KR20180129674A - Resin laminate with curved shape - Google Patents

Abstract

Provided is a resin laminate with curved shape which is excellent in shape stability. The resin laminate includes 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. The curvature radius ® of a curved surface part is 0.1 mm <= R <= 30 mm. The following formula, 180 <= UHf <= 300 120 <= UHb <= 300 0.1 <= (Df×UHf) / (Db×UHb) <= 8.0 is satisfied.

Description

[0001] RESIN LAMINATE WITH CURVED SHAPE [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curved resin laminate used in a front plate such as an image display apparatus.

In recent years, development of a smart phone, a portable game machine, an audio player, a tablet terminal, and the like, which are characterized by design characteristics, is being carried out, and it has been studied to impart a curved shape to a flat display device. Although a glass sheet is usually used in the front plate of such a display device, a resin sheet which is a substitute for a glass sheet has been studied (for example, Patent Document 1) because of a problem such as poor yield.

Japanese Unexamined Patent Application Publication No. 2014-688

However, depending on the kind of the resin used in the resin laminate, when the resin is molded into a shape having a large curvature, defective appearance such as cracks, wrinkles, and white turbidity may occur and a resin laminate having a desired shape may not be obtained. Further, the inventors of the present invention have found that a resin laminate processed into a curved shape can not be used as a front plate of a display device because the resin laminate processed in a curved shape sometimes deforms when placed under a harsh environment such as high temperature or high temperature and high humidity.

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

SUMMARY OF THE INVENTION The present inventors have completed the present invention in detail by studying a curved resin laminate suitably used as a front plate of a display device in order to solve the above problems.

That is, the present invention includes the following preferred aspects.

[1] A resin composition comprising 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, As a laminate,

The radius of curvature R of the curved surface portion is 0.1 mm? R? 30 mm,

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 represent universal hardness (N / mm 2) of the hard coat layer 1 and universal hardness (N / mm 2) of the hard coat layer 2, D _f and D _b respectively denote the hardness (1) and the thickness of the hard coat layer (2)

Of the curved surface of the curved resin laminate.

[2] The resin layer has a main layer (A) and at least one thermoplastic resin layer (B) on at least one surface of the main layer (A).

[3] The thermoplastic resin composition according to [2], wherein 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 at least one thermoplastic resin layer (B) Laminates.

[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 comprises a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B-1) and (B-2) laminated on both surfaces of the main layer (A) 1] to [4].

[6] The curved resin laminate according to any one of [2] to [5], wherein the main layer (A) comprises a (meth) acrylic resin and a vinylidene fluoride resin.

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

1 is a schematic cross-sectional view showing an example of a curved resin laminate of the present invention.
2 is a schematic cross-sectional view showing an example of the layer structure in the curved resin laminate of the present invention.
Fig. 3 is a view showing the inscribed circle formed by the curved surface section in the section of the curved resin laminate of the present invention. Fig.
4 is a schematic view showing an example of an apparatus for producing a resin layer of a curved resin laminate of the present invention.
5 is a view showing the curved resin laminate before the endurance test, the distance (A), the curved resin laminate after the endurance test, and the distance (B) in Examples and Comparative Examples.

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 portion. In the present specification, the surface of the resin layer means the visible side of the image display apparatus. In addition, the curved surface refers to a curved portion toward the back surface (opposite to the viewer 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 not less than 3.5, more preferably not less than 3.6, and more preferably not less than 3.7 from the viewpoint of obtaining a sufficient function for use in a display device such as a touch panel. The upper limit value of the dielectric constant is not particularly limited, but is usually 20. The permittivity was determined in accordance with JIS K 6911: 1995, in which the curved resin laminate of the present invention was allowed to stand for 24 hours under an environment of a relative humidity of 50% at 23 DEG C, Lt; / RTI &gt; For the measurement, a commercially available device may be used. For example, &quot; precision LCR meter HP4284A &quot; 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, polycarbonate resin, polyamide resin, polystyrene resin, Styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, polyethylene terephthalate, polyether sulfone, cycloolefin resin and the like. Among them, a (meth) acrylic resin and a vinylidene fluoride resin are preferable. These resins may be used alone or in combination of two or more. When two or more kinds of resins are used, the amount 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 a (meth) acrylic resin (M)) contained in the resin layer include (meth) acrylic acid esters and (meth) acrylic monomers such as (meth) acrylonitrile , Copolymers of two or more (meth) acrylic monomers, copolymers of (meth) acrylic monomers with monomers other than (meth) acrylic monomers, and the like. In the present specification, the term "(meth) acrylic" means "acrylic" 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. The methacrylic resin is a polymer of a monomer mainly composed of methacrylic acid ester (alkyl methacrylate), and includes, for example, a homopolymer of methacrylic acid ester (polyalkyl methacrylate), two or more methacrylic acid esters , Copolymers of 50 mass% or more of methacrylic acid ester and 50 mass% or less of methacrylic acid ester and other monomers. As the copolymer of the methacrylic acid ester and the monomer other than the methacrylic acid ester, from 70% by mass or more of the methacrylic acid ester and 30% by mass or less of the total amount of the monomers A copolymer with other monomers is preferable, and a copolymer of 90 mass% or more of methacrylic acid ester and 10 mass% or less of other monomer is more preferable.

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

Examples of monofunctional monomers include styrene monomers such as styrene,? -Methylstyrene and vinyltoluene; Cyanated alkenyl such as acrylonitrile and methacrylonitrile; Acrylic acid; Methacrylic acid; Maleic anhydride; N-substituted maleimide and the like.

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

From the viewpoint that the (meth) acrylic resin can easily increase the shape stability, hardness, weather resistance, transparency and the like of the curved resin laminate, specifically,

(a1) a homopolymer of methyl methacrylate, or

(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, more preferably 80.0 to 99.7% by mass based on the total structural units constituting the copolymer, and , 0.1 to 50 mass%, preferably 0.2 to 30 mass%, and more preferably 0.3 to 20 mass%

[Chemical Formula 1]

[Wherein, R ₁ is a hydrogen atom or a methyl group, R ₁ is R ₂ when one hydrogen atom is an alkyl group having 1 to 8 carbon atoms, when R ₁ is a methyl group R ₂ represents an alkyl group having a carbon number of 2 to 8 ]

A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by the general formula

or

(a1) and (a2)

. Here, the content of each structural unit can be calculated by analyzing the obtained polymer by thermal decomposition gas chromatography and measuring the peak area corresponding to each monomer.

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

The weight average molecular weight (hereinafter sometimes referred to as Mw) of the (meth) acrylic resin contained in the resin layer is 50,000 to 300,000. When Mw is lower than the above lower limit, transparency when exposed under a high temperature or high temperature and high humidity environment is not sufficient, and when Mw is higher than the above upper limit, film formability at the time of producing the resin layer is not obtained. The Mw of the (meth) acrylic resin is preferably 100,000 or more, more preferably 120,000 or more, and even more preferably 150,000 or more, from the viewpoint of enhancing transparency when exposed under a high temperature or high temperature and high humidity environment. The Mw of the (meth) acrylic resin is preferably 250,000 or less, more preferably 200,000 or less, from the viewpoint of the film formability in the production of the resin layer. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

(Meth) acrylic resin has a melt mass (Mw) of usually 0.1 to 20 g / 10 min, preferably 0.2 to 5 g / 10 min, and more preferably 0.5 to 3 g / 10 min, measured at 230 캜 under a load of 3.8 kg (Hereinafter sometimes referred to as MFR). The MFR is preferably not more than the above-mentioned upper limit because it is easy to increase the strength of the resulting film, and is preferably not lower than the lower limit described above from the viewpoint of the film formability of the resin layer. The MFR can be measured according to the method specified in JIS K 7210: 1999 &quot; Test Method of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastic Plastics &quot;. For the poly (methyl methacrylate) type material, measurement at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) is specified in this JIS.

