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

Definitions

• the present invention relates to a resin laminate having a plate shape and the like excellent in transparency, antireflection performance, and scratch resistance, which is suitable for uses such as a front plate of a display, and a method for producing the same.
• Transparent resins such as acrylic resins and polycarbonate resins are widely used as industrial materials and building materials. Particularly in recent years, it has been used as a front plate for various displays such as CRTs, liquid crystal televisions and plasma displays because of its transparency and impact resistance.
• an anti-reflection function has been cited as one of the important performance requirements for a front panel, and the anti-reflection function reduces reflected light from indoor fluorescent lamps and the like reflected on the front panel, and displays images. This is a function for clearer display.
• the light reflected by the high refractive index layer and the low refractive index layer are formed by forming an antireflection film having a structure having a low refractive index layer on the surface of the high refractive index layer. It is possible to reduce the reflected light by using the optical path difference between the light reflected by the light and causing the light to interfere with each other.
• a conventional antireflection film having such an antireflection function is usually formed by sequentially laminating a high refractive index layer and a low refractive index layer on a plastic substrate by a dip method. Therefore, the production efficiency is low, which has been a cause of cost increase when producing an antireflection film. Further, when the dip method is adopted, the film thickness is likely to be uneven depending on the speed at which the plastic substrate is pulled up from the dip solution, and it is usually difficult to obtain a uniform nano-order film.
• the antireflection layer (transfer layer) formed on the release material is thermally transferred or pressure-sensitive transferred to the surface of the transfer target.
• a method is disclosed (see Patent Document 1).
• a large-scale heating facility is required, and it takes time to heat, resulting in a problem that the production speed cannot be increased.
• air bubbles are likely to be caught between the base material and the antireflection layer (transfer layer), and surface irregularities due to foreign matter are likely to occur.
• UV lamination transfer method A method of peeling and transferring the antireflection layer to a transfer surface (hereinafter referred to as “UV lamination transfer method”) is disclosed (see Patent Document 2). Although this method can perform transfer with relatively simple equipment and high productivity, it has been necessary to volatilize the solvent when forming the adhesive layer. In addition, since the viscosity of the adhesive used for the adhesive layer is very high, there is a problem that air bubbles are easily bitten and surface irregularities due to foreign matter are likely to occur.
• the hard coat function and the adhesive function are carried by a single layer, there is a tendency that the adhesion to the substrate is insufficient.
• the adhesive layer has a tack, it is necessary to affix the separator film in order to store the transfer film in a roll shape, and the process is complicated for continuous production.
• a UV lamination transfer method in which an ultraviolet curable coating is applied in advance to a substrate, and an antireflection layer (transfer layer) is transferred to the surface of the transfer medium by ultraviolet irradiation (see Patent Document 3).
• an ultraviolet curable coating material is applied to the base material in advance, when an acrylic resin or a polycarbonate resin having poor solvent resistance is used as the base material, optical distortion due to non-uniform dissolution is caused.
• detailed manufacturing conditions such as temperature and a method of coating when forming the coating layer are not described.
• Patent Document 5 a method is disclosed in which an antireflection layer, a protective layer and an adhesive layer are formed in advance on a film and transferred to a substrate.
• This method is a laminated structure advantageous for increasing the hardness because the antireflection layer and the protective layer are in contact with each other.
• it is necessary to increase the thickness of the protective layer. It was greatly deformed (warped) and it was difficult to obtain a smooth surface.
• An object of the present invention is to provide a method for producing a resin laminate having a plate shape or the like excellent in transparency, antireflection performance, adhesion, scratch resistance, productivity, and appearance.
• the present invention is a solventless active energy ray curing on the adhesive layer of a transfer film in which a release layer, an antireflection layer, a first cured coating layer, and an adhesive layer are sequentially formed on one side of a transparent film.
• a first step of applying an adhesive mixture to form a coating layer a second step of sticking the coating layer side to a resin substrate, and a second curing by curing the active energy ray-curable mixture in the coating layer
• a fourth step of removing the resin laminate is a solventless active energy ray curing on the adhesive layer of a transfer film in which a release layer, an antireflection layer, a first cured coating layer, and an adhesive layer are sequentially formed on one side of a transparent film.
