KR20180129675A - Resin laminate - Google Patents

Abstract

An object of the present invention is to provide a resin laminate capable of effectively suppressing appearance defects such as cracks, wrinkles, and opacity at the time of bending. The resin laminate includes a resin layer having a dielectric constant of 3.5 or more and a hard coating layer laminated on at least one surface of the resin layer. The pencil hardness of the hard coating layer side is 4B or more, and the resin laminate satisfies the relation of formulas (1) to (3), represented by 20 <= LPET <= 130 (1), 0.4 <= LHC/LPMMA <= 1.5 (2), and 1 <= THC <= 30 (3).

Description

Resin laminate {RESIN LAMINATE}

The present invention relates to a 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, when the resin laminate is subjected to bending processing, appearance defects such as cracks, wrinkles, and white turbidity may occur. In particular, when bending is performed in a shape having a large curvature, defective appearance is remarkable. The present inventors have found that the above-mentioned problems can not be utilized.

Accordingly, an object of the present invention is to provide a resin laminate capable of effectively suppressing appearance defects such as cracking, wrinkling, and opacity at the time of bending.

Means for Solving the Problems In order to solve the above-described problems, the inventors of the present invention have conducted extensive studies on a resin laminate capable of suppressing occurrence of appearance defects repeatedly, thereby completing the present invention.

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

[1] A resin laminate comprising a resin layer having a dielectric constant of 3.5 or more and a hard coat layer laminated on at least one surface of the resin layer,

The pencil hardness of the hard coat layer side is 4B or more, and the following formulas (1) to (3)

20? L _PET ? 130 (1)

0.4? L _HC / L _PMMA ? 1.5 (2)

1? T? _HC ? 30 (3)

_Wherein L _PET is a film obtained by stretching a base material made of polyethylene terephthalate of 75 占 퐉 and a laminate having the hard coat layer on one side of the base material at a rate of 140 占 폚 and 50 mm / L _HC represents a substrate made of polymethyl methacrylate having a thickness of 500 탆 and a laminate having the hard coating layer on one side of the substrate at 100 캜 and 50 mm / _LMPMA represents the maximum elongation (%) when the base material made of polymethyl methacrylate having a thickness of 500 탆 is stretched at a rate of 100 캜 and 50 mm / min, (%), And T _HC represents the film thickness (mu m) of the hard coat layer]

Satisfies the following relationship.

[2] The resin laminate according to [1], wherein the curved surface portion has a radius of curvature R of 0.1 mm? R? 14 mm.

(3) The resin layer has a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B) laminated on at least one surface of the main layer (A)

0.2? Y / X? 15 (4)

Wherein X represents the critical elongation (%) when the main layer (A) having a thickness of 500 占 퐉 is stretched at a rate of 23 占 폚 and 50 mm / min, and Y is a thermoplastic water having a thickness of 500 占 퐉 (%) When stretching the stratum bed (B) at a rate of 23 캜 and 50 mm / min]

1] or [2].

(4) The resin layer has a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B) laminated on at least one surface of the main layer (A) The resin laminate according to any one of [1] to [3], which comprises a (meth) acrylic resin and a vinylidene fluoride resin.

The resin laminate of the present invention can effectively suppress occurrence of appearance defects such as cracks, wrinkles, and opacity at the time of bending.

1 is a schematic sectional view showing an example of a resin laminate of the present invention.
2 is a schematic cross-sectional view showing an example of a resin laminate after bending the 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 the resin laminate of the present invention.

The resin laminate of the present invention includes a resin layer having a dielectric constant of 3.5 or more and a hard coat layer laminated on at least one surface of the resin layer.

[Resin Layer]

The resin layer has a relatively high dielectric constant, preferably not less than 3.5, more preferably not less than 3.6, 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 dielectric constant was measured in accordance with JIS K 6911: 1995, and the resin laminate of the present invention was allowed to stand at 23 DEG C under an environment of 50% relative humidity for 24 hours, under the environment of 3 V at 100 kHz Measured value. 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 resins are used, the dielectric constant may be adjusted to 3.5 or more by appropriately adjusting the amount of the resin having a high dielectric constant and the resin having a low dielectric constant.

