CN108973281A - Laminated resin body - Google Patents

Abstract

The purpose of the present invention is to provide the laminated resin bodies of the generation of the bad orders such as rupture, fold, gonorrhoea when can effectively inhibit bending machining.Laminated resin body, it includes resin layers and the hard conating at least one face for being laminated in the resin layer that dielectric constant is 3.5 or more, wherein the pencil hardness of hard conating side is 4B or more, also, meet following formula (1)~(3) relationship: 20≤L_PET≤ 130 (1), 0.4≤L_HC/L_PMMA≤ 1.5 (2), 1≤T_HC≤30(3)。

Description

Laminated resin body

Technical field

The present invention relates to the laminated resin bodies for the front panel that can be applied to image display device etc..

Background technique

In recent years, with smart phone, portable game, the audio player, tablet terminal of feature in terms of design Deng exploitation energetically carrying out, before this, opposite direction be originally used for plane display device assign curve form scheme carry out Research.As the front panel of such display device, usually using glass sheet, but it is poor due to yield rate the problems such as, at (such as patent document 1) is studied for the resin sheet of the substitute of glass sheet.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2014-688 bulletin

Summary of the invention

Problems to be solved by the invention

However, the inventors of the present application found that rupture, pleat occur sometimes when carrying out bending machining to laminated resin body The bad orders such as wrinkle, gonorrhoea, especially when bending machining is at the big shape of curvature, bad order becomes significantly, therefore, it is impossible to Front panel as display device uses.

Therefore, the purpose of the present invention is to provide the appearances such as rupture, fold, gonorrhoea when can effectively inhibit bending machining not The laminated resin body of good generation.

Means for solving the problems

Present inventor in order to solve the above problems, repeatedly to the laminated resin body of the generation that can inhibit bad order Ground is studied in detail, so as to complete the present invention.

That is, the present invention includes preferred embodiment below.

[1] laminated resin body, it includes dielectric constant be 3.5 or more resin layer and be laminated at least the one of the resin layer The hard conating in a face, wherein

The pencil hardness of hard conating side is 4B or more, also, meets following formula (1)~(3) relationship:

20≤L_PET≤ 130 (1),

0.4≤L_HC/L_PMMA≤ 1.5 (2),

1≤T_HC≤ 30 (3),

[in formula, L_PETBe shown in 140 DEG C and with 50mm/ minutes speed to 75 μm by poly terephthalic acid The ultimate elongation when laminated body of substrate and the aforementioned hard conating positioned at the one side of the substrate that glycol ester is formed is stretched Rate (%), L_HCBe shown in 100 DEG C and with 50mm/ minutes speed to have with a thickness of 500 μm by poly-methyl methacrylate Maximum elongation rate (%) when the laminated body of substrate and the aforementioned hard conating positioned at the one side of the substrate that ester is formed is stretched, L_PMMAIt is shown in 100 DEG C and with 50mm/ minutes speed to a thickness of 500 μm formed by polymethyl methacrylate Maximum elongation rate (%) when substrate is stretched, T_HCIndicate the film thickness (μm) of aforementioned hard conating].

[2] laminated resin body as described in [1] is 0.1mm≤R≤14mm curved face part it includes radius of curvature R.

[3] laminated resin body as described in [1] or [2], wherein resin layer has the master comprising (methyl) acrylic resin Layer (A) and be laminated in the main layer (A) at least one face thermoplastic resin layer (B), also, meet the relationship of following formula (4):

0.2≤Y/X≤15 (4)

[in formula, X is shown in 23 DEG C and is stretched with 50mm/ minutes speed to the main layer (A) with a thickness of 500 μm When ultimate elongation (%), Y is shown in 23 DEG C and with 50mm/ minutes speed to the thermoplastic resin with a thickness of 500 μm Ultimate elongation (%) when layer (B) is stretched].

[4] laminated resin body as described in any one of [1]~[3], wherein resin layer, which has, includes (methyl) acrylic acid The main layer (A) of resin and be laminated in the main layer (A) at least one face thermoplastic resin layer (B), the main layer (A) include (first Base) acrylic resin and vinylidene fluoride resin.

The effect of invention

The hair of the bad orders such as rupture, fold, gonorrhoea when laminated resin physical efficiency of the invention effectively inhibits bending machining It is raw.

Detailed description of the invention

[Fig. 1] is the summary sectional view for indicating an example of laminated resin body of the invention.

[Fig. 2] is the outline for indicating to carry out laminated resin body of the invention an example of laminated resin body after bending machining Sectional view.

[Fig. 3] be it is in the section for indicate curved laminated resin body of the invention, curved face part is formed by inscribed circle Figure.

[Fig. 4] is the skeleton diagram for indicating an example of the device of resin layer of laminated resin body for manufacturing the present invention.

Description of symbols

1 ... laminated resin body

2 ... resin layers

3 ... main layers

4,5 ... thermoplastic resin layers

6,7 ... hard conatings

8 ... flat parts

9 ... curved face parts

Specific embodiment

Laminated resin body of the invention includes the resin layer and be laminated in the resin layer at least that dielectric constant is 3.5 or more The hard conating in one face.

[resin layer]

For resin layer, from the viewpoint for obtaining being enough to cope with the function of using in the display devices such as touch panel Consider, dielectric constant with higher (preferably 3.5 or more, more preferable 3.6 or more, further preferred 3.7 or more dielectric it is normal Number).The upper limit value of dielectric constant is not particularly limited, and usually 20.Dielectric constant is the value measured by following manner: according to JIS K 6911:1995 is small by laminated resin body standing 24 of the invention in the environment of relative humidity is 50% in 23 DEG C When, in the present context, using self-balancing bridge circuit method, it is measured with 3V, 100kHz.In measurement, commercially available equipment can be used, Such as " the precision LCR meter HP4284A " of Agilent Technologies corporation can be used.

The resin for including in resin layer is not particularly limited, as long as the tree of the dielectric constant with 3.5 or more can be formed The resin of rouge layer, as its example, can enumerate (methyl) acrylic resin, vinylidene fluoride resin, polycarbonate resin, Polyamide, polystyrene resin, acrylonitritrile-styrene resin, copolymer of methyl methacrylatestyrene, poly- pair Ethylene terephthalate, polyether sulfone, cyclic olefin resins etc..In these, preferably (methyl) acrylic resin, vinylidene fluoride tree Rouge.These resins can be used alone or combine two or more use.When using two or more resins, can suitably it adjust The amount of the high resin of dielectric constant and the low resin of dielectric constant is to be adjusted to 3.5 or more for dielectric constant.

As (methyl) acrylic resin [sometimes referred to as (methyl) acrylic resin (M)] for including in resin layer, can lift Such as homopolymer of (methyl) acrylate and (methyl) acrylonitrile etc. (methyl) acrylic monomer, (first of more than two kinds out Base) copolymer of acrylic monomer, (methyl) acrylic monomer and the monomer in addition to (methyl) acrylic monomer Copolymer etc..It should be noted that term " (methyl) propylene-" refers to " propylene-" or " metering system-" in this specification.

From the viewpoint of easy molding processibility, hardness, against weather, transparency for improving laminated resin body etc., (first Base) acrylic resin is preferably methacrylic resin.Methacrylic resin is with methacrylate (methacrylic acid alkane Base ester) based on monomer polymer, can enumerate such as methacrylate homopolymer (polyalkyl methacrylate), The copolymer of methacrylate of more than two kinds, the methacrylate of 50 mass % or more and 50 mass % are below except first The copolymer etc. of monomer other than base acrylate.As being total to for methacrylate and the monomer in addition to methacrylate Polymers, from the viewpoint of easy raising optical characteristics, against weather, for the total amount of monomer, preferably 70 matter Measure the methacrylate of % or more and the copolymer of 30 mass % other monomers below, more preferably 90 mass % or more The copolymer of methacrylate and 10 mass % other monomers below.

As the monomer in addition to methacrylate, acrylate can be enumerated, there is 1 polymerism in the molecule The monofunctional monomer of carbon-to-carbon double bond.

As monofunctional monomer, the styrene monomer such as styrene, α-methylstyrene and vinyltoluene can be enumerated； The alkenyls cyanogen such as acrylonitrile and methacrylonitrile；Acrylic acid；Methacrylic acid；Maleic anhydride；N- substituted maleimide amine etc..

From the viewpoint of heat resistance, in (methyl) acrylic resin, phenyl maleimide, hexamethylene can be copolymerized The N- substituted maleimide amine such as base maleimide and methylmaleimido, can also into strand (also referred to as polymer In main framing in or main chain in) in import lactone ring structure, glutaric anhydride structure or glutarimide structure etc..

For (methyl) acrylic resin, from the easy molding processibility for improving laminated resin body, hardness, weatherability From the viewpoint of property, transparency etc., it is particularly preferred as:

(a1) homopolymer of methyl methacrylate；Or

It (a2) include 50~99.9 mass % (preferably 70.0~99.8 for the entire infrastructure unit based on composition copolymer Quality %, more preferable 80.0~99.7 mass %) the structural unit and 0.1~50 mass % from methyl methacrylate At least the 1 of (methyl) acrylate indicated from formula (1) of (preferably 0.2~30 mass %, more preferable 0.3~20 mass %) The copolymer of kind structural unit,

[chemical formula 1]

[in formula, R₁Indicate hydrogen atom or methyl, R₁When for hydrogen atom, R₂Indicate the alkyl of carbon atom number 1~8, R₁For first When base, R₂Indicate the alkyl of carbon atom number 2~8.]；Or the mixture of (a1) and (a2).

Herein, the content of each structural unit can by being analyzed using pyrolysis gas chromatography obtained polymer, Peak area corresponding with each monomer is measured to calculate.

In formula (1), R₁Indicate hydrogen atom or methyl, R₁When for hydrogen atom, R₂Indicate the alkyl of carbon atom number 1~8, R₁For When methyl, R₂Indicate the alkyl of carbon atom number 2~8.As the alkyl of carbon atom number 2~8, ethyl, propyl, isopropyl can be enumerated Base, butyl, sec-butyl, tert-butyl, amyl, hexyl, heptyl, octyl etc..From the viewpoint of heat resistance, R₂Preferably carbon atom The alkyl of number 2~4, more preferably ethyl.

The weight average molecular weight of (methyl) acrylic resin for including in resin layer (hereinafter, be denoted as Mw sometimes.) it is 50,000 ~300,000.When Mw is lower than above-mentioned lower limit, insufficient, the Mw high of transparency when being exposed under high temperature or hot and humid environment When the above-mentioned upper limit, film forming when laminated resin body cannot be manufactured.High temperature or high temperature and humidity are exposed to from easy raising From the viewpoint of transparency when under environment, the Mw of (methyl) acrylic resin is preferably 100,000 or more, more preferably 120, 000 or more, further preferably 150,000 or more.From the viewpoint of film forming when manufacturing laminated resin body, (methyl) third The Mw of olefin(e) acid resin is preferably 250,000 hereinafter, more preferably 200, and 000 or less.Weight average molecular weight can utilize gel infiltration color (GPC) measurement is composed to measure.