• the above-described production method has a thickness of the first cured coating film layer of 0.5 ⁇ m to 10 ⁇ m and a thickness of the second cured coating film layer of 0.5 ⁇ m to 40 ⁇ m.
• the surface temperature of the resin substrate is set to 40 ° C. to 100 ° C., and the viscosity of the active energy ray-curable mixture forming the second cured coating film layer at the same temperature as the surface temperature is 15 to 120 mPa ⁇
• the production method is preferably s.
• the manufacturing method has a structure in which the antireflection layer has two or more layers.
• the antireflection layer has a single layer structure, and the refractive index of the first cured coating layer is higher than the refractive index of the antireflection layer.
• the laminate can be produced with high productivity by a simple apparatus without volatilization of the solvent of the adhesive layer.
• an antireflection resin laminate that has less optical distortion and less surface defects such as air bubble bites and foreign object defects.
• the present invention is a method for producing a resin laminate in which a second cured coating layer, an adhesive layer, a first cured coating layer, and an antireflection layer are sequentially laminated on at least one surface of a resin substrate surface.
• the cured coating film layer improves the scratch resistance of the surface of the resin laminate, and is a film obtained by curing a curable mixture made of various curable compounds that provides this scratch resistance.
• the curable mixture used as a raw material for the first cured coating layer include a curable mixture made of a radical polymerization curable compound such as an ultraviolet curable mixture, which will be described later, and condensation polymerization such as alkoxysilane and alkylalkoxysilane. Mention may be made of curable mixtures comprising curable compounds of the system. These curable compounds are preferably cured by irradiating active energy rays such as an electron beam, radiation and ultraviolet rays, or cured by heating. These curable compounds may be used alone or in combination with a plurality of curable compounds. For convenience, the curable compound is also referred to as a “curable mixture”.
• the second cured coating film layer is obtained by curing the active energy ray-curable mixture.
• the second cured coating film layer is preferably cured by ultraviolet rays from the viewpoints of productivity and physical properties.
• the ultraviolet curable mixture will be described.
• an ultraviolet curable mixture it is preferable from the viewpoint of productivity to use an ultraviolet curable mixture comprising a compound having at least two (meth) acryloyloxy groups in the molecule and a photoinitiator.
• the main compound having at least two (meth) acryloyloxy groups in the molecule is an esterified product obtained from 1 mol of polyhydric alcohol and 2 mol or more of (meth) acrylic acid or a derivative thereof. And esterified products obtained from polyhydric alcohols, polyhydric carboxylic acids or anhydrides thereof, and (meth) acrylic acid or derivatives thereof.
• Di (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6 -Di (meth) acrylates of alkyl diols such as hexanediol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, penta Glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol
• polyhydric alcohol, polyhydric carboxylic acid or anhydride and (meth) acrylic acid or derivative thereof Preferred combinations include, for example, malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (Meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / ( (Meth) acrylic acid, adipic acid / trimethylolethane / (
• compounds having at least two (meth) acryloyloxy groups in the molecule include trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis.
• diisocyanates such as (cyclohexyl isocyanate), isophorone diisocyanate, and trimethylhexamethylene diisocyanate -Methoxypropyl (meth) acrylate, N-methylol (
• Urethane (meth) acrylate; poly [(meth) acryloyloxyethylene] isocyanurate such as di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid; epoxy poly (meth) acrylate; urethane poly (Meth) acrylate; etc. are mentioned.
• (meth) acryl means “methacryl” or “acryl”.
• a macromonomer is preferable, and a urethane macromonomer is more preferable. By using these macromonomers, the warpage of the laminate can be reduced.
• photoinitiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2- Carbonyl compounds such as methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-tri Chill diphenylphosphine oxide, bis (2,
• the addition amount of the photoinitiator is preferably 0.1% by mass or more from the viewpoint of curability by ultraviolet irradiation in 100% by mass of the ultraviolet curable mixture, and 10% by mass from the viewpoint of maintaining a good color tone of the cured coating layer.
• the following is preferred. Two or more photoinitiators may be used in combination.
• Various components such as a slip improver, a leveling agent, inorganic fine particles, a light stabilizer (such as an ultraviolet absorber and HALS) can be further added to the ultraviolet curable mixture as necessary. From the viewpoint of the transparency of the laminate, the addition amount is preferably 10% by mass or less in 100% by mass of the ultraviolet curable mixture.
• the film thickness is preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 7 ⁇ m. In such a range, the film has a sufficient surface hardness, little warpage of the film by the coating layer, and good appearance.
• the film thickness is preferably 0.5 ⁇ m to 40 ⁇ m, and more preferably 3 ⁇ m to 30 ⁇ m. In such a range, the laminate has a sufficient surface hardness and there is little warpage of the laminate due to the cured coating film layer. Further, there is no surface appearance defect due to the inclusion of foreign matter or bubbles.
