TW201012646A - Manufacturing method of resin layered body - Google Patents

Abstract

A manufacturing method of resin layered body is provided. The resin layered body has fewer warps, and has excellent tightness and excoriation resistance. The manufacturing method of resin layered body includes: a first step for coating a solvent-free type active energy ray curable composition on an adhesive layer of a transfer layer to form a coating layer, wherein the transfer layer is formed by disposing a peeling layer, an anti-reflection layer, a first curing coating layer, and the adhesive layer sequentially on one surface of a transparent film; a second step for pasting a resin base material on a side of the coating layer; a third step for curing the active energy ray curable composition in the coating layer to form a second curing coating layer; and a fourth step for peeling the transparent film and retaining the laminated second curing coating layer, adhesive layer, first curing coating layer and anti-reflection layer on the resin base material.

Description

[Technical Field] The present invention relates to a resin laminate having a shape of a plate or the like which is suitable for use in a front panel or the like of a display, and which is excellent in transparency, antireflection property, and scratch resistance. A method of producing a resin laminate. [Prior Art] Transparent resins such as acrylic resins and polycarbonate resins are widely used as industrial materials, construction materials, and the like. In particular, in recent years, it has been used as a front panel of various displays such as a CRT (cathode ray tube), a liquid crystal television (television), or a plasma display because of its transparency and impact resistance. In recent years, anti-reflection function has become one of the important required performances of the front panel, which is used to reduce the reflected light of fluorescent lamps and the like in the interior of the front panel, and to display images more clearly. Features. One of the principles of the antireflection function is an antireflection film having a structure in which a layer having a low refractive index is formed on a surface of a layer having a high refractive index, and light reflected by the high refractive index layer and reflected by the low refractive index layer are used. The optical path difference between the lights causes them to interfere with each other and reduce the reflected light. A conventional anti-reflection film having such an anti-reflection function is usually produced by sequentially laminating a high refractive index layer and a low refractive index layer on a plastic substrate by a dip method, but This method is one of the reasons for the cost increase because it is a batch (1) station and also has a low productivity. This is a cause of cost increase in the production of an antireflection film. In addition, when the dipping method is used, the film thickness tends to be uneven due to the speed at which the plastic substrate is pulled from the immersion liquid, and it is generally difficult to obtain a uniform nano film of the "201010646". A method of continuously forming a functional layer such as a uniform nano-scale anti-reflection film has been disclosed in which an anti-reflection layer (transfer layer) formed on a release material is thermally transferred or pressure-sensitively transferred to a transfer. A method of the surface of the body (refer to Japanese Laid-Open Patent Publication No. 2006-45355). However, this method has the following problems. A large heating device is required, and heating takes time, and the production speed cannot be increased. Further, there is a problem in that air bubbles are easily trapped between the substrate and the antireflection layer (transfer layer), and surface unevenness defects due to foreign matter are likely to occur. On the other hand, it is disclosed that the antireflection layer is bonded to the surface of the transfer target via an ultraviolet curable adhesive layer, and ultraviolet rays (uv) are applied to cure the adhesive layer, and then the base film on which the antireflection layer is formed is peeled off. In the meantime, the anti-reflection layer is transferred to the surface of the object to be transferred (the so-called "uv layer transfer method") (refer to Japanese Laid-Open Patent Publication No. 2003-215308). This method can be transferred with high productivity using a relatively simple apparatus, but it is necessary to volatilize the solvent when forming the next layer. Further, since the adhesive layer used in the adhesive layer has a very high viscosity, there is a problem in that it is easy to entrap air bubbles, and it is easy to cause surface unevenness defects due to foreign matter. Further, since the hard coating (hard _) function and the subsequent function are carried out in a single layer, there is a tendency that the adhesion to the substrate is insufficient. Further, since the adhesive layer has a viscosity, it is necessary to attach a separator film when the transfer film is stored in a roll shape, which is troublesome in terms of continuous production. Further, it is disclosed that, in the case of the (four) (four) line-curable coating material on the substrate, the UV-transfer transfer of the antireflection layer (transfer layer) to the surface of the body by ultraviolet irradiation is referred to Japanese Patent Publication No. 20101264632274pif. In this method, since the ultraviolet curable coating material is applied to the substrate in advance, when