CN102186670B - Method for manufacture of resin laminated body - Google Patents

Method for manufacture of resin laminated body Download PDF

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Publication number
CN102186670B
CN102186670B CN200980140981.7A CN200980140981A CN102186670B CN 102186670 B CN102186670 B CN 102186670B CN 200980140981 A CN200980140981 A CN 200980140981A CN 102186670 B CN102186670 B CN 102186670B
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China
Prior art keywords
layer
cured coating
coating film
methyl
film
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Expired - Fee Related
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CN200980140981.7A
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CN102186670A (en
Inventor
冈藤宏
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/204—Plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors

Abstract

Disclosed is a method for manufacturing a resin laminated body that is minimally warped and that has excellent adhesiveness and abrasion resistance. The method includes: a first step wherein, to form a coating layer, a solventless activation energy line-hardening mixture is applied to the adhesion layer of a transfer film formed by sequentially forming a release layer, an antireflective layer, a first cured coating layer, and the adhesion layer on one face of a transparent film; a second step wherein the coating layer side is applied to a resin base material; a third step wherein the activation energy line-hardening mixture in the coating layer is hardened to form a second cured coating layer; and a fourth step wherein the transparent film is peeled off, leaving the second cured coating layer, the adhesion layer, the first cured coating layer, and the antireflective layer stacked on the resin base material.

Description

The manufacture method of laminated resin body
Technical field
The present invention relates to be applicable to the purposes such as display front plate, the transparency, antireflection property, marresistance can be good laminated resin body and the manufacture method thereof of the shape such as tabular.
Background technology
The transparent resin such as acrylic resin, polycarbonate resin, is widely used as industrial material, structure material etc.Particularly in recent years, due to its transparency and resistance to impact, constantly for the front panel of the various displays such as CTR, LCD TV, plasma display.
In recent years, as one of desired important performance of front panel, for example can enumerate antireflection property, this antireflection property is for reducing the reverberation that is irradiated to the room fluorescent lights etc. of front panel, shows more brightly the function of image.As one of principle of anti-reflective function, can exemplify the antireflection film that the structure of the layer that refractive index is low is set by being formed on the surface of the layer that refractive index is high, utilization, with light that high refractive index layer was reflected with the path difference between the light that low-index layer was reflected, is mutually interfered and is reduced reverberation.
The existing antireflection film with such anti-reflective function, conventionally by stacking gradually high refractive index layer by infusion process on plastic basis material and low-index layer is made, but the method, owing to being that batch-type thereby production efficiency are low, becomes one of reason that while making antireflection film, cost rises.In addition, when adopting infusion process, the speed owing to upwards promoting plastic base from maceration extract etc. easily produces inequality to thickness, is conventionally difficult to obtain the overlay film of nanometer scale.
Here, as the method that forms continuously the functional layers such as antireflection film of uniform nanometer scale, the method (with reference to patent documentation 1) that the hot transfer printing of the anti-reflection layer of film forming on release liner (transfer printing layer) or pressure-sensitive is transferred to transfer printing body surface is disclosed.But existence to need large-scale firing equipment, needs elapsed time in order heating, can not to improve the such problem of speed of production.And, there is between base material and anti-reflection layer (transfer printing layer) problem that is easy to sneak into bubble, is easy to produce the defect of the concave-convex surface causing because of foreign matter.
On the other hand, following method is disclosed: by anti-reflection layer is fitted in after transfer printing body surface irradiation ultraviolet radiation (UV) solidify adhesive linkage across ultraviolet hardening adhesive linkage, peel off the base film that has formed anti-reflection layer, this anti-reflection layer is transferred to the method (with reference to patent documentation 2) on transfer printing body surface.Though the method can with fairly simple equipment high productivity carry out transfer printing, when forming adhesive linkage, need solvent flashing.Therefore in addition, because the viscosity of the bonding agent using in adhesive linkage is very high, there is the problem that is easy to sneak into bubble, is easy to produce the defect of the concave-convex surface causing because of foreign matter.And, owing to being born hard conating function and binding function by individual layer, so there is the tendency with the adaptation deficiency of base material.In addition, due to adhesive linkage toughness, therefore when being taken care of with roller shape, transfer film need to attach barrier film, complex procedures aspect continuous production.
In addition, also disclose and on base material, be coated with in advance UV curable paint, by irradiation ultraviolet radiation, anti-reflection layer (transfer printing layer) has been transferred to the stacked transfer printing of UV (patent documentation 3) on transfer printing body surface.In the method, owing to being coated with in advance UV curable paint on base material, when using the acrylic resin of poor solvent resistance, polycarbonate resin as base material, by inhomogeneous dissolving, caused optical deformation.In addition, do not record while forming coating, temperature, detailed the creating conditions such as mode that are coated with.
In addition, after disclosing be coated with UV curable paint in advance on anti-reflection layer (transfer printing layer), fit to base material, by irradiation ultraviolet radiation, anti-reflection layer is transferred to the method (referring to patent documentation 4) on base material.The method is owing to being directly coated with UV curable paint to anti-reflection layer, exist be difficult to obtain duplexer adaptation, can not improve productive problem.During in addition, with no specific disclosure of formation coating, be coated with the method for ultra-violet solidified mixture.
In addition, disclose and on film, be pre-formed anti-reflection layer, protective layer, adhesive linkage, be transferred to the method (with reference to patent documentation 5) of base material.The method, because anti-reflection layer is connected with protective layer, is favourable stepped construction for high rigidity, but in order to realize high rigidity; need to increase the thickness of protective layer; therefore, because film shrinks, produce larger distortion (warpage), be difficult to obtain level and smooth face.
Especially, owing to being easy to observe significant optical deformation in antireflective layered material, thereby manufacture method and duplexer that outward appearance is better need to be proposed.
Prior art document
Patent documentation 1: TOHKEMY 2006-45355 communique
Patent documentation 2: TOHKEMY 2003-215308 communique
Patent documentation 3: Japanese kokai publication hei 7-151905 communique
Patent documentation 4: TOHKEMY 2006-212987 communique
Patent documentation 5: TOHKEMY 2005-96078 communique
Summary of the invention
The object of this invention is to provide all manufacture methods of the laminated resin body of the good shape such as tabular of a kind of transparency, antireflection property, adaptation, marresistance, productivity, outward appearance.