• the film thickness can be adjusted by the viscosity of the curable mixture, the pressure of the press roll, the press speed, and the like. Moreover, when the said curable mixture contains a solvent, a film thickness can be adjusted by prescribing
• the antireflection layer is composed of any material as long as it has a function of suppressing reflected light to 20% or less, preferably 10% or less, more preferably 5% or less of the incident light on the surface of the resin laminate. May be. In order to provide such a function, for example, various methods such as a method of forming a laminated structure of films having two or more different refractive indexes can be cited. It is preferable that the antireflection layer has two or more layers because it is easy to reduce the reflectance.
• the refractive index of each film is not particularly limited.
• the refractive index of the outermost surface facing the air is 1.3 to 1.
• the refractive index of the low refractive index layer of about 0.5 and the high refractive index layer present on the substrate side of the low refractive index layer is preferably 1.6 to 2.0. If it is this range, the reflected light of incident light can fully be suppressed.
• the thickness of the low refractive index layer and the high refractive index layer is not particularly limited, but is preferably 50 nm to 200 nm, more preferably 70 nm to 150 nm. If it is this range, the reflected light of the wavelength visually recognized can be fully suppressed.
• the first cured coating layer may be a high refractive index hard coat layer having a higher refractive index than the antireflection layer, and the antireflection layer may be a single layer of a low refractive index layer.
• the refractive index of the outermost surface facing the air is a low refractive index layer of about 1.3 to 1.5
• the refractive index of the first cured coating film layer is 1.6 to 2.0. Preferably there is. If it is this range, the reflected light of incident light can fully be suppressed.
• the reflectance of light having a wavelength in the visible light region is set to a certain value or less. Since it becomes easy to do, it can suppress that the specific color of reflected light stands out.
• the thickness of the low refractive index layer and the high refractive index hard coat layer is not particularly limited, but the thickness of the low refractive index layer is preferably 50 nm to 200 nm, more preferably 70 nm to 150 nm.
• the film thickness of the high refractive index hard coat layer is preferably 0.5 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 7 ⁇ m. In such a range, the film has a sufficient surface hardness, little warpage of the film by the coating layer, and good appearance.
• the refractive index of the adhesive layer described below is the refractive index of the high refractive index hard coat layer.
• An intermediate value between the refractive index and the refractive index of the resin substrate is preferable from the viewpoint of suppressing the interference pattern.
• the component forming the low refractive index layer preferably has a refractive index of about 1.3 to 1.5.
• a layer mainly composed of a siloxane bond made of a condensation polymerization curable compound such as alkoxysilane or alkylalkoxysilane are particularly preferable.
• a layer mainly composed of a siloxane bond made of a condensation polymerization curable compound such as alkoxysilane or alkylalkoxysilane.
• a layer mainly composed of a siloxane bond made of a condensation polymerization curable compound such as alkoxysilane or alkylalkoxysilane.
• Specific examples thereof include those formed from a compound in which a part of the siloxane bond of the siloxane-based resin is substituted with a hydrogen atom, a hydroxyl group, an unsaturated group, an alkoxyl group, or the like.
• colloidal silica is a colloidal solution in which fine particles of porous silica and / or non-porous silica are dispersed in a dispersion medium.
• the porous silica is low-density silica in which the inside of the particle is porous or hollow and contains air inside.
• the refractive index of porous silica is 1.20 to 1.40, which is lower than that of ordinary silica 1.45 to 1.47. Therefore, in order to reduce the refractive index of the low refractive index layer in the present invention, it is more preferable to use porous silica.
• a low refractive index layer may be formed by adding colloidal silica to the aforementioned ultraviolet curable mixture and curing it. Further, colloidal silica whose surface is treated with a silane coupling agent may be used.
• curable compounds are cured by, for example, irradiation with active energy rays such as electron beams, radiation, and ultraviolet rays, or are cured by heating. These curable compounds may be used alone or in combination with a plurality of curable compounds.
• the component for forming the high refractive index layer is preferably one having a refractive index of about 1.6 to 2.0, and a metal alkoxide that itself hydrolyzes to form a metal oxide and forms a dense film. What was contained can be used.
• This metal alkoxide has the chemical formula M (OR) m (In the chemical formula, M represents a metal, R represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents a valence (3 or 4) of the metal M.) It is preferable that it is shown by these.
• M titanium, aluminum, zirconium, tin, etc., particularly titanium is suitable.
• metal alkoxides include titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum Examples thereof include t-butoxide, tin t-butoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and the like.
