat layers (1) and (2) satisfy the relationship of the above formula, and for a long time in a harsh environment such as high temperature or high temperature and high humidity. Even if placed, deformation can be effectively prevented or suppressed. In addition, the scratch resistance is good, and cracking due to an endurance test or impact is less likely to occur.

The universal hardness (UH _f ) of the hard coat layer (1) is preferably 185 ≦ UH _f ≦ 300, more preferably 190 ≦ UH _f ≦ 300, and further preferably 195 ≦ UH _f ≦ 290. When the universal hardness is equal to or higher than the above lower limit, the scratch resistance can be enhanced, and when it is equal to or lower than the upper limit, cracks caused by a durability test or an impact can be effectively prevented.

The universal hardness (UH _b ) of the hard coat layer (2) is preferably 130 ≦ UH _f ≦ 290, more preferably 130 ≦ UH _f ≦ 280, still more preferably 140 ≦ UH _f ≦ 270, and particularly preferably 140 ≦ UH. _f ≦ 250. When the universal hardness is equal to or higher than the above lower limit, the scratch resistance can be enhanced, and when it is equal to or lower than the upper limit, cracks caused by a durability test or an impact can be effectively prevented. The universal hardness of the hard coat layers (1) and (2) can be measured using an ultra-micro hardness measuring instrument. A Vickers indenter (square pyramid diamond indenter) can be used as the indenter. Moreover, the universal hardness of each hard coat layer (1) and (2) is the kind and content of curable compounds and additives contained in the curable composition constituting the hard coat layer (1) or (2). By adjusting, you may adjust to the predetermined range.

The rigidity ratio of the hard coat layers (1) and (2) is preferably 0.3 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 7.0, more preferably 0.3 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 5.5, more preferably 0.4 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 4.8. When the rigidity ratio of the hard coat layers (1) and (2) is in the above range, the shape stability of the curved resin laminate can be further improved, and in a severe environment such as high temperature or high temperature and high humidity. Deformation can be prevented or suppressed more effectively.

The thickness (D _f ) of the hard coat layer (1) is preferably 1 to 50 μm, more preferably 2 to 30 μm, still more preferably 3 to 25 μm, and particularly preferably 3 to 20 μm. If the thickness of the hard coat layer (1) is not less than the above lower limit, the surface hardness can be increased, and if it is not more than the above upper limit, cracks during curing of the hard coat layer and deformation of the resin layer can be prevented. it can.

The thickness (D _b ) of the hard coat layer (2) is preferably 1 to 50 μm, more preferably 2 to 30 μm, still more preferably 3 to 25 μm, and particularly preferably 3 to 20 μm. If the thickness of the hard coat layer (2) is not less than the above lower limit, the surface hardness can be increased, and if it is not more than the above upper limit, cracking at the time of curing the hard coat layer and deformation of the resin layer can be prevented. .

  The hard coat layers (1) and (2) are made of a cured product of the curable composition. The curable composition is not particularly limited as long as a hard coat layer satisfying the universal hardness can be formed. The curable composition includes a curable compound as an essential component, and if necessary, for example, a curing catalyst, conductive particles, a solvent, a leveling agent, a stable Additives such as an agent, an antioxidant, and a colorant can be contained. Moreover, the curable composition which comprises hard-coat layer (1) and (2) may be the same or different.

  Examples of the curable compound include acrylate compounds such as polyfunctional acrylate compounds; urethane acrylate compounds such as polyfunctional urethane acrylate compounds; epoxy acrylate compounds such as polyfunctional epoxy acrylate compounds; carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, Examples thereof include copolymer acrylate compounds, alicyclic epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetane compounds, and alkoxysilane compounds such as alkoxysilanes and alkylalkoxysilanes. Among these, from the viewpoint of easily adjusting the universal hardness to a predetermined range, a radical polymerization curable compound such as a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, or a polyfunctional epoxy acrylate compound; alkoxysilane, alkylalkoxysilane, etc. A thermopolymerizable curable compound or the like is preferably used. These curable compounds are, for example, those that are cured by irradiating energy beams such as electron beams, radiation, and ultraviolet rays, and / or those that are cured by heating, and preferably at least such as electron beams, radiation, and ultraviolet rays. What cure | hardens by irradiating an energy ray is preferable. These curable compounds can be used alone or in combination of two or more.