(Meth) acrylic resin preferably has a glass transition temperature (Tmg) of at least 90 占 폚, more preferably at least 95 占 폚, and even more preferably at least 100 占 폚, from the viewpoint of heat resistance. The glass transition temperature can be obtained by using a differential scanning calorimeter (DSC) "EXSTAR DSC6100" manufactured by SII Nanotechnology under the conditions of a nitrogen atmosphere at a heating rate of 10 ° C / min. In the present specification, the glass transition temperature means the midpoint glass transition temperature (Tmg).

(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 and the like. At that time, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent. The chain transfer agent may be a suitable commercially available product. The addition amount of the chain transfer agent may be suitably determined in accordance with the type and proportion of the monomers, the required characteristics, and the like.

Examples of the vinylidene fluoride resin (sometimes referred to as vinylidene fluoride resin (F)) contained in the resin layer include homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and other monomers. From the viewpoint of enhancing the transparency of the curved resin laminate, it is preferable to use vinylidene fluoride resin as a fluorine-containing vinylidene fluoride resin such as trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene , And / or a homopolymer of vinylidene fluoride (polyvinylidene fluoride), and more preferably polyvinylidene fluoride. The copolymer of vinylidene fluoride and at least one monomer selected from the group consisting of vinylidene fluoride and vinylidene fluoride is preferable.

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, even more preferably 150,000 to 450,000, and particularly preferably 170,000 to 400,000. Mw is preferably at least the lower limit described above because it is easy to increase the transparency of the curved resin laminate when the curved resin laminate is exposed under a high temperature or high temperature and high humidity environment. Further, it is preferable that Mw is not more than the above-mentioned upper limit because it is easy to increase the film forming property. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

The vinylidene fluoride resin has a weight average molecular weight of preferably from 0.1 to 50 g / 10 min, more preferably from 1 to 50 g / 10 min, more preferably from 5 to 45 g / 10 min And a melt mass flow rate (MFR). It is preferable that the MFR is equal to or less than the upper limit because it is easy to suppress deterioration of transparency when the curved resin laminate is used for a long period of time. The MFR is preferably at least the lower limit described above because it is easy to increase the film-forming property. The MFR can be measured according to the method specified in JIS K 7210: 1999 &quot; Test Method of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastic Plastics &quot;.

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 and dispersing the monomer as a droplet in a medium with a dispersant and polymerizing the organic peroxide dissolved in the monomer as a polymerization initiator, and a granular polymer of 100 to 300 m . The suspension polymer is preferable to the emulsion polymer because the production process is simple, the handling of the powder is excellent, and the emulsion or salting agent containing an alkali metal such as an emulsion polymer is not contained.

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" &Quot; SOLEF (registered trademark) 6012, 6010 and 6008 &quot;

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

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

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

From the viewpoint of increasing the dielectric constant and increasing the transparency of the curved resin laminate, the main layer (A) contains 30 to 60 mass% of a (meth) acrylic resin based on the total resin contained in the main layer (A) More preferably 70 to 40 mass% of vinylidene fluoride resin, more preferably 35 to 45 mass% of (meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin, (Meth) acrylic resin and 63 to 55 mass% vinylidene fluoride resin, and more preferably 38 to 45 mass% (meth) acrylic resin and 62 to 55 mass% vinylidene fluoride resin, (Meth) acrylic resin and 62 to 57 mass% of vinylidene fluoride resin is particularly preferable.

The main layer (A) may further contain another resin different from the (meth) acrylic resin and the vinylidene fluoride resin. In the case of containing other resins, the kind thereof is not particularly limited as long as the transparency of the curved resin laminate is not significantly impaired. From the viewpoints of the hardness and weather resistance of the curved resin laminate, the amount of other resin is preferably 15 mass% or less, more preferably 10 mass% or less, based on the total resin contained in the main layer (A) And more preferably 5% by mass or less. Examples of the other resin include a polycarbonate resin, a polyamide resin, an acrylonitrile-styrene copolymer, a methyl methacrylate-styrene copolymer, and a polyethylene terephthalate. The main layer (A) may further contain other resins, but from the viewpoint of transparency, the amount of other resins is preferably 1% by mass or less, and the resin contained in the main layer (A) It is more preferable that the number is only a few.

The content of the alkali metal in the main layer (A) is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, based on the total resin contained in the main layer (A) Particularly preferably 1 ppm or less. The content of the alkali metal in the main layer (A) is preferably not more than the above-mentioned upper limit because it is easy to suppress deterioration of transparency when the curved resin laminate is used for a long time under high temperature or high temperature and high humidity. The lower limit of the content of the alkali metal in the main layer (A) is 0, and it is extremely preferable that the content of the alkali metal is substantially not included from the viewpoint of suppressing a decrease in transparency of the curved resin laminate. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the main layer (A), a small amount of emulsifier used in the production process remains. Therefore, an alkali metal such as sodium or potassium originating from the remaining emulsifier is contained in, for example, 0.05 ppm or more in the main layer (A). Particularly, 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 amount of the alkali metal . It is preferable to use a resin having a small alkali metal content as the (meth) acrylic resin and the vinylidene fluoride resin contained in the main layer (A) from the viewpoint of easily suppressing the lowering of the transparency of the curved resin laminate.

In order to keep the content of the alkali metal in the resin within the above range, the amount of the alkali metal-containing compound used in polymerization of the resin may be reduced, or the cleaning process after polymerization may be increased to remove the alkali metal-containing compound. The content of the alkali metal can be determined, for example, by inductively coupled plasma mass spectrometry (ICP / MS). As the inductively coupled plasma mass spectrometry, for example, the sample pellets to be measured are subjected to a suitable method such as a high-temperature ashing melting method, a high-temperature painting acid dissolution method, a Ca addition painting acid dissolution method, a combustion absorption method, , The sample is dissolved, dissolved in an acid, and the solution is adjusted. The content of the 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 占 폚, more preferably 55 to 80 占 폚, and still more preferably 55 to 70 占 폚. The Tmg of the main layer (A) can be obtained by measurement under the condition of a temperature elevation rate of 10 占 폚 / min under a nitrogen atmosphere using a differential scanning calorimeter (DSC) "EXSTAR DSC6100" manufactured by SII Nanotechnology. The case where the main layer (A) contains one kind of resin is a glass transition temperature of the resin, and the case where the main layer (A) contains two or more kinds of resins is the glass transition temperature of the mixture of plural resins .

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

The thermoplastic resin layer (B) comprises at least one thermoplastic resin. The thermoplastic resin layer (B) is preferably at least 60% by mass, more preferably at least 70% by mass, and most preferably at least 70% by mass, based on the total resin contained in each thermoplastic resin layer, from the viewpoint of maintaining transparency and moldability. And more preferably 80% by mass or more of a thermoplastic resin. The upper limit of the amount of the thermoplastic resin is 100% by mass.

If the absolute value of the difference between the main layer (A) and the glass transition temperature (Tmg) of the thermoplastic resin layer (B) is too large, There is a case. Particularly, when molding is performed in a shape having a large curvature (a shape in which the radius of curvature of the curved surface portion is small), the above-mentioned appearance defect in the layer is conspicuous. In a preferred embodiment of the present invention, 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 at least one thermoplastic resin layer (B) in the resin layer is preferably 0 to 80 Deg.] C, more preferably 20 to 80 [deg.] C, and more preferably 40 to 75 [deg.] C. Therefore, occurrence of defective appearance such as cracks, wrinkles and opacity in the interlayer can be effectively suppressed, . 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 becomes better with respect to the molding temperature and the resin layer Therefore, it is preferable.