• the metal alkoxide forming the metal oxide includes a high refractive index metal that is at least one of ZrO 2 , TiO 2 , NbO, ITO, ATO, SbO 2 , In 2 O 3 , SnO 2, and ZnO. Addition of oxide fine particles is preferable from the viewpoint of achieving further higher refractive index.
• a high refractive index layer may be formed by adding metal oxide fine particles having a high refractive index to the ultraviolet curable mixture and curing the mixture.
• metal oxide fine particles having a high refractive index may be used.
• curable compounds are cured by, for example, irradiation with active energy rays such as electron beams, radiation, and ultraviolet rays, or are cured by heating. These curable compounds may be used alone or in combination with a plurality of curable compounds.
• an active energy ray-curable organic compound having a fluorene skeleton, a sulfur atom, a halogen atom other than fluorine, an aromatic skeleton, or the like may be used.
• the organic compound having a fluorene skeleton include fluorene acrylate.
• the adhesive layer for example, acrylic resin, chlorinated olefin resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, chlorinated rubber resin, cyclized rubber resin, polyamide resin,
• thermoplastic resins such as coumarone indene resin, ethylene-vinyl acetate copolymer resin, polyester resin, polyurethane resin, styrene resin, butyral resin, rosin resin, and epoxy resin.
• the polyamide resin is mixed with at least one of a butyral resin, a rosin resin, and an epoxy resin.
• the polyurethane resin may be mixed with at least one of a butyral resin, a rosin resin, and an epoxy resin, and a mixture of a polyamide resin and a polyurethane resin may be mixed with a butyral resin or a rosin resin.
• at least one of epoxy resins may be mixed.
• the adhesive layer can be formed by a method known per se.
• the adhesive layer is made of a thermoplastic resin and the surface layer does not have tackiness, and the transfer film described later can be stored in a roll shape, it is suitable for continuous production and has good productivity.
• the adhesive layer can be formed using an adhesive obtained by dissolving the resin in a solvent.
• the solvent permeates into the first cured coating layer and the interface between the adhesive layer and the cured coating layer disappears, it is preferable that the defect of the interference pattern disappears.
• fine particles having a high refractive index can be added to the adhesive layer, and the intermediate value between the refractive index of the high refractive index hard coat layer and the refractive index of the resin substrate can be obtained.
• the resin base material examples include polymethyl methacrylate, polycarbonate, a copolymer having a methyl methacrylate unit as a main component, polystyrene, and a molded product of styrene-methyl methacrylate copolymer. Moreover, you may add a coloring agent, a light-diffusion agent, etc. to the resin base material.
• the thickness of the resin laminate is preferably 0.2 mm or more from the viewpoint of mechanical strength, and preferably 10 mm or less from the viewpoint of productivity.
• the resin laminate may be provided with another functional layer such as an antifouling film on the surface of the antireflection layer.
• an antifouling film a method (wet method) in which a commercially available antifouling paint is applied to a resin substrate and dried, or a physical vapor deposition method such as a vapor deposition method or a sputtering method, etc. are mentioned. It is done.
• the surface of the antireflection layer may be flat or matte.
• the method for producing a resin laminate of the present invention is a method for obtaining a laminate using a transfer film, and has a higher productivity and surface compared to conventional methods such as dipping, roll coating, and spin coating. This is advantageous from the viewpoint of appearance.
• the transfer film will be described in detail.
• the transparent film a known film can be used. Moreover, if it is a film which has peelability, it is still suitable, but if peelability is inadequate, you may provide a peeling layer on the surface of a film.
• the transparent film include film-like materials such as Western paper, Japanese paper, etc., or composite film-like materials, composite sheet-like materials, etc., and those provided with a release layer.
• the transparent film transmits active energy rays.
• the thickness of the transparent film is not particularly limited, but is preferably 4 ⁇ m or more, more preferably 12 ⁇ m or more, further preferably 30 ⁇ m or more, and more preferably 500 ⁇ m or less from the viewpoint of easy production of a transfer film free from wrinkles and cracks. Preferably, it is 150 ⁇ m or less, more preferably 120 ⁇ m or less.
• a release layer is formed to improve the peelability of these transparent films.
• a material for forming the release layer a polymer or wax that forms a known release layer can be appropriately selected and used.
• the method for forming the release layer include paraffin wax, acrylic resin, urethane resin, silicon resin, melamine resin, urea resin, urea-melamine resin, cellulose resin, benzoguanamine resin and surfactants alone or in combination.
• a paint dissolved in an organic solvent or water mainly composed of the above mixture is applied onto the base film by a normal printing method such as a gravure printing method, a screen printing method, or an offset printing method, and dried (thermosetting).