the acrylic resin or the polycarbonate resin having poor solvent resistance is used as the substrate, the light caused by the dissolution of the (four) is caused. Optical distortion. Further, detailed manufacturing conditions such as the temperature at which the coating layer is formed and the coating method are not described. Further, a method in which an ultraviolet curable coating material is applied to an antireflection layer f transfer layer in advance, and then adhered to a substrate and irradiated with ultraviolet rays to transfer the antireflection layer to the substrate is disclosed ( Refer to Japanese Laid-Open Patent Publication No. 2006-212987. In this method, since the ultraviolet curable coating material is directly applied to the antireflection layer, there is a problem in that it is difficult to obtain the adhesion of the obtained laminate, and productivity cannot be improved. Further, the manner in which the ultraviolet curable mixture is applied when the coating layer is formed is not specifically disclosed. Further, a method of forming an antireflection layer, a protective layer, and a subsequent layer on a film and transferring it to a substrate in advance is disclosed (refer to Japanese Laid-Open Patent Publication No. 2005-96078). This method is a laminated structure which is advantageous for high hardness because the antireflection layer is in contact with the protective layer. However, in order to achieve high hardness, the thickness of the protective layer must be increased. Therefore, the film may be largely deformed by shrinkage ( Warping), and it is difficult to form a smooth surface. In particular, in the antireflection laminate, optical distortion is remarkably visible, and therefore it is necessary to provide a production method and a laminate which are more excellent in appearance. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to provide a resin such as a plate shape having excellent transparency, antireflection performance, adhesion, scratch resistance, productivity, and appearance. 201012646 «The first ί^/^pu The method of manufacturing the laminate. [Means for Solving the Problem] The invention relates to a method for producing a resin laminate comprising: ^ 1 ' sequentially formed with a peeling layer, an anti-reverse Μ hardening Wei layer, m on a single surface of the transparent film Forming the undissolved energy ray-curable mixture of the layered transfer film to form a second step, attaching the coating layer side to the resin substrate; and the third step of making the coating layer rideable The energy ray-curable mixture is cured to form a second cured coating film layer; and in the fourth step, the transparent film is peeled off to leave a second cured coating film layer, an adhesive layer, and a first hard coating layer laminated on the resin substrate. Film layer and anti-reflection layer. Preferably, in the above production method, the film thickness of the ith hardened Wei layer is 0.5 zm 10 10 _, and the film thickness of the second hard coat film layer is 〇 5 to 40 // m. Further, in the above-described production method, it is preferred that the surface temperature of the resin substrate is thief-10 (TC) in the second step, and the second cured coating layer is formed at a JDL degree which is opposite to the surface temperature. The viscosity of the active energy ray-curable mixture is from 15 mPa·s to 120 mPa·s. Further, it is preferred that the anti-reflection layer has a structure of two or more layers in the above production method. Further, it is preferred that the anti-reflection layer is a single layer. In the structure, the refractive index of the ninth hardened coating layer is higher than the refractive index of the antireflection layer. [Effects of the Invention] According to the present invention, a resin having less warpage, excellent adhesion, and excellent scratch resistance and excellent scratch resistance can be obtained. Laminate.

Further, a simple device can be used to provide an antireflection resin laminate having small optical distortion and few defects. The above-described features and advantages of the present invention will become more apparent and easy to understand. The embodiments are described in detail below. [Embodiment] The present invention produces a second cured coating film layer, an adhesive layer, a first cured coating film layer, and an antireflection layer on at least one surface of a surface of a resin substrate. A method of a resin laminate. The hard coat layer is a layer which improves the scratch resistance of the surface of the resin laminate, and is a layer obtained by curing a curable mixture of various curable compounds which are resistant to rubbing into a film. The curable mixture which is a raw material of the ninth hardened coating layer may be a curable mixture containing a radical polymerizable curable compound, such as an alkoxy decane or an alkyl alkoxy group, as described below. A curable mixture of a condensed polymer such as decane which is a curable compound. The curable compounds are preferably hardened by, for example, irradiation with an active energy ray such as an electron beam, radiation, or ultraviolet rays, or by heating. These curable compounds may be used singly, respectively. A plurality of compounds having curability may also be used in combination. Further, it is also referred to as "curable mixture" for convenience when used alone. The second hard coat layer was obtained by hardening the active energy ray-curable mixture. According to the present invention, the second