For (methyl) acrylic resin, with the load of 3.8kg when being measured for 230 DEG C, with usually 0.1 ~20g/10 minutes, preferably 0.2~5g/10 minute, be more preferably 0.5~3g/10 minutes melt mass flow rate (with Under, it is denoted as MFR sometimes.).It is easy to improve obtained film strength when MFR is the above-mentioned upper limit or less, thus preferably, it is above-mentioned Lower limit more than when, be preferred from the viewpoint of the film forming of laminated resin body.MFR can be according to JIS K 7210:1999 Rule in " test method of plastics-thermoplastic melt mass flow rate (MFR) and melt volume-flow rate (MVR) " Fixed method is measured.About the material of poly- (methyl methacrylate) system, be specified in the JIS 230 DEG C temperature, with The load of 3.80kg (37.3N) is measured.

From the viewpoint of heat resistance, (methyl) acrylic resin have preferably 90 DEG C or more, be more preferably 95 DEG C with Glass transition temperature (Tmg) that is upper, being more preferably 100 DEG C or more.Glass transition temperature can be by using SII The differential scanning calorimetry (DSC) (DSC) " EXSTAR DSC6100 " of Nanotechnology Corporation, in nitrogen atmosphere Under, it is measured to obtain under conditions of heating rate is 10 DEG C/min.It should be noted that in this specification, glass Change the glass transition temperature (Tmg) that transition temperature refers to midpoint.

(methyl) acrylic resin can be by using known to suspension polymerisation, emulsion polymerization, polymerisation in solution, bulk polymerization etc. Method polymerize above-mentioned monomer to prepare.At this point, can be by adding chain-transferring agent appropriate thus by MFR, Mw, VST Etc. being adjusted to preferred range.About chain-transferring agent, commercially available product appropriate can be used.The additive amount of chain-transferring agent is according to monomer Type and its ratio, the characteristic of requirement etc. are suitably determined.

As the vinylidene fluoride resin [sometimes referred to as vinylidene fluoride resin (F)] for including in resin layer, can enumerate partially The copolymer of the homopolymer of difluoroethylene, vinylidene fluoride and other monomers.From the easy transparency for improving laminated resin body Viewpoint considers that vinylidene fluoride resin is preferably selected from by trifluoro-ethylene, tetrafluoroethene, hexafluoropropene, chlorotrifluoroethylene, perfluor The copolymer and/or vinylidene fluoride of at least one kind of monomer and vinylidene fluoride in the group of alkyl vinyl ether and ethylene composition Homopolymer (polyvinylidene fluoride), more preferably polyvinylidene fluoride.

The weight average molecular weight (Mw) of vinylidene fluoride resin is preferably 100,000~500,000, more preferably 130,000 ~450,000, further preferably 150,000~450,000, particularly preferably 170,000~400,000.Mw is above-mentioned When more than lower limit, it is easy to improve the saturating of laminated resin body when in the environment of laminated resin body being exposed to high temperature or high temperature and humidity Bright property, thus preferably.In addition, be easy to improve film forming when Mw is the above-mentioned upper limit or less, thus preferably.Weight average molecular weight can It is measured using gel permeation chromatography (GPC) to measure.

For vinylidene fluoride resin, with the load of 3.8kg when being measured for 230 DEG C, have preferably 0.1~ 50g/10 minutes, more preferably 1~50g/10 minutes, further preferably 5~45g/10 minutes melt mass flow rates (MFR).When MFR is the above-mentioned upper limit or less, the decline of transparency when being easy to inhibit that laminated resin body is used for a long time, thus it is excellent Choosing.When MFR is above-mentioned lower limit or more, it is easy to improve film forming, thus preferably.MFR can be according to JIS K 7210:1999 " modeling Regulation in the test method of material-thermoplastic melt mass flow rate (MFR) and melt volume-flow rate (MVR) " Method be measured.

Vinylidene fluoride resin can industrially be manufactured using suspension polymerization or emulsion polymerization.For suspension polymerisation For method, using water as medium, it is scattered in monomer in medium with drops with dispersing agent, it is organic in monomer by being dissolved in Peroxide carries out polymerizeing as polymerization initiator implementing, and 100~300 μm of granular polymer can be obtained.It suspends For polymer compared with emulsion polymer, manufacturing process is simple, and the treatability of powder is excellent, in addition, unlike emulsion polymer Comprising the emulsifier containing alkali metal, salting-out agents, thus preferably.

Commercially available product can be used in vinylidene fluoride resin.As the example of preferred commercially available product, KUREHA can be enumerated " KF Polymer (registered trademark) T#1300, T#1100, T#1000, T#850, W#850, W#1000, W# of CORPORATION " SOLEF (registered trademark) 6012,6010 and 6008 " of 1100 and W#1300 ", Solvay corporation.

Aforementioned resin layer can be single or multi-layer structure, from the viewpoint of multifunction, preferred multilayered structure.

In a preferred manner, the heat that aforementioned resin layer has main layer (A) and is located at least one face of the main layer (A) Plastic resin layers (B).Main layer (A) preferably comprises above-mentioned (methyl) acrylic resin (M) and above-mentioned vinylidene fluoride resin (F).

In a more preferred manner, for based on all resins for including in main layer (A), resin layer includes 10~90 matter Measure (methyl) acrylic resin of % and the vinylidene fluoride resin of 90~10 mass %.The amount of (methyl) acrylic resin is lower than When above-mentioned lower limit, the transparency it cannot adequately cannot be filled when the amount of (methyl) acrylic resin is higher than the above-mentioned upper limit The dielectric constant divided.When the amount of vinylidene fluoride resin is lower than above-mentioned lower limit, it cannot get sufficient dielectric constant, inclined difluoro second When the amount of olefine resin is higher than the above-mentioned upper limit, it cannot get durability and the adequately transparency.

In main layer (A), from the viewpoint of the easy transparency for improving dielectric constant, improving laminated resin body, being based on should For all resins for including in main layer (A), (methyl) acrylic resin and 70~40 matter of 30~60 mass % are preferably comprised The vinylidene fluoride resin of % is measured, more preferably includes (methyl) acrylic resin and 65~55 mass % of 35~45 mass % Vinylidene fluoride resin, even more preferably (methyl) acrylic resin comprising 37~45 mass % and 63~55 mass % Inclined the two of vinylidene fluoride resin, particularly preferably (methyl) acrylic resin comprising 38~45 mass % and 62~55 mass % Fluoroethylene resin very preferably includes (methyl) acrylic resin of 38~43 mass % and the inclined difluoro second of 62~57 mass % Olefine resin.

Main layer (A) also may include other resins different from (methyl) acrylic resin and vinylidene fluoride resin.Contain When other resins, the kind thereof is not particularly limited, as long as not damaging the transparency of laminated resin body significantly.From laminated resin From the viewpoint of the hardness and against weather of body, for all resins for including in the main layer (A), the amount of other resins is excellent 15 mass % are selected as hereinafter, more preferably 10 mass % are hereinafter, further preferably 5 mass % or less.It, can as other resins Enumerate such as polycarbonate resin, polyamide, acrylonitritrile-styrene resin, Methyl Methacrylate-Styrene copolymerization Object, polyethylene terephthalate etc..Although main layer (A) also may include other resins, from the viewpoint of the transparency, The amount of his resin is preferably 1 mass % hereinafter, the resin for including in main layer (A) is more preferably only (methyl) acrylic resin and partially Fluoride resin.

For all resins for including in main layer (A), the content of the alkali metal in main layer (A) be preferably 50ppm with Under, more preferably 30ppm is hereinafter, be even more preferably 10ppm hereinafter, particularly preferably 1ppm or less.Alkali in main layer (A) When the content of metal is the above-mentioned upper limit or less, it is easy to inhibit that laminated resin body is used for a long time under the conditions of high temperature or high temperature and humidity When the transparency decline, thus preferably.The lower limit value of the content of alkali metal in main layer (A) is 0, from easy inhibition resin layer From the viewpoint of the decline of the transparency of stack, alkali metal is not included substantially very preferably.Herein, include in main layer (A) (methyl) acrylic resin and/or vinylidene fluoride resin in, remain micro emulsifier used in the manufacturing process Deng.Therefore, including, for example, alkali metal such as the sodium from remaining emulsifier of 0.05ppm or more, potassium in main layer (A).Especially It is that (methyl) acrylic resin and/or vinylidene fluoride resin for including are the productions as obtained from emulsion polymerization in main layer (A) When object, the quantitative change of remaining emulsifier is more in resin, and the content of the alkali metal in main layer (A) also improves.It is set from easy inhibition From the viewpoint of the decline of the transparency of rouge laminated body, as (methyl) acrylic resin and inclined difluoro for including in main layer (A) Vinyl, it is preferable to use alkali metal poor resin.

In order to make the content of the alkali metal in resin within the above range, it can be reduced when carrying out the polymerization of resin and include The usage amount of the compound of alkali metal, or increase the washing procedure after polymerization to remove comprising the compound of alkali metal. The content of alkali metal can for example be found out by inductively coupled plasma mass spectrometry (ICP/MS).As inductively coupled plasma body Mass spectrography is added for example, the sample particle to be measured can be directed to using high temperature ashing melting method, high temperature ashing acid-soluble method, Ca Add the methods appropriate such as ashing acid-soluble method, burning absorption process, low temperature dry ashing acid-soluble method by sample ashing, is dissolved in acid In, by the lysate constant volume, utilize the content of inductively coupled plasma mass spectrometry measurement alkali metal.

The glass transition temperature (Tmg) of main layer (A) is preferably 50~100 DEG C, more preferably 55~80 DEG C, further excellent It is selected as 55~70 DEG C.Differential scanning calorimetry (DSC) (DSC) measurement can be used in the Tmg of main layer (A).Such as SII can be used " the EXSTAR DSC6100 " of Nanotechnology Corporation is used as differential scanning calorimetry (DSC), can be in nitrogen gas Under atmosphere, it is measured to obtain glass transition temperature under conditions of heating rate is 10 DEG C/min.It needs to illustrate It is, when main layer (A) includes a kind of resin, for the glass transition temperature of the resin, when main layer (A) includes resin of more than two kinds, For the glass transition temperature of the mixture of various kinds of resin.

Thermoplastic resin layer (B) includes at least one kind of thermoplastic resin.It is saturating from holding for thermoplastic resin layer (B) It include preferably 60 in each thermoplastic resin layer for all resins for including from the viewpoint of bright property, molding processibility It quality % or more, more preferably 70 mass % or more, is even more preferably the thermoplastic resin of 80 mass % or more.Thermoplasticity The upper limit of the amount of resin is 100 mass %.

Aforementioned resin layer preferably satisfies the relationship of following formula (4).

0.2≤Y/X≤15(4)

[the pole in formula, when X is shown in 23 DEG C and is stretched with 50mm/ minutes speed to 500 μm of main layer (A) It limits elongation (%), Y is shown in 23 DEG C and the thermoplastic resin layer (B) with 50mm/ minutes speed to 500 μm is drawn Ultimate elongation (%) when stretching]

Previously described formula (4) is more preferably 0.3≤Y/X≤10, further preferably 0.4≤Y/X≤5, particularly preferably 0.5≤ Y/X≤3.When the ultimate elongation of main layer (A) and the ultimate elongation of thermoplastic resin layer (B) meet the relationship of previously described formula (4), Tracing ability improves, and can more effectively inhibit the bad orders such as rupture, fold, the gonorrhoea when carrying out bending machining to laminated resin body Generation.It should be noted that being wrapped for previously described formula (4) using adjusting in main layer (A) and thermoplastic resin layer (B) The method of the type and content of the resin, additive that contain for example makes to contain mutually each other in main layer (A) and thermoplastic resin layer (B) Identical type or the method for similar resin etc. and be adjusted to prescribed limit.