• Curable resin, UV curable resin, electron beam curable resin, radiation curable resin and the like formed by curing The thickness of the release layer is not particularly limited, and is appropriately selected from the range of about 0.1 to 3 ⁇ m. If the release layer is too thin, it will be difficult to peel off, and conversely if the release layer is too thick, it will be easy to peel off and the layers on the film will be detached before transfer, which is not preferable.
• a transfer film can be produced by laminating the antireflection layer, the first cured coating layer, and the adhesive layer in this order on the release layer by a known coating layer forming method.
• This transfer film is usually wound into a roll.
• transfer layer When the transfer film is wound into a roll, it is wound so that the side on which the above-described antireflection layer, first cured coating layer, and adhesive layer (hereinafter collectively referred to as “transfer layer”) are formed is located on the inside. What was taken and what was wound up so that it may be located outside can be produced. By properly using these two types of wound transfer films, warpage of the obtained laminate can be suppressed.
• the winding is performed so that the transfer layer is positioned inside.
• the “arc” means “the arc of the laminate warped in an arc”.
• warping may occur such that the hard coat layer side is outside the arc.
• the transfer layer is formed on the side where the hard coat layer is not provided, a transfer film wound up so that the transfer layer is positioned on the inner side is used, and the urethane-based macro with extremely small curing shrinkage described above. It becomes possible to suppress warping of the laminate obtained by forming the second cured coating film layer using a monomer or the like as appropriate.
• a solventless ultraviolet curable mixture is applied on the adhesive layer of the obtained transfer film to form a coating layer.
• the content of the solvent in the solventless ultraviolet curable mixture is less than 1% by mass with respect to the mixture.
• a solvent-free ultraviolet curable mixture is applied in a line and perpendicular to the film traveling direction (feeding direction) by roll coating, bar coating, slit die, or the like. Is preferably formed. That is, it is preferable to apply the supply unit for applying the ultraviolet curable mixture while moving the supply unit in a direction perpendicular to the traveling direction of the film and parallel to the application surface of the film.
• optical distortion may occur due to non-uniform dissolution of the substrate if the coating layer is applied in parallel and linearly to the traveling direction of the film.
• the coating layer side is attached to the resin base material.
• a method of attaching there is a method of pressure bonding with a rubber roll.
• a method of bonding the film on which the coating layer is formed and the resin base material a method in which the film and the resin base material are transported and pressure bonded with the rubber roll, and the film and the resin base material are overlapped.
• a method in which the rubber rolls are pressed and bonded together in a state where they are in contact there may be mentioned a method in which the rubber rolls are pressed and bonded together in a state where they are in contact.
• the former method in which the film and the resin base material are bonded together is preferably used in the continuous method, and the latter film and the resin base material are bonded together with a rubber roll in a state where the latter film and the resin base material are overlapped. It is preferable that the method of applying and bonding is employed in the batch method.
• the traveling direction of the film and the resin base material is the same. On the other hand, it means that the coating is applied in a vertical direction and linearly.
• the film traveling direction is the direction in which the resin base material is overlaid and integrated and conveyed. Since it is the same as the traveling direction of the resin base material, it is described here as the traveling direction of the film for convenience.
• the traveling direction of the film the mixture is previously applied in a vertical direction and linearly on the adhesive layer to form a coating layer.
• the surface temperature of the resin base material is preferably set to 40 ° C. to 100 ° C. At a temperature in such a range, the adhesion is good, there is no decrease in hardness due to excessive dissolution of the base material, and there is little yellowing of the coating film.
• the surface temperature of the resin substrate can be adjusted by the set temperature of the heating unit, the heating time, and the like. As a method for measuring the temperature of the resin substrate, a known method such as a non-contact type surface thermometer can be used.
• the active energy ray-curable mixture that forms the second cured coating layer preferably has a viscosity of 15 to 120 mPa ⁇ s at the same temperature as the surface temperature of the resin substrate.
• the adhesion is good and there is no optical distortion.
• the viscosity range can be adjusted by appropriately adjusting the composition and temperature of the composition. Further, there is no surface appearance defect due to the entrapment of bubbles. The viscosity can be adjusted by the composition of the curable mixture.
• the active energy ray is irradiated through the transfer film to cure the active energy ray-curable mixture in the coating layer. It is set as 2 cured coating film layers.
• the active energy ray ultraviolet rays are preferable as described above.