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 moldability, hardness, weather resistance, transparency and the like of the 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 monomers 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 molding processability, hardness, weather resistance, transparency and the like of the 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. If 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 if Mw is higher than the above upper limit, the film formability at the time of producing the resin laminate can not be 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 facilitating 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, and more preferably 200,000 or less, from the viewpoint of the film formability at the time of producing the resin laminate. 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 obtained film, and is preferably not lower than the lower limit described above from the viewpoint of film formability of the resin laminate. 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 has a glass transition temperature (Tmg) of preferably 90 占 폚 or higher, more preferably 95 占 폚 or higher, and even more preferably 100 占 폚 or higher, 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 resin laminate, the vinylidene fluoride resin is preferably selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene And vinylidene fluoride, and / or a homopolymer of vinylidene fluoride (polyvinylidene fluoride), and 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, and particularly preferably 170,000 to 400,000. It is preferable that Mw is not less than the lower limit described above because transparency of the resin laminate can be easily increased when the resin laminate is exposed under an environment of high temperature or high temperature and high humidity. 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). The MFR is preferably not more than the upper limit of the above range because it is easy to suppress the decrease in transparency when the 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 in accordance with the method specified in JIS K 7210: 1999 "Testing method of melt-mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastics".

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 a 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 enhancing the transparency of the resin laminate, the main layer (A) is a resin composition containing 30 to 60 mass% of a (meth) acrylic resin and 70 to 60 mass% of a (meth) acrylic resin based on the total resin contained in the main layer (A) (Meth) acrylic resin and 65 to 55 mass% vinylidene fluoride resin, and more preferably 37 to 45 mass% 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 , Particularly preferably 38 to 43 mass% of a (meth) acrylic resin and 62 to 57 mass% of a vinylidene fluoride resin.

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 resin, the kind thereof is not particularly limited as long as the transparency of the resin laminate is not significantly impaired. From the viewpoint of the hardness and weather resistance of the resin laminate, the amount of other resin is preferably 15 mass% or less, more preferably 10 mass% or less, and more preferably 5 mass% or less based on the total resin contained in the main layer (A) % 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 upper limit described above because it is easy to suppress the decrease in transparency when the resin laminate is used for a long time under high temperature or high temperature and high humidity. The lower limit value 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 the lowering of the transparency of the 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 decrease in transparency of the 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 measured using a differential scanning calorimeter (DSC). As the differential scanning calorimeter, for example, &quot; EXSTAR DSC6100 &quot; manufactured by SII Nanotechnology Co., Ltd. can be used and the glass transition temperature can be obtained by measuring under a nitrogen atmosphere at a temperature raising rate of 10 DEG C / min. 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) 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.

Wherein the resin layer has the following formula (4)

0.2? Y / X? 15 (4)

X represents the critical elongation (%) when the main layer (A) of 500 占 퐉 is stretched at a rate of 23 占 폚 and 50 mm / min; Y represents the thermoplastic resin layer (B) of 500 占 퐉; (%) When stretched at a speed of 23 캜 and 50 mm / min]

Is satisfied. More preferably, the formula (4) is 0.3? Y / X? 10, more preferably 0.4 Y / X? 5, and particularly preferably 0.5 Y / X? If the critical elongation of the main layer (A) and the critical elongation of the thermoplastic resin layer (B) satisfy the relation of the above formula (4), the followability is improved and cracks, wrinkles, It is possible to more effectively suppress occurrence of defective appearance of the display device. The formula (4) is a method of adjusting the type and content of the resin or additives contained in the main layer (A) and the thermoplastic resin layer (B), for example, Or may be adjusted to a predetermined range by, for example, a method of adding it to the thermoplastic resin layer (B).

The tensile test was carried out under the following conditions in accordance with JIS K-7161, and the tensile elongation X and Y (%) of the resin sheets constituting the main layer (A) or the thermoplastic resin layer (B) (Mm) at the time of occurrence of the chucking is calculated and can be calculated using the following formula (A). The tensile test under the following conditions can be performed by, for example, a method of measuring a resin sheet having a width of 1 cm, a length of 10 cm, and a thickness of 500 占 퐉 using a tensile tester manufactured by Strong Co.,

Limit elongation (%) = (chuck distance at crack / breakage - initial chuck distance) / initial chuck distance x 100 (A)

(Condition)

Device: Tensile testing machine

Test temperature: 23 ℃

Tensile speed: 50 mm / min

Resin sheet: thickness 500 탆

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 it is easy to satisfy the relationship of the formula (4) and has good adhesion with the main layer (A). In addition, since the polycarbonate resin has a large critical elongation, the relationship of the above formula (4) may not be satisfied. Therefore, when a polycarbonate resin is used, a polymer alloy of a resin and a polycarbonate resin capable of reducing the critical elongation Y (hereinafter referred to as PCalloy), for example, a polycarbonate resin and a (meth) acrylic resin , Polystyrene resin or the like is preferably used.

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 glass transition temperature can be measured using a differential scanning calorimeter (DSC).

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 laminate Therefore, it is preferable.

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 preferred embodiment, the resin layer has a main layer containing a (meth) acrylic resin and thermoplastic resin layers (B-1) and (B-2) laminated on both surfaces of the main layer. The thermoplastic resin layers (B-1) and (B-2) may contain the same thermoplastic resin or may contain different thermoplastic resins. It is preferable that the thermoplastic resin layers (B-1) and (B-2) include the same thermoplastic resin from the viewpoint of preventing appearance defects during bending processing.