  A compound having at least three (meth) acryloyloxy groups in the molecule can also be used. The (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.

  Examples of the compound having at least three (meth) acryloyloxy groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaglycerol tri ( (Meth) acrylate, pentaerythritol tri- or tetra- (meth) acrylate, dipentaerythritol tri-, tetra-, penta- or hexa- (meth) acrylate, tripentaerythritol tetra-, penta-, hexa- or hepta- ( Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as (meth) acrylate; compounds having at least two isocyanato groups in the molecule, (meth) acrylates having hydroxyl groups, hydroxyl groups with respect to isocyanato groups, etc. The urethane (meth) acrylate obtained by reacting at a ratio of at least 3 and having 3 or more (meth) acryloyloxy groups in the molecule [for example, by reaction of diisocyanate and pentaerythritol tri (meth) acrylate, Hexafunctional urethane (meth) acrylate is obtained]; tris (2-hydroxyethyl) isocyanuric acid tri (meth) acrylate and the like. In addition, although the monomer was illustrated here, you may use these monomers as it is, for example, you may use what was in the form of oligomers, such as a dimer and a trimer. Moreover, you may use a monomer and an oligomer together. These (meth) acrylate compounds may be used alone or in combination of two or more.

  When a compound having at least three (meth) acryloyloxy groups in the molecule is used as the curable compound, other curable compounds such as ethylene glycol di (meth) acrylate, diethylene glycol di ( You may use together the compound which has two (meth) acryloyloxy groups in a molecule | numerator, such as a meth) acrylate, 1, 6- hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. The amount of the other curable compound used is usually up to 20 parts by mass with respect to 100 parts by mass of the compound having at least 3 (meth) acryloyloxy groups in the molecule.

  When the curable composition is cured with ultraviolet rays, it is preferable to use a photopolymerization initiator as a curing catalyst. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides, and the like. Depending on the situation, two or more of them can be used. The usage-amount of a photoinitiator is 0.1-5 mass parts normally with respect to 100 mass parts of sclerosing | hardenable compounds.

  The curable composition may contain other additives. Examples of the additive include an ion trap agent, an antioxidant, a chain transfer agent, a polymerization accelerator, a sensitizer, a sensitizer, a light stabilizer, a tackifier, a filler, a flow modifier, a plasticizer, a quencher. Examples include foaming agents, leveling agents, antistatic agents, ultraviolet absorbers, and solvents. Among these, it is preferable to use a filler. The filler may be contained in one or both of the curable compositions constituting the hard coat layers (1) and (2), but at least from the viewpoint of increasing the surface hardness of the curved resin laminate. It is preferable that a filler is included in the curable composition constituting the hard coat layer (1).

  Examples of the filler include organic fine particles and inorganic fine particles, and inorganic fine particles are particularly preferable. Examples of the inorganic fine particles include silica, zirconia, alumina, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide and other metal oxide fine particles, magnesium fluoride, fluorine Examples thereof include fine metal fluoride particles such as sodium fluoride. Among these, silica, zirconia, and alumina can be preferably used. Further, hollow silica fine particles can be used as appropriate, and in order to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be used as appropriate.

  In a preferred embodiment, the inorganic fine particles are colloidal silica. Colloidal silica synthesis methods include gas phase synthesis methods such as aerosil synthesis by thermal decomposition of silicon tetrachloride, methods using water glass as a raw material, and liquid phase synthesis methods such as hydrolysis of alkoxides. Is possible. As the commercial products of colloidal silica, each product of “organosilica sol” (organic solvent-dispersed silica sol) from Nissan Chemical Industries, Ltd. and each product of “high-purity organosol” from Fuso Chemical Industries, Ltd. are preferred. Can be mentioned. In these, colloidal silica is dispersed in an organic solvent.

The curable composition may contain a solvent for the purpose of adjusting the viscosity thereof. For example, when the inorganic particles are contained, a solvent may be contained for the dispersion. When preparing a curable composition containing inorganic particles and a solvent, for example, the inorganic particles and the solvent are mixed, the inorganic particles are dispersed in the solvent, and then the dispersion is mixed with the curable composition. May be. In this case, commercially available inorganic particles dispersed in an organic solvent and a curable composition may be mixed.
Alternatively, the inorganic particles may be dispersed in the mixed solution after mixing the curable compound and the solvent. The solvent should be one that can dissolve the curable compound and can easily volatilize after coating. If the curable composition contains inorganic particles, the inorganic particles may be dispersed. What you can do is good. Examples of such a solvent include alcohols such as diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol; Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; and water. What is necessary is just to adjust the usage-amount of a solvent suitably according to the property of a curable compound, etc.

