CN102186670A - Method for manufacture of resin laminated body - Google Patents

Method for manufacture of resin laminated body Download PDF

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Publication number
CN102186670A
CN102186670A CN2009801409817A CN200980140981A CN102186670A CN 102186670 A CN102186670 A CN 102186670A CN 2009801409817 A CN2009801409817 A CN 2009801409817A CN 200980140981 A CN200980140981 A CN 200980140981A CN 102186670 A CN102186670 A CN 102186670A
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CN
China
Prior art keywords
layer
cured coating
coating film
methyl
film
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Granted
Application number
CN2009801409817A
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Chinese (zh)
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CN102186670B (en
Inventor
冈藤宏
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Mitsubishi Chemical Corp
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Mitsubishi Rayon Co Ltd
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Publication of CN102186670A publication Critical patent/CN102186670A/en
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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
    • 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
    • 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
    • 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

Landscapes

  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

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 purposes such as display front plate, the transparency, antireflection property, marresistance can be good the laminated resin body and the manufacture method thereof of shape such as tabular.
Background technology
Transparent resin such as acrylic resin, polycarbonate resin is widely used as industrial material, structure material etc.Particularly in recent years, owing to its transparency and resistance to impact, constantly be used for the front panel of various displays such as CTR, LCD TV, plasma display.
In recent years, for example can enumerate antireflection property as one of desired important performance of front panel, this antireflection property is to be used to reduce the reverberation of room fluorescent lights of shining front panel etc., the function of display image more brightly.As one of principle of anti-reflective function, can exemplify the antireflection film that the structure of the low layer of refractive index is set by the surface that is formed on the high layer of refractive index, utilization is interfered mutually and is reduced reverberation with light that high refractive index layer was reflected with the path difference between the light that low-index layer was reflected.
Existing antireflection film with such anti-reflective function, usually by on plastic basis material, stacking gradually high refractive index layer by infusion process and low-index layer is made, but this method becomes one of reason that cost rises when making antireflection film owing to be that batch-type thereby production efficiency are low.In addition, when adopting infusion process,, be difficult to obtain the overlay film of nanometer scale usually because the speed when maceration extract upwards promotes plastic base etc. are easy to generate inequality to thickness.
Here, as the method for the functional layers such as antireflection film that form uniform nanometer scale continuously, disclose will be on release liner the hot transfer printing of anti-reflection layer (transfer printing layer) of film forming or the method (with reference to patent documentation 1) that pressure-sensitive is transferred to the transfer printing body surface.But, exist and need large-scale firing equipment, need elapsed time, can not improve the such problem of speed of production in order to heat.And, the problem that is easy to sneak into bubble, is easy to produce the defective of the concave-convex surface that causes because of foreign matter is arranged between base material and anti-reflection layer (transfer printing layer).
On the other hand, following method is disclosed: by anti-reflection layer is fitted in after transfer printing body surface and irradiation ultraviolet radiation (UV) solidify adhesive linkage across the 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 this method can be carried out transfer printing with fairly simple equipment high productivity ground, when forming adhesive linkage, need solvent flashing.In addition, because the viscosity of the bonding agent that uses is very high in the adhesive linkage, therefore the problem that is easy to sneak into bubble, is easy to produce the defective of the concave-convex surface that causes because of foreign matter is arranged.And, owing to bear hard conating function and binding function, so tendency with the adaptation deficiency of base material is arranged by individual layer.In addition, because therefore the adhesive linkage toughness need attach barrier film, complex procedures aspect continuous production when transfer film is come keeping with the roller shape.
In addition, also disclose and on base material, be coated with UV curable paint in advance, anti-reflection layer (transfer printing layer) has been transferred to the stacked transfer printing of UV (patent documentation 3) on transfer printing body surface by irradiation ultraviolet radiation.In this method, owing on base material, be coated with UV curable paint in advance, during as base material, cause optical deformation by uneven dissolving at the acrylic resin that uses poor solvent resistance, polycarbonate resin.When in addition, record does not form coating, temperature, detailed the creating conditions such as mode that are coated with.
In addition, disclose on anti-reflection layer (transfer printing layer), be coated with UV curable paint in advance after, fit to base material, by irradiation ultraviolet radiation anti-reflection layer is transferred to method (referring to patent documentation 4) on the base material.This method is owing to directly be coated with UV curable paint to anti-reflection layer, has the adaptation that is difficult to obtain duplexer, can not improve productive problem.Be coated with the method for ultra-violet solidified mixture when in addition, not having specifically openly to form coating.
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.This method is favourable stepped construction because anti-reflection layer is connected with protective layer for high rigidityization, but in order to realize high rigidityization; need to increase the thickness of protective layer; therefore, produce bigger distortion (warpage), be difficult to obtain level and smooth face because of film shrinks.
Especially, owing to be easy to observe significant optical deformation in the antireflective layered material, thereby need to propose better manufacture method and the duplexer of outward appearance.