Ultimate elongation X and Y (%) can be calculated respectively by following manner: according to JIS K-7161, in following conditions Lower carry out tension test reads and cracks, ruptures on the sheet material of resin for constituting main layer (A) or thermoplastic resin layer (B) Time point collet between distance (mm), calculated using following formula (A).The tension test of following conditions for example can be by using The cupping machine of Instron corporation as device, be 1cm, length 10cm and tree with a thickness of 500 μm to width Method that rouge sheet material is measured is implemented.

Ultimate elongation (%)=(distance between the initial collet of distance-between collet when fracture breaks occur)/initial folder Distance × 100 (A) between head

(condition)

Device: cupping machine

Test temperature: 23 DEG C

Tensile speed: 50mm/ minutes

Resin sheet: with a thickness of 500 μm

As the thermoplastic resin for including in thermoplastic resin layer (B), for example above-mentioned (methyl) acrylic resin can be enumerated (M), polycarbonate resin, cyclic olefin resins etc..These thermoplastic resins can be used alone or combine two or more use. If including (methyl) acrylic resin (M) in thermoplastic resin layer (B), the relationship of previously described formula (3) is readily satisfied, also, There is good cementability with main layer (A), thus preferably.In addition, polycarbonate resin is since ultimate elongation is big, thus sometimes It is unsatisfactory for the relationship of previously described formula (4).Therefore, it is preferable to use the tree of tensile elongation Y can be reduced when using polycarbonate resin Rouge and the polymer alloy (hereinafter referred to as PC alloy) of polycarbonate resin, such as polycarbonate resin and (methyl) acrylic acid The alloy of resin, polystyrene resin etc..

As polycarbonate resin, the light for example by making various dihydroxy diaryl compounds and phosgene reaction can be enumerated Gas method makes polymer obtained from the ester-interchange method of the carbonate reactions such as dihydroxy diaryl compound and diphenyl carbonate, Specifically, can enumerate by the polycarbonate resin of bis- (4- hydroxy phenyl) propane of 2,2- (common name bisphenol-A) manufacture.

As above-mentioned dihydroxy diaryl compound, other than bisphenol-A, can also enumerate bis- (4- hydroxy phenyl) methane, Bis- (4- hydroxy phenyl) ethane of 1,1-, bis- (4- hydroxy phenyl) butane of 2,2-, bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4- hydroxyls Base phenyl) phenylmethane, bis- (4- hydroxy phenyl -3- aminomethyl phenyl) propane of 2,2-, 1,1- bis- (4- hydroxyl -3- tert-butyl-phenyls) Bis- (4- hydroxyl -3- bromophenyl) propane of propane, 2,2-, bis- (4- hydroxyl -3,5- dibromo phenyl) propane of 2,2-, bis- (the 4- hydroxyls of 2,2- Base -3,5- dichlorophenyl) bis- (hydroxyaryl) alkanes as propane, bis- (4- hydroxy phenyl) pentamethylene of 1,1-, 1,1- be bis- Bis- (hydroxyaryl) cycloalkanes, 4,4 '-dihydroxydiphenyl ethers, 4,4 '-dihydroxy-as (4- hydroxy phenyl) hexamethylene Dihydroxy diaryl ethers as 3,3 '-dimethyl diphenyl ethers, dihydroxy two as 4,4 '-dihydroxydiphenyl thioethers Aryl thioethers class, 4,4 '-dihydroxydiphenyl sulfoxides, dihydroxy as 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfoxide Dihydroxy as base diaryl sulphoxide class, 4,4 '-dihydroxy-diphenyl sulfones, 4,4 '-dihydroxy -3,3 '-dimethyl diphenyl sulfone Base diaryl sulfone class.

They can be used alone or mix two or more and use, in addition, piperazine, dipiperidino can also be mixed to benzene Diphenol, resorcinol, 4,4 '-dihydroxybiphenyls (4,4 '-dihydroxydiphenyl) etc. and use.

In addition, above-mentioned dihydroxy aryl compound can be mixed with such 3 yuan as shown below or more of phenolic compounds It uses.As 3 yuan or more of phenol, phloroglucin, 4,6- dimethyl -2,4 can be enumerated, 6- tri--(4- hydroxy phenyl)-heptene, 2, 4,6- dimethyl -2,4,6- three-(4- hydroxy phenyl)-heptane, 1,3,5- tri--(4- hydroxy phenyl)-benzene, 1,1,1- tri--(4- hydroxyl Base phenyl)-ethane and 2,2- it is bis--(4,4- (4,4 '-dihydroxydiphenyl)-cyclohexyl)-propane etc..

As the polycarbonate resin other than above-mentioned polycarbonate resin, can enumerate by isobide and aromatic diol conjunction At polycarbonate.As the example of the polycarbonate, Mitsubishi Chemical's system " DURABIO (trade mark registration) " can be enumerated.

As polycarbonate resin, commercially available product can be used, such as Sumika Styron Polycarbonate can be enumerated Limited system " CALIBRE (registered trademark) 301-4,301-10,301-15,301-22,301-30,301-40, SD2221W, SD2201W, TR2201 " etc..

There can be the resin of compatibility to form PC alloy by such polycarbonate resin and with the polycarbonate resin.

As the preferred commercially available product of PC alloy, such as Sumika Styron Polycarbonate can be enumerated Limited SD POLYCA (registered trademark) " PCX-6648 ", " PCX-6630 ", " PCX-6684 ", " PCX-6680 ", Mitsubishi Engineering-Plastics Corporation Iupilon (registered trademark) " KH4210UR ", " KH3310UR ", " KH3410UR ", " KH3520UR ", " KS3410UR ", " KS2410UR " etc..

The glass transition temperature of thermoplastic resin layer (B) is preferably 80~180 DEG C, and more preferably 90~150 DEG C, into one Preferably 100~140 DEG C of step.It should be noted that when thermoplastic resin layer (B) includes a kind of thermoplastic resin, for the resin Glass transition temperature is the mixture of various kinds of resin when thermoplastic resin layer (B) includes thermoplastic resin of more than two kinds Glass transition temperature.Differential scanning calorimetry (DSC) (DSC) can be used to measure for glass transition temperature.

In a preferred manner, the thickness of main layer (A) is greater than the thickness of thermoplastic resin layer (B).In this case, if it is main The Tmg of layer (A) is higher than the Tmg of thermoplastic resin layer (B), then relative to forming temperature, the flexibility of the big main layer of thickness (A) becomes Must be better, laminated resin body becomes easy carry out curved surface forming, thus preferably.

For intensity, the elasticity etc. for improving thermoplastic resin layer, thermoplastic resin layer (B) also may include thermoplastic resin with Other outer resins (such as the thermosetting resins such as filler, resin particle).In this case, based on being wrapped in each thermoplastic resin layer For all resins contained, the amount of other resins is preferably 40 mass % hereinafter, more preferably 30 mass % are hereinafter, further more Preferably 20 mass % or less.The lower limit of the amount of other resins is 0 mass %.

In a preferred manner, resin layer has the main layer comprising (methyl) acrylic resin and is respectively laminated on the main layer Two sides thermoplastic resin layer (B-1) and (B-2).Thermoplastic resin layer (B-1) and (B-2) may include identical thermoplastic resin Rouge also may include mutually different thermoplastic resin.From prevent in bending machining occur bad order from the viewpoint of, preferably Thermoplastic resin layer (B-1) and (B-2) include identical thermoplastic resin.

Even if good from the transparency, surface hardness, molding processibility of laminated resin body, be shaped to the big (curved surface of curvature The radius of curvature in portion is small) shape also be easy inhibit bad order generation from the viewpoint of, thermoplastic resin layer (B-1) and (B- It 2) is preferably (methyl) acrylate resin layer or PC alloy-layer.

It is hereinafter of the invention one of (methyl) acrylate resin layer to thermoplastic resin layer (B-1) and (B-2) Mode is illustrated.In which, thermoplastic resin layer (B-1) and (B-2) include a kind or more (methyl) acrylic resin. For thermoplastic resin layer (B-1) and (B-2), from the viewpoint of molding processibility, based in each thermoplastic resin layer For all resins for including, comprising preferably 50 mass % or more, more preferably 60 mass % or more, even more preferably it is (methyl) acrylic resin of 70 mass % or more.

As (methyl) acrylic resin, above-mentioned (methyl) acrylic resin (M) can be enumerated.Thermoplastic resin layer (B-1) And in (B-2) include (methyl) acrylic resin, with include in main layer (A) (methyl) acrylic resin can it is identical can also With difference.

From the viewpoint of good from molding processibility, easy raising mechanical strength, (methyl) acrylic resin is divided equally again Son amount (Mw) is preferably 50,000~300,000, more preferably 70,000~250,000.Weight average molecular weight can be seeped using gel Saturating chromatography (GPC) measurement is to measure.

In which, thermoplastic resin layer (B-1) and (B-2) also may include a kind or more except (methyl) acrylic resin Thermoplastic resin in addition.As the thermoplastic resin in addition to (methyl) acrylic resin, preferably with (methyl) acrylic acid The compatible thermoplastic resin of resin.Specifically, can enumerate Methyl Methacrylate-Styrene-copolymer-maleic anhydride (such as Electrochemically industry system " RESISFY "), Eudragit S100 (such as Arkema system "ALTUGLAS HT121").From the viewpoint of heat resistance, the glass of the thermoplastic resin in addition to (methyl) acrylic resin Changing transition temperature is preferably 80~180 DEG C, more preferably 90~150 DEG C, further preferably 100~140 DEG C.From heat resistance and From the viewpoint of surface hardness, preferred thermoplastic resin layer (B-1) and (B-2) do not include vinylidene fluoride resin substantially.

Next, being hereinafter another side of the invention of PC alloy-layer to thermoplastic resin layer (B-1) and (B-2) Formula is illustrated.In which, thermoplastic resin layer (B-1) and (B-2) include a kind or more of PC alloy.From impact resistance Viewpoint considers that for all resins for including in each thermoplastic resin layer, thermoplastic resin layer (B-1) and (B-2) include It preferably 60 mass % or more, more preferably 70 mass % or more, is even more preferably the PC alloy of 80 mass % or more.

In which, from the viewpoint of easy raising impact resistance and molding processibility, the weight average molecular weight of PC alloy It (Mw) is preferably 25,000~60,000, more preferably 30,000~50,000.Weight average molecular weight can utilize gel permeation chromatography (GPC) measurement is to measure.

In which, when being measured under conditions of temperature is 275 DEG C and load is 1.2kg, thermoplastic resin layer (B- 1) the PC alloy for and in (B-2) including has preferably 1~100cm³/ 10 minutes, more preferably 2~80cm³/ 10 minutes, into one Step is more preferably 3~40cm³/ 10 minutes, particularly preferably 4~20cm³/ 10 minutes melt volume-flow rate (hereinafter, Referred to as MVR.).When MVR is above-mentioned lower limit or more, mobility is sufficiently high, is easy to be formed in melting co-extrusion modling etc. Processing is not susceptible to bad order, thus preferably.When MVR is the above-mentioned upper limit or less, it is easy to improve the intensity etc. of PC alloy-layer Mechanical property, thus preferably.

MVR can be measured under the load of 1.2kg, under conditions of 275 DEG C according to JIS K 7210.