Examples of the thermoplastic resin contained in the thermoplastic resin layer (B) include the above (meth) acrylic resin (M), polycarbonate resin, cycloolefin resin and the like. These thermoplastic resins may be used alone or in combination of two or more. The (meth) acrylic resin (M) is preferably contained in the thermoplastic resin layer (B) because the difference in glass transition temperature from the main layer (A) is small and good adhesion with the main layer (A) is obtained. In addition, the polycarbonate resin has a high Tmg, which may lead to a large difference in Tmg from the main layer (A). Therefore, when a polycarbonate resin is used, a polymer alloy of a resin capable of reducing Tmg and a polycarbonate resin (hereinafter referred to as PCalloy), for example, a polycarbonate resin and a (meth) acrylic resin, a polystyrene resin, etc. It is preferable to use an alloy.

As the polycarbonate resin, for example, a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or a polymer obtained by an ester exchange method in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate Specific examples thereof include polycarbonate resins prepared from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxy diaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo Bis (4-hydroxyphenyl) cyclopentane, 1, 2-bis (4-hydroxyphenyl) (Hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy- Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide and the like, Dihydroxydiaryl sulfoxides such as dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4 , 4'-dihydroxy-3,3'-dimethyldiphenylsulfone, and the like.

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

The dihydroxy diaryl compound may be used in combination with a trivalent or higher phenol compound as shown below. Examples of phenols having three or more hydroxyl groups include fluoroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1- Bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane, and the like.

Examples of the polycarbonate resin other than the above polycarbonate resin include polycarbonates synthesized from isosorbide and aromatic diol. An example of such a polycarbonate is DURABIO (registered trademark) manufactured by Mitsubishi Chemical Corporation.

As a polycarbonate resin, a commercially available product may be used. For example, "GARBAR (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301- 40, SD2221W, SD2201W, TR2201 &quot;

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

PCX-6648 "," PCX-6684 "," PCX-6684 ", and" PCX-6680 "manufactured by Sumikastar Theory Polycarbonate Co., Ltd. as preferable commercially available products of PC alloys, KH4210UR "," KH3310UR "," KH3410UR "," KH3520UR "," KS3410UR ", and" KS2410UR "manufactured by Mitsubishi Engineering Plastic Corporation.

The glass transition temperature of the thermoplastic resin layer (B) is preferably 80 to 180 占 폚, more preferably 90 to 150 占 폚, and still more preferably 100 to 140 占 폚. When the thermoplastic resin layer (B) contains one kind of thermoplastic resin, it is the glass transition temperature of the resin. When the thermoplastic resin layer (B) contains two or more kinds of thermoplastic resins, It is the glass transition temperature of the mixture.

The thermoplastic resin layer (B) may further contain other resin (for example, a thermosetting resin such as a filler or a resin particle) other than the thermoplastic resin for the purpose of enhancing the strength, elasticity, etc. of the thermoplastic resin layer. In this case, the amount of the other resin is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 20 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 mass%.

In a more preferred embodiment, from the viewpoint of the shape stability of the curved resin laminate, the resin layer comprises a main layer containing a (meth) acrylic resin, a thermoplastic resin layer (B-1) laminated on both surfaces of the main layer, (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 in view of the shape stability of the curved resin laminate.

The thermoplastic resin layers (B-1) and (B-2) preferably have a good transparency, a high surface hardness and a good moldability and a high curvature, Methacrylate resin layer or a PC alloy layer.

An 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 aspect, the thermoplastic resin layers (B-1) and (B-2) include at least one (meth) acrylic resin. The thermoplastic resin layers (B-1) and (B-2) are preferably at least 50 mass%, more preferably at least 60 mass%, based on the total resin contained in each thermoplastic resin layer, , And even more preferably 70 mass% or more of (meth) acrylic resin.

As the (meth) acrylic resin, there may be mentioned the above (meth) acrylic resin (M). The (meth) acrylic resin contained in the thermoplastic resin layers (B-1) and (B-2) may be the same as or different from the (meth) acrylic resin contained in the main layer (A).

The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000 from the viewpoint of good molding processability and easy increase in mechanical strength. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

In this aspect, the thermoplastic resin layers (B-1) and (B-2) may further include a thermoplastic resin other than (meth) acrylic resin. As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. Specific examples include methyl methacrylate-styrene-maleic anhydride copolymer (for example, "RESISFY" manufactured by the electrochemical industry), methyl methacrylate-methacrylic acid copolymer (for example, Quot; ALTUGLAS HT121 &quot; manufactured by ARKEMA). The glass transition temperature of the thermoplastic resin other than the (meth) acrylic resin is preferably 80 to 180 占 폚, more preferably 90 to 150 占 폚, and still more preferably 100 to 140 占 폚, 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) do not substantially contain a vinylidene fluoride resin.

Next, another embodiment of the present invention in which the thermoplastic resin layers (B-1) and (B-2) are the PC alloy layers will be described below. In this aspect, the thermoplastic resin layers (B-1) and (B-2) include at least one PCalloy. The thermoplastic resin layers (B-1) and (B-2) are preferably at least 60 mass%, more preferably at least 70 mass%, based on the total resin contained in each thermoplastic resin layer, from the viewpoint of impact resistance , And even more preferably 80 mass% or more of PC alloys.

In this aspect, the weight average molecular weight (Mw) of the PC alloy is preferably 25,000 to 60,000, and more preferably 30,000 to 50,000 from the viewpoint of easily improving the impact resistance and the moldability. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

In this aspect, the PC alloys contained in the thermoplastic resin layers (B-1) and (B-2) are preferably measured under conditions of a temperature of 275 캜 and a load of 1.2 kg, preferably 1 to 100 cm 3 / (Hereinafter, also referred to as MVR) of 2 to 80 cm 3/10 min, more preferably 3 to 40 cm 3/10 min, and particularly preferably 4 to 20 cm 3/10 min . When the MVR is not lower than the lower limit described above, the flowability is sufficiently high and molding is easy in the melt co-extrusion molding and the appearance defect is unlikely to occur. When the MVR is not more than the upper limit, the mechanical properties such as the strength of the PC alloy layer can be easily increased.

The MVR can be measured under the condition of 275 캜 under a load of 1.2 kg in accordance with JIS K 7210.

In this aspect, the thermoplastic resin layers (B-1) and (B-2) may also include thermoplastic resins other than one or more kinds of PC alloys. 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 further contains various commonly used additives within the range not impairing the effect of the present invention . Examples of the additive include additives such as stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, release agents, antistatic agents, flame retardants, polymerization inhibitors, flame retardant additives, reinforcing agents, nucleating agents, .

Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phthalocyanine skeleton. Among them, 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 comprises a coloring agent, the content of the coloring agent in each layer can be appropriately selected depending on the purpose, type of coloring agent and the like. When a bluing agent is used as the coloring agent, the content thereof may be about 0.01 to 10 ppm based on the total resin contained in each layer containing the bluing agent. The content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, further preferably 7 ppm or less, further preferably 5 ppm or less, further preferably 4 ppm or less , Particularly preferably 3 ppm or less. The blueing agent may be any of those known in the art and may be suitably used, for example, under the trade names of Mark Rolex (registered trademark) Blue RR (manufactured by Bayer), Markorox (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast (Manufactured by Mitsubishi Chemical Corporation), Violet B (manufactured by Sumika Chemical) and Polysincrene (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G and Diaresin Blue N

The ultraviolet absorber is not particularly limited, and various conventionally known ultraviolet absorbers may be used. For example, an ultraviolet absorber having an absorption maximum at 200 to 320 nm or 320 to 400 nm. Specific examples include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. As the ultraviolet absorber, one of these ultraviolet absorbers may be used alone, or two or more of them may be used in combination. The use of at least one ultraviolet ray absorbing agent having an absorption maximum at 200 to 320 nm and at least one ultraviolet ray absorbing agent having an ultraviolet ray absorption maximum at 320 to 400 nm can be more effectively prevented from being damaged by ultraviolet rays desirable. A commercially available product may be used as the ultraviolet absorber. For example, &quot; Kemisorb 102 &quot; (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy- Phenyl) -1,3,5-triazine) (absorbance 0.1), Adekastab LA-F70 (2,4,6-tris (2-hydroxy-4-hexyloxy- (Absorbance 0.6), "adecastab LA-31, LA-31RG, LA-31G" (2,2'-methylenebis (4- (Absorbance: 0.2), &quot; Adecastab LA-46 &quot; (2- (4,6-di Phenyl) -1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or "Chinuvin 1577" 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine) (absorbance 0.1), etc. The absorbance of the exemplified ultraviolet absorbent is 380 nm Absorbance of 10 mg / m &lt; 2 &gt; L of the ultraviolet absorber is dissolved in chloroform and can be measured using a spectrophotometer (for example, a spectrophotometer U-4100 manufactured by HITACHI).

When at least one of the main layer (A) and the thermoplastic resin layer (B) further contains an ultraviolet absorber, the content of the ultraviolet absorber in each layer may be appropriately selected depending on the purpose, the kind of the ultraviolet absorber and the like. For example, the content of the ultraviolet absorber may be about 0.005 to 2.0% by mass based on the total resin contained in each layer containing the ultraviolet absorber. The content of the ultraviolet absorber is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.03 mass% or more. The content of the ultraviolet absorber is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. It is preferable that the content of the ultraviolet absorber is not less than the lower limit described above from the viewpoint of easily enhancing the ultraviolet ray absorbing effect and it is preferable that the content is not more than the upper limit described above to prevent the change of the hue (for example, yellowness YI) of the curved resin laminate It is preferable because it is easy. For example, it is preferable to use the commercially available products "adecastab LA-31, LA-31RG, and LA-31G" in the amounts described above.

In another embodiment of the present invention, the thermoplastic resin layers (B-1) and (B-2) are the PC alloy layers, and the ultraviolet absorber is preferably used in an amount of 0.005 to 2.0% by mass based on the total resin contained in each thermoplastic resin layer Is preferable because it is easy to obtain a curved resin laminate having excellent light resistance.

The thickness of the resin layer is preferably 100 占 퐉 or more, more preferably 200 占 퐉 or more, and still more preferably 300 占 퐉 or more, from the viewpoint of the shape stability of the curved resin laminate. From the viewpoints of transparency and moldability, it is preferably 2000 占 퐉 or less, more preferably 1,500 占 퐉 or less, and even more preferably 1,000 占 퐉 or less. The thickness of the curved resin laminate can be measured by a digital micrometer.

The thickness of the main layer (A) is preferably 100 占 퐉 or more, more preferably 200 占 퐉 or more, and still more preferably 300 占 퐉 or more, from the viewpoints of the shape stability and the dielectric constant of the curved resin laminate. From the viewpoints of transparency and moldability, it is preferably 1500 占 퐉 or less, more preferably 1200 占 퐉 or less, and further preferably 1000 占 퐉 or less. The thickness of the main layer (A) can be measured by a digital microscope.

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

The resin layer can be produced by a common method. For example, the resin layer can be formed by a method comprising the steps of: forming a main layer (A) comprising a (meth) acrylic resin and a vinylidene fluoride resin, The resin layer having the laminated thermoplastic resin layers (B-1) and (B-2) can be produced by the following method.

The main layer (A) can be produced from the resin composition (A) comprising a (meth) acrylic resin and a vinylidene fluoride resin, and the thermoplastic resin layers (B-1) and (B- B-1) and (B-2). The resin compositions (B-1) and (B-2) may contain at least a resin which imparts the thermoplastic resin layers (B-1) and (B-2) Or may be a single kind of resin.

The resin composition (A) is usually obtained by kneading a (meth) acrylic resin, a vinylidene fluoride resin or the like. The kneading can be carried out by, for example, a method including a step of melting and kneading at a temperature of 150 to 350 DEG C at a shearing rate of 10 to 1000 / sec.

The temperature at which the melt-kneading is carried out is preferably at least 150 ° C., because the resin can be sufficiently melted, and preferably at most 350 ° C., because thermal decomposition of the resin is easily suppressed. The shear rate at the time of melt kneading is preferably 10 / sec or more because the resin is easily kneaded sufficiently, and 1000 / sec or less is preferable because decomposition of the resin is easily suppressed.

In order to obtain a resin composition in which each component is more uniformly mixed, melt kneading is preferably performed at a temperature of 180 to 300 캜, more preferably 200 to 300 캜, preferably 20 to 700 / Is performed at a shear rate of 30 to 500 / sec.

As a device used for melt kneading, a usual mixer or kneader can be used. Specific examples thereof include a uniaxial kneader, a twin-screw kneader, a twin-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. When the shearing speed is increased within the above range, a high shearing machine or the like may be used.

The resin compositions (B-1) and (B-2) can also be produced in the same manner as the resin composition (A), for example, by melt kneading under the above temperature and shearing rate. In the case where the thermoplastic resin layers (B-1) and (B-2) include one kind of thermoplastic resin, for example, the resin layer may be obtained by melt-extrusion described below without preliminary melt-kneading.

The resin layer having the main layer (A) as the preferred embodiment of the present invention and the thermoplastic resin layers (B-1) and (B-2) present on both sides of the main layer (A) can be obtained, for example, (A), (B-1) and (B-2) from the resin compositions (A), (B-1) and (B- 2) by a casting method, a hot press method, The resin compositions (A), (B-1) and (B-2) may be prepared by melt co-extrusion molding Or the like. When the resin layer is produced by the bonding, it is preferable to use the injection molding method and the melt extrusion molding method for the production of each layer, and it is more preferable to use the melt extrusion molding method.

The melt co-extrusion molding can be carried out, for example, by separately feeding the resin composition (A) and the resin compositions (B-1) and (B-2) into two or three single- After melt-kneading, the main layer (A) formed from the resin composition (A) and the thermoplastic resin layers (B-1) and (B-2) are laminated and integrated through a feed block die or a multi-manifold die or the like and extruded Molding method. In the case where the resin compositions (B-1) and (B-2) are the same composition, one composition melt-kneaded in one extruder is divided into two through a feed block die or the like to form the thermoplastic resin layers (B- (B-2) may be formed. The obtained resin layer is preferably cooled and solidified by, for example, a roll unit or the like.

The curved resin laminate of the present invention may be produced by laminating hard coat layers (1) and (2) described below on a resin layer (for example, a flat resin layer) obtained by the above method and then bending. In a preferred embodiment, the resin layer obtained by the above method is subjected to a bending process so that the radius of curvature R of the curved surface portion of the curved surface resin laminate after the hard coating layer lamination is 0.1 mm? R? 30 mm, (1) and (2) are preferably laminated.