The 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 manufacture method that the purpose of this invention is to provide the laminated resin body of all 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 single face of transparent membrane, be formed with peel ply successively, anti-reflection layer, the active energy of coating no-solvent type ray-curable mixture forms first operation of coating on this adhesive linkage of the transfer film of the first cured coating film layer and adhesive linkage, above-mentioned coated side is fitted to second operation on the resin base material, make the activity in the above-mentioned coating can the ray-curable mixture solidified and form the 3rd operation of the second cured coating film layer, and with second stacked on the above-mentioned resin base material cured coating film layer, 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, the thickness of the preferred 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, the surface temperature of resin base material is 40～100 ℃ in preferred second operation, form the activity of the second cured coating film layer can ray-curable the viscosity of mixture the time with above-mentioned surface temperature uniform temp be 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 a single layer structure, and the refractive index height of the refractive index ratio anti-reflection layer of the first cured coating film layer.
The 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 make the duplexer of the volatilization of the solvent that does not carry out adhesive linkage with simple device, high productivity ground.
And then, can provide that optical deformation is few, the sneaking into and the antireflection laminated resin body of few surface defects such as foreign matter defective 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 single face on resin base material surface.
The cured coating film layer is the layer that improves the marresistance of laminated resin surface, is that the hardening mixtures that will be made of the various curing compounds that bring this marresistance is solidified into membranaceous layer.Hardening mixtures as the first cured coating film layer raw material, can exemplify the hardening mixtures that the curing compound by the radical polymerization syzygy such as ultra-violet solidified mixture as described later constitutes, perhaps the hardening mixture that constitutes by condensation polymerization hardening compounds such as alkoxy silane, alkylalkoxy silanes.Preferably electron beam, radioactive ray, ultraviolet isoreactivity can solidify by ray these curing property compounds by for example shining, and perhaps solidify by heating.These curing property compounds can be distinguished use separately, also multiple compound with curing property can be used in combination.In addition, for convenience, the situation that curing property compound is used separately is also referred to as " hardening mixtures ".
The second cured coating film layer can be by making active can the ray-curable mixture solidified obtaining.Among the present invention, consider that from productivity and rerum natura aspect the preferred second cured coating film layer solidifies by ultraviolet ray.Below ultra-violet solidified mixture is described.
From productive angle, preferably use the ultra-violet solidified mixture that constitutes by compound that has 2 (methyl) acryloxies in the molecule at least and light trigger as ultra-violet solidified mixture.
For example, as the main compound of the compound that has 2 (methyl) acryloxies in the molecule at least, carboxylate that for example can enumerate the carboxylate that obtains by 1 mole polyalcohol and (methyl) acrylic acid or derivatives thereof more than 2 moles, obtains by polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid or derivatives thereof etc.
In addition, object lesson as the carboxylate that obtains by 1 mole polyalcohol and (methyl) acrylic acid or derivatives thereof more than 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, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1, two (methyl) acrylic acid alkyl alcohol esters such as 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 ester that 3 functional groups such as seven (methyl) acrylic acid tripentaerythritol ester are above.
Further, in the carboxylate that obtains by polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid or derivatives thereof, for example can exemplify as polyalcohol and polybasic carboxylic acid or its acid anhydrides and (methyl) acrylic acid preferred compositions: 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/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.
Other example as the compound that has 2 (methyl) acryloxies in the molecule at least, can exemplify by the 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 vulcabond such as trimethyl hexamethylene diisocyanate and the polyisocyanates that obtains, with 2-ethoxy (methyl) acrylate more than 3 moles, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl-3-methoxy-propyl (methyl) acrylate, N-methylol (methyl) acrylamide, N-hydroxyl (methyl) acrylamide, 15,3-glycerine-1,3-two (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; the benzoin ethylether; the benzoin isopropyl ether; the benzoin isobutyl ether; 3-hydroxy-2-butanone; butyroin; the toluene accidental cause; benzyl; benzophenone; to methoxy benzophenone; 2; the 2-diethoxy acetophenone; α; alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone; the aminomethyl phenyl glyoxalic acid; the ethylphenyl glyoxalic acid; 4; 4 '-two (dimethylamino) benzophenone; 1-hydroxyl-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl-1-phenyl-propane-carbonyls such as 1-ketone; tetramethylthiuram monosulfide; sulphur compounds such as tetramethylthiuram disulfide; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide; phosphorus compounds such as benzoyl diethoxy phosphine oxide.
The addition of light trigger is more than the 0.1 quality % in ultra-violet solidified mixture 100 quality % preferably from the angle because of the curing of ultraviolet ray irradiation, is preferably below the 10 quality % from the angle of the good tone of keeping the cured coating film layer.In addition, also can use two or more light triggers simultaneously.