• an ultraviolet lamp may be used. Examples of the ultraviolet lamp include a high pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp. Curing by ultraviolet irradiation may be performed in one step through a transfer film, or the first step is performed through a transfer film (third step), and the transparent film is peeled off (fourth step).
• Step) and then curing may be carried out in two stages, for example, by further irradiating ultraviolet rays to carry out the second stage curing.
• an active energy ray such as an electron beam or radiation may be appropriately selected and cured by irradiation through a transfer film.
• the curable mixture is cured in the third step to form a second cured coating layer, and then the second cured coating layer and adhesive layer provided on the resin substrate as the fourth step.
• the transparent film of the transfer film is peeled off leaving the first cured coating film layer and the antireflection layer. That is, the adhesive layer, the first cured coating layer, and the antireflection layer of the transfer film are transferred onto the second cured coating layer on the resin substrate.
• the release layer remains on the transparent film side.
• the resin laminate obtained by the above method is suitable for applications such as a display front plate.
• TAS Condensation mixture of succinic acid / trimethylolethane / acrylic acid in a molar ratio of 15: 4 (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• C6DA 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• M305 Pentaerythritol triacrylate M-305 (manufactured by Toagosei Co., Ltd.)
• M309 Trimethylolpropane triacrylate M-309 (manufactured by Toagosei Co., Ltd.)
• M400 Dipentaerythritol hexaacrylate M-400 (manufactured by Toagosei Co., Ltd.)
• Art Resin SUX-1 Urethane macromonomer
• DAROCUR TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by Ciba Japan)
• Irgacure 184 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by Ciba Japan Co., Ltd.)
• Acrylite EX001 acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd.).
• Acrylite MR100 polymethyl methacrylate with a single-sided hard coat layer (manufactured by Mitsubishi Rayon Co., Ltd.).
• ⁇ Viscosity measurement method> The viscosity of a B-type viscometer at 6 rpm was measured at each temperature. The viscosity was measured at the same temperature as the substrate temperature.
• ⁇ Antireflection performance evaluation> The back side of the sheet is roughened with sandpaper and then applied with a matte black spray. This is used as a sample, and a spectrophotometer (“U-4000” manufactured by Hitachi, Ltd.) is used. The reflectance of the surface of the sample was measured in accordance with the measurement method shown in JIS R3106 in the range of ⁇ 780 nm.
• ⁇ Evaluation of warpage of resin laminate The amount of warpage of the 30 cm ⁇ 30 cm resin laminate after being left for 15 hours in an environment of 80 ° C. was measured. The amount of warpage was measured by placing a sample on a flat plate and measuring the distance from the flat plate to the warped sample. ⁇ : Warpage amount 5 mm or less ⁇ : Warpage amount 5 mm or more
• ⁇ Refractive index and film thickness measurement method About the antireflection layer and the cured coating film layer, the refractive index and film thickness in a 594 nm laser were measured using (manufactured by Metricon, film thickness / refractive index measuring device, model 2010, prism coupler).
• ⁇ Thickness measurement method> The film thickness of the sample without measuring the refractive index was measured by cutting the sample to a thickness of 100 nm with a microtome and observing with a transmission electron microscope. The transmission electron microscope was measured using JEOL JEM-1010.
• Example 1 To the adhesive layer side of the antireflection transfer film (manufactured by Oike Kogyo Co., Ltd., trade name: STEP PAR-1; film (PET film), release layer, antireflection layer, cured coating layer, adhesive layer in that order) A paint composed of an ultraviolet curable mixture composed of 35 parts by weight of TAS, 30 parts by weight of C6DA, 10 parts by weight of M305, 25 parts by weight of M400, and 2 parts by weight of DAROCUR TPO is perpendicular to the film traveling direction and linearly After coating, a planar coating layer was formed using a bar coater (No. 50). In addition, the antireflection transfer film was not used as it was wound up in a roll shape, but was cut out from a portion wound up in a roll shape, and used what was stored in a flat shape. .
• a bar coater No. 50
• the antireflection transfer film in which the coating layer is formed on the acrylic resin base material (Acrylite EX001) having a thickness of 2 mm heated to 60 ° C. is placed with the coating layer facing the resin base material side. After being superposed, they are passed through a fixed rubber roll with a JIS hardness of 40 ° at a constant speed (traveling direction of the film), and the coating film containing the UV curable mixture is excessively thick so that the thickness becomes 15 ⁇ m. While squeezing out a simple paint, it was pressure-bonded so as not to contain bubbles.
• the thickness of the coating film containing the ultraviolet curable mixture was calculated from the supply amount and development area of the ultraviolet curable mixture.
• UV light was irradiated through the transfer film through a position 20 cm below the metal halide lamp with an output of 9.6 kW at a speed of 2.5 m / min. Then, the ultraviolet curable mixture was cured to form a second cured coating film layer.
• the antireflection layer, the first cured coating layer and the adhesive layer are all transferred to the second cured coating layer, and the antireflection layer and the first cured coating layer are transferred.