As a method of bending the resin layer, for example, there can be mentioned a method of forming a thermal press by using a three-dimensional bending mold having a predetermined radius of curvature, a thermal bending method, a vacuum molding method and the like.

The molding processing temperature may be at least Tmg of the layer having the highest Tmg among the layers constituting the resin layer. In a preferred embodiment, when the glass transition temperature of the main layer (A) is Tmg _A and the glass transition temperature of the thermoplastic resin layer (B) is Tmg _B , the molding processing temperature (T)

_{Tmg A + 40 <T <Tmg} A + 90

Tmg _B <T

Lt; / RTI &gt; For example, the molding processing temperature may be 90 to 170 캜, more preferably 100 to 150 캜. The glass transition temperature can be measured by, for example, differential scanning calorimetry (DSC).

[Hard Coating Layer]

The curved resin laminate of the present invention comprises 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 following relationship.

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 represent universal hardness (N / mm 2) of the hard coat layer 1 and universal hardness (N / mm 2) of the hard coat layer 2, D _f and D _b respectively denote the hardness (1) and the thickness of the hard coat layer (2)

In the present specification, (D _f × UH _f) a surface-side stiffness, (D _f × UH _f) of the hard coating layer (1) rigid, (D _b × UH _b) the back-side hard coating layer (2) of / (D _b x UH _b ) is called 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 can be used even under a harsh environment, for example, , The deformation can be effectively prevented or suppressed. In addition, the scratch resistance is good, and cracking due to the durability test or impact is also unlikely to occur.

The universal hardness of the hard coating layer (1) (UH _f) is preferably 185 ≤ UH _f ≤ 300, more preferably 190 ≤ UH _f ≤ 300, more preferably 195 ≤ UH _f ≤ 290. If the universal hardness is above the lower limit, the scratch resistance can be enhanced. If the universal hardness is not more than the upper limit, cracking caused by the durability test or 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, more preferably 140 ≤ UH _f ≤ 270, particularly preferably 140 ≤ UH _f ≤ 250. If the universal hardness is above the lower limit, the scratch resistance can be enhanced. If the universal hardness is not more than the upper limit, cracking caused by the durability test or impact can be effectively prevented.

The universal hardness of the hard coat layers 1 and 2 can be measured with a Vickers indenter (diamond-shaped diamond indenter) using a micro-hardness tester. The universal hardness of each of the hard coat layers 1 and 2 is adjusted to a predetermined range by adjusting the kind and content of the curable compound and additive contained in the curable composition constituting the hard coat layer 1 or 2 You can.

Rigidity ratio of the hard coating layer (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. If the rigidity ratios of the hard coat layers 1 and 2 are within the above ranges, the shape stability of the curved resin laminate can be further improved and deformation under a harsh environment, for example, at high temperature or high temperature and high humidity, Prevention or suppression.

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, 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. If it is not more than the upper limit, cracking of the hard coat layer and deformation of the resin layer can be prevented.

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, 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. If the hard coat layer 2 is not more than the upper limit, cracking of the hard coat layer and deformation of the resin layer can be prevented.

The hard coat layers (1) and (2) consist of a cured product of the curable composition. The curable composition is not particularly limited as long as it can form a hard coat layer that satisfies the above universal hardness. The curable composition contains a curable compound as an essential component and can be cured with a curing catalyst, a conductive particle, a solvent, An antioxidant, a coloring agent, and the like. The curable compositions constituting the hard coat layers (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; A carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate compound, an alicyclic epoxy resin, a glycidyl ether epoxy resin, a vinyl ether compound, an oxetane compound, an alkoxysilane compound such as an alkoxysilane or an alkylalkoxysilane And the like. Among these, radical polymerization type curing compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds and polyfunctional epoxy acrylate compounds from the viewpoint of easy adjustment of universal hardness to a predetermined range; A thermosetting curable compound such as alkoxysilane or alkylalkoxysilane is preferably used. These curable compounds are cured by, for example, irradiating energy rays such as electron beam, radiation, and ultraviolet rays, and / or curing by heating. Preferably, the curable compounds are irradiated with at least energy rays such as electron beam, It is preferable to cure. These curable compounds may be used alone or in combination of two or more.

A compound having at least three (meth) acryloyloxy groups in the molecule may be used. Further, (meth) acryloyloxy group means acryloyloxy group or methacryloyloxy group.

Examples of the compound having at least three (meth) acryloyloxy groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerin tri (meth) (Meth) acrylate, pentaerythritol tri- or tetra- (meth) acrylate, dipentaerythritol tri-, tetra-, penta- or hexa (meth) acrylate, tripentaerythritol tetra-, Poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups such as hexa-or hepta- (meth) acrylate; (Meth) acrylate having a hydroxyl group in a proportion of at least one hydroxyl group to an isocyanato group in a compound having at least two isocyanato groups in the molecule, and (meth) acryloyl A urethane (meth) acrylate having a number of 3 or more in terms of the number of solar hours is obtained by reaction of a urethane (meth) acrylate (for example, diisocyanate and pentaerythritol tri (meth) acrylate); Tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid, and the like. In addition, monomers are exemplified herein, but they may be used as these monomers. For example, oligomers such as dimers and trimer may be used. Further, a monomer and an oligomer may be used in combination. 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 (Meth) acryloyloxy group in the molecule, such as 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate. The amount of the other curable compound to be used is usually up to 20 parts by mass based on 100 parts by mass of the compound having at least three (meth) acryloyloxy groups in the molecule.

When the curable composition is cured by 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, thioacid dyes, benzyldimethyl ketone,? -Hydroxyalkylphenones, hydroxy ketones, aminoalkylphenones, acylphosphine oxides and the like. And two or more of them may be used as needed. The amount of the photopolymerization initiator to be used is usually 0.1 to 5 parts by mass based on 100 parts by mass of the curable compound.

The curable composition may contain other additives. Examples of the additive include additives such as 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 regulator, a plasticizer, a defoaming agent, a leveling agent, an antistatic agent, Solvents, and the like. Among these, it is preferable to use a filler. The filler may be included in one or both of the hard coating layers constituting the hard coating layers 1 and 2, but in particular, from the viewpoint of increasing the surface hardness of the curved resin laminated body, the hard coating layer 1 ) In the curable composition of the present invention.

Examples of the filler include organic fine particles and inorganic fine particles, and particularly preferred are inorganic fine particles. Examples of the inorganic fine particles include metal oxide fine particles such as silica, zirconia, alumina, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide and cerium oxide, metal fluorides such as magnesium fluoride Fine particles, etc. Among them, silica, zirconia and alumina can be preferably used. In addition, indium tin oxide (ITO), tin oxide and the like can be appropriately used when it is desired to appropriately use the hollow silica fine particles and to provide antistatic property and conductivity.

In a preferred embodiment, the inorganic fine particles are colloidal silica. Methods for synthesizing colloidal silica include gas phase synthesis methods such as aerosol synthesis by thermal decomposition of silicon tetrachloride, water glass as raw materials, and liquid phase synthesis methods such as hydrolysis of alkoxide. Examples of commercially available products of colloidal silica include products of "Organosilica sol" (organic solvent-dispersed silica sol) manufactured by Nissan Chemical Industries, Ltd. and products of "High purity organosol" of Fuso Chemical Industry Co., , Which is preferable. These are colloidal silica dispersed in an organic solvent.