The present invention is the manufacture method of laminated resin body, comprise: on the one side of transparent membrane, be formed with successively peel ply, anti-reflection layer, on this adhesive linkage of the transfer film of the first cured coating film layer and adhesive linkage, be coated with the first operation that the active energy of no-solvent type ray-curable mixture forms coating, above-mentioned coated side is fitted to the second operation on resin base material, make the activity energy ray-curable mixture solidified in above-mentioned coating and form the 3rd operation of the second cured coating film layer, and by the second cured coating film layer stacked on above-mentioned resin base material, adhesive linkage, residual and the 4th operation that described transparent membrane is peeled off of the first cured coating film layer and anti-reflection layer.
In above-mentioned manufacture method, preferably the thickness of the first cured coating film layer is 0.5 μ m～10 μ m, and the thickness of the second cured coating film layer is 0.5 μ m～40 μ m.
In addition, in above-mentioned manufacture method, preferably in the second operation, the surface temperature of resin base material is 40～100 ℃, and the viscosity of the activity energy ray-curable mixture that forms the second cured coating film layer when with above-mentioned surface temperature uniform temp is 15～120mPas.
In addition, in above-mentioned manufacture method, preferred anti reflection layers is two-layer above structure.
And then preferred anti reflection layers is single layer structure, and the refractive index of the refractive index ratio anti-reflection layer of the first cured coating film layer is high.
Invention effect
According to the present invention, can obtain the laminated resin body that warpage is few, adaptation is good and marresistance is good.
In addition, can be simply to install, to manufacture high productivity the duplexer of the volatilization of the solvent that does not carry out adhesive linkage.
And then, can provide that optical deformation is few, the sneaking into and the antireflection laminated resin body of the few surface defects such as foreign matter defect of bubble.
The specific embodiment
The present invention is the manufacture method that stacks gradually the laminated resin body of the second cured coating film layer, adhesive linkage, the first cured coating film layer, anti-reflection layer at least one one side on resin base material surface.
Cured coating film layer is the layer that improves the marresistance of laminated resin surface, is that the hardening mixtures that the various curability compounds by bringing this marresistance are formed is solidified into membranaceous layer.Hardening mixtures as the first cured coating film layer raw material, can exemplify the hardening mixtures that the curability compound by radical polymerization syzygy such as ultra-violet solidified mixture as described later forms, or the hardening mixture being formed by condensation polymerization hardening compounds such as alkoxy silane, alkylalkoxy silanes.These curability compounds preferably solidify, or solidify by heating by irradiating for example electron beam, radioactive ray, ultraviolet isoreactivity energy ray.These curability compounds can be distinguished use separately, also the multiple compound combination with curability can be used.In addition, for convenient, the situation that curability compound is used is separately also referred to as " hardening mixtures ".
The second cured coating film layer can be by making active can ray-curable mixture solidified obtaining.In the present invention, from the viewpoint of productivity and physical property, preferably the second cured coating film layer solidifies by ultraviolet ray.Below ultra-violet solidified mixture is described.
From productive angle, as ultra-violet solidified mixture, preferably use and in molecule, at least there is the compound of 2 (methyl) acryloxies and the ultra-violet solidified mixture that light trigger forms.
For example, as the main compound at least in molecule with the compound of 2 (methyl) acryloxies, such as the carboxylate that can enumerate the carboxylate that obtained by the polyalcohol of 1 mole and 2 moles of above (methyl) acrylic acid or derivatives thereofs, be obtained by polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid or derivatives thereof etc.
In addition, the object lesson of the carboxylate obtaining as above (methyl) acrylic acid or derivatives thereof of the polyalcohol by 1 mole and 2 moles, can exemplify out: diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, two (methyl) polyalkylene glycol acrylate esters such as TEG two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two (methyl) acrylic acid alkyl alcohol esters such as 1,9-nonanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, three (methyl) acrylic acid, five polyglycerol esters, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid glyceride, three (methyl) acrylic acid dipentaerythritol ester, four (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, four (methyl) acrylic acid tripentaerythritol ester, five (methyl) acrylic acid tripentaerythritol ester, six (methyl) acrylic acid tripentaerythritol ester, many (methyl) acrylic acid polyol esters more than seven (methyl) acrylic acid tripentaerythritol Zhi Deng, 3 functional groups.
Further, in the carboxylate being obtained by polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid or derivatives thereof, as polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid preferred compositions, for example can exemplify: maleic acid/trimethylolethane/(methyl) acrylic acid, maleic acid/trimethylolpropane/(methyl) acrylic acid, maleic acid/glycerine/(methyl) acrylic acid, maleic acid/pentaerythrite/(methyl) acrylic acid, butanedioic acid/trimethylolethane/(methyl) acrylic acid, butanedioic acid/trimethylolpropane/(methyl) acrylic acid, butanedioic acid/glycerine/(methyl) acrylic acid, butanedioic acid/pentaerythrite/(methyl) acrylic acid, adipic acid/trimethylolethane/(methyl) acrylic acid, adipic acid/trimethylolpropane/(methyl) acrylic acid, adipic acid/glycerine/(methyl) acrylic acid, adipic acid/pentaerythrite/(methyl) acrylic acid, glutaric acid/trimethylolethane/(methyl) acrylic acid, glutaric acid/trimethylolpropane/(methyl) acrylic acid, glutaric acid/glycerine/(methyl) acrylic acid, glutaric acid/pentaerythrite/(methyl) acrylic acid, decanedioic acid/trimethylolethane/(methyl) acrylic acid, decanedioic acid/trimethylolpropane/(methyl) acrylic acid, decanedioic acid/glycerine/(methyl) acrylic acid, decanedioic acid/pentaerythrite/(methyl) acrylic acid, fumaric acid/trimethylolethane/(methyl) acrylic acid, fumaric acid/trimethylolpropane/(methyl) acrylic acid, fumaric acid/glycerine/(methyl) acrylic acid, fumaric acid/pentaerythrite/(methyl) acrylic acid, itaconic acid acid/trimethylolethane/(methyl) acrylic acid, itaconic acid/trimethylolpropane/(methyl) acrylic acid, itaconic acid/glycerine/(methyl) acrylic acid, itaconic acid/pentaerythrite/(methyl) acrylic acid, maleic anhydride/trimethylolethane/(methyl) acrylic acid, maleic anhydride/trimethylolpropane/(methyl) acrylic acid, maleic anhydride/glycerine/(methyl) acrylic acid, maleic anhydride/pentaerythrite/(methyl) acrylic acid etc.