In ultra-violet solidified mixture, can also add smoothing preparation, levelling agent, inorganic fine particles, light stabilizer various compositions such as (ultra-violet absorber, HALS etc.) as required.From the viewpoint of the duplexer transparency, these addition is preferably below the 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.In this scope, have sufficient surface hardness, make that because of being coated with rete the warpage of film is 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.In this scope, have sufficient surface hardness, make that because of being coated with rete the warpage of duplexer is few.In addition, the appearance defective that does not also cause because of sneaking into of foreign matter or bubble.
The viscosity that above-mentioned thickness can be by hardening mixtures, the pressure of squeeze roll, extrusion speed etc. are regulated.In addition, described hardening mixtures can be adjusted thickness by the concentration of setting solid constituent when containing solvent.
Anti-reflection layer is so long as have below 20% of incident light that reverberation is suppressed to the laminated resin surface, and preferred below 10%, more preferably the function below 5% gets final product, and can be made of any material.In order to give such function, can exemplify the whole bag of tricks such as method that for example form the stepped construction of film with two or more different refractivities.If anti-reflection layer be two-layer more than, then easier reduction reflectivity, thereby preferred.
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 is about 1.3～1.5 low-index layer as the refractive index in the outmost surface that faces air, and the refractive index of the high refractive index layer that exists in the base material side of low-index layer is 1.6～2.0.In this scope, can fully suppress reflection of incident light 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 in this scope, just can fully suppress the reverberation of discernible wavelength.
In addition, also can be that anti-reflection layer is as the individual layer of low-index layer with the hard conating of the first cured coating film layer as the high index of refraction higher than the refractive index of anti-reflection layer.In this case, the refractive index that preferably faces the outmost surface of air is about 1.3～1.5 low-index layer, and the refractive index of the first cured coating film layer is 1.6～2.0.As long as in this scope, just can fully suppress reflection of incident light light.Such anti-reflection layer is the structure of individual layer, the refractive index height of the refractive index ratio anti-reflection layer of the first cured coating film layer, thereby make the reflection of light rate of wavelength of visible region be controlled in below the certain value easily, thereby the light of particular color is outstanding in can inhibitory reflex light.
Thickness for above-mentioned low-index layer, high index of refraction hard conating is not particularly limited, but the thickness of preferred 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.In this scope, have sufficient surface hardness, make that because of being coated with rete the warpage of film is few, outward appearance is also good.
In addition, with the first cured coating film layer as the high index of refraction hard conating, with anti-reflection layer during as the individual layer of 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 the refractive index of high index of refraction hard conating and resin base material.
As the composition that forms low-index layer, preferred index is about 1.3～1.5 material, the layer of the siloxane bond main body that constitutes by the curing compound of condensation polymerization system such as alkoxy silane, alkylalkoxy silane for example, 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, consider, preferably in the layer of siloxane-based resin, add silica colloidal from the aspect of further realization low-refractionization.Silica colloidal is that the particulate with porous silica and/or non-porous matter silica is dispersed in the decentralized medium colloidal solution of formation.Wherein, porous matter carbon dioxide is to be porous in the particle or hollow, inside contain the low-density silicon dioxide of 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 order to reduce the refractive index of low-index layer, more preferably use porous silica among the present invention.
And, also can in above-mentioned ultra-violet solidified mixture, add silica colloidal and solidify the formation low-index layer.In addition, the silica colloidal that also can use the surface to be handled by silane coupling agent.
These hardening compounds for example can solidify by ray by irradiating electron beam, radioactive ray, ultraviolet isoreactivity, perhaps solidify by heating.These curing property compounds can be distinguished use separately, also multiple compound with curing property can be used in combination.
As the composition that forms high index of refraction, preferred index is about 1.6～2.0 material, can use to contain the material that himself hydrolysis 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 of expression.In the 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 titanium, aluminium, zirconium, tin etc., preferred especially 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 that forms metal oxide, add ZrO 2, TiO 2, NbO, ITO, ATO, SbO 2, In 2O 3, SnO 2With at least a high refractive index metal oxide particulate among the ZnO, be preferred from the angle that reaches further high index of refractionization.
And then, also can add metal oxide microparticle of high index of refraction and solidify the formation high refractive index layer to above-mentioned ultra-violet solidified mixture.Also can use metal oxide microparticle of the high index of refraction after the surface treatment in addition.
These hardening compounds for example can solidify by ray by irradiating electron beam, radioactive ray, ultraviolet isoreactivity, perhaps solidify by heating.These curing property compounds can be distinguished use separately, also multiple compound with curing property can be used in combination.
In addition, as the method for not using atomic high index of refractionization, exemplify use have fluorenes (fluorene) skeleton, organic compound that the activity of the halogen atom beyond the sulphur atom, fluorine, aromatic series skeleton etc. can ray-curable.As organic compound, exemplify fluorinated acrylate (fluorine acrylate) with fluorene skeleton.
Then, for example can list as adhesive linkage: 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 thermoplastic resins such as resin.