• a resin laminate having a configuration of an adhesive layer, a second cured coating film layer, and an acrylic resin substrate was obtained.
• the film thickness of the 1st cured coating film layer of the obtained resin laminated body was 2 micrometers, and the film thickness of the 2nd cured coating film layer was 13 micrometers.
• the obtained antireflection laminate had a total light transmittance of 94% and a haze of 0.2%, was excellent in transparency, and had no appearance defect due to optical distortion. Furthermore, it had a good surface layer without appearance defects due to foreign matters and biting of bubbles.
• the haze increment after scratching of the antireflection layer was 0.1%, and the number of scratches was 3.
• the minimum reflectance was 1% at a wavelength of 580 nm.
• the adhesion test the coating film was not peeled off and the adhesion was good.
• the amount of warpage was less than 5 mm. The results are shown in Table 1.
• Example 2 A resin laminate was produced in the same manner as in Example 1 except that the film thickness of the second cured coating film layer was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 3 A resin laminate was produced in the same manner as in Example 1 except that the film thickness of the second cured coating film layer was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 4 In Example 1, a resin laminate was produced in the same manner as in Example 1 except that the temperature of the resin base material was changed as shown in Table 1. The results are shown in Table 1.
• Example 5 A resin laminate was prepared in the same manner as in Example 1 except that the ultraviolet curable mixture was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 6 A resin laminate was prepared in the same manner as in Example 1 except that the ultraviolet curable mixture was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 7 A resin laminate was prepared in the same manner as in Example 1 except that the ultraviolet curable mixture was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 8 In Example 7, a resin laminate was produced in the same manner as in Example 7 except that the temperature of the resin base material was changed as shown in Table 1. The results are shown in Table 1.
• Example 9 A resin laminate was prepared in the same manner as in Example 1 except that the ultraviolet curable mixture was changed as shown in Table 1 in Example 1. The results are shown in Table 1.
• Example 10 In Example 1, an antireflection transfer film (made by Oike Kogyo Co., Ltd., trade name: STEP PAR-2; film (PET film), release layer, antireflection layer, cured coating layer, and adhesive layer was laminated in this order. A resin laminate was produced in the same manner as in Example 1 except that the change was made to). The results are shown in Table 1.
• Example 11 A resin laminate was produced in the same manner as in Example 1 except that the resin base material was changed to a 2 mm thick polycarbonate resin (trade name: Panlite AD-5503, manufactured by Teijin Chemicals Ltd.) in Example 1. did. The results are shown in Table 1.
• Example 12 A resin laminate was produced in the same manner as in Example 1 except that the film thickness of the second cured coating film layer was changed as shown in Table 1 in Example 1. Since the film thickness of the second cured coating film layer was less than 3 ⁇ m, the hardness was lower than that of Example 1. Further, unlike Example 1, a surface layer foreign matter defect occurred. The results are shown in Table 2.
• Example 13 A resin laminate was produced in the same manner as in Example 1 except that the film thickness of the second cured coating film layer was changed as shown in Table 1 in Example 1. Unlike Example 1, warpage occurred because the film thickness of the second cured coating film layer was 30 ⁇ m or more. The results are shown in Table 2.
• Example 14 In Example 1, a resin laminate was produced in the same manner as in Example 1 except that the surface temperature of the substrate was changed as shown in Table 1. Since the substrate surface temperature was less than 40 ° C., the adhesion was lower than in Example 1. The results are shown in Table 2.
• Example 15 In Example 1, a resin laminate was produced in the same manner as in Example 1 except that the surface temperature of the substrate was changed as shown in Table 1. Since the substrate surface temperature was 100 ° C. or higher, the substrate was excessively dissolved as compared with Example 1, and the hardness was low. Moreover, since the viscosity of the ultraviolet curable mixture was 15 mPa ⁇ s or less, optical distortion occurred unlike Example 1. The results are shown in Table 2.
• Example 16 A resin laminate was produced in the same manner as in Example 1 except that the ultraviolet curable mixture composition was changed as shown in Table 1 in Example 1. Since the viscosity of the ultraviolet curable mixture was 120 mPa ⁇ s or more, the adhesion was lower than that of Example 1. Further, unlike Example 1, a surface layer foreign matter defect occurred. The results are shown in Table 2.
• Example 17 In Example 1, a resin laminate was produced in the same manner as in Example 1 except that the temperature was increased and the viscosity of the ultraviolet curable mixture was changed as shown in Table 2. Unlike Example 1, optical distortion occurred because the viscosity of the ultraviolet curable mixture was 15 mPa ⁇ s or less.
• Example 18 In Example 1, resin was applied in the same manner as in Example 1 except that the film was applied in parallel and linearly with respect to the film traveling direction, and a planar coating layer was formed using a No. 50 bar coder. A laminate was produced. When a planar coating layer was formed using a bar coder, a portion that was not partially coated was formed. Therefore, unlike in Example 1, streaky optical distortion was generated in the resin laminate. The results are shown in Table 2.