hard coat film layer is preferably cured by ultraviolet rays from the viewpoint of productivity and physical properties. Hereinafter, the ultraviolet curable mixture will be described. From the viewpoint of productivity, the ultraviolet curable mixture is preferably an ultraviolet curable mixture containing a compound having at least two (meth)acryloyloxy groups in the molecule and a photoinitiator. ϋ For example, an amide having at least 2 (fluorenyl) acryloxy groups in the molecule is mainly obtained by bridging a polyol with 2 mol of (methyl) propane or its derivative. An acetate, obtained by hydration of a polyol and a multi-ship or its needle, with (meth)acrylic acid or a derivative thereof, and a xylenol with 2 or more methic acids or its street creatures. Specific examples of the obtained esterified product include: ethyl acetate-(meth)acrylic acid vinegar, triethylenediamine, tetraethylene glycol bis(▼-)acrylic acid vinegar, etc. (A φ acrylic vinegar, w壬Diol (meth) propyl: : (methyl) ethane mono (meth) acrylate, pentapoly glycerol trimethyl carbitol tetraol (meth) acrylate vinegar, pentaerythritol: (meth), vinegar, Pentaerythrine (meth) oleic acid vinegar, dipentaerythritol oleic acid vinegar, glycerol tetrakis (meth) propyl hydrazine, dipentaerythritol vinegar, dipentaenoic acid vinegar, tripentaerythritol S 曰, two Pentaerythritol penta(methyl) acrylate vinegar, tris(yinyl) propyl benzoic acid 9 201012646 32274pif capable of poly(mercapto) acrylates of polyols, etc. and 'in polyols and more Among the esterified compounds obtained by the use of citric acid or its acid and (meth)acrylic acid or a derivative thereof, a preferred combination of a polyhydric alcohol and a polyhistreic acid or its acid and (mercapto)acrylic acid, for example, Diacid/trimethylolethane/(meth)acrylic acid, malonic acid/trishydroxypropylpropyl/(mercapto)acrylic acid, malonic acid/glycerol/(mercapto)acrylic acid, malonic acid/pentaerythritol /(Meth)acrylic acid, succinic acid/trihydroxydecylethane/(meth)acrylic acid, succinic acid/tris-propyl propyl acrylate/(mercapto)acrylic acid, succinic acid/glycerol/(fluorenyl) )Acrylic acid, succinic acid/pentaerythritol/(meth)acrylic acid, adipic acid/trimethylol ethanetane/(meth) propylene oxime, adipic acid/trihydroxydecylpropane/(methyl) Acrylic acid, adipic acid/glycerol/(meth)acrylic acid, adipic acid/pentaerythritol/(mercapto)propionic acid, glutaric acid/trimethylacetate/(mercapto)propionic acid, pentane Diacid/trimethylpropane/(meth)acrylic acid, glutaric acid/glycerol/(meth)acrylic acid, glutaric acid 'pentaerythritol/(mercapto)acrylic acid, azelaic acid/trihydroxydecylethane/ (曱基)acrylic acid, azelaic acid/trishydroxyl Propane/(meth)acrylic acid, sebacic acid/glycerol/(meth)acrylic acid, sebacic acid/pentaerythritol/(meth)acrylic acid, fumaric acid/trimethylolethane/(mercapto)acrylic acid , fumaric acid/trihydroxymethyl propyl hydrazine/(meth)acrylic acid, fumaric acid/glycerol/(meth)acrylic acid, transbutanyl disaccharide/pentaerythritol/(mercapto)propionic acid , itaconic acid / tri-propyl sulfonate / (fluorenyl) acrylic acid, itaconic acid / trihydroxymethyl propane / (mercapto) acrylic acid, itaconic acid / glycerol / (meth) acrylic acid, itaconic acid / Pentaerythritol/(meth)acrylic acid, cis-succinic anhydride/trihydroxydecylethane/(meth)acrylic acid, maleic anhydride/trimethylolpropane/(mercapto)acrylic acid, maleic anhydride /glycerol / (meth)acrylic acid, maleic anhydride / pentaerythritol / (mercapto) propionic acid, and the like. 10 201012646 /Hpu Other examples of compounds having at least two (meth) acryloxy groups in the molecule may be exemplified by the use of tri-f-propyl propionate toluene sulphate and hexamethylene per 1 mole. Diisocyanatoacetic acid, methyl diisocyanate, diphenyl methane diisocyanate, xylene diisocyanate, 4, [methylene bis(cyclohexyl) cyanide, diiso-cyano Acidic g, tridecyl hexamethylene diisocyanate, etc., polyisocyanuric acid obtained by trimerization of isocyanic acid vinegar, and (meth)acrylic acid _2 greater than or equal to 3 mol _ by vinegar, (meth)acrylic acid _2_ via hydrazine, hydroxy-3-methoxypropyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, N-hydroxyl (Methyl) acrylamide, 15,3-propanetriol-1,3-di(methyl)propanoate, (meth)acrylic acid-3-propenyloxy-2-hydroxypropyl ester, etc. The active hydrogen (tetra) enoic acid monomer rides the reaction of the called amino carboxylic acid vinegar (methyl diester; tris(2-hydroxyethyl) isocyanuric acid di(meth)acrylic acid vinegar or tris(methyl) ) Acrylic vinegar and other [[meth) propylene oxime extension ethyl] ', - Cyanuric acid, epoxy poly(meth)acrylic acid g; amino phthalic acid poly(methyl)acrylic acid g, etc. Here, "(meth)acrylic acid" means "A Acrylic acid or acrylic acid. The ultraviolet curable mixture of the ageing and ft forming 帛2 hardening coating layer is preferably a micr〇m〇n〇mer, more preferably an amine carboxylic acid vinegar Monomer 2 can reduce the bell curvature of the laminate by making these E monomers. Light, beginning _ as exemplified by: benzoin, benzoin A (10), benzoin ethyl ether, female isopropyl isopropyl, benzoin ACE〇in, bUtyroin, dimethylbenzoin (t〇lu〇in), benzophenone ibenZU), dimeroline, p-methoxybenzophenone 2,2-diethoxye-e-ketone, di-methoxy-α-phenylacetophenone, methyl benzhydrazide 11 201012646 32274pif (methyl Phenylglyoxylate ), Pygmy armor Pheny_Xy_, 4,4'· Bis(didecylamino)diphenyl]dithiocarbamate monosulfide monosulfide, tetramethylmethylglycolyl diphenylphosphine disulfide disulfide, double (2,4 , 6-: A 2 2 t Oxygen benzoyl group phosphide diethoxy phosphine oxide; and the like widely present