  A commercial item can be used for the curable composition which forms hard-coat layer (1) and (2). Examples of commercially available products include AICA AITRON (registered trademark) “Z-778-3”, “Z-850”, “Z-700K-2”, “Z-700AF-5”, “Z” manufactured by Aika Industries, Ltd. -912 "," Z-773 "," Z-774 "," Z-980 "," Z-700W-3 "," Z-700W-7 "," Z-776-5W / Z-P800B "; Rioduras (registered trademark) “MOL5000”, “MOL2112”, 1500 series, 2000 series, 2500 series manufactured by Toyo Ink Co., Ltd. “Nicer” “Acier”; Taisei Fine Chemical Co., Ltd. “STR-SiA”, “8KX-” 078 "," 8KX-089 "; DIC Corporation Unidic" V-4000BA "," V-4001EA "," V-4005 "," V- " 018 ”,“ V-4025 ”,“ V-4200-70 ”,“ V42-5 ”,“ V-4221 ”,“ V-4260 ”,“ V-4263 ”,“ 15-829 ”,“ 17- ” 813 "," S2-371 "," 17-806 "," 17-824-9 "," ERS-958 "," ESS-177 "," ESS-107 "," ERS-830 ", etc. .

  In a preferred embodiment, the curved resin laminate of the present invention is the resin that is curved so that the curvature radius R of the curved surface portion of the curved resin laminate after laminating the hard coat layer is 0.1 mm ≦ R ≦ 30 mm. The curable composition can be applied to both sides of the layer to form a curable coating film, which is then cured.

  Examples of the method for applying the curable composition include a bar coating method, a micro gravure coating method, a roll coating method, a flow coating method, a dip coating method, a spin coating method, a die coating method, and a spray coating method. In order to cure the curable coating film, irradiation with energy rays, heating, or the like may be performed according to the type of the curable composition.

  Examples of energy rays for curing a curable coating film by irradiation with energy rays include ultraviolet rays, electron beams, and radiation. Conditions such as intensity and irradiation time depend on the type of curable composition. Are appropriately selected. Moreover, when hardening a curable coating film by heating, conditions, such as the temperature and time, are suitably selected according to the kind of curable composition. The heating temperature is usually 100 or less, preferably 80 ° C. or less, more preferably 60 ° C. or less so that the resin layer does not deform. When the curable composition contains a solvent, the curable coating film may be cured after the solvent is volatilized after coating, or the solvent may be volatilized and the curable coating film may be cured simultaneously. Good.

[Curved resin laminate]
FIG. 1 is a schematic sectional view showing an example of the curved resin laminate of the present invention. The curved resin laminate 1 has a flat portion 2 and a curved portion 3 that curves from both ends of the flat portion 2 in the back surface direction (downward in FIG. 1). The curved surface portion 3 is curved so that the radius of curvature R is 0.1 mm ≦ R ≦ 30 mm.
FIG. 2 is a schematic sectional view showing an example of the layer structure of the curved resin laminate of the present invention. The curved resin laminate 1 has a resin layer 4, a hard coat layer 8 laminated on the surface of the resin layer 4, and a hard coat layer 9 laminated on the back surface. The resin layer 4 includes a main layer 5, a thermoplastic resin layer 6 laminated on the front surface side of the main layer 5, and a thermoplastic resin layer 7 laminated on the back surface side.

  The curved resin laminate of the present invention can exhibit excellent shape stability even when the curvature radius R of the curved surface portion is small, and even when placed in a harsh environment such as a high temperature or high temperature and high humidity environment for a long time. , Deformation can be effectively suppressed or prevented. For this reason, the curvature radius R of a curved-surface part can also be 13 mm or less, 7 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, 1 mm or less. In the curved resin laminate of the present invention, the curvature radius R of the curved surface portion can be selected from 0.1 mm ≦ R ≦ 30 mm, for example, 0.1 mm ≦ R ≦ 20 mm, preferably 0.1 mm ≦ R ≦ 15 mm, more preferably 0.5 mm ≦ R ≦ 14 mm, more preferably 1 mm ≦ R ≦ 13 mm, even more preferably 1 mm ≦ R ≦ 12 mm, particularly preferably 1 mm ≦ R ≦ 10 mm, especially 1 mm ≦ R ≦ 7 mm. The curvature radius R of the curved surface portion of the curved resin laminate is, for example, as shown in FIG. 3, the radius of the inscribed circle 24 formed along the curved surface portion 3 in the cross section of the curved resin laminate 1. R is meant.