As other example at least in molecule with the compound of 2 (methyl) acryloxies, can exemplify by trimethylolpropane toluene di-isocyanate(TDI), hexamethylene diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, XDI, 4,4 '-vulcabond dicyclohexyl methyl hydride, IPDI, 1 mole of the trimerizing of the vulcabond such as trimethyl hexamethylene diisocyanate and the polyisocyanates that obtains, with 3 moles of above 2-ethoxy (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxy-3-methoxy propyl group (methyl) acrylate, N-methylol (methyl) acrylamide, N-hydroxyl (methyl) acrylamide, Glycerin-1,3-bis-(methyl) acrylate, the acrylic monomer that 3-acryloxy-2-hydroxypropyl (methyl) acrylate etc. has a reactive hydrogen reacts and obtains (methyl) acroleic acid polyurethane, two (methyl) acrylate of three (2-ethoxy) isocyanic acid or three (methyl) acrylate etc. gather [(methyl) acryloxy ethene] isocyanates, epoxy gathers (methyl) acrylate, (methyl) acroleic acid polyurethane." (methyl) acrylic acid " expression " methacrylic acid " or " acrylic acid " wherein.
In addition, as the ultra-violet solidified mixture that forms the second cured coating film layer, preferred macromonomer, more preferably polyurethane series macromonomer.By using these macromonomers, can reduce the warpage of duplexer.
As light trigger, for example can exemplify: benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether, 3-hydroxy-2-butanone, butyroin, toluene accidental cause, benzyl, benzophenone, to methoxy benzophenone, 2, 2-diethoxy acetophenone, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, aminomethyl phenyl glyoxalic acid, ethylphenyl glyoxalic acid, 4, 4 '-bis-(dimethylamino) benzophenone, the carbonyls such as 1-hydroxyl-cyclohexyl-phenyl-one and 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, tetramethylthiuram monosulfide, the sulphur compounds such as tetramethylthiuram disulfide, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, two (2, 4, 6-trimethylbenzoyl)-phenyl phosphine oxide, the phosphorus compounds such as benzoyl diethoxy phosphine oxide.
The addition of light trigger, from the angle of the curability because of ultraviolet ray irradiation, is preferably more than 0.1 quality % in ultra-violet solidified mixture 100 quality %, from maintaining the angle of the good tone of cured coating film layer, is preferably below 10 quality %.In addition, also can use two or more light triggers simultaneously.
In ultra-violet solidified mixture, can also add as required the various compositions such as smoothing preparation, levelling agent, inorganic fine particles, light stabilizer (ultra-violet absorber, HALS etc.).From the viewpoint of the duplexer transparency, these addition is preferably below 10 quality % in ultra-violet solidified mixture 100 quality %.
As the first cured coating film layer, thickness is preferably 0.5 μ m～10 μ m, and thickness is 1 μ m～7 μ m more preferably.Within the scope of this, there is sufficient case hardness, because film layer makes the warpage of film few, outward appearance is also good.
As the second cured coating film layer, thickness is preferably 0.5 μ m～40 μ m, and thickness is 3 μ m～30 μ m more preferably.Within the scope of this, there is sufficient case hardness, because film layer makes the warpage of duplexer few.In addition, the appearance defect also not causing because of sneaking into of foreign matter or bubble.
Above-mentioned thickness can be by the viscosity of hardening mixtures, pressure of squeeze roll, extrusion speed etc. regulate.In addition, described hardening mixtures, when containing solvent, can be adjusted thickness by setting the concentration of solid constituent.
Anti-reflection layer is so long as have below 20% of incident light that reverberation is suppressed to laminated resin surface, and preferably, below 10%, more preferably the function below 5%, can consist of any material.In order to give such function, can exemplify the whole bag of tricks such as method of stepped construction such as formation with the film of two or more different refractivities.If anti-reflection layer be two-layer more than, more easily reduce reflectivity, thereby preferably.
When formation has the stepped construction of film of two kinds of different refractivities, refractive index to each film is not particularly limited, but preference as the refractive index facing the outmost surface of air be the low-index layer of 1.3～1.5 left and right, the refractive index of the high refractive index layer existing in the base material side of low-index layer is 1.6～2.0.Within the scope of this, can fully suppress the reverberation of incident light.
Thickness for low-index layer, high refractive index layer is not particularly limited, but preferably respectively do for oneself 50nm～200nm, more preferably 70nm～150nm.As long as within the scope of this, just can fully suppress the reverberation of discernible wavelength.
In addition, can be also the hard conating using the first cured coating film layer as the high index of refraction higher than the refractive index of anti-reflection layer, anti-reflection layer is as the individual layer of low-index layer.In this case, the refractive index that preferably faces the outmost surface of air is the low-index layer of 1.3～1.5 left and right, and the refractive index of the first cured coating film layer is 1.6～2.0.As long as within the scope of this, just can fully suppress the reverberation of incident light.Such anti-reflection layer is the structure of individual layer, the refractive index of the refractive index ratio anti-reflection layer of the first cured coating film layer is high, thereby the reflection of light rate of the wavelength of visible region is easily controlled in below certain value, thereby in can inhibitory reflex light, the light of particular color be outstanding.
Thickness for above-mentioned low-index layer, high index of refraction hard conating is not particularly limited, but preferably the thickness of low-index layer is 50nm～200nm, more preferably 70nm～150nm.In addition, the thickness of high index of refraction hard conating is preferably 0.5 μ m～10 μ m, and thickness is 1 μ m～7 μ m more preferably.Within the scope of this, there is sufficient case hardness, because film layer makes the warpage of film few, outward appearance is also good.
In addition, when the individual layer using the first cured coating film layer as high index of refraction hard conating, using anti-reflection layer as low-index layer, from suppressing the angle of interference fringe, the refractive index of preferred adhesive linkage described later is the value between the refractive index of high index of refraction hard conating and the refractive index of resin base material.
As the composition that forms low-index layer, preferred index is the material of 1.3～1.5 left and right, the layer of the siloxane bond main body that the curability compound that by condensation polymerization is such as alkoxy silane, alkylalkoxy silane etc. forms, as its concrete example, can exemplify the material that compound that the part by the siloxane bond of siloxane-based resin replaced by hydrogen atom, hydroxyl, unsaturated group, alkoxyl etc. etc. forms.
In addition,, from the viewpoint of further realizing low-refraction, preferably in the layer of siloxane-based resin, add silica colloidal.Silica colloidal is that the particulate of porous silica and/or non-porous matter silica is dispersed in decentralized medium, the colloidal solution of formation.Wherein, Porous carbon dioxide is in particle, to be porous or hollow, the inside low-density silicon dioxide that contains air.The refractive index of porous silica is 1.20～1.40, compares low with the refractive index 1.45～1.47 of common silica.Therefore, in the present invention, in order to reduce the refractive index of low-index layer, more preferably use porous silica.