Be that at least a resin in the resin constitutes preferably by in polyamide, mixing butyral resin, rosin series resin and epoxy.Perhaps also can be that to mix butyral resin, rosin series resin and epoxy in polyurethane resin be that at least a resin in the resin constitutes, can also be that to mix butyral resin, rosin series resin and epoxy in the mixture of polyamide and polyurethane resin be that at least a resin in the resin constitutes.Under 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 is made of thermoplastic resin, the top layer does not have viscosity, and because transfer film as described later can come keeping with the roller shape, thereby be fit to produce continuously, productivity is good
Adhesive linkage can be dissolved in solvent with above-mentioned resin, forms as bonding agent.In this case, if solvent soaks into to the first cured coating film layer, the interface of adhesive linkage and hardened coating film layer disappears, and makes the defective of interference fringe disappear, thereby preferred.
In addition, if add the particulate of high index of refraction, can be the value between the refractive index of the refractive index of above-mentioned high index of refraction hard conating and resin base material to adhesive linkage.
As resin base material, can exemplify polymethyl methacrylate for example, Merlon, be copolymer, the polystyrene of main composition composition, the formed products of styrene-methylmethacrylate copolymer with the methyl methacrylate units.In addition, also can add colouring agent, light diffusing agent etc. in the resin base material.The thickness of laminated resin body is considered from the mechanical strength aspect, is preferably more than the 0.2mm, considers from the productivity aspect to be preferably below the 10mm.
In addition, on this laminated resin body, as required, other functional layer of antifouling film etc. can also for example be set on the surface of anti-reflection layer.For example when forming antifouling film, can exemplify commercially available antifouling paint of on resin base material coating and dry and method (damp process) formation, perhaps physical vapor such as vapour deposition method, sputtering method method of piling etc.In addition, the surface of anti-reflection layer can be smooth, also can be 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 to use transfer film to obtain the method for duplexer, and make the method for film with in the past infusion process, rolling method, spin-coating method etc. successively and compare, be favourable from the viewpoint of productivity, appearance.
Transfer film is elaborated.
Can utilize known film as transparent membrane.In addition, suit so long as have the film of fissility, if but fissility is insufficient, can peel ply be set at film surface.
As transparent membrane, can exemplify built up membranes such as pet film, polypropylene film, polycarbonate film, polystyrene film, polyamide film, polyamidoimide film, polyethylene film, polyvinyl chloride film, cellulose-based film such as acetyl cellulose film, tympans such as Japan paper such as glassine paper, glassine and foreign paper, the perhaps 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, the aspect that does not have the transfer film of fold, be full of cracks etc. from easy manufacturing, be preferably more than the 4 μ m, more preferably more than the 12 μ m, be preferably especially more than the 30 μ m, below the preferred in addition 500 μ m, more preferably below the 150 μ m, below the preferred especially 120 μ m.
In order to improve the fissility of these transparent membranes, form peel ply.The formation material of peel ply can select to use polymer, wax of known formation peel ply etc. aptly.Formation method as peel ply, for example paraffin is arranged, acrylic acid series, polyurethane series, silicon system, melamine system, urea system, urea-melamine system, cellulose-based, the resin of benzoguanamine system etc. and surfactant separately or these mixture as principal component, be dissolved in organic solvent or the water, form coating, coating is passed through woodburytype, silk screen print method, common printing processes such as hectographic printing method are coated on the above-mentioned matrix film, and it is dry (with thermosetting resin, uv curing resin, the electronic beam curing resin, radiation-curable resin etc. is solidified into curing property and films) form the method for peel ply.The thickness of peel ply is not particularly limited, the suitable scope that adopts about 0.1～3 μ m.Peel ply is crossed when approaching, and is difficult to peel off, and when opposite peel ply is blocked up, peels off too easily, can cause the disengaging of each layer on the film before transfer printing, thereby not preferred.
Then, on peel ply, stack gradually above-mentioned anti-reflection layer, the first cured coating film layer, adhesive linkage by known coating formation method, thereby make transfer film.Usually this transfer film is rolled into the roller shape.
When transfer film is rolled into the roller shape, can makes and to be formed with above-mentioned anti-reflection layer, the first cured coating film layer, adhesive linkage (below be referred to as " transfer printing layer ") side and to be positioned at the transfer film of reeling the inboard and to 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 big, when becoming circular arc inboard when this hardened coating film layer generation warpage of resin base material, be positioned at inboard transfer film by using transfer printing layer is wound into, thereby can suppress the warpage of the duplexer of gained.Here " circular arc " is meant " this circular arc that warpage becomes circular-arc duplexer ".
In addition, the duplexer that will be provided with cured coating film (hard conating) by casting polymerization single face is during as resin base material, can warpage take place and makes the hard conating side become the outside of circular arc.In this case, by when the face side that hard conating is not set forms transfer printing layer, use is wound into transfer printing layer and is positioned at inboard transfer film, and further use the minimum polyurethane series macromonomer of above-mentioned cure shrinkage etc. aptly, form the second cured coating film layer, thereby can suppress the warpage of the duplexer that obtained.