  The curved resin laminate of the present invention can exhibit excellent shape stability even when the curvature of the curved surface portion is large, and even when placed in a harsh environment such as a high temperature or high temperature and high humidity environment for a long time, Deformation can be effectively suppressed or prevented. For this reason, the angle (curvature angle) at which the curved surface portion bends is preferably 10 ° or more, more preferably 30 ° or more, still more preferably 60 ° or more, even more preferably 70 ° or more, and particularly preferably 80 ° or more. The curved angle of the curved surface portion is, for example, as shown in FIG. 3, in an inscribed circle 24 formed along the curved surface portion 3, an end point (or start point) 25 and an end point (or end point) 26 of the curved surface portion 3. And the central angle α of the sector formed by the center point 27 of the inscribed circle.

  Furthermore, since the curved resin laminate of the present invention has the hard coat layer (1), it has excellent surface hardness. That is, the pencil hardness on the surface (hard coat layer side) is preferably H or higher, more preferably 2H or higher, still more preferably 3H or higher, even more preferably 4H or higher, particularly preferably 5H or higher, particularly more preferably 6H or higher, In particular, it is 7H or more. When the pencil hardness is equal to or higher than the above lower limit, it is possible to improve the scratch resistance of the surface, and even when used as a front plate of a display device such as a touch panel, it is possible to effectively suppress or prevent damage to the screen. Become. The pencil hardness can be measured in accordance with JIS K5600-5-4.

  As described above, since the curved laminate of the present invention can achieve both excellent shape stability and excellent surface hardness, various display devices such as liquid crystal display devices, organic electroluminescence (EL) display devices, and touch panel display devices can be used. It can be used as a front plate. In addition, since it has a curved surface shape, it can be used as a front plate of a display device with high design, unlike a conventional flat display device.

  The curved resin laminate has a relatively high dielectric constant, preferably 3.5 or higher, more preferably 3.6 or higher, and still more preferably 3.7 or higher. The dielectric constant of the curved resin laminate can be measured by the method indicated by the dielectric constant of the resin layer.

  The curved resin laminate of the present invention is preferably transparent when visually observed. Specifically, the curved resin laminate of the present invention is preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more, as measured according to JIS K7361-1: 1997. It has a light transmittance (Tt). The upper limit of the total light transmittance is 100%. Even after being exposed to a severe environment such as high temperature or high temperature and high humidity, the curved resin laminate preferably has a total light transmittance in the above range.

  The thickness of the curved resin laminate of the present invention is preferably 100 to 1500 μm, more preferably 150 to 1300 μm, and still more preferably 200 to 1000 μm. If the thickness of the curved resin laminate is equal to or greater than the above lower limit, the sheet has good rigidity, can be prevented from being deformed when pressed, and if less than the upper limit, the distance to the touch sensor when used on the front surface , And good sensitivity can be expressed.

  The curved resin laminate of the present invention may further include at least one functional layer in addition to the resin layer and the hard coat layers (1) and (2). Examples of the functional layer include an antireflection layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer. These functional layers may be preferably arranged on the side opposite to the resin layer in the hard coat layers (1) and (2). The functional layer may be laminated via an adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a cured film as described in JP 2013-86273 A may be used.

  The thickness of the functional layer may be appropriately selected according to the purpose of each functional layer, but is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more from the viewpoint of easily expressing the function. From the viewpoint of easily preventing cracking, the thickness is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.

[Glass transition temperature (Tmg)]
The glass transition temperature (Tmg) was measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6100” manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min.

[Alkali metal content]
It was measured by inductively coupled plasma mass spectrometry.

[MFR]
Measured in accordance with JIS K 7210: 1999 “Plastics—Testing Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics”. This JIS stipulates that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C. and a load of 3.80 kg (37.3 N).