And, also can in above-mentioned ultra-violet solidified mixture, add silica colloidal and solidify, form low-index layer.In addition, the silica colloidal that also can use surface to be processed by silane coupling agent.
These hardening compounds are for example solidified, or are solidified by heating by irradiating electron beam, radioactive ray, ultraviolet isoreactivity energy ray.These curability compounds can be distinguished use separately, also the multiple compound combination with curability can be used.
As the composition that forms high index of refraction, preferred index is the material of 1.6～2.0 left and right, can use to contain himself to be hydrolyzed the material that forms metal oxide and can form the metal alkoxide of dense film.Such metal alkoxide is preferably by chemical formula
M(OR)m
The material representing.In chemical formula, M represents metal, and R represents that carbon number is 1～5 alkyl, and m represents the valence (3 or 4) of metal M.As metal M, be suitable for for titanium, aluminium, zirconium, tin etc., particularly preferably titanium.As the concrete example of metal alkoxide, can exemplify: methyl alcohol titanium, titanium ethanolate, normal propyl alcohol titanium, isopropyl titanate, four titanium n-butoxide, four isobutoxy titaniums, aluminium ethylate, aluminium isopropoxide, aluminium butoxide, tert-butyl alcohol aluminium, tert-butyl alcohol tin, ethanol zirconium, zirconium-n-propylate, zirconium iso-propoxide, zirconium-n-butylate etc.
In addition, in the metal alkoxide of formation metal oxide, add ZrO 2, TiO 2, NbO, ITO, ATO, SbO 2, In 2o 3, SnO 2with at least one the high refractive index metal oxide particulate in ZnO, from reaching the angle of further high index of refraction, be preferred.
And then, also can add metal oxide microparticle of high index of refraction and solidify to above-mentioned ultra-violet solidified mixture, form high refractive index layer.Also can use in addition metal oxide microparticle of the high index of refraction after surface treatment.
These hardening compounds are for example solidified, or are solidified by heating by irradiating electron beam, radioactive ray, ultraviolet isoreactivity energy ray.These curability compounds can be distinguished use separately, also the multiple compound combination with curability can be used.
In addition, as the method for not using atomic high index of refraction, exemplify use there is fluorenes (fluorene) skeleton, the organic compound of the activity energy ray-curable of the halogen atom beyond sulphur atom, fluorine, aromatic series skeleton etc.As the organic compound with fluorene skeleton, exemplify fluorinated acrylate (fluorine acrylate).
Then, as adhesive linkage such as listing: acrylic resin, chlorinated alkenes are that resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid are that resin, chlorinated rubber are that resin, thermoprene are that resin, polyamide-based resin, coumarone-indene are that resin, ethylene-vinyl acetate copolymer are that resin, polyester based resin, polyurethane series resin, phenylethylene resin series, butyral resin, rosin series resin, epoxy are the thermoplastic resins such as resin.
By mix butyral resin, rosin series resin and epoxy in polyamide, be preferably that at least one resin in resin forms.Or can be also that in polyurethane resin, to mix butyral resin, rosin series resin and epoxy be that at least one resin in resin forms, can also be that in the mixture of polyamide and polyurethane resin, to mix butyral resin, rosin series resin and epoxy be that at least one resin in resin forms.In any situation, though can obtain at low temperatures also can be bonding adhesive linkage.In addition, the formation of adhesive linkage can form by himself known method.
Because adhesive linkage consists of thermoplastic resin, top layer does not have viscosity, and because transfer film as described later can be taken care of with roller shape, thereby be applicable to producing continuously, productivity is good
Adhesive linkage can be dissolved in solvent by above-mentioned resin, as bonding agent, forms.In this case, if solvent soaks into the first cured coating film layer, the interface of adhesive linkage and hardened coating film layer disappears, and the defect of interference fringe is disappeared, thereby preferably.
In addition, if add the particulate of high index of refraction to adhesive linkage, can be the value between the refractive index of above-mentioned high index of refraction hard conating and the refractive index of resin base material.
As resin base material, can exemplify the formed products of copolymer that for example polymethyl methacrylate, Merlon, the methyl methacrylate units of take are main composition composition, polystyrene, styrene-methylmethacrylate copolymer.In addition, in resin base material, also can add colouring agent, light diffusing agent etc.The thickness of laminated resin body, from the viewpoint of mechanical strength, more than being preferably 0.2mm, is preferably below 10mm from the viewpoint of productivity.
In addition,, on this laminated resin body, as required, other functional layer of anti-soil film etc. can also be set such as the surface at anti-reflection layer.For example, when forming anti-soil film, can exemplify and on resin base material, be coated with commercially available antifouling paint method (damp process) dry and that form, or the physical vapor method of piling such as vapour deposition method, sputtering method etc.In addition, the surface of anti-reflection layer can be smooth, can be also concavo-convex.
Next, describe the manufacture method of laminated resin body of the present invention in detail.
The manufacture method of laminated resin body of the present invention is the method for duplexer that obtains with transfer film, compares with infusion process in the past, rolling method, spin-coating method etc. the successively method of masking, and from the viewpoint of productivity, appearance, be favourable.
Transfer film is elaborated.
As transparent membrane, can utilize known film.In addition, so long as there is the film of fissility, be exactly suitable, if but fissility is insufficient, can peel ply be set at film surface.
As transparent membrane, can exemplify the built up membranes such as pet film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamidoimide film, polyethylene film, polyvinyl chloride film, the cellulose-based film such as acetyl cellulose film, the tympans such as the Japan paper such as glassine paper, glassine and foreign paper, or the membranaceous thing of these THIN COMPOSITE, compound sheet thing etc., and film that peel ply forms etc. is set on these.This transparent membrane is for seeing through the film of active energy ray.
The thickness of transparent membrane is not particularly limited, from easy manufacture, there is no the aspect of the transfer film of fold, be full of cracks etc., more than being preferably 4 μ m, more preferably more than 12 μ m, more than being particularly preferably 30 μ m, in addition preferably below 500 μ m, more preferably below 150 μ m, particularly preferably below 120 μ m.