By adopting such method,, also can make the little duplexer of warpage simply even in the thicker situation of the thickness of solidified coating film.
As 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 be coated with, slit die etc., with the ultra-violet solidified mixture of no-solvent type vertically and the coating of wire ground, form coating with respect to the direct of travel (direction of the supply) of film.That is, the supply unit that preferably will be used to be coated with above-mentioned ultra-violet solidified mixture is coated with in mobile parallel on vertical direction and the coated face at film with respect to the direct of travel of film.When forming the method for coating, if with respect to the direct of travel of film abreast and the coating of wire ground, the situation that is produced optical deformation by the uneven dissolution of base material is arranged to film.
In addition, entrained air in order to prevent to fit, the preferably excessive ultra-violet solidified mixture of coating on film.
Then, in second operation, described coated side is attached on the resin base material.As the method for this attaching, exemplify the method for carrying out crimping by rubber rollers.
As forming the method that cated film and resin base material are fitted, have for example film, resin base material in method that the state of carrying is respectively fitted by above-mentioned rubber rollers crimping, the method for under the overlapping state of film and resin base material, fitting etc. by above-mentioned rubber rollers crimping.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 the rubber rollers crimping under the overlapping state of film and resin base material preferably adopts when batch mode.
In addition, in the method for above-mentioned formation coating, put down in writing " with respect to the direct of travel of film vertically and the coating of wire ground " be elaborated.
Adopting when film, resin base material carried out method that crimping fits by above-mentioned rubber rollers 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 ground be coated with.
On the other hand, adopting under the overlapping state of film and resin base material when carrying out method that crimping fits by rubber rollers, the direct of travel of film is to be overlapped into integrated and direction that carry with resin base material, identical with the direct of travel of resin base material, therefore be recited as the direct of travel of film here for convenience.With respect to the direct of travel of this film, on above-mentioned adhesive linkage,, form coating in advance at vertical direction and wire ground coating said mixture.
In second operation, the surface temperature of resin base material is preferably 40 ℃～100 ℃.In this temperature range, adaptation is good, and the hardness that causes less than the excessive dissolution because of base material descends the xanthochromia of also not filming.The surface temperature of resin base material can be adjusted by design temperature, the heat time heating time of heating part.Method of temperature as measuring resin base material exemplifies known method 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 temperature identical with the surface temperature of resin base material is 15～120mPas.In this scope, adaptation is also good, does not also have optical deformation.Composition, temperature by suitable adjustment above-mentioned composition are controlled in the above-mentioned range of viscosities.In addition, do not have because of sneaking into the appearance defective that bubble causes yet.In addition, viscosity can be adjusted by the composition of above-mentioned hardening mixtures.
In above-mentioned second operation, after attaching transfer film on the mould, as the 3rd operation, across the transfer film irradiation is active can ray, make that the activity in the described coating can the ray-curable mixture solidified, become the second cured coating film layer.As active energy ray, preferred aforesaid ultraviolet ray.When irradiation ultraviolet radiation, can use ultraviolet lamp.As ultraviolet lamp, for example exemplify high-pressure mercury-vapor lamp, metal halide lamp, fluorescent ultra-violet lamp etc.Curing by the ultraviolet ray irradiation, can carry out a stage across transfer film, perhaps also can be divided into for two stages implements, promptly across transfer film carry out the phase I curing (the 3rd operation), peel off transparent membrane (the 4th operation), further irradiation ultraviolet radiation carries out the curing etc. of second stage afterwards.During curable resin beyond using ultra-violet solidified mixture, for example can suitably select the electron beam, radioactive ray isoreactivity can ray, shine across transfer film and solidify.
Among the present invention, after in the 3rd operation, after hardening mixtures is solidified, forming the second cured coating film layer, as the 4th operation, the transparent membrane of transfer film is peeled off, stay the second cured coating film layer, adhesive linkage, first cured coating film layer and the anti-reflection layer that on resin base material, are provided with.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 the resin base material transfer printing.Wherein, peel ply remains in the transparent membrane side.
The laminated resin body that is obtained by said method is applicable in the purposes such as front panel of display.
Embodiment
Below, describe the present invention in detail by embodiment, but the present invention is not limited thereto, here, the abbreviation of the compound that uses in embodiment and the comparative example is as follows.