In which, thermoplastic resin layer (B-1) and (B-2) also may include a kind or more of the thermoplastic in addition to PC alloy Property resin.As the thermoplastic resin in addition to PC alloy, the preferably thermoplastic resin compatible with the resin for including in PC alloy Rouge.

Main layer (A) and thermoplastic resin in the range of not interfering effect of the invention, in laminated resin body of the invention At least 1 layer in rouge layer (B) can further include usually used various additives.As additive, can enumerate for example stable Agent, antioxidant, ultraviolet absorbing agent, light stabilizer, foaming agent, lubricant, release agent, antistatic agent, fire retardant, polymerization suppression Colorants such as preparation, flame retardant, reinforcing agent, nucleating agent, blueing agent etc..

As colorant, the compound with anthraquinone skeleton, compound with phthalocyanine frame etc. can be enumerated.In these, From the viewpoint of heat resistance, preferably with the compound of anthraquinone skeleton.

At least 1 layer in main layer (A) and thermoplastic resin layer (B) colorant when further including colorant, in each layer Content can according to purpose, type of colorant etc. suitably select.When using blueing agent as colorant, based on containing blueing agent Each layer in include all resins for, 0.01~10ppm of its content or so can be made.The content be preferably 0.01ppm with On, more preferably 0.05ppm or more, further preferably 0.1ppm or more, additionally, it is preferred that being 7ppm hereinafter, more preferably 5ppm hereinafter, further preferably 4ppm hereinafter, particularly preferably 3ppm or less.About blueing agent, can be suitably used known Substance can enumerate such as MACROLEX (registered trademark) Blue RR (Bayer corporation), MACROLEX (registered trademark) Blue 3R (Bayer corporation), Sumiplast (registered trademark) Violet B (Sumika Chemtex Co., Ltd. system) and Polysynthren (registered trademark) Blue RLS (Clariant corporation), Diaresin Violet D, Diaresin Blue G, Diaresin Blue N (the above are Mitsubishi chemical Co., Ltd's systems) (respectively trade name).

It as ultraviolet absorbing agent, is not particularly limited, existing known various ultraviolet absorbing agents can be used.For example, The ultraviolet absorbing agent at 200~320nm or 320~400nm with maximum absorption can be enumerated.Specifically, three can be enumerated Piperazine system ultraviolet absorbing agent, benzophenone series ultraviolet absorbing agent, enumerate BTA system ultraviolet absorbing agent, benzoic ether system are ultraviolet Light absorbers, cyanoacrylate system ultraviolet absorbing agent.As ultraviolet absorbing agent, can be used alone these ultraviolet radiation absorptions 1 kind in agent, or also can be used in combination two or more.From more effectively defending the viewpoint of damage caused by due to ultraviolet light to examine Consider, and is used at least one kind of ultraviolet absorbing agent at 200~320nm with maximum absorption and there is pole at 320~400nm At least one kind of ultraviolet absorbing agent absorbed greatly is also preferred.As ultraviolet absorbing agent, commercially available product can be used, example can be enumerated Such as " Kemisorb102 " (bis- (2,4- 3,5-dimethylphenyl) -6- (2- hydroxyls of 2,4- of CHEMIPRO KASEI KAISHA, LTD. Base -4-N- octyl phenyl) -1,3,5- triazine) (absorbance 0.1), Asahi Denka Co., Ltd. " ADK STAB LA- F70 " (2,4,6- tri- (2- hydroxyl -4- hexyloxy -3- aminomethyl phenyl) -1,3,5- triazine) (absorbance 0.6), " ADK STAB LA-31, LA-31RG, LA-31G " (2,2 '-di-2-ethylhexylphosphine oxides (4- (1,1,3,3- tetramethyl butyl) -6- (2H- benzotriazole -2- Base) phenol) (absorbance 0.2), Asahi Denka Co., Ltd. " ADK STAB LA-46 " (2- (4,6- diphenyl -1,3,5- Triazine -2- base) -5- (2- (2- ethyl hexanoyl oxygroup) ethyoxyl) phenol) (absorbance 0.05) or Japan plants of formula meetings of BASF " Tinuvin 1577 " (2,4- diphenyl -6- (2- hydroxyl -4- hexyl phenyl) -1,3,5- triazine) (absorbance of society 0.1) etc. for.The absorbance of the ultraviolet absorbing agent enumerated is the absorbance at 380nm.The absorbance can be by with lower section Ultraviolet absorbing agent: being dissolved in chloroform by formula measurement with the concentration of 10mg/L, uses spectrophotometer (such as HITACHI system Spectrophotometer U-4100) it is measured.

At least 1 layer in main layer (A) and thermoplastic resin layer (B) when further including ultraviolet absorbing agent, in each layer The content of ultraviolet absorbing agent can suitably be selected according to purpose, type of ultraviolet absorbing agent etc..For example, based on ultraviolet light is contained For all resins for including in each layer of absorbent, 0.005~2.0 mass % of content of ultraviolet absorbing agent can be made left It is right.The content of ultraviolet absorbing agent is preferably 0.01 mass % or more, more preferably 0.02 mass % or more, even more preferably For 0.03 mass % or more.In addition, the content of ultraviolet absorbing agent is preferably 1.5 mass % hereinafter, more preferably 1.0 mass % Below.From the viewpoint of easy raising ultraviolet radiation absorption effect, preferably the content of ultraviolet absorbing agent be above-mentioned lower limit with On, when being the above-mentioned upper limit or less, it is easy to prevent the variation of the tone (such as yellow chromaticity YI) of laminated resin body, thus preferably. Such as above-mentioned commercially available product " ADK STAB LA-31, LA-31RG, LA-31G " is preferably used with above-mentioned amount.

In another mode of the invention, thermoplastic resin layer (B-1) and (B-2) are PC alloy-layer, and are based on each thermoplastic Property resin layer in include all resins for include 0.005~2.0 mass % ultraviolet absorbing agent when, be easy to get fast light Property excellent laminated resin body, thus preferably.

From the viewpoint of the durability of laminated resin body, the thickness of resin layer is preferably 100 μm or more, more preferably 200 μm or more, further preferably 300 μm or more.In addition, from the viewpoint of the transparency and molding processibility, resin layer Thickness be preferably 2000 μm hereinafter, more preferably 1500 μm hereinafter, further preferably 1000 μm or less.The thickness of resin layer can It is measured using digital micrometer (digital micrometer).

From the viewpoint of the durability and dielectric constant of laminated resin body, the thickness of main layer (A) be preferably 100 μm with On, more preferably 200 μm or more, further preferably 300 μm or more.In addition, being examined from the viewpoint of the transparency and molding processibility Consider, the thickness of main layer (A) be preferably 1500 μm hereinafter, more preferably 1200 μm hereinafter, further preferably 1000 μm or less.It is main The thickness of layer (A) can be measured using digit microscope.

It is preferred respectively from the viewpoint of the durability of laminated resin body for the thickness of thermoplastic resin layer (B) It is 10 μm or more, more preferably 30 μm or more, further preferably 50 μm or more.In addition, from molding processibility and dielectric constant From the viewpoint of, be respectively preferably 200 μm hereinafter, more preferably 175 μm hereinafter, even more preferably for 150 μm or less.Thermoplastic Property resin layer thickness can using digit microscope measure.

Resin layer can be manufactured using customary way.For example, including (methyl) as having for preferred embodiment of the invention The main layer (A) of acrylic resin and vinylidene fluoride resin and be respectively laminated on the main layer (A) two sides thermoplastic resin layer (B-1) and the resin layer of (B-2) can be manufactured using the following method.

Main layer (A) can be manufactured by the resin combination (A) comprising (methyl) acrylic resin and vinylidene fluoride resin, heat Plastic resin layers (B-1) and (B-2) can be manufactured respectively by resin combination (B-1) and (B-2).Resin combination (B-1) and (B- 2) it includes at least and forms thermoplastic resin layer (B-1) and the resin of (B-2), can be comprising resin and arbitrary additive Deng the composition of two or more ingredient, it is also possible to individual a kind of resin.

Resin combination (A) usually can be by obtaining (methyl) acrylic resin and vinylidene fluoride resin mixing. Being kneaded for example can be by being included in 150~350 DEG C of temperature, carrying out the work of melting mixing with 10~1000/ seconds shear velocities The method of sequence is implemented.

Carry out melting mixing when temperature be 150 DEG C or more when, resin can be made sufficiently to melt, thus preferably, be 350 DEG C with When lower, it is easy to inhibit the pyrolysis of resin, thus preferably.In addition, when shear velocity when carrying out melting mixing is 10/ second or more, It is easy abundant compounded resin, thus preferably, when being 1000/ second or less, it is easy to inhibit the decomposition of resin, thus preferably.

The resin combination that each ingredient is more uniformly mixed in order to obtain, melting mixing in preferably 180~300 DEG C, More preferably 200~300 DEG C of temperature carries out, and to be preferably 20~700/ seconds, more preferably 30~500/ seconds shearing speed Degree carries out.

As the equipment for melting mixing, common mixing machine, kneading machine can be used.Specifically, single spiral shell can be enumerated Bar kneading machine, twin screw compounder, multi-screw extruder, Henschel mixer (Henschel mixer), Banbury mixer, Kneader, roller mill etc..In addition, high shear processing unit (plant) etc. can be used when increasing shear velocity within the above range.

For resin combination (B-1) and (B-2), also equally with resin combination (A), such as can be by above-mentioned Melting mixing at temperature and shear velocity etc. manufactures.In addition, such as thermoplastic resin layer (B-1) and (B-2) include a kind of heat When plastic resin, aftermentioned melting extrusion can be carried out in the case where not carrying out melting mixing in advance to obtain resin layer.

For the thermoplastic with main layer (A) and the two sides for being respectively present in main layer (A) as preferred embodiment of the invention Property resin layer (B-1) and (B-2) resin layer for, can by using such as the melting extrusion method of forming, solution curtain coating be film-made method, Pressure sintering, injection moulding etc. make each layer (A), (B-1) and (B-2) by resin combination (A), (B-1) and (B-2) respectively, They are bonded to manufacture via such as adhesive, bonding agent；Melting co-extrusion modling can also be used by resin combination (A), (B-1) and (B-2) stacking integration is to manufacture.When by being bonded to manufacture resin layer, in the production of each layer, preferably Using injection moulding and the melting extrusion method of forming, the melting extrusion method of forming is more preferably utilized.

Melting co-extrusion modling is, for example, following forming methods: by resin combination (A) and resin combination (B-1) and (B-2) it puts into respectively into the extruder of 2 or 3 single screw rods or twin-screw, carries out melting mixing respectively, then, via Material feeding block die head (feed block die), multi-manifold etc., will be by main layer (A) and thermoplastic that resin combination (A) is formed Property resin layer (B-1) and (B-2) be laminated integration and squeeze out.When resin combination (B-1) and (B-2) are identical composition, It can will be divided into 2 parts via material feeding block die head etc. by a kind of composition obtained from melting mixing in 1 extruder, and form it into heat Plastic resin layers (B-1) and (B-2).Obtained resin layer carries out cooling preferably by such as roller unit etc., solidifies.

[hard conating]

Laminated resin body of the invention includes the hard painting for being laminated at least one face (surface or the back side) of aforementioned resin layer Layer.From the viewpoint of the durability of laminated resin body, surface hardness, hard conating is preferably at least laminated in the surface of resin layer Side is more preferably laminated in two surface sides of resin layer.In addition, the surface of resin layer refers to the viewing side of image display device.