The thermoplastic resin layers (B-1) and (B-2) are excellent in transparency, surface hardness and molding processability of the resin laminate and exhibit appearance defects even when molded into a shape having a large curvature Is preferably a (meth) acrylic resin layer or a PC alloy layer from the viewpoint that it is easy to suppress the occurrence of a crack.

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 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 viewpoints of heat resistance and surface hardness, 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 layer of the main layer (A) and the thermoplastic resin layer (B) in the resin laminate of the present invention may further contain various commonly used additives in the range not hindering the effect of the present invention do. 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 layer 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, kind of the coloring agent and the like. When a bluing agent is used as the colorant, its content 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, more preferably 5 ppm or less, still more preferably 4 ppm 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), Mark Rolex (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast Diaresin Blue G, Diaresin Blue G and Diaresin Blue N (trade names, manufactured by Mitsubishi Chemical Corporation) can be given as examples of the resin (trade name) Violet B (manufactured by Sumika Chemical Co., Ltd.) and Polysincrene (registered trademark) Blue RLS (manufactured by Clariant) .

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. The content of the ultraviolet absorber is preferably at least the lower limit described above from the viewpoint of easily increasing the ultraviolet absorbing effect and it is easier to prevent the change of the color tone (for example, the yellowness YI) of the resin laminate desirable. 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 since it is easy to obtain a 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 durability of the resin laminate. From the viewpoints of transparency and molding processability, it is preferably not more than 2000 占 퐉, more preferably not more than 1,500 占 퐉, still more preferably not more than 1,000 占 퐉. The thickness of the resin layer 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 durability and dielectric constant of the resin laminate. From the viewpoints of transparency and molding processability, 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 still more preferably 50 占 퐉 or more, from the viewpoint of durability of the resin laminate. From the viewpoints of molding processability 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 can be measured by a digital microscope.

The resin layer can be prepared by a conventional method. For example, a main layer (A) comprising a (meth) acrylic resin and a vinylidene fluoride resin, which is a preferred embodiment of the present invention, and a thermoplastic resin layer (B-1) -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 and a vinylidene fluoride resin. 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 can be sufficiently kneaded easily, and it is preferable that the shear rate is 1000 / sec or less 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.

[Hard Coating Layer]

The resin laminate of the present invention comprises a hard coating layer laminated on at least one surface (front surface or back surface) of the resin layer. From the viewpoints of durability and surface hardness of the resin laminate, the hard coat layer is preferably laminated at least on the surface side of the resin layer, and more preferably laminated on both sides of the resin layer. The surface of the resin layer means the visible side of the image display apparatus.

The hard coating layer has the following formulas (1) to (3)

20? L _PET ? 130 (1)

0.4? L _HC / L _PMMA ? 1.5 (2)

1? T? _HC ? 30 (3)

_Wherein L _PET is a polyethylene terephthalate substrate having a thickness of 75 占 퐉 and a limit elongation at the time of stretching the laminate having the hard coat layer on one side thereof at a rate of 140 占 폚 and 50 mm / (%), L _HC represents a substrate made of polymethyl methacrylate having a thickness of 500 μm and a laminate having the hard coating layer on one side of the substrate at a temperature of 100 ° C. and a rate of 50 mm / min L _PMMA represents the maximum elongation (%) when a base made of polymethyl methacrylate of 500 탆 is stretched at a rate of 100 캜 and 50 mm / min, and T _HC represents the film thickness of the hard coat layer.

Lt; / RTI &gt;

Since the hard coat layer of the resin laminate of the present invention satisfies the relations of the above formulas (1) to (3), when the resin laminate is subjected to bending processing, defective appearance such as cracks, It is possible to inhibit or prevent it. Particularly, even when molding is performed in a shape having a large curvature (a shape in which the curvature radius of the curved surface portion is small), occurrence of defective appearance can be effectively suppressed or prevented.

The above formula (1) is preferably 25? L _PET ? 110, more preferably 30? L _PET ? 100, more preferably 30? L _PET ? 80. When the lower limit is more than the lower limit, occurrence of cracking or whitening during bending can be suppressed more effectively. When the upper limit is not more than the upper limit, generation of wrinkles at the time of bending can be suppressed more effectively.

In the above formula (1), L _PET was subjected to a tensile test under the following conditions in accordance with JIS K-7161, and the distance (mm) between chucks at the time when cracks and cracks occurred in the hard coat layer were read, Can be calculated using the following formula (B). For the tensile test under the following conditions, for example, a tensile tester manufactured by INSTRONG Corp. may be used as the apparatus. As the laminate, a sheet obtained by laminating a hard coat layer having a thickness of 5 占 퐉 on one side of a 75 占 퐉 -bond-treated PET film (Lumira (registered trademark) U34 # 100, Toray Co., Ltd.) .