The curable composition may contain a solvent for the purpose of adjusting its viscosity or the like. For example, when the inorganic particles are included, a solvent may be added for dispersion. In the case of preparing a curable composition containing inorganic particles and a solvent, for example, the inorganic particles and the solvent may be mixed to disperse the inorganic particles in the solvent, and then the dispersion may be mixed with the curable composition. In this case, inorganic particles of a commercially available product dispersed in an organic solvent may be mixed with a curing composition. Alternatively, the inorganic particles may be dispersed in the mixed solution after mixing the curable compound and the solvent. The solvent is preferably one capable of dissolving the curable compound and capable of volatilizing easily after application, and in the case where inorganic particles are contained in the curable composition, it is preferable that the solvent can disperse the inorganic particles. Examples of the solvent include diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy- ; 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; Water and the like. The amount of the solvent to be used may be suitably adjusted in accordance with properties of the curable compound.

As the curable composition for forming the hard coat layers (1) and (2), a commercially available product can be used. Z-850 "," Z-700K-2 "," Z-700AF-5 ", and" Z-700AF-5 "manufactured by Aika Kogyo KK are commercially available products such as AICAAITRON (registered trademark) Z-700W-7 "," Z-776-5W / Z-P800B "; Lioduras (registered trademark) "MOL5000", "MOL2112", 1500 series, 2000 series, 2500 series manufactured by Toyo Ink Co., Ltd.; "Acier" manufactured by Nidec Corporation; "STR-SiA", "8KX-078", "8KX-089" manufactured by Daesung Fine Chemical Co., Ltd.; V-4000BA "," V-4001EA "," V-4005 "," V-4018 "," 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 ", and" ERS-830 ".

In a preferred aspect of the present invention, the curved resin laminate of the present invention is a curved resin laminate in which both surfaces of the resin layer curved so that the radius of curvature R of the curved surface portion of the curved surface resin laminate after lamination of the hard coating layer is 0.1 mm R R 30 30 mm By applying the curable composition to a curable coating film, followed by curing.

Examples of the application method of the curable composition include bar coating, micro gravure coating, roll coating, flow coating, dip coating, spin coating, die coating, spray coating and the like. In order to cure the curable coating film, irradiation with energy rays or heating may be performed depending on the kind of the curable composition.

As the energy ray for curing the curable coating film by the irradiation of the energy ray, for example, ultraviolet ray, electron beam, radiation and the like can be mentioned, and the conditions such as the strength and irradiation time are appropriately selected according to the kind of the curable composition . In the case of curing the curable coating film by heating, the conditions such as the temperature and the time are appropriately selected according to the kind of the curable composition. The heating temperature is usually 100 占 폚 or lower, preferably 80 占 폚 or lower, more preferably 60 占 폚 or lower so as not to cause deformation of the resin layer. When the curable composition contains a solvent, the curable coating film may be cured after the application and after the solvent is volatilized, and the volatilization of the solvent and the curing of the curable coating film may be performed at the same time.

[Curved resin laminate]

1 is a schematic cross-sectional view showing an example of a curved resin laminate of the present invention. The curved resin laminate 1 has a flat portion 2 and a curved portion 3 curved in the backward direction (downward in Fig. 1) from both ends of the flat portion 2. 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 cross-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 has a main layer 5, a thermoplastic resin layer 6 laminated on the surface side of the main layer 5, and a thermoplastic resin layer 7 laminated on the back side.

The curved resin laminate of the present invention can exhibit excellent shape stability even when the radius of curvature R of the curved surface portion is small and is particularly effective even when placed under a harsh environment such as a high temperature or high temperature and high humidity environment for a long time Can be suppressed or prevented. Therefore, the radius of curvature R of the curved surface portion may be 13 mm or less, 10 mm or less, 7 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, or 1 mm or less. In the curved resin laminate of the present invention, the radius of curvature 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? 15 mm, more preferably 0.5 mm? R? 14 mm, more preferably 1 mm? R? 13 mm, still more preferably 1 mm? R? 12 mm, particularly preferably 1 mm? R? Mm, and in particular, 1 mm? R? 7 mm. 3, the radius of curvature R of the curved surface portion of the curved surface resin laminate is set so that the radius of curvature of the curved surface portion 3 in the cross section of the curved surface resin laminate 1 is And thus the radius R of the inscribed circle 24 formed.

The curved resin laminate of the present invention can exhibit excellent shape stability even when the degree of curvature of the curved surface portion is large and can effectively suppress or prevent deformation even under a harsh environment such as a high temperature or high temperature and high humidity environment for a long time. can do. Therefore, the angle of curvature (curvature angle) of the curved portion is preferably 10 degrees or more, more preferably 30 degrees or more, still more preferably 60 degrees or more, still more preferably 70 degrees or more, Or more. The curvature angle of the curved surface portion is set such that the end point (or starting point) of the curved surface portion 3 in the inscribed circle 24 formed along the curved surface portion 3, for example, ) 25 and a central angle (?) Of a sector formed by a disadvantage (or an end point) 26 and a center point 27 of an inscribed circle.

Further, 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 of the surface (hard coat layer side) is preferably not less than H, more preferably not less than 2H, more preferably not less than 3H, even more preferably not less than 4H, particularly preferably not less than 5H, Is not less than 6H, particularly not less than 7H. If the pencil hardness is above the lower limit, scratch resistance of the surface can be improved, and scratches on the screen can be effectively suppressed or prevented even when used as a front panel of a display device such as a touch panel. The pencil hardness can be measured in accordance with JIS K5600-5-4.

As described above, the curved resin laminate of the present invention can be used for various display devices such as a liquid crystal display device, an organic electroluminescence (EL) display device, a touch device, And can be used as a front panel of a panel display device. Moreover, since the display device has a curved shape, it can be used as a front plate of a display device having high design characteristics, unlike a conventional flat display device.

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

The curved resin laminate of the present invention is preferably transparent when observed with naked eyes. Concretely, the curved resin laminate of the present invention preferably has a curvature radius of at least 85%, more preferably at least 88%, even more preferably at least 90% as measured in accordance with JIS K7361-1: 1997 And has a transmittance (Tt). The upper limit of the total light transmittance is 100%. It is preferable that the curved resin laminate has a total light transmittance in the above range even after it is exposed in a harsh environment such as high temperature or high temperature and high humidity.

The thickness of the curved resin laminate of the present invention is preferably 100 to 1500 m, more preferably 150 to 1300 m, and still more preferably 200 to 1000 m. If the thickness of the curved resin laminate is not less than the above lower limit, the rigidity of the sheet is good and deformation during pressing can be prevented. When the thickness is less than the upper limit, the distance to the touch sensor becomes closer to the front surface, Sensitivity can be expressed.

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

The thickness of the functional layer may be appropriately selected in accordance with the purpose of each functional layer, but is preferably 1 占 퐉 or more, more preferably 3 占 퐉 or more, even more preferably 5 占 퐉 or more from the viewpoint of easy functioning Is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, and even more preferably 70 占 퐉 or less from the viewpoint of easily preventing breakage of the functional layer.

[Example]

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present 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 under the conditions of a nitrogen atmosphere and a temperature raising rate of 10 ° C / min.

[Content of alkali metal]

Inductively coupled plasma mass spectrometry.

[MFR]

Was measured according to the method specified in JIS K 7210: 1999 &quot; Test Method of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastic Plastics &quot;. With respect to the poly (methyl methacrylate) type material, measurement at a temperature of 230 캜 and a load of 3.80 kg (37.3 N) is specified in this JIS.

[MVR]

Using semi-automatic melt indexer 2A manufactured by TOYO SEIKI KOGYO CO., LTD., The measurement was carried out under the condition of 275 DEG C under a load of 1.2 kg in accordance with JIS K 7210.