[MVR]
Using “Semi-auto melt indexer 2A” manufactured by Toyo Seiki Seisakusho Co., Ltd., the measurement was performed under the condition of 275 ° C. under a load of 1.2 kg according to JIS K 7210.

[Dielectric constant]
The resin layer or the curved resin laminate is allowed to stand for 24 hours in an environment with a relative humidity of 50% at 23 ° C. Under this environment, the resin layer or the resin laminate is subjected to an automatic equilibrium bridge method at 3 V and 100 kHz. It was measured. For measurement, “precision LCR meter HP4284A” manufactured by Agilent Technologies, Inc. was used.

[Production Example 1]
98.5 parts by mass of methyl methacrylate and 1.5 parts by mass of methyl acrylate were mixed, and 0.16 parts by mass of a chain transfer agent (octyl mercaptan) and 0.1 parts by mass of a release agent (stearyl alcohol) were added. A mass mixture was obtained. Further, 0.036 parts by mass of a polymerization initiator [1,1-di (tert-butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate to obtain an initiator mixed solution. Continuously fed to the fully mixed polymerization reactor so that the flow ratio of the monomer mixture to the initiator mixture was 8.8: 1, the average residence time was 20 minutes, and the average polymerization rate was 54% at a temperature of 175 ° C. Until partial polymerization was obtained. The resulting partially polymerized product is heated to 200 ° C. and led to a vented devolatilizing extruder, and unreacted monomers are devolatilized from the vent at 240 ° C., and the devolatilized polymer is extruded in a molten state. After cooling with water, it was cut to obtain a pellet-shaped methacrylic resin (i).

  The obtained pellet-like methacrylic resin (i) was analyzed by pyrolysis gas chromatography under the following conditions, and each peak area corresponding to methyl methacrylate and acrylate ester was measured. As a result, in the methacrylic resin (i), the structural unit derived from methyl methacrylate was 97.5% by mass, and the structural unit derived from methyl acrylate was 2.5% by mass.

(Pyrolysis conditions)
Sample preparation: A methacrylic resin composition was precisely weighed (standard 2-3 mg), placed in the center of a bowl-shaped metal cell, the metal cell was folded, and both ends were lightly pressed with pliers and sealed.
Thermal decomposition apparatus: CURIE POINT PYROLYZER JHP-22 (manufactured by Nippon Analytical Industries, Ltd.)
Metal cell: Pyrofoil F590 [Nippon Analytical Industries, Ltd.]
Thermostatic bath set temperature: 200 ° C
Set temperature of heat insulation pipe: 250 ℃
Thermal decomposition temperature: 590 ° C
Thermal decomposition time: 5 seconds

(Gas chromatography analysis conditions)
Gas chromatography analyzer: GC-14B [manufactured by Shimadzu Corporation]
Detection method: FID
Column: 7G 3.2 m × 3.1 mmφ (manufactured by Shimadzu Corporation)
Filler: FAL-M [manufactured by Shimadzu Corporation]
Carrier gas: Air / N ₂ / H ₂ = 50/100/50 (kPa), 80 ml / min Column heating condition: held at 100 ° C. for 15 minutes, then raised to 150 ° C. at 10 ° C./minute, 150 Hold for 14 minutes at ℃ INJ temperature: 200 ℃
DET temperature: 200 ° C

The methacrylic resin composition is pyrolyzed under the above pyrolysis conditions, and the peak area (a1) corresponding to methyl methacrylate detected when the generated decomposition product is measured under the above gas chromatography analysis conditions and the acrylate ester The peak area (b1) corresponding to was measured. And peak area ratio A (= b1 / a1) was calculated | required from these peak areas. On the other hand, a standard product of a methacrylic resin having a mass ratio of acrylic ester units to methyl methacrylate units of W ₀ (known) is pyrolyzed under the above pyrolysis conditions, and the generated decomposition product is subjected to the above gas chromatography analysis conditions. The peak area (a ₀ ) corresponding to methyl methacrylate and the peak area (b ₀ ) corresponding to acrylate detected when the measurement is performed are measured, and the peak area ratio A ₀ (= b ₀ ) is measured from these peak areas. / A ₀ ). Then, the factor f (= W ₀ / A ₀ ) was determined from the peak area ratio A ₀ and the mass ratio W ₀ .