Limit elongation (%) = (chuck distance at crack / breakage - initial chuck distance) / initial chuck distance x 100 (B)

(Condition)

Device: Tensile testing machine

Test temperature: 140 ° C

Tensile speed: 50 mm / min

Laminate: 75 占 퐉 A sheet obtained by laminating a hard coat layer having a thickness of 1 to 30 占 퐉 on one side of this adhesive-treated PET film base material

In addition, the critical elongation L _PET can be calculated on the basis of the time when cracks and cracks have occurred in the hard coat layer of the laminate. At this point, cracks, cracks, and the like may not be generated in the PET film as a substrate.

The above formula (2) is preferably 0.6? L _HC / L _PMMA ? 1.4, more preferably 0.8? L _HC / L _PMMA ? 1.3, more preferably 0.9? L _HC / L _PMMA ? 1.3. When the above formula (2) is in the above-mentioned range, it is possible to more effectively suppress occurrence of appearance defects such as cracks, wrinkles and opacity of the resin laminate at the time of bending.

A tensile test was conducted under the following conditions in accordance with JIS K-7161 using L _HC as the following laminate (HC) and L _PMMA as the following laminate (PMMA) in the above formula (2) The distance (mm) between chucks at the time when the body itself is broken can be read and calculated using the following formula (C). For the tensile test under the following conditions, for example, a tensile tester manufactured by INSTRONG Corp. may be used as the apparatus. As the layered product (HC), for example, a sheet obtained by laminating a hard coat layer of 5 占 퐉 on one side of PMMA (Techoloy (registered trademark) S000 made by Escabosite Co., Ltd.) having a thickness of 500 占 퐉 can be used As the layered product (PMMA), for example, PMMA (Techoloy (registered trademark) S000] sheet having a thickness of 500 탆 can be used.

Maximum elongation (%) = (chuck distance at break - initial chuck distance) / initial chuck distance x 100 (C)

(Condition)

Device: Tensile testing machine

Test temperature: 100 ° C

Tensile speed: 50 mm / min

Laminate (HC): A laminate (HC) was formed by laminating a hard coat layer having a thickness of 1 to 30 占 퐉 on one side of a PMMA substrate having a thickness of 500 占 퐉

Laminate (PMMA): A PMMA sheet having a thickness of 500 탆

Further, the maximum elongation (L _HC ) can be calculated on the basis of the time point at which the laminate itself is broken, and cracking, cracking, or breakage of the hard coating layer may occur before fracture of the PMMA base material.

The hard coat layer may be laminated on at least one surface of the resin layer. However, it is preferable that the hard coat layer is laminated on both surfaces of the resin layer from the viewpoint of easily exhibiting shape stability even when the resin laminate is exposed to a harsh environment.

The thickness (T _HC ) of the hard coat layer is 1 to 30 mu m, preferably 2 to 25 mu m, more preferably 2 to 20 mu m, further preferably 3 to 10 mu m. If the thickness of the hard coating layer is not less than the above lower limit, the surface hardness can be increased. If the thickness of the hard coating layer is less than the upper limit, occurrence of defective appearance such as breakage of the hard coating layer during bending can be suppressed. When a hard coating layer is laminated on both sides of the resin laminate, the thickness of each hard coating layer may be different or may be the same.

The hard coat layer is composed 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 satisfying the above formulas (1) to (3), and includes a curable compound as an essential component and, if necessary, , Leveling agents, stabilizers, antioxidants, coloring agents, and the like. When the hard coat layer is laminated on both sides of the resin layer, the curable composition constituting each hard coat layer may be the same or different. In addition, the type and content of the compound and the additive contained in the curable composition constituting the hard coat layer can be adjusted to the ranges shown by the formulas (1) to (3).

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, from the viewpoint of easily forming a hard coat layer satisfying the above formulas (1) to (3), it is preferable to use a radical polymerization system such as a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound or a polyfunctional epoxy acrylate compound Curable compounds; 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.

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 one embodiment, the inorganic microfine particle is 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 can contain a small amount of the filler in view of surface hardness. On the other hand, from the viewpoint of curvature moldability, it is preferable that no filler is contained. That is, the content of the filler in the curable composition is, for example, 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less, and still more preferably 3 mass% or less based on the total amount of the curable composition of 100 mass% By mass or less, particularly 0% by mass or less.