〔permittivity〕

The resin layer or the curved resin laminate was allowed to stand under an environment of 23% and 50% relative humidity for 24 hours. Under this environment, the resin layer or the resin laminate was measured at 3 V and 100 kHz by an automatic balancing bridge method Respectively. A precision LCR meter HP4284A manufactured by Agilent Technologies, Inc. was used for the measurement.

[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 (octylmercaptan) and 0.1 part by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixture. Further, 0.036 part 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 mixture. The mixture was continuously fed into a complete mixing type polymerization reactor so that the flow rate ratio of the monomer mixture liquid and the initiator mixture liquid was 8.8: 1, and the polymerization was carried out at an average polymerization time of 20 minutes and a temperature of 175 ° C at an average polymerization rate of 54%. The resulting partial polymer was heated to 200 ° C. and introduced into a vented devolatilizing extruder. The unreacted monomer was deflected from the vent at 240 ° C., and the polymer after devolatilization was extruded in a molten state. After water cooling, To obtain a pellet-shaped methacrylic resin (i).

The obtained pellet-shaped methacrylic resin (i) was analyzed by thermal decomposition gas chromatography under the following conditions, and the respective peak areas corresponding to methyl methacrylate and acrylic ester were measured. As a result, the methacrylic resin (i) had a structural unit derived from methyl methacrylate of 97.5% by mass and a structural unit derived from methyl acrylate of 2.5% by mass.

(Thermal decomposition conditions)

Sample Preparation: A methacrylic resin composition was precisely weighed (standard: 2 to 3 mg) and placed in a central portion of a metal cell having a trough shape. The metal cells were folded and both ends were lightly pinched by pressing.

Thermal decomposition apparatus: CURIE POINT PYROLYZER JHP-22 (manufactured by Japan Analytical Industry Co., Ltd.)

Metal cell: Pyrofoil F590 (manufactured by Japan Analytical Industry Co., Ltd.)

Setting temperature of thermostat: 200 ℃

Setting temperature of heat pipe: 250 ℃

Thermal decomposition temperature: 590 ℃

Thermal decomposition time: 5 seconds

(Gas chromatographic analysis conditions)

Gas chromatographic analysis apparatus: GC-14B (manufactured by Shimadzu Corporation)

Detection method: FID

Column: 7G 3.2 m 占 3.1 mm? (Manufactured by Shimadzu Corporation)

Filler: FAL-M (manufactured by Shimadzu Corporation)

Carrier gas: Air / N ₂ / H ₂ = 50/100/50 (㎪), 80 ml / min

The temperature of the column was elevated to 150 ° C at a rate of 10 ° C / minute, held at 150 ° C for 14 minutes,

INJ Temperature: 200 ° C

DET temperature: 200 DEG C

The methacrylic resin composition is thermally decomposed under the thermal decomposition conditions, and a peak area (a1) corresponding to the methyl methacrylate detected when the decomposition product produced under the gas chromatography analysis conditions is measured and a peak area corresponding to the acrylic acid ester The peak area (b1) was measured. Then, the peak area ratio A (= b1 / a1) was determined from these peak areas. On the other hand, the mass ratio of acrylic ester units to methyl methacrylate units of W ₀ (base (旣知)) of methacrylic resins by standard and thermal decomposition of the pyrolysis conditions, the generated decomposition products of the gas chromatographic analysis conditions (A ₀ ) corresponding to the methyl methacrylate and a peak area (b ₀ ) corresponding to the acrylic acid ester which are detected when the measurement is carried out with the peak area ratio (A ₀ ) (= b ₀ / a ₀ ). Then, a factor f (= W ₀ / A ₀ ) was obtained from the peak area ratio (A ₀ ) and the mass ratio (W ₀ ).

The mass ratio (W) of the acrylic acid ester unit to the methyl methacrylate unit in the copolymer contained in the methacrylic resin composition is determined by multiplying the peak area ratio (A) by the factor (f), and the mass ratio W), the ratio (mass%) of the methyl methacrylate units relative to the total of the methyl methacrylate units and the acrylic ester units and the ratio (mass%) of the acrylic ester units to the total amount were calculated.

The obtained methacrylic resin (i) had a methyl acrylate unit content of 2.5 wt%, MFR of 2 g / 10 min, Mw of 120,000, glass transition temperature (Tmg) of 109 DEG C, Na content of less than 0.01 ppm, And less than 0.01 ppm.

The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). In order to prepare a calibration curve of GPC, a calibration curve was prepared from the elution time and the molecular weight using a methacrylic resin of a narrow molecular weight distribution and a known molecular weight, manufactured by Showa Denko Co., The weight average molecular weight of the composition was measured. Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. Two TSHel SuperHM-H columns and one SuperH2500 column, which were columns made by Tosoh Corporation, were used in the measuring apparatus, which were installed in series and employing an RI detector as the detector. The measured molecular weight distribution curve was fitting by using the normal distribution function by taking the logarithm of the molecular weight of the abscissa, and fitting was performed using the normal distribution function of the following formula.

[Equation 1]

[Production Example 2]

(Ii) was obtained 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 part by mass of a chain transfer agent were used, Respectively. The methacrylic resin (ii) had 97.0% by mass of a structural unit derived from methyl methacrylate and 3.0% by mass of a structural unit derived from methyl acrylate.

The obtained methacrylic resin (ii) had a methyl acrylate unit content of 3 wt%, an MFR of 0.5 g / 10 min, an Mw of 180,000, a glass transition temperature (Tmg) of 106 DEG C, an Na content of less than 0.01 ppm, And less than 0.01 ppm.

In the 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). For preparing the calibration curve of GPC, polystyrene was used as a standard reagent, a calibration curve was prepared from the elution time and the molecular weight, and the weight average molecular weight of each resin was measured. Specifically, 40 mg of the resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. Two TSHel SuperHM-H columns and one SuperH2500 column, which were columns made by Tosoh Corporation, were used in the measuring apparatus, which were installed in series and employing an RI detector as the detector.

[Production Example 3]

The methacrylic resin (ii) and the colorant were dry-blended at a ratio of 99.99: 0.01 in order to masterbatch the bluing agent (MB), and the blend was set by a 40 mmφ single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.) And melted and mixed at a temperature of 250 to 260 캜 to obtain a colored master batch pellet. As the coloring agent, a bluing agent ("Sumiplast (registered trademark) Violet B" manufactured by Sumika Chemtech Co., Ltd.) was used.

[Production Example 4]

First, the methacrylic resin (ii), the vinylidene fluoride resin (i), and the master batch pellets produced in Production Example 3, which were obtained in Production Example 2, were used as materials for forming the main layer (A) (Manufactured by Toshiba Machine Co., Ltd.) at a temperature of 250 占 폚 in a 32 mm? Biaxial kneader at a ratio of 100 parts by mass to obtain a resin composition for use in the main layer (A) of the present invention. Subsequently, a resin layer was produced by using the apparatus shown in Fig. Specifically, the resin composition was applied to a thermoplastic resin layer (B-1) and a thermoplastic resin layer (B-2) by a 65 mmφ single screw extruder 12 (manufactured by Toshiba Machine Co., Ltd.) i) were melted by 45 mmφ single screw extruders 11 and 13 (manufactured by Hitachi, Ltd.). Subsequently, the thermoplastic resin layer (B-1) / the main layer (A) / the thermoplastic resin layer (B-2) were laminated via the feed block 14 (made by Hitachi, Ltd.) having a set temperature of 250 to 270 캜 And extruded from a multi-manifold die 15 (distribution of two-kind three layers, made by Hitachi, Ltd.) to obtain a film-like molten resin 16. The molten resin 16 thus obtained was sandwiched between the first cooling roll 17 (roll temperature 100 캜) and the second cooling roll 18 (roll temperature 97 캜) opposed to each other, And then wound around the second cooling roll 18 and sandwiched between the second cooling roll 18 and the third cooling roll 19 (roll temperature 95 캜), and then wound around the third cooling roll 19 Molded, and cooled to obtain a three-layered resin layer 10 having a main layer thickness of 300 占 퐉 and a thermoplastic resin layer thickness of 100 占 퐉. All of the obtained resin layers 10 had a total film thickness of 500 占 퐉 and were colorless transparent when observed with naked eyes. The amount of the 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]