  By multiplying the peak area ratio A by the factor f, a mass ratio W of acrylate units to methyl methacrylate units in the copolymer contained in the methacrylic resin composition is obtained, and from the mass ratio W, methacrylic acid is obtained. The ratio (mass%) of the methyl methacrylate unit to the total of the methyl unit and the acrylate unit and the ratio (mass%) of the acrylate unit to the total were calculated.

  The ratio of methyl acrylate units in the obtained methacrylic resin (i) is 2.5 wt%, MFR is 2 g / 10 min, Mw is 120,000, glass transition temperature (Tmg) is 109 ° C., and Na content is 0.01 ppm. The K content was less than 0.01 ppm.

The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). To create a GPC calibration curve, use a methacrylic resin made by Showa Denko KK with a narrow molecular weight distribution and known molecular weight as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the weight of each resin composition. Average molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample. For the measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. . The measured molecular weight distribution curve was fitted using the normal distribution function by taking the logarithm of the molecular weight on the horizontal axis and fitting using the normal distribution function of the following equation.

[Production Example 2]
A pellet-like methacrylic resin (ii) was prepared in the same manner as in Production Example 1 except that 97.7 parts by mass of methyl methacrylate, 2.3 parts by mass of methyl acrylate, and 0.05 parts by mass of the chain transfer agent were changed. And the content of the structural unit was measured. In the methacrylic resin (ii), the structural unit derived from methyl methacrylate was 97.0% by mass, and the structural unit derived from methyl acrylate was 3.0% by mass.

  The ratio of methyl acrylate units in the obtained methacrylic resin (ii) is 3 wt%, MFR is 0.5 g / 10 min, Mw is 180,000, glass transition temperature (Tmg) is 106 ° C., and Na content is 0.01 ppm. The K content was less than 0.01 ppm.

  In Examples, a vinylidene fluoride resin (i) having an MFR of 30 g / 10 min, an Mw of 200,000, an Na content of 0.3 ppm, and a K content of 0.05 ppm was used.

  The weight average molecular weight (Mw) of the vinylidene fluoride resin was measured by gel permeation chromatography (GPC). To prepare a GPC calibration curve, polystyrene was used as a standard reagent, a calibration curve was created from the elution time and molecular weight, and the weight average molecular weight of each resin was measured. Specifically, 40 mg of resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. For the measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. .

[Production Example 3]
In order to convert the blueing agent into a master batch (MB), methacrylic resin (ii) and a colorant were dry blended at a ratio of 99.99: 0.01, and a 40 mmφ single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.). ) And melt-mixed at a set temperature of 250 to 260 ° C. to obtain colored master batch pellets. As the colorant, a bluing agent (“Sumiplast (registered trademark) Violet B” manufactured by Sumika Chemtex Co., Ltd.) was used.

[Production Example 4]
First, as a material for forming the main layer (A) (intermediate layer), the methacrylic resin (ii) obtained in Production Example 2 and the vinylidene fluoride resin (i) and the master batch pellet produced in Production Example 3 were used. Was melt kneaded at 250 ° C. using a 32 mmφ biaxial kneader (manufactured by Toshiba Machine Co., Ltd.) at a ratio of 60: 1 to obtain a resin composition used for the main layer (A) of the present invention. Subsequently, the resin layer was manufactured using the apparatus shown in FIG. Specifically, the resin composition is methacrylic resin (i) 100 as a material for forming the thermoplastic resin layers (B-1) and (B-2) using a 65 mmφ single screw extruder 12 (manufactured by Toshiba Machine Co., Ltd.). The mass parts were respectively melted by 45 mmφ single screw extruders 11 and 13 (manufactured by Hitachi Zosen). Subsequently, these are sent through the feed block 14 (manufactured by Hitachi Zosen Co., Ltd.) having a set temperature of 250 to 270 ° C. to the thermoplastic resin layer (B-1) / main layer (A) / thermoplastic resin layer (B It laminated | stacked so that it might become the structure represented by 2), it extruded from the multi-manifold type | mold die 15 [The Hitachi Zosen Co., Ltd. make, 2 types, 3 layer distribution], and the film-form molten resin 16 was obtained. Then, the obtained film-like molten resin 16 is sandwiched between a first cooling roll 17 (roll temperature 100 ° C.) and a second cooling roll 18 (roll temperature 97 ° C.) arranged opposite to each other, and then a second cooling roll. The film is sandwiched between the second cooling roll 18 and the third cooling roll 19 (roll temperature 95 ° C.) while being wound around 18, and then wound around the third cooling roll 19 to be molded and cooled, and the film thickness of the main layer A resin layer 10 having a three-layer structure having a thickness of 300 μm and a thermoplastic resin layer thickness of 100 μm was obtained. All of the obtained resin layers 10 had a total film thickness of 500 μm and were colorless and transparent when visually observed. The amount of alkali metal (Na + K) contained in the main layer was determined to be 0.21 ppm. The dielectric constant of the resin layer 10 was 4.0.