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 layer, a commercially available product can be used. As a commercial product, for example, AICAAITRON (registered trademark) "Z-850" manufactured by Aika Kogyo Co., Ltd.; Lioduras (registered trademark) "MOL5000", "MOL5100", "MOL5200", "MOL2112" manufactured by Toyo Ink Co., Unidick "ERS-958", "ESS-177", "ESS-107", "ERS-830" manufactured by DIC Corporation; 8KY-058C "," 8KY-056C "," 8KY-058 "," 8KY-077 ", and" 8KY-012C "manufactured by Daesung Fine Chemical Co., Ltd., New Frontier" RST- -078 "; UA-122P "manufactured by Shin Nakamura Chemical Industry Co., Ltd., and the like.

The resin laminate of the present invention can be produced by coating the curable composition on at least one surface of the resin layer to form 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.

[Resin laminate]

1 is a schematic cross-sectional view showing an example of the resin laminate of the present invention. The resin laminate 1 has a resin layer 2, a hard coat layer 6 laminated on the surface of the resin layer 2, and a hard coat layer 7 laminated on the back surface. The resin layer 2 has a main layer 3, a thermoplastic resin layer 4 laminated on the surface side of the main layer 3, and a thermoplastic resin layer 5 laminated on the back side.

Since the resin laminate of the present invention has a relatively high permittivity, preferably not less than 3.5, more preferably not less than 3.6, and more preferably not less than 3.7, the resin laminate of the present invention has a bending-processed resin laminate (referred to as a curved resin laminate Can be sufficiently used even if it is used in a display device such as a touch panel. The dielectric constant of the resin laminate can be measured by a method represented by the dielectric constant of the resin layer.

Since the pencil hardness of the hard coat side of the resin laminate of the present invention is preferably 4B or more, more preferably F or more, more preferably H or more, particularly preferably 2H or more, and good surface hardness , Scratch resistance on the surface can be improved, and scratches on the screen can be effectively suppressed or prevented even when the curved resin laminate is used as the front plate of the display device. The pencil hardness can be measured in accordance with JIS K5600-5-4.

The resin laminate of the present invention can effectively inhibit or prevent occurrence of defective appearance such as cracks, wrinkles, and white turbidity at the time of bending, and even if the resin laminate is formed into a shape having a large curvature (the curvature radius of the curved surface portion is small) Occurrence of defective appearance can be effectively suppressed. Therefore, when the resin laminate of the present invention is used, the resin laminate having a relatively small curvature radius R of the curved surface portion, for example, R of 13 mm or less, 10 mm or less, 7 mm or less, Mm or less, 3 mm or less, or 2 mm or less. The radius of curvature R of the curved surface portion in the resin laminate after the bending process is preferably 0.1 mm? R? 15 mm, more preferably 0.5 mm? R? 14 mm, and more preferably 1 mm? R? More preferably 1 mm? R? 12, particularly preferably 1 mm? R? 10 mm, particularly 1 mm? R? 7 mm. 3, the radius of curvature R of the curved surface portion is set so that the radius of the inscribed circle 21 formed along the curved surface portion 9 in the cross-section of the curved surface resin laminate 1 (for example, R). The curved surface portion may be curved in the direction (surface direction) of the display device (surface side) of the display device or may be curved in the direction opposite to the viewer side (back side) Direction.

The resin laminate of the present invention can effectively inhibit or prevent occurrence of appearance defects such as cracks, wrinkles, and opacity at the time of bending, and effectively suppress occurrence of appearance defects even when molding is performed in a shape having a large curvature of curved portions can do. Therefore, when the resin laminate of the present invention is used, the laminated body having a relatively large angle of curvature (curved angle) of the curved surface portion, preferably 10 degrees or more, more preferably 30 degrees or more, more preferably 60 degrees or more , Even more preferably 70 DEG or more, particularly 80 DEG or more. The curvature angle of the curved surface portion may be set to be a curvature angle of the curved surface portion 9 in the inscribed circle 21 formed along the curved surface portion 9 as shown in Fig. ) 22 and the central point (?) Of the sector formed by the end point (or end point) 23 and the center point 24 of the inscribed circle.

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

The molding processing temperature of the resin laminate of the present invention may be a temperature higher than 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 temperature may be 100 to 160 占 폚, and more preferably 120 to 140 占 폚.

Fig. 2 is a schematic cross-sectional view showing an example of the resin laminate after the bending process. The curved resin laminate 1 has a flat portion 8 and a curved portion 9 curved in the backward direction (downward in Fig. 2) from both ends of the flat portion 8. The curved surface portion 9 is curved such that the radius of curvature R is 0.1? R? 14.