In order to improve the fissility of these transparent membranes, form peel ply.The formation material of peel ply is the polymer, wax etc. of the known formation peel ply of choice for use aptly.Formation method as peel ply, there is for example paraffin, acrylic acid series, polyurethane series, silicon system, melamine series, Urea Series, urea-melamine series, cellulose-based, the resin of benzoguanamine system etc. and surfactant separately or these mixture as principal component, be dissolved in organic solvent or water, form coating, coating is passed through to woodburytype, silk screen print method, the common printing processes such as hectographic printing method are coated on above-mentioned matrix film, and dry (by thermosetting resin, uv curing resin, electronic beam curing resin, radiation-curable resin etc. is solidified into curability and films) form the method for peel ply.The thickness of peel ply is not particularly limited, the scope of suitable employing 0.1～3 μ m left and right.Peel ply is crossed when thin, is difficult to peel off, and when contrary peel ply is blocked up, too easily peels off, and can cause the disengaging of each layer on film before transfer printing, thereby not preferred.
Then, on peel ply, by known coating shaping method, stack gradually above-mentioned anti-reflection layer, the first cured coating film layer, adhesive linkage, thereby make transfer film.Conventionally this transfer film is rolled into roller shape.
When transfer film is rolled into roller shape, can makes and will be formed with above-mentioned anti-reflection layer, the first cured coating film layer, adhesive linkage (being referred to as below " transfer printing layer ") side and be positioned at the transfer film of reeling in inner side, and be positioned at the transfer film that skin is reeled.By the transfer film of these two kinds of winding methods of applying in a flexible way, can suppress the warpage of resulting duplexer.
For example, the polymerization shrinkage that the second cured coating film layer is accompanied by ultraviolet curing is large, while becoming the inner side of circular arc when this hardened coating film layer generation warpage of resin base material, by using, transfer printing layer is wound into the transfer film that is positioned at inner side, thereby can suppresses the warpage of the duplexer of gained.Here " circular arc " refers to " this circular arc that warpage becomes circular-arc duplexer ".
In addition, at the duplexer that will be provided with cured coating film (hard conating) on one side by casting polymerization during as resin base material, can there is warpage and make hard conating side become the outside of circular arc.In this case, while forming transfer printing layer by the face side hard conating is not set, use is wound into transfer printing layer the transfer film that is positioned at inner side, and further use aptly the minimum polyurethane series macromonomer of above-mentioned cure shrinkage etc., form the second cured coating film layer, thereby can suppress the warpage of obtained duplexer.
By adopting such method, even in the thicker situation of the thickness of solidified coating film, also can make simply the duplexer that warpage is little.
As the first operation, on this adhesive linkage of resulting transfer film, the ultra-violet solidified mixture of coating no-solvent type forms coating.Here, in the ultra-violet solidified mixture of no-solvent type the content of solvent with respect to this mixture less than 1 quality %.
As the formation method of coating, preferably by roller coat, rod paintings, slit die etc., by the ultra-violet solidified mixture of no-solvent type with respect to the direct of travel (direction of the supply) of film vertically and the coating of wire ground, formation coating.That is, preferably will with respect to the direct of travel of film, in parallel, be coated with in the vertical direction and on the coated face of film for being coated with the supply unit of above-mentioned ultra-violet solidified mixture.When forming the method for coating to film, if with respect to the direct of travel of film abreast and wire be coated with, have the situation that is produced optical deformation by the uneven dissolution of base material.
In addition, entrained air in order to prevent from fitting is preferably coated with excessive ultra-violet solidified mixture on film.
Then, in the second operation, described coated side is attached on resin base material.As the method for this attaching, exemplify the method for being carried out crimping by rubber rollers.
As forming the method for cated film with resin base material laminating, have for example film, resin base material at the state of carrying respectively by the method for above-mentioned rubber rollers crimping laminating, the method for being fitted by above-mentioned rubber rollers crimping under film and the overlapping state of resin base material etc.The former method that film, resin base material are fitted under the state of carrying respectively preferably adopts when continuation mode, and the latter's the method for being fitted by rubber rollers crimping under film and the overlapping state of resin base material preferably adopts when batch mode.
In addition, in the method in above-mentioned formation coating, record " with respect to the direct of travel of film vertically and wire be coated with " be elaborated.
When employing is carried out the method for crimping laminating by above-mentioned rubber rollers by film, resin base material under the state of carrying respectively, because film is identical with the direct of travel of resin base material, mean with respect to the direct of travel of resin base material in vertical direction and wire be coated with.
On the other hand, adopting while carrying out the method for crimping laminating by rubber rollers under film and the overlapping state of resin base material, the direct of travel of film is to be overlapped into direction integrated and that carry with resin base material, identical with the direct of travel of resin base material, therefore here in order to be conveniently recited as the direct of travel of film.With respect to the direct of travel of this film, on above-mentioned adhesive linkage in advance in the vertical direction and wire be coated with said mixture, form coating.
In the second operation, the surface temperature of resin base material is preferably 40 ℃～100 ℃.In this temperature range, adaptation is good, and the hardness causing less than the excessive dissolution because of base material declines, the xanthochromia of also not filming.The surface temperature of resin base material can be adjusted by design temperature, the heat time of heating part.Method as measuring the temperature of resin base material, exemplifies the known methods such as non-contact type land surface pyrometer.As the activity energy ray-curable mixture that forms the second cured coating film layer, preferably the viscosity in the identical temperature of the surface temperature with resin base material is 15～120mPas.Within the scope of this, adaptation is also good, also there is no optical deformation.Composition, temperature by suitable adjustment above-mentioned composition are controlled in above-mentioned range of viscosities.In addition, there is no the appearance defect that causes because sneaking into bubble yet.In addition, viscosity can be adjusted by the composition of above-mentioned hardening mixtures.
In above-mentioned the second operation, on mould, attach after transfer film, as the 3rd operation, across transfer film, irradiate active energy ray, make the activity energy ray-curable mixture solidified in described coating, become the second cured coating film layer.As active energy ray, preferred ultraviolet ray as above.When irradiation ultraviolet radiation, can use ultraviolet lamp.As ultraviolet lamp, such as exemplifying high-pressure mercury-vapor lamp, metal halide lamp, fluorescent ultra-violet lamp etc.What by ultraviolet ray, irradiate solidifies, can a stage, carry out across transfer film, or also can be divided into for two stages implements, across transfer film carry out the solidifying (the 3rd operation), peel off transparent membrane (the 4th operation) of first stage, further irradiation ultraviolet radiation carries out solidifying of second stage etc. afterwards.During curable resin beyond using ultra-violet solidified mixture, can suitably select for example electron beam, radioactive ray isoreactivity energy ray, across transfer film, irradiate and solidify.