The amount of the photoinitiator to be added is determined by the curing property of the ultraviolet ray, and the ultraviolet ray curable mixture is more than or equal to 〇, and the color tone of the film layer T is preferable. It is preferably less than /〇. Further, the photoinitiator may be used in combination of two or more kinds. The Sword can be added to the Wei-aged body towel with smoothness, eVdmg agent, inorganic microparticles, light stabilizer (UV = "resistance amine first stabilizer (HALS, Hi = 丄紫 ega lizer), etc.) Various components, such as the transparency of the laminate

Hey. On the other hand, the amount of the above component added is in the amount of the ultraviolet curable mixture 1 (8). It is preferably less than or equal to 1% by weight. The film thickness of the first hard coat layer is preferably G5 _, and the thickness of S3 is ～7 (four). Within this range, the film is 'sufficient' and the warpage caused by the coating layer is also small, and the appearance is also good. The rainbow second hard coat layer _ is preferably G 5 _~ initial (four), and more preferably the film thickness is 3 _~3 〇 _. Within this range, there is sufficient surface hardness of 12 201012646 /^pu, and the laminate of the hardened coating layer is also less curved. In addition, there is no surface appearance defect caused by inclusion of foreign matter or bubbles. The film thickness can be made by the viscosity of the curable mixture, the pressure of the light pressure, and the speed of the (four) speed. Correctly, when the above-mentioned Wei-aged material contains a solvent, the film thickness can be adjusted by specifying the solid content concentration. The antireflection layer S has a function of suppressing the reflected light on the surface of the resin laminate by 20% or less, more preferably 1% by weight or less, and particularly preferably 5% or less. It can be made of any material. In order to provide such a function, for example, various methods such as a method of forming a laminated structure of two or more films having the same refractive index are mentioned. If the antireflection layer is equal to or greater than two layers, the reflectance is easily lowered, which is preferable. When two types of films having different refractive indices are formed into a laminated structure, the refractive index of each film is not particularly limited. For example, it is preferable that Table 5 = a low refractive index layer of about 1 Μ 5 exists at a low rate of 0. The refractive index of the same refractive index layer on the substrate side is 16 to 2 Å. When the refractive index of each film is within this range, the reflected light of the incident light can be sufficiently suppressed. The film thickness of the refractive index layer is not particularly limited, and is preferably 疋50 nm to 200 nm, more preferably 7 〇 nm to 75 〇 leg. If it is within this range, the reflected light of the wavelength visible to the naked eye can be sufficiently suppressed. The first hard coat layer may be a single layer having a refractive index higher than that of the antireflection layer and a low refractive index layer. In this case, it is preferable that the outer surface facing the air is a low refractive index layer having a refractive index of 13 to •5 left and right, the first! The refractive index of the hardened coating layer is 16 to right. In this case, the reflected light of the human light can be sufficiently suppressed. Thus 13 201012646 32274pif The anti-reflection layer has a single-layer structure, and the refractive index of the first hard coat layer is higher than that of the anti-reflection layer, and the reflectance of the light of the visible light region is easily made equal to or less than a constant value. Therefore, the reflection # can be suppressed. The film thickness of the above-mentioned low refractive index layer and high refractive index hard coat layer is not particularly limited. The film thickness of the low refractive index layer is preferably 50 nm to 200 nm, more preferably = 70 nm to ISO nm. Further, the film thickness of the high refractive index hard coat layer is preferably a film thickness of G.5 _~1 (), and more preferably a film thickness of 1 /zm 〜 7 in this range 'having sufficient surface hardness Moreover, the film caused by the coating layer has less bell curvature and a good appearance. In addition, when the first hard coat layer is a high refractive index hard coat layer and the antireflection layer is a single layer of a low refractive index layer, it is preferable to suppress the interference pattern (mmre^attem). It is preferable that the following laminate layer has a refractive index of a high refractive index hard coat layer and a refractive index of the resin substrate, and a component having a low refractive index layer is preferably a composition having a refractive index of about 1.3 to 1.5. For example, a layer mainly composed of a silQxane bond containing a condensation polymerization-based curable compound such as a silk-based or a silk-based base stone can be cited, and specific examples thereof include a partial oxygen generation from a Wei-based resin. A layer formed by a hydrogen atom, a substituent such as a hydrogen atom, an unsaturated group or an alkoxy group. Further, from the viewpoint of achieving the lower refractive index of the further step, it is preferred to add a colloidal oxygen cut to the layer of the Wei-based resin. Colloidal oxygen cleavage is the porous oxygen oxidizing and/or non-porous oxidizing. 