Hard conating meets following formula (1)~(3) relationship.

20≤L_PET≤130 (1)

0.4≤L_HC/L_PMMA≤1.5 (2)

1≤T_HC≤30 (3)

[in formula, L_PETBe shown in 140 DEG C and with 50mm/ minutes speed to 75 μm by poly terephthalic acid The ultimate elongation when laminated body of substrate and the aforementioned hard conating positioned at the one side of the substrate that glycol ester is formed is stretched Rate (%), L_HCIt is shown in 100 DEG C and is formed to 500 μm by polymethyl methacrylate with 50mm/ minutes speed Maximum elongation rate (%) when being stretched of substrate and the laminated body of the aforementioned hard conating positioned at the one side of the substrate, L_PMMATable It is shown in 100 DEG C and 500 μm is stretched by the substrate that polymethyl methacrylate is formed with 50mm/ minutes speed When maximum elongation rate (%), T_HCIndicate the film thickness of hard conating.]

For laminated resin body of the invention, since hard conating meets previously described formula (1)~(3) relationship, thus When carrying out bending machining to laminated resin body, the generation of the bad orders such as rupture, fold, gonorrhoea can be effectively inhibited or prevented. Especially, even if also can effectively press down when processing and forming is at the big shape of curvature (the small shape of the radius of curvature of curved face part) Make or prevent the generation of bad order.

Previously described formula (1) is preferably 25≤L_PET≤ 110, more preferably 30≤L_PET≤ 100, further preferably 30≤L_PET ≤80.When to be more than above-mentioned lower limit, the generation of rupture, gonorrhoea when can more effectively inhibit bending machining is above-mentioned upper When limit is following, the generation of fold when can more effectively inhibit bending machining.

In previously described formula (1), L_PETIt can be calculated by following manner: according to JIS K-7161, be drawn under conditions of following Stretch test, read cracked on hard conating, distance (mm) between the collet at time point that ruptures, counted using following formula (B) It calculates.In the tension test of following conditions, for example, can be used the cupping machine of Instron corporation as device.In addition, making For laminated body, it may be used at 75 μm easy bonding processing PET film [TORAY Co. Ltd. system LUMIRROR (registered trademark) U34# 100] sheet material obtained from 5 μm of hard conating is laminated in the one side of substrate.

Ultimate elongation (%)=(distance between the initial collet of distance-between collet when fracture breaks occur)/initial folder Distance × 100 (B) between head

(condition)

Device: cupping machine

Test temperature: 140 DEG C

Tensile speed: 50mm/ minutes

Laminated body: in the one side of 75 μm of easy bonding processing PET film substrate stacking with a thickness of 1~30 μm hard conating and Obtained sheet material

It should be noted that ultimate elongation L_PETThe time point that can will be cracked, rupture on the hard conating of laminated body It is calculated as benchmark, at the time point, can not also crack, rupture on the PET film as substrate.

Previously described formula (2) is preferably 0.6≤L_HC/L_PMMA≤ 1.4, more preferably 0.8≤L_HC/L_PMMA≤ 1.3, further preferably For 0.9≤L_HC/L_PMMA≤1.3.When previously described formula (2) is above-mentioned range, it can more effectively inhibit resin layer when bending machining The generation of the bad orders such as rupture, fold, the gonorrhoea of stack.

In previously described formula (2), for L_HCFor, using following laminated bodies (HC), for L_PMMAFor, use following laminated bodies (PMMA), according to JIS K-7161, tension test is carried out under conditions of following, reads the time of laminated resin body itself fracture Distance (mm) between the collet of point, is calculated using following formula (C).In the tension test of following conditions, such as Instron can be used The cupping machine of corporation is as device.In addition, as laminated body (HC), for example, maying be used at the PMMA with a thickness of 500 μm The one side of [Escarbo Sheet Co., Ltd. TECHNOLLOY (registered trademark) S000] substrate be laminated 5 μm of hard conating and Obtained sheet material, as laminated body (PMMA), for example, can be used with a thickness of 500 μm PMMA [Escarbo Sheet Co., Ltd. TECHNOLLOY (registered trademark) S000 processed] sheet material.

Distance between maximum elongation rate (%)=(distance between the initial collet of distance-between collet when fracture)/initial collet × 100 (C)

(condition)

Device: cupping machine

Test temperature: 100 DEG C

Tensile speed: 50mm/ minutes

Laminated body (HC): the hard conating with a thickness of 1~30 μm is laminated in the one side of the PMMA substrate with a thickness of 500 μm and obtains The sheet material arrived

Laminated body (PMMA): with a thickness of 500 μm of PMMA sheet material

It should be noted that for maximum elongation rate L_HCFor, the time point that can be broken laminated body itself is as benchmark It calculates, before the fracture of PMMA substrate, can crack, rupture or hard conating or be broken on hard conating.

Hard conating is laminated at least one face of aforementioned resin layer, even if but being exposed to harshness from laminated resin body Environment, also be easy present shape stability from the viewpoint of, be preferably laminated in the two sides of aforementioned resin layer.

Thickness (the T of hard conating_HC) it is 1~30 μm, preferably 2~25 μm, more preferably 2~20 μm, further preferably 3 ~10 μm.Hard conating with a thickness of more than above-mentioned lower limit when, surface hardness can be improved, be the above-mentioned upper limit below when, can press down Make the generation of the bad orders such as hard conating rupture in bending machining.It is each hard when hard conating is laminated in the two sides of laminated resin body The thickness of coating can be different, can also be identical.

Hard conating is formed by the solidfied material of solidification compound.Solidification compound is not particularly limited, as long as can be formed Meet previously described formula (1)~(3) hard conating, using curability compound as essential component, example can be contained as needed Such as curing catalysts, electroconductive particle, solvent, levelling agent, stabilizer, antioxidant, colorant additive.In addition, hard apply When layer is laminated in the two sides of resin layer, the solidification compound for constituting each hard conating can be the same or different.It needs It is bright, by suitably adjusting the type of the compound for including in the solidification compound for constituting hard conating, additive and containing Amount, so as to be adjusted to previously described formula (1)~(3) it is various shown in range.

As curability compound, the acrylate compounds such as polyfunctional acrylic ester compound can be enumerated；More officials The urethane acrylates compounds such as energy urethane acrylate compound；Multifunctional epoxy acrylate compound Equal epoxy acrylics ester compounds；Carboxy-modified epoxy acrylic ester compounds, polyester acrylic ester compounds, copolymerization are propylene Ester compound, alicyclic epoxy resin, glycidyl ether epoxy, vinyl ether compound, oxetanes chemical combination Alkoxysilane compound containing trialkylsilyl group in molecular structure such as object, alkoxy silane, alkylalkoxy silane etc..In these, meet previously described formula from easy to form (1) from the viewpoint of~(3) hard conating is such, polyfunctional acrylic ester compound, multifunctional carbamic acid are preferably used The curability compound of the radical polymerizations collaborations such as ester acrylate compounds, multifunctional epoxy acrylate compound；Alkoxy The curability compound etc. of the hot polymerizations collaboration such as silane, alkylalkoxy silane.These curability compounds are, for example, to pass through irradiation The energy-rays such as electron beam, radioactive ray, ultraviolet light and the curability compound that is cured and/or occurred by heating solid The curability compound of change, it is preferable that be cured at least through energy-rays such as irradiating electron beam, radioactive ray, ultraviolet lights Curability compound be preferred.These curability compounds can be used alone or combine two or more and use.

Compound in the molecule at least three (methyl) acryloyl group oxygroup can also be used.It should be noted that (methyl) acryloyl group oxygroup indicates acryloyl group oxygroup or methylacryloyl oxygroup.

As the compound in the molecule at least three (methyl) acryloyl group oxygroup, such as trihydroxy methyl can be enumerated Propane three (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerol three (methyl) acrylate, five glycerol Three (methyl) acrylate, pentaerythrite three-or four-(methyl) acrylate, dipentaerythritol three-, four-, five-or six-(first Base) acrylate, tripentaerythritol four -, five -, six-or seven -3 yuan or more of the polyalcohol such as (methyl) acrylate poly- (first Base) acrylate；Make (methyl) with hydroxyl with the ratio that hydroxyl becomes equimolar or more for isocyanate group Acrylate reacts (methyl) obtained from, in molecule with the compound in the molecule at least two isocyanate group Carbamate (methyl) acrylate that the number of acryloyl group oxygroup is 3 or more is (for example, pass through diisocyanate and season The reaction of penta tetrol three (methyl) acrylate obtains carbamate (methyl) acrylate of 6 functions)；Three (2- hydroxyl second Base) isocyanuric acid three (methyl) acrylate etc..It should be noted that, although illustrating monomer herein, but can directly make With these monomers, it is possible to use become the substance of the form of the oligomer such as dimer, trimer.In addition, can also be simultaneously Use monomer and oligomer.These (methyl) acrylate compounds can use individually, or mix two or more and make With.

When using that the compound at least three (methyl) acryloyl group oxygroup is as curability compound in the molecule, As needed, other curability compounds, such as ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) can be used together Acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc. have 2 in the molecule The compound of (methyl) acryloyl group oxygroup.Relative in the molecule with the chemical combination of at least three (methyl) acryloyl group oxygroup For 100 mass parts of object, the usage amount of other curability compounds is typically not greater than 20 mass parts.

In the case where using ultraviolet light to make the cured situation of solidification compound, it is preferable to use Photoepolymerizationinitiater initiater is catalyzed as solidification Agent.As Photoepolymerizationinitiater initiater, such as benzil, benzophenone and its derivative, thioxanthene ketone class, benzil dimethyl can be enumerated Ketal class, Alpha-hydroxy alkylbenzene ketone, hydroxyl ketone, amino alkylphenone class, acylphosphine oxide class etc., can also make as needed With two or more in them.For 100 mass parts of curability compound, the usage amount of Photoepolymerizationinitiater initiater is usually 0.1~5 mass parts.

Solidification compound may include other additives.As additive, such as ion trap agent, anti-oxidant can be enumerated Agent, chain-transferring agent, polymerization accelerant, sensitizer, sensitization auxiliary agent, light stabilizer, tackifiers, filler, flowing regulator, plasticising Agent, defoaming agent, levelling agent, antistatic agent, ultraviolet absorbing agent, solvent etc..

As filler, can enumerate such as organic fine particles, inorganic particles, particularly preferred inorganic particles.As inorganic particles, Silica, zirconium oxide, aluminium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide can be enumerated (ITO), metal fluorides particle such as the metal oxide microparticles such as antimony oxide, cerium oxide, magnesium fluoride, sodium fluoride etc. can in these It is preferable to use silica, zirconium oxide, aluminium oxide.In addition, hollow silica particles can be suitably used, it is anti-wanting to assign In the case where static behaviour, electric conductivity, indium tin oxide (ITO), tin oxide etc. can be suitably used.

In one embodiment, inorganic particles are colloidal silicon dioxide.The synthetic method of colloidal silicon dioxide includes benefit The AEROSIL carried out with the pyrolysis of silicon tetrachloride synthesizes such gas phase synthesis method, using waterglass as the method for raw material, alcoholization The liquid phase synthesizing method etc. of the hydrolysis of object etc, they can be used.As the commercially available product of colloidal silicon dioxide, daily outputization can be enumerated Learn each product and Japan's chemistry work of " Organic silica sols " (organosol of silica) of industrial (strain) Each product of " the high-purity organosol " of industry (strain) is as preferred example.They are to make colloidal silica in organic solvent Obtained from silicon dispersion.