In the present invention, in the 3rd operation, after being solidified, hardening mixtures forms after the second cured coating film layer, as the 4th operation, the transparent membrane of transfer film is peeled off, leave the second cured coating film layer, adhesive linkage, the first cured coating film layer and the anti-reflection layer that on resin base material, arrange.That is the structure of the adhesive linkage of transfer film, the first cured coating film layer and anti-reflection layer that, become on the second hardened coating film layer on resin base material transfer printing.Wherein, peel ply remains in transparent membrane side.
The laminated resin body being obtained by said method is applicable in the purposes such as front panel of display.
Embodiment
Below, by embodiment, describe the present invention in detail, but the present invention is not limited thereto, here, the abbreviation of the compound using in embodiment and comparative example is as follows.
" TAS ": butanedioic acid/trimethylolethane/acrylic acid condensation mixture (Osaka organic chemistry industry (strain) is manufactured)
" C6DA ": 1,6-hexanediyl ester (Osaka organic chemistry industry (strain) is manufactured)
" M305 ": pentaerythritol triacrylate M-305(East Asia synthetic (strain) manufactures)
" M309 ": trimethylolpropane triacrylate M-309(East Asia synthetic (strain) manufactures)
" M400 ": six acrylic acid dipentaerythritol ester M-400(East Asia synthetic (strain) manufactures)
" Art Resin SUX-1 ": polyurethane series macromonomer (industry on root (strain) manufacture)
" Optool AR ": fluorine is low-refraction acrylate, solid component concentration 15 % by weight, methyl isobutyl ketone solution (Daikin changes into product and peddles (strain) manufacture)
" OGSOL EA-F5010 ": containing the acrylate (Osaka aerochemistry (strain) manufacture) of fluorene skeleton
" DIANAL BR-80 ": acrylic resin (the beautiful sun of Mitsubishi (strain) manufacture)
" DAROCUR TPO ": 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (vapour bar Japan (strain) manufactures)
" gorgeous good solid (Irgacure) 184 ": 1-hydroxyl-cyclohexyl-phenyl ketone (vapour bar Japan (strain) manufactures)
" ACRYLITE EX001 ": acrylic resin board (the beautiful sun of Mitsubishi (strain) manufacture)
" ACRYLITE MR001 ": the polymethacrylates of one-side band hard conating (the beautiful sun of Mitsubishi (strain) manufacture)
In addition, in embodiment, the evaluation of physical property is carried out based on following method.
Viscosity measurement
Measure the viscosity of the rotation number 6rpm of Brookfield viscometer at each temperature.Wherein, viscosity is to measure at the identical temperature of the temperature with base material.
The temperature measuring of resin base material
Base material is heated and is given heating, use non-contact type land surface pyrometer (CHINO(strain) manufacture), handheld radiation thermometer IR-TA) measure.
Full light transmission rate and mist degree (haze)
The HAZE METER NDH2000 (trade name) that uses Japanese electric look to manufacture, measures full light transmission rate according to the assay method shown in JIS K7361-1, according to the assay method shown in JIS K7136, measures mist degree.
Marresistance
According to the variation (Δ haze) of the mist degree before and after scoring test, evaluate.; the circular pad that is 25.4mm by the diameter that #000 steel wool (steel wool) is installed is placed on the cured coating film layer surface of duplexer; under the loading of 500g, carry out 10 times of 20mm distance scratches back and forth, before obtaining scratch by following formula (1) and the mist degree after scratch poor.
[Δ haze (%)]=[haze value (%) after scratch]-[haze value (%) before scratch] ... (1)
In addition, number goes out the number of the scar of the rear sample of test.
Antireflection property is evaluated
With sand paper, the back side of sheet is carried out after roughening, be coated with delustring black spray (anti-glare black spray), using it as sample, use spectrophotometer (Hitachi's manufacture, " U-4000 "), under the scope of 5 ° of incidence angles, wavelength 380～780nm, according to the assay method shown in JIS R3106, the reflectivity on working sample surface.
Adaptation is evaluated
According to adhesion test (cross cut test) (JIS K5600-5-6), evaluate.Repeatedly carry out 4 tests, add up to for 4 times that are expressed as number positional unstripped and residual in each 25 positions.
The ocular estimate on top layer
Whether Visual Confirmation sample surfaces has bubble, foreign matter.
Zero: do not sneak into bubble, there is no foreign matter
△: do not sneak into bubble, have foreign matter
*: there is bubble, have foreign matter
Optical deformation
Whether Visual Confirmation has sample deformation
Zero: there is no deformation
*: there is deformation
The warpage evaluation of laminated resin body
In the environment of 80 ℃, place after 15 hours, measure the amount of warpage of the laminated resin body of 30cm * 30cm.Wherein, amount of warpage is that sample is positioned over to the dull and stereotyped upper distance of measuring from sheet warpage to sample.
Zero: below amount of warpage 5mm
*: more than amount of warpage 5mm
The assay method of refractive index and film thickness
For anti-reflection layer, cured coating film layer, use the thickness-refractive index measuring apparatus (style 2010, prism coupler) of Metricon company system to be determined at the refractive index and film thickness under 594nm laser.
Film thickness measuring method
The determining film thickness of not measuring the sample of refractive index is with microtome, to cut out the sample of 100nm thickness, by transmission electron microscope, observed and carried out.The JEM-1010 that transmission electron microscope is used NEC (JEOL) to manufacture measures.
Embodiment 1
To antireflection transfer film, (tail vat industry (strain) is manufactured, trade name: STEP PAR-1, according to the sequential cascade of film (PET film), peel ply, anti-reflection layer, cured coating film layer, adhesive linkage) adhesive linkage side with respect to film direct of travel vertically and wire be coated with the coating being formed by ultra-violet solidified mixture, described ultra-violet solidified mixture consists of 35 mass parts TAS, 30 mass parts C6DA, 10 mass parts M305,25 mass parts M400,2 mass parts DAROCUR TPO, uses excellent painting machine (No. 50) to form planar coating.In addition, antireflection transfer film is not directly to use and be rolled into the film of roller shape, but cuts out a part from being rolled into the film of roller shape, uses and takes care of into plane film.