201012646 1. The granules are dispersed in the aging solution of the ageing f towel (4). Among them, the two-quality, yam-yarn particles are porous or have a low-temperature oxidized oxide containing air inside the hollow. The refractive index of the porous oxidized oxide is 120 ^ 4 〇, which is lower than the refractive index (10) of the usual oxidized dream. Therefore, in the present invention, the refractive index of the emissivity layer is lowered, and it is more preferable to make the pores oxidized. Further, colloidal oxygen freshening may be added to the ultraviolet curable mixture described below and hardened to form a low refractive index layer. Alternatively, a colloidal oxidized stone treated with a silane eGupKng agent may be used. These curable compounds can be hardened by, for example, irradiation with an active energy ray such as an electron beam, radiation, or ultraviolet rays, or by heating. These curable compounds may be used singly or in combination of a plurality of compounds having curability. The component forming the high refractive index layer is preferably a component having a refractive index of about 16 to 2 Å. A metal alkoxide which itself hydrolyzes to form a metal oxide and which forms a dense film can be used. The metal alkoxide is preferably represented by the following chemical formula: "" M(OR)m (In the chemical formula, Μ represents that the metal 'R represents a sulphur radical having a carbon number of 5' represents the valence of the metal ruthenium ( 3 or 4)). Suitable metals are titanium, aluminum, zirconium, tin, etc., particularly suitable for titanium. Specific examples of the gold alkoxide include titanium methoxide, cesium ethoxide, n-propanol chin, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, ethanol, isopropanol, butanol, 15 201012646 32274pif Third butanol, third fermented tin, ethanol, n-propanol, isopropanol, n-butanol and the like. Further, from the viewpoint of achieving further high precipitation rate, it is preferred to add zirconia (Zr〇2), titanium dioxide (Ti〇2), and oxidized sharp (Nb0) to the metal alkoxide forming metal alkoxide. ), Oxidation_ (Indium-Ten Oxide, ITO), antimony tin oxide (Antim〇ny D〇ped (10), ΑΤΟ), cerium oxide (Sb02), indium bis(In2〇3), tin dioxide At least one type of high-refractive-index metal oxide fine particles of (Sn02) and zinc oxide (Zn〇). Further, a metal oxide fine particle having a high refractive index may be added to the ultraviolet curable mixture to be cured. Further, a high refractive index layer is formed. Further, a surface-treated high refractive index metal oxide fine particle may be used. The curable compound may be hardened by, for example, irradiation with an active energy ray such as an electron beam, radiation, or ultraviolet light, or may be borrowed. The curable compounds may be used singly or in combination with a plurality of curable compounds. Further, a method of not using a high refractive index of fine particles may be mentioned: An active energy ray-curable organic compound having an anthracene skeleton, a sulfur atom, a halogen atom other than fluorine, an aromatic skeleton, etc. Examples of the organic compound having an anthracene skeleton include % acrylic acid (f|U〇rene acrylate). Examples of the layer include an acrylic resin, a vaporized olefin resin, a gas-vinyl acetate copolymer resin, a cis-butanic acid resin, a chlorinated rubber resin, and a cyclized rubber resin (Cydized 201012646 JZZ / <tpu resin ), polyamine resin, coumarone-indene resin, ethylene-ethyl acetate copolymer resin, polyester resin, polyurethane resin a thermoplastic resin such as a styrene resin, a butyral resin, a rosin resin or an epoxy resin. It is preferred to mix a butyral resin, a rosin resin, and a composition of at least one of an epoxy resin, or may be a polyamine

The urethane resin is mixed with at least one of a butyral resin, a rosin-based resin, and an epoxy resin, and may be mixed in a mixture of a polyamine resin and a polyurethane resin. A constitution of at least one of a butyral resin, a rosin-based resin, and an epoxy resin. In either case, it is possible to obtain a subsequent layer which can be followed by a lower temperature. Further, the formation of the subsequent layer can be carried out by a known method. s Since the adhesive layer contains a thermoplastic resin, the surface layer does not have a viscous property, and since the transfer film described below can be stored in a roll shape, it is suitable for production and has good productivity. a The above resin can be dissolved in a solvent to make a == adhesion layer. At this time, if the solvent penetrates to the first hard surface, the interface between the contact layer and the cured coating layer is eliminated: the defect of the pattern is preferable. In addition, the high refractive index is added to the adhesive layer, and then the refractive index of the layer becomes the intermediate value of the refractive index of the material. Examples of the refractive index of the hard coat layer and the resin-based polycarbonate substrate include polymethyl-acid methyl vinegar, 17 201012646 32274 pif ester, copolymer with methyl methacrylate unit as a main component, and polystyrene. A molded article of a stupid ethylene-methyl methacrylate copolymer. Further, a coloring agent, a light diffusing agent, or the like may be added to the resin substrate. The thickness of the resin laminate is preferably 大于.2 mm or more in terms of mechanical strength, and is preferably 1 〇mm or less from the viewpoint of productivity. Further, as the resin laminate, for example, another functional layer such as an antifouling film may be provided on the surface of the antireflection layer. For example, when the antifouling film is formed, a method of applying a commercially available antifouling paint to a resin substrate and drying it to form an antifouling film (wet method), or a secret method or a weiss Jsputtermg method may be mentioned. Such as physical vapor deposition and the like. Further, the surface of the antireflection layer may be flat or may be mat-shaped. Next, the method for producing the resin laminate of the present invention is described in detail. The method for producing the resin laminate is (4) the method of obtaining the transfer film is compared with the previous method of dipping, roller, and == Qi. 