Layer structure having a thickness of the main layer of 300 占 퐉 and a thickness of 100 占 퐉 of the thermoplastic resin layer was formed by the same method except that the resin used in the thermoplastic resin layer of Production Example 4 was changed to PCX-6648 made by Sumikastar Theory Polycarbonate Whereby a resin layer 20 was obtained. The glass transition temperature (Tmg) was 121 占 폚, the Na content was 0.2 ppm, the K content was 0.2 ppm, and the dielectric constant of the resin layer 20 was 4.0. The glass transition temperature (Tmg) of the PCX-6648 was 6.7 cm 3/10 min.

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 Tmg of the main layer and Tmg of the thermoplastic resin layer are shown in Table 1.

[Production Example 6]

The resin layer 10 is formed by a three-dimensional bending mold having a radius of curvature R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm, 90 [deg.] At an angle of 90 [deg.]) To obtain a resin layer 10 having a curved surface. The curved resin layer 10 including the curved surface portion and the flat portion was free from appearance defects such as cracks and wrinkles.

[Production Example 7]

A resin layer 20 having a curved surface was obtained in the same manner as in Production Example 6, except that the resin layer 10 was replaced with the resin layer 20. The curved resin layer 20 including the curved surface portion and the flat portion was free from appearance defects such as cracks and wrinkles.

[Example 1]

AICAAITRON (registered trademark) Z-778-3 manufactured by Aika Kogyo Co., Ltd. was coated on the surface (upper surface) of the resin layer 10 curved in Production Example 6, and AICAAITRON (registered trademark) Z-778 -3 was coated by spraying so as to have a thickness of 15 탆 and left in an oven at 50 캜 for 10 minutes to remove the solvent and then UV-cured by using a UV irradiation apparatus of a high-pressure mercury lamp, (R) of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm. The resulting curved resin laminate did not suffer from appearance defects such as cracks, wrinkles and opacity, including curved portions and flat portions.

[Examples 2 to 10]

AICAAITRON (registered trademark) Z-850 manufactured by Aika Kogyo Co., Ltd., ZY-850 manufactured by AIKA INDUSTRIAL CO., LTD. LAS (Registered Trademark) MOL5000 manufactured by Toyo Ink Co., Ltd., and ZERO DURAS (registered trademark) MOL2112 available from Toyo Ink Co., Ltd. were coated to a predetermined film thickness and UV cured to form a film having a radius of curvature R of 1 mm, 2 mm, 7 mm, Or 14 mm curved resin laminate was obtained. The hardcoat treatment was carried out for the Zerio Durax (registered trademark) MOL5000 manufactured by Toyo Ink Co., Ltd., and the ZERO Dyuras (registered trademark) MOL2112 manufactured by Toyo Ink Co., Ltd. for 15 minutes at 140 ° C. The resulting curved resin laminate did not suffer from appearance defects such as cracks, wrinkles and opacity, including curved portions and flat portions.

[Examples 11 and 12]

The curvature radius R of the curved surface portion was set to 1 mm, 2 mm, 7 mm, and 2 mm in the same manner as in Example 1 or 10 except that the resin layer was changed to the resin layer 20 curved in Production Example 7, 13 mm, or 14 mm. The resulting curved resin laminate did not suffer from appearance defects such as cracks, wrinkles and opacity, including curved portions and flat portions.

[Comparative Example 1]

A curved surface resin laminate body having a curved surface radius R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm was formed in the same manner as in Example 1, . The resulting curved resin laminate did not suffer from appearance defects such as cracks, wrinkles and opacity, including curved portions and flat portions.

[Comparative Example 2]

The curved surface resin laminate body having the curved surface radius R of 1 mm, 2 mm, 7 mm, 13 mm, or 14 mm was formed in the same manner as in Example 11, . The resulting curved resin laminate did not suffer from appearance defects such as cracks, wrinkles and opacity, including curved portions and flat portions.

In order to measure the hardness of various hard coating agents, the universal hardness (UH) was measured with a Vickers indenter (diamond-shaped diamond indenter) using a very small hardness meter. The results are shown in Table 3.

The universal hardness (UH _f ) and the film thickness (D _f ) of the hard coating agent used on the surface and the universal hardness (UH _b ) of the hard coating agent used on the back surface, The stiffness ratio obtained from the film thickness (D _b ) = (D _f × UH _f ) / (D _b × UH _b ) and the deformation amount after the endurance test (100 hours of dropping into the oven at 80 ° C.) 4. The amount of deformation was calculated according to the following formula.

Deformation amount = [distance after endurance test (B)] - [distance before endurance test (A)]

5, when the curved resin laminate 1 is placed on the plane surface 21 toward the front side before the endurance test, the distance A before the endurance test is set so that the curved resin laminate 1 Represents the distance from the flat portion 2 of the body 1 to the plane 21 in question. As shown in Fig. 5, the distance B after the durability test is set so that when the curved resin laminate 1 is placed on the plane 21 toward the front surface side after the endurance test, the curved surface resin laminate 1 The distance from the deformed portion 22 in the flat portion 2 to the plane 21 in question. The distance from the portion of the deformed portion 22 where the distance to the plane 22 is the longest to the plane 21 is taken as the distance B. [ The distances A and B were measured using the static pressure gauge 23, respectively.

The pencil hardness of the surface side of the curved resin laminate obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was measured according to JIS K5600-5-4. 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 laminate obtained in Examples 1 to 12 had a smaller deformation amount after the durability test and was superior in shape stability as compared with the curved resin laminate obtained in Comparative Examples 1 and 2 . Further, it was confirmed that any of the examples had a high pencil hardness and an excellent surface hardness.

1: curved resin laminate, 2: flat part, 3: curved part, 4: resin layer, 5: main layer, 6, 7: thermoplastic resin layer,

Claims (6)

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, the curved resin laminate comprising a curved surface portion curved in the backward direction ,
The radius of curvature R of the curved surface portion is 0.1 mm? R? 30 mm,
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 represent universal hardness (N / mm 2) of the hard coat layer 1 and universal hardness (N / mm 2) of the hard coat layer 2, D _f and D _b respectively denote the hardness (1) and the thickness of the hard coat layer (2)
Of the curved surface of the curved resin laminate. The method according to claim 1,
The resin layer has a main layer (A) and at least one thermoplastic resin layer (B) on at least one surface of the main layer (A). 3. The method of claim 2,
Wherein 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 at least one thermoplastic resin layer (B) is 0 to 80 占 폚. 4. The method according to any one of claims 1 to 3,
Wherein the pencil hardness of the surface is 4H or more. 5. The method according to any one of claims 1 to 4,
The resin layer is composed of a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B-1) and (B-2) laminated on both sides of the main layer (A) sieve. 6. The method according to any one of claims 2 to 5,
The main layer (A) comprises a (meth) acrylic resin and a vinylidene fluoride resin.

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