Then, be warmed on the acrylic resin base material (ACRYLITE EX001) of the 2mm thickness of slab of 60 ℃, the antireflection transfer film of above-mentioned coating will be formed with, make coating towards this resin base material side and after above-mentioned transfer film is overlapped, under the rubber rollers of 40 ° of the JIS hardness being fixed, with certain speed by (direction of advance of above-mentioned film), when extruding the thickness of filming that unnecessary coating makes to comprise ultra-violet solidified mixture and be 15 μ m, push and make not contain bubble.
In addition the thickness of filming that, comprises ultra-violet solidified mixture is calculated from quantity delivered and the developed area of this ultra-violet solidified mixture.
Then, be warmed under the state of 60 ℃, after 120 seconds, when being output as across above-mentioned transfer film under the metal halide lamp of 9.6kW, with the speed of 2.5m/min, the position of 20cm being passed through, irradiation ultraviolet radiation, carry out solidifying of ultra-violet solidified mixture, form the second hardened coating film layer.
Afterwards, above-mentioned transfer film is peeled off, anti-reflection layer, the first cured coating film layer, adhesive linkage are all transferred on the second hardened coating film layer to the laminated resin body that obtain thering is anti-reflection layer, the first cured coating film layer, adhesive linkage, the second cured coating film layer and acrylic resin base material forms like this.The thickness of the first cured coating film layer of resulting laminated resin body is 2 μ m, and the thickness of the second cured coating film layer is 13 μ m.
The full light transmission rate of resulting antireflective layered material is 94%, and mist degree is 0.2%, and the transparency is good, does not also follow the bad order of optical deformation.And sneak into etc. for the open defect, the bubble that not do not cause because of foreign matter, there is the duplexer on good top layer.The increment of the mist degree after anti-reflection layer scratch is 0.1%, and the number of scar is 3.Minimum reflectance is 1% when the wavelength of 580nm, and the result of carrying out in addition fitness test is peeling off of not filming, and adaptation is good.The result of carrying out camber test is, amount of warpage is not enough 5mm.Result is as shown in table 1.
Embodiment 2
Except the thickness of the second cured coating film layer in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 3
Except the thickness of the second cured coating film layer in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 4
Except the temperature of the resin base material in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 5
Except the ultra-violet solidified mixture in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 6
Except the ultra-violet solidified mixture in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 7
Except the ultra-violet solidified mixture in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 8
Except the temperature of the resin base material in embodiment 7 is changed to as shown in table 1, make similarly to Example 7 laminated resin body.The results are shown in table 1.
Embodiment 9
Except the ultra-violet solidified mixture in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 10
Except the antireflection transfer film in embodiment 1 is changed to, (tail vat industry (strain) is manufactured, trade name: STEP PAR-2, according to the sequential cascade of film (PET film), peel ply, anti-reflection layer, cured coating film layer, adhesive linkage) outside, laminated resin body made similarly to Example 1.The results are shown in table 1.
Embodiment 11
Except the resin base material in embodiment 1 being changed to the polycarbonate resin that 2mm is thick, (Supreme Being people changes into (strain) and manufactures, trade name: PanliteAD-5503), make similarly to Example 1 laminated resin body.The results are shown in table 1.
Embodiment 12
Except the thickness of the second cured coating film layer in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The thickness of the second cured coating film layer is due to less than 3 μ m, and to compare hardness low with embodiment 1.In addition the foreign matter defect on generations different from embodiment 1 top layer.The results are shown in table 2.
Embodiment 13
Except the thickness of the second cured coating film layer in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.The thickness of the second cured coating film layer is owing to being more than 30 μ m, different from embodiment 1, produces warpage.The results are shown in table 2.
Embodiment 14
Except the surface temperature of the base material in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.Due to 40 ℃ of substrate surface temperature less thaies, to compare adaptation low with embodiment 1.The results are shown in table 2.
Embodiment 15
Except the surface temperature of the base material in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.Because substrate surface temperature is more than 100 ℃, to compare with embodiment 1 excessive base material dissolving occurs, hardness is low.In addition, because the viscosity of ultra-violet solidified mixture is below 15mPas, different from embodiment 1, produce optical deformation.The results are shown in table 2.
Embodiment 16
Except the ultraviolet curing compositions of mixtures in embodiment 1 is changed to as shown in table 1, make similarly to Example 1 laminated resin body.Because the viscosity of ultra-violet solidified mixture is more than 120mPas, to compare with embodiment 1, adaptation is low.In addition, different from embodiment 1, produce the foreign matter defect on top layer.The results are shown in table 2.
Embodiment 17
Except by embodiment 1, temperature improves, make the viscosity of ultraviolet curing mixture change to as shown in table 2 outside, make similarly to Example 1 laminated resin body.Because the viscosity of ultra-violet solidified mixture is below 15mPas, different from embodiment 1, produce optical deformation.
Embodiment 18
Except by embodiment 1, with respect to film direct of travel abreast and wire be coated with, and form outside planar coating with No. 50 excellent painting machines, make similarly to Example 1 laminated resin body.When forming planar coating with excellent painting machine, forming section does not have applied position.Therefore, this laminated resin body is different from embodiment 1, produces the optical deformation of strip.The results are shown in table 2.
Embodiment 19
Except by the thickness of the second cured coating film layer in embodiment 1, form change to as shown in table 3, make similarly to Example 1 laminated resin body.Although the thickness of the second cured coating film layer is more than 30 μ m, owing to having used polyurethane macromolecular monomer (Art Resin SUX-1), there is not warpage.The results are shown in table 3.
Embodiment 20
Except use by embodiment 13, antireflection transfer film is rolled on paper tube with following content the film of roller shape, makes similarly to Example 13 laminated resin body.
Paper tube: 6 inches of diameters
PET base material thickness: 100 μ m
Volume is long: 500m
The coiling direction of transfer printing layer: be wound into transfer printing layer and be positioned at inner side
Even if the thickness of the second cured coating film layer is more than 30 μ m, in laminated resin body, do not produce warpage yet.The results are shown in table 3.
Embodiment 21
Except using in embodiment 20, use ACRYLITE MR100 as resin base material, to it, do not form on the face of hard conating outside the second cured coating film layer transfer printing transfer printing layer of thickness as shown in table 3, composition, make similarly to Example 20 laminated resin body.Can eliminate the warpage of ACRYLITE MR100 self, that is, eliminate anti-reflection layer and formed face side and become such warpage inside circular arc.The results are shown in table 3.
Embodiment 22
Except by the coiling direction of the transfer printing layer in embodiment 21 towards the outside of roller, make similarly to Example 21 laminated resin body.Different from embodiment 21, there is no the inhibition of warpage, produce the warpage of duplexer.The results are shown in table 3.