For solidification compound, from the viewpoint of surface hardness, a small amount of aforementioned filler can be contained.Another party Face does not preferably contain filler from the viewpoint of curved surface forming.That is, for the filler in solidification compound content and Speech, on the basis of the 100 mass % of total amount of solidification compound, such as can be 10 mass % hereinafter, preferably 5 mass % with Under, more preferably 3 mass % hereinafter, further preferably 1 mass % hereinafter, particularly preferably 0 mass %.

In order to adjust the viscosity etc. of solidification compound, solvent can be contained in solidification compound, such as comprising before When stating inorganic particulate, in order to be dispersed, solvent can also be contained.In solidification compound of the preparation containing inorganic particulate and solvent When, for example, aforementioned inorganic particle and solvent can be mixed, inorganic particulate be made to be scattered in solvent, then by the dispersion liquid with Solidification compound mixing.It in this case, can be by the inorganic particulate for the commercially available product being scattered in organic solvent and curability group Close object mixing.Alternatively, inorganic particulate can be made to be scattered in mixed liquor after mixing curability compound and solvent.Solvent is only If the solvent that can easily volatilize after curability compound being dissolved and is coated with, in addition, in solidification compound In include inorganic particulate when, can preferably make inorganic particulate disperse solvent.As such solvent, such as diacetone can be enumerated Alcohol, methanol, ethyl alcohol, isopropanol, isobutanol, 2-methyl cellosolve, cellosolvo, butoxy ethanol, 1- methoxyl group -2- The alcohols such as propyl alcohol；The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diacetone alcohol；The aromatic hydrocarbons such as toluene, dimethylbenzene Class；The esters such as ethyl acetate, butyl acetate；Water etc..The usage amount of solvent can suitably be adjusted according to character of curability compound etc. Section.

Commercially available product can be used in the solidification compound for forming hard conating.As commercially available product, such as AICA Kogyo can be enumerated Co., the AICAAITRON (registered trademark) " Z-850 " of Ltd.；Lioduras (the registrar of Toyo Ink Co., Ltd. Mark) " MOL5000 ", " MOL5100 ", " MOL5200 ", " MOL2112 "；Dainippon Ink Chemicals UNIDIC " ERS-958 ", " ESS- 177","ESS-107","ERS-830"；Di-ichi Kogyo Seiyaku Co., Ltd. NEW FRONTIER " RST-402 ", TAISEI FINE CHEMICAL CO., LTD. system " 8KY-012C ", " 8KY-052C ", " 8KY-056C ", " 8KY-058 ", " 8KY-077 ", "8KY-078"；The village Xin Zhong chemical industry Co. Ltd. system " UA-122P " etc..

Laminated resin body of the invention can be manufactured in the following manner: before being coated at least one face of aforementioned resin layer Solidification compound is stated, curability film is formed, next makes its solidification.

As the coating method of solidification compound, such as stick coating method, micro-gravure coating process, rolling method, flow coat can be enumerated Method, dip coating, spin-coating method, die coating method, spray coating method etc..When making curability curing of coating, according to the type of solidification compound And implement the irradiation of energy-ray, heating etc..

As energy-ray when making curability curing of coating by irradiation energy ray, can enumerate such as ultraviolet light, Electron beam, radioactive ray etc., the conditions such as intensity, irradiation time can suitably be selected according to the type of solidification compound.In addition, When making curability curing of coating by heating, the conditions such as temperature, time can be fitted according to the type of solidification compound Work as selection.In order not to make resin layer deform, heating temperature be usually 100 DEG C hereinafter, preferably 80 DEG C hereinafter, more preferably 60 DEG C or less.When solidification compound contains solvent, can after coating, make solvent volatilize after make curability curing of coating, The volatilization of solvent and the solidification of curability film can be carried out simultaneously.

[laminated resin body]

The summary sectional view of an example for the laminated resin body for indicating of the invention is shown in Fig. 1.Laminated resin body 1 has tree Rouge layer 2 and be laminated in the resin layer 2 surface hard conating 6 and be laminated in the resin layer 2 the back side hard conating 7.Resin layer 2 have main layer 3 and are laminated in the thermoplastic resin layer 4 of the surface side of the main layer 3 and are laminated in the heat of the back side of the main layer 3 Plastic resin layers 5.

Laminated resin body of the invention dielectric constant with higher, have preferably 3.5 or more, more preferably 3.6 with Therefore upper, further preferably 3.7 or more dielectric constants add even if utilizing in the display devices such as touch panel through bending The laminated resin body (sometimes referred to as curved laminated resin body) of work, also can fully function.It should be noted that resin The dielectric constant of laminated body can utilize the method illustrated in the dielectric constant of resin layer to measure.

For laminated resin body of the invention, the pencil hardness of hard conating side is preferably 4B or more, more preferably F with On, further preferably H or more, particularly preferably 2H or more since surface hardness is good, thus can improve the damage resistant on surface Property, even if also can effectively inhibit or prevent to shield when utilizing curved laminated resin body as the front panel of display device The scuffing of curtain.It should be noted that pencil hardness can be measured according to JIS K5600-5-4.

The appearances such as rupture, fold, gonorrhoea when laminated resin physical efficiency of the invention effectively inhibits or prevent bending machining Undesirable generation also can be effectively even if especially processing and forming (radius of curvature of curved face part small) shape big at curvature Inhibit the generation of bad order.Therefore, if using laminated resin body of the invention, even the radius of curvature R of curved face part compared with Small laminated resin body, such as R be 13mm or less, 10mm or less, 7mm or less, 5mm or less, 4mm or less, 3mm or less, 2mm with Under laminated resin body, also can be carried out molding.The radius of curvature R of the curved face part in laminated resin body after bending machining is preferably 0.1mm≤R≤15mm, more preferably 0.5mm≤R≤14mm, further preferably 1mm≤R≤13mm, still more preferably for 1mm≤R≤12, particularly preferably 1mm≤R≤10mm, especially preferably 1mm≤R≤7mm.It should be noted that for curved surface For the radius of curvature R in portion, such as shown in Figure 3, refer in the section of curved laminated resin body 1 along curved face part 3 The radius R of the inscribed circle 21 of formation.In addition, for curved face part, it can be to the side of the viewing side (surface side) of display device It is bent to (surface direction), can also be bent to the direction (back side direction) of the opposite side (back side) of viewing side, preferably support or oppose The bending of face direction.

The appearances such as rupture, fold, gonorrhoea when laminated resin physical efficiency of the invention effectively inhibits or prevent bending machining Undesirable generation, even if the shape that processing and forming is big at the curvature of curved face part, can also effectively inhibit the generation of bad order. Therefore, if using laminated resin body of the invention, even the biggish laminated body of bending angle (bending angle), the tool of curved face part There are preferably 10 ° or more, more preferably 30 ° or more, further preferably 60 ° or more, be even more preferably 70 ° or more, special The laminated resin body of bending angle that You Xuanwei be 80 ° or more, also can be carried out molding.It should be noted that for the curved of curved face part For bent angle, such as shown in Figure 3, refer to that in the inscribed circle 21 that curved face part 3 the is formed, endpoint of curved face part 3 (or rises Point) 22 and endpoint (or terminal) 23 and inscribed circle the fan-shaped central angle alpha that is formed of central point 24.

As the method for carrying out bending machining to laminated resin body, can enumerate for example using with defined radius of curvature Three-dimensional bending mold carries out hot-forming method, thermal flexure processing method, vacuum forming etc..

The processing and forming temperature of laminated resin body of the invention be constitute resin layer layer in the highest layer of Tmg Tmg with On temperature.In a preferred manner, the glass transition temperature of main layer (A) is denoted as Tmg_A, by thermoplastic resin layer (B) glass transition temperature is denoted as Tmg_BWhen, processing and forming temperature (T) meets the relationship of following formula: Tmg_A+40<T<Tmg_A+ 90, Tmg_B<T.For example, processing and forming temperature can be 100~160 DEG C, more preferably 120~140 DEG C.

The summary sectional view of an example of the laminated resin body after indicating bending machining is shown in Fig. 2.Curved resin layer Stack 1 has flat part 8 and both ends from the flat part 8 rearwardly direction (being lower section in Fig. 2) curved curved face part 9.Curved surface Portion 9 is bent in such a way that radius of curvature R becomes 0.1≤R≤14.

For laminated resin body of the invention, due to the generation of bad order when can not only inhibit bending machining, And there is good surface hardness, therefore, even if can also be used as various display devices, such as liquid after implementing bending machining The front panel use of crystal device, organic electroluminescent (EL) display device, touch panel display device.Moreover, because by Curve form is imparted, thus it is different from previous flat display device, before display device that can be high as design Plate uses.

Laminated resin body of the invention is preferably transparent when being observed by visual observation.Specifically, according to JIS When K7361-1:1997 is measured, laminated resin body of the invention have preferably 85% or more, more preferably 88% or more, It is even more preferably 90% or more total light transmittance (Tt).The upper limit of total light transmittance is 100%.Preferably, Even if laminated resin body of the invention also has above range after being exposed under the harsh environments such as high temperature or high temperature and humidity Total light transmittance.

The thickness of laminated resin body of the invention is preferably 100~1500 μm, and more preferably 150~1300 μm, further Preferably 200~1000 μm.The thickness of laminated resin body if above-mentioned lower limit more than, then the rigidity of sheet material is good, can prevent Deformation when extruding, if the above-mentioned upper limit hereinafter, then when being used for front panel, until touch sensor (touch Sensor distance) becomes close, and good sensitivity can be presented.

For laminated resin body of the invention, other than aforementioned resin layer and aforementioned hard conating, can also have At least 1 one functional layer.As functional layer, can enumerate such as anti-reflection layer, antiglare layer, antistatic backing and anti-fingerprint layer.These Functional layer can be with preferred disposition in the side opposite with resin layer of hard conating.Functional layer can carry out layer via adhesive phase It is folded, it is also possible to the coat being laminated by coating.As functional layer, such as Japanese Unexamined Patent Publication 2013-86273 public affairs can be used Solidification envelope as being recorded in report.

The thickness of functional layer can suitably be selected according to the purpose of each functional layer, from the viewpoint of easy presentation function, Preferably 1 μm or more, more preferably 3 μm or more are even more preferably 5 μm or more, from the sight for being easy to prevent functional layer from rupturing Point consider, preferably 100 μm hereinafter, more preferably 80 μm hereinafter, even more preferably be 70 μm or less.

Embodiment

Hereinafter, enumerating Examples and Comparative Examples to illustrate the present invention, but the present invention is not limited to these Examples.

(glass transition temperature (Tmg))

For glass transition temperature (Tmg), the difference of SII Nanotechnology Corporation is used Show scanning calorimeter (DSC) " EXSTAR DSC6100 ", in a nitrogen atmosphere, under conditions of heating rate is 10 DEG C/min It is measured.

(content of alkali metal)

It is measured using inductively coupled plasma mass spectrometry.

〔MFR〕

According to JIS K 7210:1999 " plastics-thermoplastic melt mass flow rate (MFR) and melt volume Method specified in the test method of flow rate (MVR) " is measured.About the material of poly- (methyl methacrylate) system, It is specified in 230 DEG C of temperature in the JIS, is measured with the load of 3.80kg (37.3N).