'In terms of productivity and appearance of the outer surface, the transfer 臈 will be described in detail below. A well-known film can be utilized for a transparent film. In addition: better 'but if peeled off, then can be in Qi, poly_film = B = 夂::: two: film, polypropylene baking% 18 201012646 and other cellulose (cellulose) film, transparent paper (cen〇phane paper ), a film such as a glass paper, a film such as Japanese paper, or a composite film or a composite sheet, or a film obtained by providing a release layer thereon. This transparent film is a film that transmits an active energy ray. The thickness of the transparent film is not particularly limited, and from the viewpoint of easily producing a transfer film such as wrinkles or cracks, it is preferable that 岐 is 4 or more and m is more preferably 12 _ or more. Is greater than or equal to % to 9 mm 'other' is preferably less than or equal to (four), more preferably less than or equal to 150, and particularly preferably less than or equal to 12 〇. A release layer is formed in order to improve the peelability of the transparent films. As the material for forming the release layer, a polymer or a wax which is known as a release layer can be appropriately selected and used. Examples of the method for forming the release layer include a single use of paraffin wax, a bupropion acid system, an amino carboxylic acid system, a melamine system, a gland system, a urea-melamine system, a cellulose system, and a benzoguanamine. (benzoguanamine)-based resin and surfactant, or a mixture of these substances as a main component dissolved in an organic solvent or water' and the resulting coating by printing method (g printing), screen printing (screen printing) A normal printing method such as a "printing method" is applied to a base film (kg) and dried (if it is a thermosetting resin, an ultraviolet curable resin, a beam hardening position, and radiation) The hardened coating film is hardened to form a release layer. The thickness of the release layer is not particularly limited, and may be suitably a thickness in the range of about 0.1 /zm to 3. When the peeling layer is too thin, 'it becomes difficult to turn off'. Conversely, when the layer is too thick, 19 201012646 32274pif becomes too easy to peel off and causes detachment of each layer on the film before transfer, which is not preferable. In the coating layer forming method, the cured coating film layer and the subsequent layer are sequentially formed on the peeling layer, and then the above-mentioned antireflection layer and the first printing film are formed by a known layer. When the transfer film is wound into a roll shape, the transfer film can be formed such that the antireflection layer, the first cured coating film layer, and the subsequent layer (hereinafter referred to as "transfer layer" are collectively formed. The transfer film in which one side is located on the inner side and the transfer film in which the side is located on the outer side is wound. By using these two kinds of wound transfer films separately, the resulting laminate can be suppressed from being warped. For example, the second cured coating film layer has a large polymerization shrinkage at the time of ultraviolet curing, and when the cured coating film layer side of the resin substrate is warped so as to become an inner side of the arc, the transfer layer is positioned by use. The transfer film "wound in the inner side" can suppress the warpage of the obtained laminate. Here, the "arc" refers to "this arc of a laminated body in which an enchantment is formed into an arc shape". In addition, when a laminate in which a hard coat film (hard coat) layer is provided on one surface by a wash polymerization method is used as a resin substrate, 'hard coat is sometimes generated. The layer side becomes a warp on the outer side of the arc. In this case, when a transfer layer is formed on the surface side where the hard coat layer is not provided, a transfer film wound so that the transfer layer is located inside is used, and the above-described amine phthalate type having a small hardening shrinkage is suitably used. By forming a second hard coating film layer by a giant monomer or the like, warpage of the obtained laminate can be suppressed. By using such a method, even in the case of the thick film thickness of the cured coating film layer 20 201012646 JZ.^/WLl, it is possible to easily produce a laminate having a small warpage. In the first step, a solvent-free ultraviolet curable mixture is applied onto the subsequent layer of the obtained transfer film to form a coating layer. Here, the content of the solvent in the solventless plastic ultraviolet curable mixture is less than 1% by weight relative to the mixture.