• Example 19 In Example 1, a resin laminate was produced in the same manner as in Example 1 except that the film thickness and composition of the second cured coating layer were changed as shown in Table 3. The film thickness of the second cured coating layer was 30 ⁇ m or more, but no warpage occurred because the urethane macromonomer (Art Resin SUX-1) was used. The results are shown in Table 3.
• Example 20 a resin laminate was produced in the same manner as in Example 13 except that the antireflection transfer film was rolled up around a paper tube with the following contents.
• ⁇ Paper tube 6 inches in diameter
• ⁇ PET base material thickness 100 ⁇ m
• Winding length 500m
• -Direction of winding of transfer layer Rolled up so that transfer layer is located on the inner side. Even when the thickness of the second cured coating film layer was 30 ⁇ m or more, no warpage occurred in the resin laminate. The results are shown in Table 3.
• Example 21 In Example 20, using acrylite MR100 as the resin base material, transfer to the surface where the hard coat layer was not formed via the second cured coating film layer having the film thickness and composition as shown in Table 3 A resin laminate was produced in the same manner as in Example 20 except that the layer was transferred. It was possible to cancel the warpage of the acrylite MR100 itself, that is, the warp that the antireflection layer forming surface side was inside the arc. The results are shown in Table 31.
• Example 22 In Example 21, a resin laminate was produced in the same manner as in Example 21 except that the winding direction of the transfer layer was changed to the outside of the roll. Unlike Example 21, there was no effect of suppressing warping, and warping of the laminate occurred. The results are shown in Table 3.
• Example 23 A resin laminate was prepared in the same manner as in Example 1 except that the antireflection transfer film in Example 1 was changed to the following single-layer antireflection film having only a low refractive index layer.
• MIBK methyl isobutyl ketone
• the low refractive index coating material was applied to a 100 ⁇ m PET film with a melamine release layer (product name AC-J, manufactured by Reiko Co., Ltd.) using a No. 4 bar coater and dried at 80 ° C. for 5 minutes. Thereafter, a low refractive index layer was formed by passing a position 20 cm below the 9.6 kW high-pressure mercury lamp at a speed of 2.5 m / min. Its refractive index was 1.38.
• the high refractive index paint was applied onto the low refractive index layer using a No. 4 bar coater and dried at 80 ° C. for 5 minutes. Thereafter, a high refractive index hard coat layer was formed by passing a position 20 cm below the 9.6 kW high-pressure mercury lamp at a speed of 2.5 m / min. Its refractive index was 1.60.
• an adhesive layer forming paint was applied onto the high refractive index layer using a No. 4 bar coater and dried at 80 ° C. for 5 minutes to form an adhesive layer.
• the film thickness of the low refractive index layer was 100 nm
• the film thickness of the high refractive index hard coat layer was 4 ⁇ m
• the film thickness of the adhesive layer was 200 nm.
• Table 3 Since it was a single-layer antireflection laminate, the reflection color was thinner than the laminates of the other examples.
• the adhesive layer side of the antireflection transfer film (Oike Kogyo Co., Ltd., trade name: STEP PAR-1) was the methacrylic resin substrate (Mitsubishi Rayon Co., Ltd., trade name: Acrylite EX001) side, and was laminated After that, it was pressed using a hydraulic molding machine (manufactured by Shoji Steel Co., Ltd.), and a pressure of 10 MPa was applied, and the upper and lower set temperatures were 120 ° C., and the pressure was applied for 10 minutes. When a thermocouple was attached to the film surface and the film surface temperature was measured, the surface temperature after 10 minutes was 100 ° C.
• Example 2 In Example 1, except that an antireflection transfer film having no adhesive layer (made by Oike Kogyo Co., Ltd., trade name: STEP PAR-1 was immersed in acetone for 10 minutes and the adhesive layer was removed) was used. In the same manner as in Example 1, a resin laminate was produced. Since it did not have an adhesive layer, the adhesion was insufficient. The results are shown in Table 2.
• the resin laminate of the present invention is a front panel of various displays such as a CRT, a liquid crystal display, an organic EL display, a plasma display, and a projection TV, and in front of an information display unit of an information terminal such as a mobile phone, a portable music player, and a mobile personal computer. It can be suitably used for a face plate or the like.

Landscapes

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

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

Family

ID=41721441

Family Applications (1)

Country Status (5)

Cited By (4)

Families Citing this family (8)

Citations (6)

Family Cites Families (9)

• 2009
  • 2009-04-03 JP JP2009090894A patent/JP2010076423A/ja active Pending
  • 2009-08-26 CN CN200980140981.7A patent/CN102186670B/zh not_active Expired - Fee Related
  • 2009-08-26 WO PCT/JP2009/064832 patent/WO2010024274A1/ja active Application Filing
  • 2009-08-26 KR KR1020117007118A patent/KR101578254B1/ko active IP Right Grant
  • 2009-08-27 TW TW098128893A patent/TWI404629B/zh not_active IP Right Cessation

Patent Citations (6)

Also Published As

Similar Documents

Legal Events