〔MVR〕

Make made " semi-automatic melt index apparatus 2A (Semi-auto Melt using Toyo Co., Ltd.'s essence mechanism Indexer 2A) ", according to JIS K 7210, it is measured under the load of 1.2kg, under conditions of 275 DEG C.

(dielectric constant)

In 23 DEG C, resin layer or curved laminated resin body are stood 24 hours in the environment of relative humidity is 50%, In the present context, resin layer or laminated resin body are measured using self-balancing bridge circuit method with 3V, 100kHz.Measurement In, it uses " the precision LCR meter HP4284A " of Agilent Technologies corporation.

[Production Example 1]

1.5 mass parts of 98.5 mass parts of mixed methyl methyl acrylate and methyl acrylate add chain-transferring agent (pungent sulphur Alcohol) 0.1 mass parts of 0.16 mass parts and release agent (stearyl alcohol), obtain monomer mixed solution.In addition, to methyl methacrylate Polymerization initiator (1,1- bis- (tert-butyl hydroperoxide) 3,3,5- trimethyl-cyclohexane) 0.036 mass parts are added in 100 mass parts, Obtain initiator mixed liquor.In such a way that the flow-rate ratio of monomer mixed solution and initiator mixed liquor becomes 8.8:1, it is continuously fed into It is thoroughly mixed type polymer reactor, is polymerize under conditions of mean residence time is 20 minutes, temperature is 175 DEG C, until Average polymerization rate becomes 54%, obtains partial polymer.Obtained partial polymer is heated to 200 DEG C, is directed into logical In the devolatilization extruder in air port (vent), make unreacted monomer from ventilation opening devolatilization in 240 DEG C, also, will be poly- after devolatilization It closes object to squeeze out with molten condition, after being water-cooled, is cut, obtain granular methacrylic resin (i).

Under conditions of as shown below, using pyrolysis gas chromatography to obtained granular methacrylic resin (i) it is analyzed, measures each peak area corresponding with methyl methacrylate and acrylate.As a result, methacrylic resin (i) structural unit from methyl methacrylate in is 97.5 mass %, and the structural unit from methyl acrylate is 2.5 Quality %.

(pyrolytical condition)

Sample preparation: accurate weighing methacrylic resin composition (aim parameter be 2~3mg) is put it into being made At the central portion of the metal chamber (cell) of tubular, close up metal chamber, presses lightly on both ends with pliers to be packaged.

Pyrolysis installation: CURIE POINT PYROLYZER JHP-22 (Japanese analytical industry (strain) system)

Metal chamber: Pyrofoil F590 (Japanese analytical industry (strain) system)

The set temperature of thermostat: 200 DEG C

The set temperature of insulating tube: 250 DEG C

Pyrolysis temperature: 590 DEG C

Pyrolysis time: 5 seconds

(gas chromatography analysis condition)

Gas chromatography analysis device: GC-14B ((strain) Shimadzu Seisakusho Ltd. system)

Detection method: FID

Column: 7G 3.2m × φ 3.1mm ((strain) Shimadzu Seisakusho Ltd. system)

Filler: FAL-M ((strain) Shimadzu Seisakusho Ltd. system)

Carrier gas: air/N₂/H₂=50/100/50 (kPa), 80ml/ minutes

The Elevated Temperature Conditions of column: being kept for 15 minutes in 100 DEG C, then, be warming up to 150 DEG C with 10 DEG C/min, is protected in 150 DEG C It holds 14 minutes

INJ temperature: 200 DEG C

DET temperature: 200 DEG C

It is pyrolyzed methacrylic resin composition under above-mentioned pyrolytical condition, in above-mentioned gas chromatography analysis item The decomposition product of generation is measured under part, and measures peak area corresponding with methyl methacrylate detected at this time (a1) and peak area corresponding with acrylate (b1).Then, peak area ratio A (=b1/a1) is found out by these peak areas.It is another Aspect makes mass ratio W of the acrylic ester unit relative to methyl methacrylate units under above-mentioned pyrolytical condition₀(known) The standard items of methacrylic resin be pyrolyzed, under the conditions of above-mentioned gas chromatography analysis to the decomposition product of generation into Row measurement, and measure peak area (a corresponding with methyl methacrylate detected at this time₀) and it is corresponding with acrylate Peak area (b₀), peak area ratio A is found out by these peak areas₀(=b₀/a₀).Then, by aforementioned peak area ratio A₀With aforementioned quality Compare W₀, find out coefficient f (=W₀/A₀)。

By by aforementioned peak area ratio A multiplied by foregoing coefficient f, so as to find out being wrapped in aforementioned methacrylic resin composition Mass ratio W of the acrylic ester unit in copolymer contained relative to methyl methacrylate units is calculated by mass ratio W Methyl methacrylate units relative to the ratio (quality %) of methyl methacrylate units and the summation of acrylic ester unit, Ratio (quality %) with acrylic ester unit relative to methyl methacrylate units and the summation of acrylic ester unit.

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

The weight average molecular weight (Mw) of (methyl) acrylic resin is measured using gel permeation chromatography (GPC).In order to which GPC is made Standard curve, use Showa electrician (strain) known to narrow molecular weight distribution, molecular weight make methacrylic resin as mark Standard curve is made by elution time and molecular weight in quasi- reagent, measures the weight average molecular weight of each resin combination.Specifically, Resin 40mg is dissolved in tetrahydrofuran (THF) solvent 20ml, production measurement sample.As measurement device, following surveys are used Determine device: by 2, the column " TSKgel SuperHM-H " of Tosoh Corporation and " SuperH2500 " 1 with series connection The mode of arrangement is arranged, using RI detector as detector.For the molecular weight distribution curve of measurement, point of horizontal axis is taken The logarithm of son amount, is thus fitted using normal distyribution function, is fitted using the normal distyribution function of following formula.

[mathematical expression 1]

[Production Example 2]

Methyl methacrylate is changed to 97.7 mass parts, methyl acrylate is changed to 2.3 mass parts, by chain tra nsfer Agent is changed to 0.05 mass parts, in addition to this, operates in the same way with Production Example 1, obtains granular methacrylic resin (ii), the content of structural unit is measured.The structural unit from methyl methacrylate in methacrylic resin (ii) is 97.0 mass %, the structural unit from methyl acrylate are 3.0 mass %.

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

In embodiment, having used MFR is 30g/10min, Mw 200,000, Na content is that 0.3ppm, K content are The vinylidene fluoride resin (i) of 0.05ppm.

The weight average molecular weight (Mw) of vinylidene fluoride resin is measured using gel permeation chromatography (GPC).In order to be made GPC's Standard curve, uses polystyrene as standard reagent, and standard curve is made by elution time and molecular weight, measures each resin Weight average molecular weight.Specifically, resin 40mg is dissolved in N-Methyl pyrrolidone (NMP) solvent 20ml, production measurement examination Sample.As measurement device, following measurement devices are used: by the column " TSKgel SuperHM-H " 2 of Tosoh Corporation Root and " SuperH2500 " 1 are arranged in a manner of arranged in series, using RI detector as detector.

[Production Example 3]

Change in order to which blueing agent is carried out masterbatch (MB), by methacrylic resin (ii) and colorant with 99.99:0.01's Ratio carry out it is dry-mixed, with φ 40mm single screw extrusion machine (field side plastics machinery (strain) system), in 250~260 DEG C of set temperature Melting mixing is carried out, the masterbatch pellet through colouring is obtained.As colorant, using blueing agent (Sumika Chemtex Co., Ltd. " Sumiplast (registered trademark) the Violet B " made).

[Production Example 4]

Firstly, the forming material as main layer (A) (middle layer), uses φ 32mm twin screw compounder (toshiba machine (strain) system), in 250 DEG C, by methacrylic resin obtained in Production Example 2 (ii) and vinylidene fluoride resin (i) and manufacture The masterbatch pellet made in example 3 carries out melting mixing with the ratio of 39:60:1, obtains the resin for main layer (A) of the invention Composition.Next, using device manufacturing resin layer shown in Fig. 4.Specifically, with the (east of φ 65mm single screw extrusion machine 12 Sesame machinery (strain) system) aforementioned resin is melted, (the Hitachi's shipbuilding (strain) of φ 45mm single screw extrusion machine 11 and 13 is used respectively System) melt 100 mass parts of methacrylic resin (i) of the forming material as thermoplastic resin layer (B-1) and (B-2). Next, the material feeding block 14 (Hitachi's shipbuilding (strain) system) for being 250~270 DEG C via set temperature, they is become above-mentioned The mode for the structure that thermoplastic resin layer (B-1)/main layer (A)/thermoplastic resin layer (B-2) indicates is laminated, by it from branch manifold Pattern tool 15 (Hitachi's shipbuilding (strain) system, 2 kind of 3 Layer assignment) squeezes out, and obtains membranaceous molten resin 16.Then, the film that will be obtained The molten resin 16 of shape sandwiches the 1st chill roll 17 (100 DEG C of roll temperature) and the 2nd chill roll 18 (97 DEG C of roll temperature) of relative configuration Between, next, being wound in the 2nd chill roll 18 on one side, 19 (roll temperature 95 of the 2nd chill roll 18 and the 3rd chill roll is sandwiched on one side DEG C) between, it is then wound in the 3rd chill roll 19, carries out molding cooling, the film thickness for obtaining main layer is 300 μm, thermoplastic resin The resin layer 1 for the 3-tier architecture that the film thickness of layer is 100 μm.The total film thickness of obtained resin layer 1 is 500 μm, is carried out by visual observation It is colorless and transparent when observation.Find out the amount for the alkali metal (Na+K) for including in main layer (A), result 0.21ppm.Main layer (A) Used in resin midpoint glass transition temperature (Tmg) be 60 DEG C.In addition, the dielectric constant of resin layer 1 is 4.0.

[Production Example 5]

The resin for being used for thermoplastic resin layer of Production Example 4 is changed to Sumika Styron Polycarbonate Limited PCX-6648, in addition to this, using same method, the film thickness for obtaining main layer is 300 μm, thermoplastic resin layer Film thickness be 100 μm 3-tier architecture resin layer 2.The MVR of PCX-6648 is 6.7cm³/ 10 minutes, Mw 54,000, glass Changing transition temperature (Tmg) is 121 DEG C, and Na content is 0.2ppm, and K content is 0.2ppm, and the dielectric constant of resin layer 2 is 4.0.

[the ratio between the ultimate elongation X of main layer and the ultimate elongation Y of thermoplastic resin layer (Y/X)]

(the ultimate elongation X of main layer (A))

It is press-formed in 220 DEG C to for the above-mentioned resin combination of main layer (A), obtains that width is 1cm, length is 10cm, with a thickness of 500 μm of resin sheets, according to JIS K-7161, with Instron corporation cupping machine, 23 DEG C, The resin sheet is stretched under conditions of 50mm/min, read cracked on resin sheet, time point for rupturing Distance (mm) between collet calculates the ultimate elongation X (%) of main layer (A) using following formula (A).

Ultimate elongation (%)=(distance between the initial collet of distance-between collet when fracture breaks occur)/initial folder Distance × 100 (A) between head

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

(the ultimate elongation Y of thermoplastic resin layer (B-1) and (B-2))

Instead of being used for the above-mentioned resin combination of main layer (A), above-mentioned methacrylic resin (i) or Sumika are used Styron Polycarbonate Limited PCX-6648, in addition to this, using same with the ultimate elongation X of main layer (A) The method of sample calculates the ultimate elongation Y (%) of thermoplastic resin layer.As a result, the thermoplastic formed by methacrylic resin (i) Property resin layer ultimate elongation Y (%) be 4, be by the ultimate elongation Y (%) of the PCX-6648 thermoplastic resin layer formed 3。

In resin layer 1, Y/X 0.8, in resin layer 2, Y/X 0.6.