The method for forming the coating layer is preferably a solvent-free coating in a direction perpendicular to the traveling direction (extraction direction) of the film by a roll coating, a hard coating, a slit die or the like. A UV curable mixture forms a coating layer. In other words, it is preferred that the supply portion for applying the ultraviolet curable mixture is applied perpendicularly to the traveling direction of the film and moved in parallel with the coated surface of the film. As for the method of forming the layer on the film, optical distortion occurs due to uneven dissolution of the substrate in a manner parallel to the traveling direction of the film and in a line shape. Further, in order to prevent air from entering during bonding, it is preferred to apply an excessive ultraviolet curable mixture to the film. Next, the coating layer side was attached to the resin substrate in the second step. The method of the sticking method is a method of crimping using a rubber roller. In the state in which the film is laminated and the resin substrate is used, the above-described rubber roll method can be used, and the film and the resin substrate are superposed on each other. := 21 201012646 32274ρίί' The style is used. In the method of forming, the method of "coating in a direction along the detailed description" is carried out by using a method of crimping and bonding in a slightly divided, heterogeneous rubber roller. The rubber is the same, so it means that the Vt·荽I is also aimed at, and the substrate is broken (5). The coating is performed in a lined manner with the direction in which the film or the resin substrate travels. In the case of J, the direction of travel is the same as that of the green tree in which the bismuth and the resin substrate are overlapped. Therefore, for the sake of convenience, it is described above. On the layer, the above mixture is applied in a direction along the direction of the film: the direction of the layer and in a line shape, and in the step of forming a coating ❹ = 2, it is preferred to set the surface temperature of the resin substrate. It is 4〇C. At this temperature range, the adhesion is good, the hardness of the helmet caused by the dissolution of the enamel is reduced, and the yellowing of the coating film is also less. The substrate temperature = the surface temperature can be set by the heating unit, the heating time, etc. To make adjustments. The method for measuring the temperature of the resin substrate is a known method such as a non-contact type surface. The activity of forming the second hard coat layer is preferably such that the temperature at the same temperature as the surface temperature of the resin substrate is 15 mPa·s to 12 g mIVs. Within this range, the adhesion is good' and there is no light distortion. By properly adjusting the composition of the above-mentioned shouts 22

201012646 JZZ/*pu or warm and fine above. After the transfer film is attached to the mold in the second step, the step of irradiating the active energy ray through the transfer film to harden the active energy ray-curable mixture in the coating layer. The second hard coat layer is formed. The viability line is preferably an ultraviolet ray as described above. In the case of ultraviolet light, use an ultraviolet lamp. Examples of the ultraviolet lamp include a high pressure mercury lamp, a metal halide lamp, a fluorescent ultraviolet lamp, and the like. The hardening by irradiation of ultraviolet rays may be carried out in a single stage via the transfer film, or may be divided into two stages, that is, hardening in the second stage via the transfer film (third step) 'peeling the transparent film (fourth) Step), and then hardening is performed by irradiating the ultraviolet rays to the second stage of hardening or the like. When a curable resin other than the ultraviolet curable mixture is used, for example, an active energy ray such as an electron beam or an ray is appropriately selected and irradiated through the transfer film to be cured. In the present invention, after the curable mixture is cured in the third step to form the second cured coating film layer, the fourth step is performed: the transparent film of the transfer film is peeled off, and the second hardening provided on the resin substrate is left. A coating layer, an adhesive layer, a first cured coating film layer, and an antireflection layer. That is, a resin laminate in which an adhesive layer of a transfer film, a first cured coating film layer, and an antireflection layer are transferred onto a second cured coating film layer on a resin substrate is formed. Further, the release layer remains on the side of the transparent film. The resin laminate obtained by the above method is suitable for use in a front panel or the like of a display. 23 201012646 32274pif [Experimental Example] and the details are described in detail, but the compound of the present invention is simplified, and the "TAS" used in the experimental example and the comparative example: Ding_ deficiency/one y Η. 4 66 others, 曰Monoacid 7 dimethylolethane / acrylic acid molar ratio is made,, 'mouth, compound (Osaka Organic Chemical Industry Co., Ltd. factory

A hexanediol II__ (Manufactured by Osaka Organic Chemical Industry Co., Ltd.) · Pentaerythritol triacrylate M-305 (manufactured by Toagosei Co., Ltd.) Μ309". Dimethylolpropane triacrylate μ_3〇9 (East Asian synthesis) Co., Ltd. manufactures Μ400". Pentaerythritol hexaacrylate Μ4〇〇 (manufactured by Toagosei Co., Ltd.)