INDUSTRIAL APPLICABILITY The resin laminate of the present invention can suppress the occurrence of defective appearance at the time of bending and has a good surface hardness. Therefore, even after bending, various kinds of display devices such as a liquid crystal display device, An organic electroluminescence (EL) display device, and a front panel of a touch panel display device. Moreover, since the curved surface shape is provided, unlike a conventional flat display device, it can be used as a front plate of a display device having high design quality.

The resin laminate of the present invention is preferably transparent when observed with naked eyes. Concretely, the resin laminate of the present invention has a total light transmittance (measured by JIS K7361-1: 1997, preferably not less than 85%, more preferably not less than 88%, and even more preferably not less than 90% Tt). The upper limit of the total light transmittance is 100%. It is preferable that the resin laminate of the present invention has a total light transmittance within the above range even after being exposed in a harsh environment such as high temperature or high temperature and high humidity.

The thickness of the 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. When the thickness of the 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 above upper limit, the distance to the touch sensor becomes closer to the front plate, Lt; / RTI &gt;

The resin laminate of the present invention may have at least one functional layer in addition to the resin layer and the hard coat layer. 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 of the hard coat layer. 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]

Was measured under the condition of 275 DEG C under a load of 1.2 kg in accordance with JIS K 7210 by using &quot; Semi Auto Melt Indexer 2A &quot; manufactured by Toyo Seiki Seisaku-Sho, Ltd.

〔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 obtained partial polymer was heated to 200 ° C. and introduced into a vented devolatilizing extruder. Unreacted monomers were 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

Temperature rise condition of the column: After holding for 15 minutes at 100 ° C, the temperature was raised from 10 ° C / min to 150 ° C, 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 TSKgel SuperHM-H columns and one SuperH2500 column, which were columns made by TOSOH CORPORATION, were set up in series, and a detector employing an RI detector was used. 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 TSKel 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 1 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 1 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 (A) was determined to be 0.21 ppm. The midpoint glass transition temperature (Tmg) of the resin used for the main layer (A) was 60 占 폚. The dielectric constant of the resin layer 1 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 2 was obtained. PCX-6648 had an MVR of 6.7 cm &lt; 3 &gt; / 10 min, a Mw of 54,000, a glass transition temperature (Tmg) of 121 DEG C, an Na content of 0.2 ppm, a K content of 0.2 ppm and a dielectric constant of 4.0.

(Y / X ratio of the critical elongation (X) of the main layer to the critical elongation (Y) of the thermoplastic resin layer)

(The critical elongation X of the main layer (A)

The resin composition used for the main layer (A) was press-molded at 220 占 폚 to obtain a resin sheet having a width of 1 cm, a length of 10 cm and a thickness of 500 占 퐉, and the resin sheet was extruded in accordance with JIS K- (Mm) at the time of occurrence of cracks and cracks in the resin sheet by reading the tensile stress at 23 占 폚 and 50 mm / min by a tensile tester, and using the following formula (A) The critical elongation X (%) of the main layer (A) was calculated.

Limit elongation (%) = (chuck distance at crack / breakage - initial chuck distance) / initial chuck distance x 100 (A)

As a result, the critical elongation X (%) of the main layer (A) was 5.

(Y) of the thermoplastic resin layers (B-1) and (B-2)

Except that the methacrylic resin (i) or the PCX-6648 made by Sumikastar Theory Polycarbonate was used in place of the above-mentioned resin composition used for the main layer (A), by the same method as the critical elongation X of the main layer (A) , And the critical elongation (Y) (%) of the thermoplastic resin layer were calculated. As a result, the critical elongation Y (%) of the thermoplastic resin layer made of the methacrylic resin (i) was 4 and the critical elongation Y (%) of the thermoplastic resin layer made of PCX-6648 was 3.

Y / X in the resin layer 1 was 0.8, and Y / X in the resin layer 2 was 0.6.

[Production Example 6]

(5 占 퐉, 7 占 퐉, or 36 占 퐉) shown in Table 2 was coated on 75 占 퐉 of Jerumira 占 U34 # 100 (PET film) manufactured by Toray Industries, Inc. , And the mixture was allowed to stand in an oven at 80 캜 for 3 minutes to remove the solvent. Then, the solvent was removed, and the resultant was UV-cured using a UV irradiation apparatus made by Igraphics of a high-pressure mercury lamp to obtain a PET film with a hard coating layer. Further, for the Rio Dylas (registered trademark) MOL5000, MOL5100, and MOL5200, after the above UV curing, they were placed in an oven at 140 deg. C for 10 minutes to perform post curing.