" TAS ": butanedioic acid/trimethylolethane/15: 4 condensation mixture of acrylic acid mol ratio (Osaka organic chemistry industry (strain) manufacturing)
" C6DA ": 1,6-hexanediyl ester (Osaka organic chemistry industry (strain) manufacturing)
" M305 ": pentaerythritol triacrylate M-305 (East Asia synthetic (strain) makes)
" M309 ": trimethylolpropane triacrylate M-309 (East Asia synthetic (strain) makes)
" M400 ": six acrylic acid dipentaerythritol ester M-400 (East Asia synthetic (strain) makes)
" Art Resin SUX-1 ": polyurethane series macromonomer (industry on the root (strain) manufacturing)
" Optool AR ": fluorine is the low-refraction acrylate, solid component concentration 15 weight %, methyl isobutyl ketone solution (the Daikin product of changing into are peddled (strain) and made)
" OGSOL EA-F5010 ": the acrylate (Osaka aerochemistry (strain) manufacturing) that contains fluorene skeleton
" DIANAL BR-80 ": acrylic resin (the beautiful sun of Mitsubishi (strain) manufacturing)
" DAROCUR TPO ": 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (vapour crust Japan (strain) makes)
" gorgeous good solid (Irgacure) 184 ": 1-hydroxyl-cyclohexyl-phenyl ketone (vapour crust Japan (strain) makes)
" ACRYLITE EX001 ": acrylic resin board (the beautiful sun of Mitsubishi (strain) manufacturing)
" ACRYLITE MR001 ": the polymethacrylates of one-side band hard conating (the beautiful sun of Mitsubishi (strain) manufacturing)
In addition, the evaluation of rerum natura is based on that following method carries out among the embodiment.
Viscosity measurement
Measure the viscosity of the rotation number 6rpm of Brookfield viscometer at each temperature.Wherein, viscosity is to measure under the temperature identical with the temperature of base material.
The temperature measuring of resin base material
Base material heated gives heating, use non-contact type land surface pyrometer (CHINO (strain) manufacturing), 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 make measures full light transmission rate according to the assay method shown in the JIS K7361-1, measures mist degree according to the assay method shown in the JIS K7136.
Marresistance
Variation (Δ haze) according to the mist degree before and after the scoring test is estimated.Promptly, the diameter that #000 steel wool (steel wool) will be installed is that the circular pad of 25.4mm is placed on the cured coating film laminar surface of duplexer, under the loading of 500g, carry out 10 times of 20mm distance scratches back and forth, obtain before the scratch and mist degree after the scratch poor by following formula (1).
[Δ haze (%)]=[scratch back haze value (%)]-[haze value (%) before the scratch] ... (1)
In addition, number goes out the bar number of the scar of test back sample.
Antireflection property is estimated
After with sand paper roughening being carried out at the back side of sheet, be coated with delustring black spray (anti-glare black spray), with it as sample, use spectrophotometer (Hitachi's manufacturing, " U-4000 "), under the scope of 5 ° of incidence angles, wavelength 380～780nm, according to the assay method shown in the JIS R3106, the reflectivity on working sample surface.
Adaptation is estimated
(cross cut test) (JIS K5600-5-6) estimates according to adhesion test.Carry out 4 tests repeatedly, be expressed as 4 totals of number positional unstripped and residual in each 25 position.
The ocular estimate on top layer
Whether the Visual Confirmation sample surfaces has bubble, foreign matter.
Zero: do not sneak into bubble, do not have foreign matter
△: do not sneak into bubble, foreign matter is arranged
*: bubble is arranged, foreign matter is arranged
Optical deformation
Whether Visual Confirmation has sample deformation
Zero: do not have deformation
*: deformation is arranged
The warpage evaluation of laminated resin body
In 80 ℃ environment, 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 the dull and stereotyped distance of measuring from the sheet warpage to the sample that goes up.
Zero: below the amount of warpage 5mm
*: more than the amount of warpage 5mm
The assay method of refractive index and thickness
For anti-reflection layer, cured coating film layer, the thickness-refractive index measuring apparatus (style 2010, prism coupler) of use Metricon corporate system is determined at refractive index and the thickness under the 594nm laser.
Film thickness measuring method
The determining film thickness of not measuring the sample of refractive index is the sample that cuts out 100nm thickness with microtome, is undertaken by the transmission electron microscope observation.The JEM-1010 that transmission electron microscope uses NEC (JEOL) to make measures.
Embodiment 1
(tail vat industry (strain) is made to the antireflection transfer film, trade name: STEP PAR-1, sequential cascade according to film (PET film), peel ply, anti-reflection layer, cured coating film layer, adhesive linkage) adhesive linkage side with respect to the film direct of travel vertically and the coating that formed by ultra-violet solidified mixture of wire ground coating, described ultra-violet solidified mixture is made of 35 mass parts TAS, 30 mass parts C6DA, 10 mass parts M305,25 mass parts M400,2 mass parts DAROCUR TPO, uses rod to be coated with machine (No. 50) and forms planar coating.In addition, the antireflection transfer film is not directly to use to be rolled into the film of roller shape, but cuts out a part from the film that is rolled into the roller shape, uses and takes care of into plane film.
Then, on the acrylic resin base material that is warmed to 60 ℃ 2mm thickness of slab (ACRYLITE EX001), to be formed with the antireflection transfer film of above-mentioned coating, after making that coating overlaps towards this resin base material side and with above-mentioned transfer film, under the rubber rollers of 40 ° of the JIS hardness that is fixed, with certain speed by (direction of advance of above-mentioned film), extrude unnecessary coating and make when the thickness of filming that comprises ultra-violet solidified mixture is 15 μ m, push the feasible bubble that do not contain.