[Production Example 6]

On 75 μm of TORAY Co. Ltd. system LUMIRROR (registered trademark) U34#100 (PET film), to become 2 institute of table The mode of the film thickness (5 μm, 7 μm or 36 μm) shown is coated with the hard painting material recorded in table 2, stands 3 minutes in 80 DEG C of baking oven, Solvent is removed, then, used as the Eye graphics UV irradiation unit of high-pressure sodium lamp, UV solidification is carried out, obtains band There is the PET film of hard conating.It should be noted that for Lioduras (registered trademark) MOL5000, MOL5100, MOL5200, After above-mentioned UV solidification, puts into 140 DEG C of baking oven 10 minutes, solidify after progress.

[table 1]

[Production Example 7]

LUMIRROR (registered trademark) U34#100 is replaced with to 500 μm of Escarbo Sheet Co., Ltd. system TECHNOLLOY (registered trademark) S000 (PMMA sheet material) in addition to this using method same as Production Example 6, is respectively obtained PMMA sheet material with hard conating.

[ultimate elongation L_PETMeasurement]

According to JIS K-7161, with Instron corporation cupping machine, to system under conditions of 140 DEG C, 50mm/min It makes obtained in example 6 the respectively PET film with hard conating to be stretched, reads the time point for cracking, rupturing on hard conating Collet between distance (mm), using respectively the limit of PET film with hard conating is stretched obtained in following formula (B) computational manufacturing example 6 Long rate L_PET.Show the result in table 2.In table 2, by the thickness (T of hard conating_HC) be recorded in the column of " HC thickness ".

Ultimate elongation (%)=(distance between the initial collet of distance-between collet when fracture breaks occur)/initial folder Distance × 100 (B) between head

[maximum elongation rate L_HCMeasurement]

According to JIS K-7161, with Instron corporation cupping machine, to system under conditions of 100 DEG C, 50mm/min The respectively PMMA sheet material with hard conating is made obtained in example 7 to be stretched, read that the PMMA sheet material with hard conating is broken when Between between the collet put distance (mm) using following formula (C) the PMMA sheet material of hard conating is respectively had obtained in computational manufacturing example 7 Maximum elongation rate L_HC(%).Show the result in table 2.

Distance between maximum elongation rate (%)=(distance between the initial collet of distance-between collet when fracture)/initial collet × 100 (C)

[maximum elongation rate L_PMMAMeasurement]

By 500 μm obtained in Production Example 7 of the Escarbo for replacing with 500 μm with the PMMA sheet material of hard conating Sheet Co., Ltd. TECHNOLLOY (registered trademark) S000 (PMMA sheet material), in addition to this, using with maximum elongation rate L_HCSame method calculates maximum elongation rate L_PMMA(%).As a result, L_PMMAIt is 250%.

[table 2]

[embodiment 1]

In such a way that hard conating becomes 5 μm, by AICA Kogyo Co., Ltd. AICAAITRON (registered trademark) Z- 850 are coated on the one side of resin layer 1 obtained in Production Example 4, stand 10 minutes in 50 DEG C of baking oven, solvent are removed, so Afterwards, it used as the Eye graphics UV irradiation unit of high-pressure sodium lamp, carries out UV solidification and then utilizes same method AICA Kogyo Co., Ltd. AICAAITRON (registered trademark) Z-850 is also coated with to another side, obtains resin layer as a result, Stack.Using the three-dimensional bending mold with defined radius of curvature R, in 120~130 DEG C, carry out keeping its curved by hot pressing The bend test of bent 90 ° (90 ° of bending angle), as a result, until when radius of curvature R=13mm, have been assigned the band of curve form The appearance for having the laminated resin body of hard conating includes curved face part, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 2]

Instead of AICAAITRON (registered trademark) Z-850, Toyo Ink Co., Ltd. Lioduras (registrar is used Mark) MOL5000, carry out UV solidification after, put into 140 DEG C of baking oven 10 minutes, solidify after progress, in addition to this, using with The same method of embodiment 1 obtains laminated resin body (hard conating is 5 μm thick).Using method similarly to Example 1 to obtaining Laminated resin body carries out hot-bend test, as a result, even if when radius of curvature R=2mm, having been assigned applying with hard for curve form The appearance of the laminated resin body of layer also includes curved face part, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 3]

Instead of Toyo Ink Co., Ltd. Lioduras (registered trademark) MOL5000, using Toyo Ink Co., Ltd. in addition to this Lioduras (registered trademark) MOL5100 processed using method similarly to Example 2, obtains laminated resin Body (hard conating is 5 μm thick).Hot-bend test is carried out to obtained laminated resin body using method similarly to Example 1, as a result, Even if when radius of curvature R=2mm, the appearance for having been assigned the laminated resin body with hard conating of curve form also includes curved surface Portion, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 4]

Instead of Toyo Ink Co., Ltd. Lioduras (registered trademark) MOL5000, using Toyo Ink Co., Ltd. in addition to this Lioduras (registered trademark) MOL5200 processed using method similarly to Example 2, obtains laminated resin Body (hard conating is 5 μm thick).Hot-bend test is carried out to obtained laminated resin body using method similarly to Example 1, as a result, Even if when radius of curvature R=2mm, the appearance for having been assigned the laminated resin body with hard conating of curve form also includes curved surface Portion, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 5]

Instead of AICAAITRON (registered trademark) Z-850, Toyo Ink Co., Ltd. Lioduras (registrar is used Mark) in addition to this MOL2112 using method similarly to Example 1, obtains laminated resin body (hard conating is 5 μm thick).It utilizes Method similarly to Example 1 carries out hot-bend test to obtained laminated resin body, as a result, even if radius of curvature R=7mm When, the appearance for having been assigned the laminated resin body with hard conating of curve form also includes curved face part, flat part, and is not present The bad orders such as rupture, fold.

[embodiment 6]

Resin layer 1 is replaced with into resin layer 2, in addition to this, using method similarly to Example 1, obtains laminated resin Body (hard conating is 5 μm thick).Hot-bend test is carried out to obtained laminated resin body using method similarly to Example 1, as a result, Even if when radius of curvature R=13mm, the appearance for having been assigned the laminated resin body with hard conating of curve form also includes song Face, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 7]

Resin layer 1 is replaced with into resin layer 2, in addition to this, using method similarly to Example 2, obtains laminated resin Body (hard conating is 5 μm thick).Hot-bend test is carried out to obtained laminated resin body using method similarly to Example 1, as a result, Even if when radius of curvature R=2mm, the appearance for having been assigned the laminated resin body with hard conating of curve form also includes curved surface Portion, flat part, and there is no the bad orders such as rupture, fold.

[embodiment 8]

The film thickness of hard conating is changed to 7 μm, in addition to this, using method similarly to Example 3, obtains laminated resin Body.Until when radius of curvature R=13mm, the appearance for having been assigned the laminated resin body with hard conating of curve form includes Curved face part, flat part, and there is no the bad orders such as rupture, fold.

[comparative example 1]

Instead of AICAAITRON (registered trademark) Z-850, using SilFORT (registered trademark) UVHC7800FS, except this it Outside, using method similarly to Example 1, obtain laminated resin body (hard conating is 5 μm thick).With radius of curvature R for 15mm or less Condition when implementing bend test, the appearances such as fold, gonorrhoea are produced on any part in curved face part, flat part not It is good.

[comparative example 2]

Instead of AICAAITRON (registered trademark) Z-850, using by SilFORT (registered trademark) UVHC7800FS and ACRIT (registered trademark) 8BR-500 is removed according to the substance being obtained by mixing in such a way that solid state component mass ratio is calculated as 60:40 Except this, using method similarly to Example 1, laminated resin body is obtained.It is that 15mm condition below is come in fact with radius of curvature R When applying bend test, the bad orders such as fold, gonorrhoea are produced on any part in curved face part, flat part.

[comparative example 3]

In such a way that hard conating becomes 36 μm, AICA Kogyo Co., Ltd. AITRON (registered trademark) Z- is coated 850, in addition to this, using method similarly to Example 1, obtain laminated resin body.With radius of curvature R for 15mm item below Part when implementing bend test, produces the bad orders such as fold, gonorrhoea on any part in curved face part, flat part.

The resin layer through Machining of Curved Surface obtained in Examples 1 to 7 and Comparative Examples 1 and 2 is measured according to JIS K5600-5-4 The pencil hardness of the surface side of stack is shown in table 3 together with the result of bend test.It should be noted that in bend test, zero Indicate that laminated resin body includes curved face part, flat part and there is no the bad orders such as rupture, fold, × expression is in laminated resin The bad orders such as rupture, fold, gonorrhoea are produced on any part in the curved face part of body, flat part.

[table 3]

Laminated resin body obtained in Examples 1 to 7 and Comparative Examples 1 and 2 is compared with comparative example 1 and 2, even if in curvature half In the case that diameter R is small, the bad orders such as rupture, fold, gonorrhoea do not occur yet.It is thus identified that laminated resin body of the invention The generation of bad order when can effectively inhibit or prevent processing and forming.

Claims (4)

1. laminated resin body, it includes dielectric constant be 3.5 or more resin layer and be laminated in the resin layer at least one The hard conating in face, wherein

The pencil hardness of hard conating side is 4B or more, also, meets following formula (1)~(3) relationship:

20≤L_PET≤ 130 (1),

0.4≤L_HC/L_PMMA≤ 1.5 (2),

1≤T_HC≤ 30 (3),

In formula, L_PETBe shown in 140 DEG C and with 50mm/ minutes speed to 75 μm by polyethylene terephthalate Ultimate elongation (%) when the laminated body of substrate and the hard conating positioned at the one side of the substrate that ester is formed is stretched, L_HCIt is shown in 100 DEG C and with 50mm/ minutes speed to the substrate formed by polymethyl methacrylate with 500 μm Maximum elongation rate (%) when being stretched with the laminated body of the hard conating for the one side for being located at the substrate, L_PMMAIt is shown in 100 DEG C and with 50mm/ minutes speed to 500 μm when being stretched by the substrate that polymethyl methacrylate is formed Maximum elongation rate (%), T_HCIndicate the film thickness of hard conating.

2. laminated resin body as described in claim 1 is 0.1mm≤R≤14mm curved face part it includes radius of curvature R.

3. laminated resin body as claimed in claim 1 or 2, wherein resin layer has the master comprising (methyl) acrylic resin Layer (A) and be laminated in the main layer (A) at least one face thermoplastic resin layer (B), and meet the pass of following formula (4) System:

0.2≤Y/X≤15 (4)

In formula, limit when X is shown in 23 DEG C and is stretched with 50mm/ minutes speed to 500 μm of main layer (A) is stretched Long rate (%), when Y is shown in 23 DEG C and is stretched with 50mm/ minutes speed to 500 μm of thermoplastic resin layer (B) Ultimate elongation (%).

4. laminated resin body according to any one of claims 1 to 3, wherein resin layer, which has, includes (methyl) acrylic acid The main layer (A) of resin and be laminated in the main layer (A) at least one face thermoplastic resin layer (B), the main layer (A) includes (methyl) acrylic resin and vinylidene fluoride resin.