[Production Example 7]

A PMMA sheet having a hard coat layer was obtained in the same manner as in Production Example 6, except that Lumirra (registered trademark) U34 # 100 was changed to 500 mu m Technoloy (registered trademark) S000 (PMMA sheet) manufactured by Escaboset Co.,

[Measurement of limit elongation L _PET ]

According to JIS K-7161, each hard coat layer-provided PET film obtained in Production Example 6 was stretched under the condition of 140 占 폚 and 50 mm / min by a tensile tester manufactured by Strong Co., and the hard coat layer cracked and cracked (Mm) at a time point when the hard coat layer-containing PET film with the hard coating layer obtained in Production Example 6 was read and the critical elongation (L _PET ) of each hard coat layer-provided PET film obtained in Production Example 6 was calculated using the following formula (B). Table 2 shows the results. In Table 2, the thickness ( _HC ) of the hard coating layer is described in the column of &quot; HC thickness &quot;.

Limit elongation (%) = (chuck distance at crack / breakage - initial chuck distance) / initial chuck distance x 100 (B)

[Measurement of maximum elongation (L _HC )] [

The PMMA sheet with each hard coating layer obtained in Production Example 7 was stretched under the condition of 100 占 폚 and 50 mm / min by a tensile tester manufactured by In-Strong Co., in accordance with JIS K-7161, The maximum elongation (L _HC ) (%) of each of the PMMA sheets with hard coat layers obtained in Production Example 7 was calculated by using the following formula (C). Table 2 shows the results.

Maximum elongation (%) = (chuck distance at break - initial chuck distance) / initial chuck distance x 100 (C)

[Measurement of maximum elongation (L _PMMA )] [

(L _HC ) was obtained in the same manner as in the maximum elongation (L _HC ) except that the PMMA sheet having a hard coat layer of 500 탆 obtained in Production Example 7 was replaced with a 500 탆 Techoloy (registered trademark) S000 (PMMA sheet) , The maximum elongation (L _PMMA ) (%) was calculated. As a result, L _PMMA was 250%.

[Example 1]

AICAAITRON (registered trademark) Z-850 manufactured by Aika Kogyo Co., Ltd. was coated on one side of the resin layer (1) obtained in Production Example 4 so as to have a hard coat layer of 5 占 퐉, left in an oven at 50 占 폚 for 10 minutes, Thereafter, a UV-curable UV-curing UV-irradiating apparatus of a high-pressure mercury lamp was used to cure the UV-curable resin, and then AICAAITRON (registered trademark) Z-850 manufactured by Aika Kogyo Co., Ltd. was coated on the other side by the same method to obtain a resin laminate. A bending test was carried out by using a three-dimensional bending mold having a predetermined radius of curvature R to make a 90 占 bend (a bending angle of 90 占 at 120 to 130 占 폚 by hot pressing. , The outer appearance of the resin laminate with hard coating including the curved surface portion and the flat portion was free from appearance defects such as cracks and wrinkles.

[Example 2]

Except that in place of AICAAITRON (registered trademark) Z-850, the product was UV-cured by using Rio Dylas (registered trademark) MOL5000 manufactured by Toyo Ink Co., Ltd., and then placed in an oven at 140 캜 for 10 minutes, A resin laminate was obtained in the same manner as in (1) (hard coat layer thickness: 5 占 퐉). The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even if the radius of curvature (R) = 2 mm had a curved surface portion and a flat portion So that there was no defective appearance such as cracks or wrinkles.

[Example 3]

A resin laminate was obtained in the same manner as in Example 2 except that MOL5100 manufactured by Toyo Ink Co., Ltd. was used in place of Zolio Durax (registered trademark) MOL5000 (available from Toyo Ink Co., Ltd. 5 탆). The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even if the radius of curvature (R) = 2 mm had a curved surface portion and a flat portion So that there was no defective appearance such as cracks or wrinkles.

[Example 4]

A resin laminate was obtained in the same manner as in Example 2 except that MOL5200 (manufactured by Toyo Ink Co., Ltd.) was used in place of Zolio Durax (registered trademark) MOL5000 (available from Toyo Ink Co., Ltd. 5 탆). The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even if the radius of curvature (R) = 2 mm had a curved surface portion and a flat portion So that there was no defective appearance such as cracks or wrinkles.

[Example 5]

A resin laminate was obtained (hard coating layer thickness: 5 占 퐉) by the same method as in Example 1, except that MOL2112 manufactured by Toyo Ink Co., Ltd. was used instead of AICAAITRON (registered trademark) Z-850. The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even with a radius of curvature (R) = 7 mm So that there was no defective appearance such as cracks or wrinkles.

[Example 6]

A resin laminate was obtained in the same manner as in Example 1 except that the resin layer 1 was changed to the resin layer 2 (hard coat layer thickness: 5 占 퐉). The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even if the radius of curvature (R) = 13 mm included the curved surface portion and the flat portion So that there was no defective appearance such as cracks or wrinkles.