In addition, the thickness of filming that comprises ultra-violet solidified mixture is calculated from the quantity delivered and the developed area of this ultra-violet solidified mixture.
Then, be warmed under 60 ℃ the state, after 120 seconds, when being output as across above-mentioned transfer film under the metal halide lamp of 9.6kW, the position of 20cm being passed through with the speed of 2.5m/min, irradiation ultraviolet radiation, carry out the curing 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 all are transferred on the second hardened coating film layer laminated resin body that obtain having anti-reflection layer, the first cured coating film layer, adhesive linkage, the second cured coating film layer and acrylic resin base material constitutes 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, have the duplexer on good top layer.The increment of the mist degree after the anti-reflection layer scratch is 0.1%, and the bar number of scar is 3.Minimum reflectance is 1% when the wavelength of 580nm, and the result who carries out fitness test in addition is peeling off of not filming, and adaptation is good.The result who carries out camber test is the not enough 5mm of amount of warpage.The result is as shown in table 1.
Embodiment 2
Except the thickness with the second cured coating film layer among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 3
Except the thickness with the second cured coating film layer among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 4
Except the temperature with the resin base material among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 5
Except the ultra-violet solidified mixture among the embodiment 1 is changed to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 6
Except the ultra-violet solidified mixture among the embodiment 1 is changed to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 7
Except the ultra-violet solidified mixture among the embodiment 1 is changed to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 8
Except the temperature with the resin base material among the embodiment 7 change to as shown in table 1, make laminated resin body similarly to Example 7.The results are shown in table 1.
Embodiment 9
Except the ultra-violet solidified mixture among the embodiment 1 is changed to as shown in table 1, make laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 10
(tail vat industry (strain) is made except the antireflection transfer film among the embodiment 1 is changed to, trade name: STEP PAR-2, sequential cascade according to film (PET film), peel ply, anti-reflection layer, cured coating film layer, adhesive linkage) outside, makes laminated resin body similarly to Example 1.The results are shown in table 1.
Embodiment 11
(Supreme Being people changes into (strain) and makes, trade name: PanliteAD-5503), make laminated resin body similarly to Example 1 except the resin base material among the embodiment 1 being changed to the thick polycarbonate resin of 2mm.The results are shown in table 1.
Embodiment 12
Except the thickness with the second cured coating film layer among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.The thickness of the second cured coating film layer is because less than 3 μ m, and to compare hardness low with embodiment 1.In addition, with the foreign matter defective on embodiment 1 different generations top layer.The results are shown in table 2.
Embodiment 13
Except the thickness with the second cured coating film layer among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.The thickness of the second cured coating film layer is owing to being more than the 30 μ m, and is different with embodiment 1, produces warpage.The results are shown in table 2.
Embodiment 14
Except the surface temperature with the base material among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.Because 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 with the base material among the embodiment 1 change to as shown in table 1, make laminated resin body similarly to Example 1.Because substrate surface temperature is more than 100 ℃, to compare with embodiment 1 excessive base material dissolving takes place, hardness is low.In addition, different because the viscosity of ultra-violet solidified mixture is below the 15mPas with embodiment 1, produce optical deformation.The results are shown in table 2.
Embodiment 16
Except the ultraviolet curing mixture among the embodiment 1 is formed change to as shown in table 1, make laminated resin body similarly to Example 1.Because the viscosity of ultra-violet solidified mixture is more than the 120mPas, compares with embodiment 1, adaptation is low.In addition, different with embodiment 1, produce the foreign matter defective on top layer.The results are shown in table 2.
Embodiment 17
Except with among the embodiment 1, temperature improves, make the viscosity of ultraviolet curing mixture change to as shown in table 2 outside, make laminated resin body similarly to Example 1.Because the viscosity of ultra-violet solidified mixture is below the 15mPas, and is different with embodiment 1, produce optical deformation.
Embodiment 18
Except with among the embodiment 1, with respect to the film direct of travel abreast and wire ground coating, and be coated with machine with No. 50 rods and form outside the planar coating, make laminated resin body similarly to Example 1.When being coated with machine with rod and forming planar coating, forming part does not have applied position.Therefore, this laminated resin body is different with embodiment 1, produces the optical deformation of strip.The results are shown in table 2.
Embodiment 19
Except with the thickness of the second cured coating film layer among the embodiment 1, form change to as shown in table 3, make laminated resin body similarly to Example 1.Though the thickness of the second cured coating film layer is more than the 30 μ m, owing to used polyurethane macromolecular monomer (Art Resin SUX-1), warpage does not take place.The results are shown in table 3.
Embodiment 20
Except use with among the embodiment 13, the antireflection transfer film the film that is rolled into the roller shape on the paper tube, makes laminated resin body with following content similarly to Example 13.
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 the inboard
Even the thickness of the second cured coating film layer is more than the 30 μ m, do not produce warpage in the laminated resin body yet.The results are shown in table 3.