[Production Example 5]
Three layers having a main layer thickness of 300 μm and a thermoplastic resin layer thickness of 100 μm by the same method except that the resin used for the thermoplastic resin layer of Production Example 4 is changed to Sumika Stylon Polycarbonate PCX-6648 A resin layer 20 having a configuration was obtained. MVR of PCX-6648 is 6.7 cm ^3/10 min, Mw is 54,000, a glass transition temperature (Tmg) is 121 ° C., Na content 0.2 ppm, K content is 0.2 ppm, the resin layer The dielectric constant of 20 was 4.0.

Table 1 shows the glass transition temperature (Tmg) obtained by DSC measurement of the resin used as the main layer and the thermoplastic resin layer, and the difference between the Tmg of the main layer and the Tmg of the thermoplastic resin layer.

[Production Example 6]
By using a three-dimensional bending mold with a radius of curvature R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm, the resin layer 10 is bent by 90 ° (bending angle 90 °) with a hot press at 120 to 130 ° C. A curved resin layer 10 was obtained. The resin layer 10 formed into a curved surface had no appearance defects such as cracks and wrinkles including the curved surface portion and the flat portion.

[Production Example 7]
A curved resin layer 20 was obtained by the same method as in Production Example 6 except that the resin layer 10 was changed to the resin layer 20. The resin layer 20 formed into a curved surface had no appearance defects such as cracks and wrinkles including the curved surface portion and the flat portion.

[Example 1]
AICA AITRON (registered trademark) Z-778-3 manufactured by Aika Industry Co., Ltd. is 15 μm on the front surface (upper surface) of the resin layer 10 that is curved in Production Example 6, and AICA AITRON (registered trademark) Z-778 manufactured by Aika Industry Co., Ltd. -3 was sprayed to 15 μm, left in an oven at 50 ° C. for 10 minutes to remove the solvent, and then UV-cured using a high-pressure mercury lamp, Eyegraphics UV irradiation device. A curved resin laminate having a curvature radius R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm was obtained. In the obtained curved resin laminate, there were no appearance defects such as cracks, wrinkles, and white turbidity including curved surface portions and flat portions.

[Examples 2 to 10]
In the same manner as in Example 1, as shown in Table 2, in addition to AICA AITRON (registered trademark) Z-778-3 manufactured by Aika Industry Co., Ltd., AICA AITRON (registered trademark) Z-850 manufactured by Aika Industry Co., Ltd., Toyo Ink Rioduras (registered trademark) MOL5000 manufactured by Toyo Ink Co., Ltd. and Rioduras (registered trademark) MOL2112 manufactured by Toyo Ink Co., Ltd. were coated to a predetermined film thickness, UV cured, and the curvature radius R of the curved surface portion was 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm. A curved resin laminate was obtained. About Rio Duras (registered trademark) MOL5000 manufactured by Toyo Ink Co., Ltd. and Rio Duras (registered trademark) MOL 2112 manufactured by Toyo Ink Co., Ltd. were subjected to heat treatment at 140 ° C. for 15 minutes after the hard coat treatment. In the obtained curved resin laminate, there were no appearance defects such as cracks, wrinkles, and white turbidity including curved surface portions and flat portions.

[Examples 11 and 12]
Except that the resin layer was changed to the curved surface molded resin layer 20 in Production Example 7, it was produced by the same method as in Example 1 or 10, and the curvature radius R of the curved surface portion was 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm. A curved resin laminate was obtained. In the obtained curved resin laminate, there were no appearance defects such as cracks, wrinkles, and white turbidity including curved surface portions and flat portions.

[Comparative Example 1]
A curved resin laminate having a curvature radius R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm was obtained in the same manner as in Example 1 except that the back surface was not hard-coated. In the obtained curved resin laminate, there were no appearance defects such as cracks, wrinkles, and white turbidity including curved surface portions and flat portions.