Embodiment 23
Except by embodiment 1, antireflection transfer film changes to the following individual layer antireflective film only with low-index layer, makes similarly to Example 1 laminated resin body.
The modulation of low-refraction coating
In Optool AR (solid component concentration 15 quality %), add MIBK (methyl iso-butyl ketone (MIBK)), being diluted to solid component concentration is 1 quality %, with respect to solid constituent 100 mass parts of Optool AR, add the gorgeous good of 5 mass parts and consolidate 184, modulation low-refraction coating.
The modulation of high index of refraction coating
In OGSOL EA-F5010, add MIBK (methyl iso-butyl ketone (MIBK)), being diluted to solid component concentration is 50 quality %, with respect to solid constituent 100 mass parts of OGSOL EA-F5010, adds the gorgeous good of 5 mass parts and consolidates 184, modulation high index of refraction coating.
Adhesive linkage forms the modulation of coating
By 50 mass parts DIANAL BR-80 and (Osaka, Sumitomo cement (strain) manufacture of 166 mass parts zirconia sols, the MEK of solid component concentration (zirconia) 30 quality % disperses colloidal sol) mix, further add MIBK (methyl iso-butyl ketone (MIBK)), being modulated into solid component concentration (with respect to the total of 100 mass parts DIANAL BR-80 and zirconic solid constituent) is 2 quality %.
The making of individual layer antireflection transfer film
Use excellent painting machine No. 4, the above-mentioned low-refraction coating of the PET film that posts melamine peel ply (Li Guang Co., Ltd. (Reiko Co., Ltd.) makes, trade name AC-J) upper coating to 100 μ m, is dried 5 minutes at 80 ℃.Afterwards, under the high-pressure mercury-vapor lamp of 9.6kW, the position of 20cm is passed through with the speed of 2.5m/min, form low-index layer.Its refractive index is 1.38.
Then, use excellent painting machine No. 4, on low-index layer, be coated with above-mentioned high index of refraction coating, at 80 ℃, be dried 5 minutes.Afterwards, under the high-pressure mercury-vapor lamp of 9.6kW, the position of 20cm is passed through with the speed of 2.5m/min, form high index of refraction hard conating.Its refractive index is 1.60.
Then, on high refractive index layer, use No. 4 excellent painting machine coating adhesive linkages to form coating, at 80 ℃, be dried 5 minutes, form adhesive linkage.
From the determining film thickness result of resulting laminated resin body, the thickness of low-index layer is 100nm, and the thickness of high index of refraction hard conating is 4 μ m, and the thickness of adhesive linkage is 200nm.The results are shown in table 3.Owing to being the antireflective layered material of individual layer, reflected colour is thinner than the duplexer of other embodiment.
Comparative example 1
By antireflection transfer film, (tail vat industry (strain) is manufactured, trade name: (manufacture by the beautiful sun of Mitsubishi (strain) as methacrylic resin base material for adhesive linkage one side STEP PAR-1), trade name: ACRYLITE EX001) side, after laminating, use oil pressure forming machine (village department iron steel (strain) manufacture) to push, apply the pressure of 10MPa, the design temperature of top, bottom is 120 ℃, applies 10 minutes pressure.At film surface, thermocouple is installed, is measured film surface temperature, its result is that the surface temperature after 10 minutes is 100 ℃.Afterwards, under the state of exerting pressure, be cooled to after 30 ℃ stripping film.For resulting laminated resin body, owing to there not being the second hardened coating film layer, so hardness is not enough.In addition, produce the foreign matter defect on top layer.And the adaptation of the first hardened coating film layer and resin base material is insufficient.The results are shown in table 2.
Comparative example 2
In embodiment 1, (the commodity STEP PAR-1 by name that tail vat industry (strain) is manufactured impregnated in acetone 10 minutes except using, not have the antireflection transfer film of adhesive linkage, remove adhesive linkage) outside, laminated resin body made similarly to Example 1.Owing to there is no adhesive linkage, adaptation is insufficient.The results are shown in table 2.
Figure RE-BPA00001348236600211
Figure RE-BPA00001348236600221
Table 3
The possibility of utilizing in industry
Laminated resin body of the present invention is suitable for the front panel of the various displays such as CRT, liquid crystal display, OLED display, plasma display, projection TV, and the front panel of the information display section of the information terminal such as mobile phone, portable music player, notebook computer etc.

Claims (5)

1. a manufacture method for laminated resin body, is characterized in that, comprising:
On the one side of transparent membrane, be formed with successively on this adhesive linkage of transfer film of peel ply, anti-reflection layer, the first cured coating film layer and adhesive linkage, the active energy of coating no-solvent type ray-curable mixture forms the first operation of coating, described no-solvent type is active can ray-curable mixture be in molecule, at least to have the compound of 2 (methyl) acryloxies and the ultra-violet solidified mixture that light trigger forms
Described coated side is fitted to the second operation on resin base material,
Make the activity energy ray-curable mixture solidified in described coating and form the 3rd operation of the second cured coating film layer, and
The 4th operation that leaves the second cured coating film layer stacked on described resin base material, adhesive linkage, the first cured coating film layer and anti-reflection layer and described transparent membrane is peeled off.
2. the manufacture method of laminated resin body according to claim 1, wherein, the thickness of the first cured coating film layer is 0.5 μ m～10 μ m, the thickness of the second cured coating film layer is 0.5 μ m～40 μ m.
3. the manufacture method of laminated resin body according to claim 1, wherein, in the second operation, the surface temperature of resin base material is 40 ℃～100 ℃, and the viscosity of the activity energy ray-curable mixture that forms the second cured coating film layer when with described surface temperature uniform temp is 15～120mPas.
4. the manufacture method of laminated resin body according to claim 1, wherein, anti-reflection layer is two-layer above structure.
5. the manufacture method of laminated resin body according to claim 1, wherein, anti-reflection layer is single layer structure, and the refractive index of the refractive index ratio anti-reflection layer of the first cured coating film layer is high.
CN200980140981.7A 2008-08-29 2009-08-26 Method for manufacture of resin laminated body Expired - Fee Related CN102186670B (en)

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JP2009090894A JP2010076423A (en) 2008-08-29 2009-04-03 Resin laminated body and method for manufacturing the same
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PCT/JP2009/064832 WO2010024274A1 (en) 2008-08-29 2009-08-26 Method for manufacture of resin laminated body

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TWI404629B (en) 2013-08-11
CN102186670A (en) 2011-09-14

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