Embodiment 21
Except with among the embodiment 20, use ACRYLITE MR100 as resin base material, 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 to it, make laminated resin body similarly to Example 20.Can eliminate the warpage of ACRYLITE MR100 self, that is, having eliminated anti-reflection layer formation face side becomes the inboard such warpage of circular arc.The results are shown in table 3.
Embodiment 22
Except with the coiling direction of the transfer printing layer among the embodiment 21 towards the outside of roller, make laminated resin body similarly to Example 21.Different with embodiment 21, there is not the inhibition effect of warpage, produce the warpage of duplexer.The results are shown in table 3.
Embodiment 23
Except with among the embodiment 1, the antireflection transfer film changes to the following individual layer antireflective film that only has low-index layer, makes laminated resin body similarly to Example 1.
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
Add MIBK (methyl iso-butyl ketone (MIBK)) in OGSOL EA-F5010, 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
With 50 mass parts DIANAL BR-80 and (Osaka, Sumitomo cement (strain) manufacturing 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 No. 4 rods to be coated with machine, (the above-mentioned low-refraction coating of coating was gone up by beautiful smooth Co., Ltd. (Reiko Co. Ltd.) makes trade name AC-J), 80 ℃ of dryings 5 minutes to the PET film that posts the melamine peel ply of 100 μ m.Afterwards, under the high-pressure mercury-vapor lamp of 9.6kW, the position of 20cm is passed through, form low-index layer with the speed of 2.5m/min.Its refractive index is 1.38.
Then, use No. 4 rods to be coated with machine, the above-mentioned high index of refraction coating of coating on low-index layer was 80 ℃ of dryings 5 minutes.Afterwards, under the high-pressure mercury-vapor lamp of 9.6kW, the position of 20cm is passed through, form the high index of refraction hard conating with the speed of 2.5m/min.Its refractive index is 1.60.
Then, on high refractive index layer, use No. 4 rods to be coated with machine coating adhesive linkage and form coating,, form adhesive linkage 80 ℃ of dryings 5 minutes.
From the determining film thickness result of resulting laminated resin body as can be known, 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 be the antireflective layered material of individual layer, reflected colour is thinner than the duplexer of other embodiment.
Comparative example 1
(tail vat industry (strain) is made with the antireflection transfer film, trade name: (make by the beautiful sun of Mitsubishi (strain) as the methacrylic resin base material for adhesive linkage one side STEP PAR-1), trade name: side ACRYLITE EX001), after the applying, use oil pressure forming machine (village department iron steel (strain) manufacturing) 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 30 ℃ after, stripping film.For resulting laminated resin body owing to there is not the second hardened coating film layer, so hardness deficiency.In addition, produce the foreign matter defective 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,, make laminated resin body similarly to Example 1 except using outside the antireflection transfer film do not have adhesive linkage (the commodity STEP PAR-1 by name that tail vat industry (strain) is made impregnated in the acetone 10 minutes, removes adhesive linkage).Owing to there is not adhesive linkage, adaptation is insufficient.The results are shown in table 2.
Figure BPA00001348236600211
Figure BPA00001348236600221
Table 3
Figure BPA00001348236600231
The possibility of utilizing on the industry
Laminated resin body of the present invention is suitable for the front panel of various displays such as CRT, LCD, OLED display, plasma display, projection TV, and the front panel of the information display section of information terminal such as mobile phone, portable music player, notebook computer etc.

Claims (5)

1. the manufacture method of a laminated resin body is characterized in that, comprising:
On this adhesive linkage of the transfer film that is formed with peel ply, anti-reflection layer, the first cured coating film layer and adhesive linkage on the single face of transparent membrane successively, the active energy of coating no-solvent type ray-curable mixture forms first operation of coating,
Described coated side is fitted to second operation on the resin base material,
Make the activity in the described coating can the ray-curable mixture solidified and form the 3rd operation of the second cured coating film layer, and
The 4th operation that stays second stacked on the described resin base material cured coating film layer, 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, the surface temperature of resin base material is 40 ℃～100 ℃ in second operation, form the activity of the second cured coating film layer can ray-curable the viscosity of mixture the time with described surface temperature uniform temp be 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 a single layer structure, and the refractive index height of the refractive index ratio anti-reflection layer of the first cured coating film layer.
CN200980140981.7A 2008-08-29 2009-08-26 Method for manufacture of resin laminated body Expired - Fee Related CN102186670B (en)

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JP2008221993 2008-08-29
JP2008-221993 2008-08-29
JP2009090894A JP2010076423A (en) 2008-08-29 2009-04-03 Resin laminated body and method for manufacturing the same
JP2009-090894 2009-04-03
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
JP2010076423A (en) 2010-04-08
WO2010024274A1 (en) 2010-03-04
KR101578254B1 (en) 2015-12-16
CN102186670B (en) 2014-02-12
KR20110063495A (en) 2011-06-10
TW201012646A (en) 2010-04-01

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