[Comparative Example 2]
A curved resin laminate having a radius of curvature R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm was obtained in the same manner as in Example 11 except that the back surface was not hard-coated. In the obtained curved resin laminate, there were no appearance defects such as cracks, wrinkles, and white turbidity including curved surface portions and flat portions.

In order to measure the hardness of various hard coating agents, universal hardness (UH) was measured using an ultra-micro hardness measuring instrument. A Vickers indenter (square pyramid diamond indenter) was used as the indenter. The results are shown in Table 3.

In Examples 1 to 12 and Comparative Examples 1 and 2, the universal hardness (UH _f ) of the hard coating agent used on the surface and its film thickness (D _f ) and the universal hardness (UH _b ) of the hard coating agent used on the back surface ) And the rigidity ratio obtained from the film thickness (D _b ) = (D _f × UH _f ) / (D _b × UH _b ), and durability test of the curved resin laminate (dropped in an oven at 80 ° C. for 100 hours) ) Later deformation amount is shown in Table 4. The deformation amount was calculated according to the following formula.
Deformation amount = [distance after endurance test (B)] − [distance before endurance test (A)]
In the formula, the distance (A) before the durability test is as shown in FIG. 5 when the curved resin laminate 1 is placed on the flat surface 21 facing the front side before the durability test. The distance from the flat part 2 of the body 1 to the plane 21 is represented. As shown in FIG. 5, the distance (B) after the durability test is the flatness of the curved resin laminate 1 when the curved resin laminate 1 is placed on the flat surface 21 facing the front side after the durability test. The distance from the deformation | transformation part 22 in this part 2 to this plane 21 is represented. However, the distance from the portion having the longest distance to the plane 22 to the plane 21 in the deformed portion 22 is defined as the distance (B). The distances (A) and (B) were measured using a constant pressure thickness measuring instrument 23, respectively.

  The pencil hardness on the surface side of the curved resin laminates obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was measured according to JIS K5600-5-4. Further, the dielectric constant of the curved resin laminate was measured. The results are shown in Table 4.

  As shown in Table 4, the curved resin laminates obtained in Examples 1 to 12 are smaller in the amount of deformation after the durability test than the curved resin laminates obtained in Comparative Examples 1 and 2, It was confirmed that the shape stability was excellent. Further, it was confirmed that all examples had high pencil hardness and excellent surface hardness.

  DESCRIPTION OF SYMBOLS 1 ... Curved resin laminated body, 2 ... Flat part, 3 ... Curved part, 4 ... Resin layer, 5 ... Main layer, 6, 7 ... Thermoplastic resin layer, 8, 9 ... Hard-coat layer

Claims (4)

A curved surface portion including a resin layer having a dielectric constant of 3.5 or more, a hard coat layer (1) laminated on the surface of the resin layer, and a hard coat layer (2) laminated on the back surface, and curved in the back surface direction. A curved resin laminate comprising:
The curvature radius R of the curved surface portion is 0.1 mm ≦ R ≦ 30 mm, and the following formula 180 ≦ UH _f ≦ 300
120 ≦ UH _b ≦ 300
0.1 ≦ (D _f × UH _f ) / (D _b × UH _b ) ≦ 8.0
Wherein, UH _f and UH _b each represent a universal hardness of the universal hardness of the hard coat layer ^{(1) (N / mm 2} ) and a hard coat layer ^{(2) (N / mm 2} ), D f and _{D b} Indicates the thickness of the hard coat layer (1) and the thickness of the hard coat layer (2), respectively]
Meet the relationship,
The resin layer has a main layer (A) and one or more thermoplastic resin layers (B) on both sides of the main layer (A), and the main layer (A) is composed of (meth) acrylic resin and fluorine. Curved resin laminate comprising a vinylidene chloride resin . Of the main layer (A) and one or more thermoplastic resin layer (B), the most difference in glass transition temperature is higher layers most the glass transition temperature is lower layers 0 to 80 ° C., according to claim 1 Curved resin laminate. The curved resin laminate according to claim 1 or 2 , wherein the surface has a pencil hardness of 4H or more. Resin layer, the main layer and (A), and a thermoplastic resin layer laminated on both surfaces of the main layer (A) (B-1) and (B-2), one of the claims 1-3 A curved resin laminate according to any one of the above.

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