[Example 7]

A resin laminate was obtained in the same manner as in Example 2 except that the resin layer 1 was changed to the resin layer 2 (hard coat layer thickness: 5 占 퐉). The resin laminate thus obtained was subjected to a thermal bending test in the same manner as in Example 1. As a result, the outer appearance of the resin laminate with hard coating having a curved surface shape even if the radius of curvature (R) = 2 mm had a curved surface portion and a flat portion So that there was no defective appearance such as cracks or wrinkles.

[Example 8]

A resin laminate was obtained in the same manner as in Example 3 except that the film thickness of the hard coat layer was changed to 7 mu m. The outer appearance of the resin laminate with a hard coating to which a curved surface shape was imparted to a radius of curvature (R) = 13 mm did not include appearance defects such as cracks and wrinkles including curved and flat portions.

[Comparative Example 1]

A resin laminate was obtained in the same manner as in Example 1 except that SilFORT (registered trademark) UVHC7800FS was used instead of AICAAITRON (registered trademark) Z-850 (hard coating layer thickness: 5 mu m). When the bending test was carried out at a radius of curvature (R) of 15 mm or less, appearance defects such as wrinkles and opacity occurred in any of the curved portion and the flat portion.

[Comparative Example 2]

Except that SilFORT (registered trademark) UVHC7800FS and Acryl (registered trademark) 8BR-500 were mixed in a solid mass ratio of 60:40 instead of AICAAITRON (registered trademark) Z-850 To obtain a resin laminate. When the bending test was carried out at a radius of curvature (R) of 15 mm or less, appearance defects such as wrinkles and opacity occurred in any of the curved portion and the flat portion.

[Comparative Example 3]

A resin laminate was obtained in the same manner as in Example 1 except that AITRON (registered trademark) Z-850 manufactured by Aika Kogyo Co., Ltd. was coated so that the hard coat layer was 36 占 퐉. When the bending test was carried out at a radius of curvature (R) of 15 mm or less, appearance defects such as wrinkles and opacity occurred in any of the curved portion and the flat portion.

The pencil hardness of the surface side of the curved resin laminate obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was measured in accordance with JIS K5600-5-4 and shown in Table 3 together with the results of the bending test. In the bending test,? Indicates that there was no appearance defects such as cracks and wrinkles including the curved surface portion and the flat portion of the resin laminate, and X indicates that any of the curved surface portion and the flat portion of the resin laminate was cracked, Wrinkles, opacity, and the like.

Compared with the comparative examples 1 to 3, the resin laminate obtained in Examples 1 to 8 does not suffer appearance defects such as cracks, wrinkles and opacity even when the radius of curvature R is small. Therefore, it was confirmed that the resin laminate of the present invention can effectively suppress or prevent occurrence of defective appearance at the time of molding processing.

1: resin laminate 2: resin layer 3: main layer 4: 5: thermoplastic resin layer 6: 7: hard coat layer 8: flat part 9:

Claims (4)

A resin laminate comprising a resin layer having a dielectric constant of 3.5 or more and a hard coat layer laminated on at least one surface of the resin layer,
The pencil hardness of the hard coat layer side is 4B or more, and the following formulas (1) to (3)
20? L _PET ? 130 (1)
0.4? L _HC / L _PMMA ? 1.5 (2)
1? T? _HC ? 30 (3)
_Wherein L _PET is a polyethylene terephthalate substrate having a thickness of 75 占 퐉 and a limit elongation at the time of stretching the laminate having the hard coat layer on one side thereof at a rate of 140 占 폚 and 50 mm / (%), L _HC represents a substrate made of polymethyl methacrylate having a thickness of 500 μm and a laminate having the hard coating layer on one side of the substrate at a temperature of 100 ° C. and a rate of 50 mm / min L _PMMA represents the maximum elongation (%) when a substrate made of polymethyl methacrylate of 500 탆 is stretched at a rate of 100 캜 and 50 mm / min, and T _HC represents a maximum elongation Indicates the film thickness of the hard coat layer]
Satisfies the following relationship. The method according to claim 1,
And a curvature radius (R) of 0.1 mm? R? 14 mm. 3. The method according to claim 1 or 2,
The resin layer has a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B) laminated on at least one surface of the main layer (A)
0.2? Y / X? 15 (4)
X represents the critical elongation (%) when the main layer (A) of 500 占 퐉 is stretched at a rate of 23 占 폚 and 50 mm / min; Y represents the thermoplastic resin layer (B) of 500 占 퐉; (%) When stretched at a speed of 23 캜 and 50 mm / min]
Satisfies the following relationship. 4. The method according to any one of claims 1 to 3,
The resin layer has a main layer (A) containing a (meth) acrylic resin and a thermoplastic resin layer (B) laminated on at least one surface of the main layer (A) An acrylic resin, and a vinylidene fluoride resin.

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