"ART RESIN SUX-1": urethane-based macromonomer (manufactured by Gensal Industries Co., Ltd.) "OptoolAR": fluorine-based low-refractive-index acrylate, solid content concentration: 15% by weight, mercaptoisobutyl ketone Solution (manufactured by Daikin Chemicals Sales Co., Ltd.) "OGSOL EA-F5010": Acrylic vinegar containing ruthenium skeleton (manufactured by 〇saka Gas Chemicals Co., Ltd.) "Dianal BR-80": Acrylic resin (Mitsubishi Riyang ( Mitsubishi Rayon Co., Ltd.). 24 201012646 Factory DAROCUR ΤΡΟ"·· 2,4,6-trimethylbenzylidene-diphenylphosphine oxide (manufactured by Ciba Japan Co., Ltd.) "Irgacurel84": 1-hydroxycyclohexyl phenyl ketone (Ciba Japan shares Manufactured by the company "Acrylite EXOOl": Acrylic resin sheet (manufactured by Mitsubishi Rayon Co., Ltd.). "Acrylite MR100": polymethyl methacrylate with a hard coat layer on one side (manufactured by Mitsubishi Rayon Co., Ltd.) In addition, the evaluation of physical properties in the experimental example was carried out based on the following method. &lt;Measurement method of viscosity&gt; The viscosity at the time of rotation of the B-type viscometer at 6 rpm was measured at each temperature. The viscosity was measured at the same temperature as the substrate temperature. <Measurement of Temperature of Resin Substrate> Heating the substrate Preheating was carried out and measured using a non-contact surface thermometer (manufactured by CHINO, Inc., hand-shaped radiation temperature § 10 IR-TA). ® &lt;Total light transmittance and haze&gt; Manufactured using Nippon Electric Co., Ltd. HAZE METER NDH2000 (trade name) 'Measures the total light transmittance according to the measurement method shown in JIS K7361-1 and measures the haze according to the measurement method shown in JIS K7136. &lt;Scratch resistance&gt; According to the scratch test The change in haze (A haze) was evaluated. That is, a circular pad having a diameter of 25.4 mm with a steel wool of #〇〇〇 was placed on the hardened coating film of the laminate. Floor Table 25 201012646 32274pif surface, scratching the distance of 20 mm back and forth under a load of 500 g, and determining the difference between the haze value before and after the abrasion according to the following formula (1). %)]=[Haze value after scratching (%)]—[Haze value before scratching (%)] (1) In addition, the number of flaws in the sample after the count test. &lt;Anti-reflection performance Evaluation&gt;

The back surface of the sheet was roughened by sand paper, and then matted, and then applied by a black spray, and used as a sample, and a spectrophotometer (manufactured by Hitachi, Ltd., Γυ 〇〇〇 4 〇〇〇) was 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 the incident angle of 5 and the wavelength of 380 nm to 780 nm. &lt;Adhesion evaluation&gt; Evaluation was performed by a Cross Cut Test (JIS K5600-5-6). The test was repeated four times, and the total number of the portions remaining in each of the 25 portions in the four tests was determined. &lt;Appearance evaluation of the surface layer&gt;

Visual # Recognize the surface of the sample for bubbles or foreign objects. 〇: No air bubbles, no foreign matter △: No air bubbles, no foreign matter X: Mixed air bubbles, foreign matter &lt; Optical distortion &gt; Visually confirm whether the sample has a change or not. 〇: No distortion X · There is a change. 26 201012646 &lt;Evaluation of warpage of resin laminate&gt; The amount of warpage of the resin laminate of 3 〇 cmx3 () em after standing for 15 hours in an environment of 80 ° C was measured. In addition, the amount of warpage is to place the sample on a flat plate and measure the distance from the flat plate to the sample where the tortoise has occurred. 〇: the amount of curvature of the face is less than or equal to 5 mm. X: The amount of warpage is greater than or equal to 5 mm. &lt;Measurement method of refractive index and film thickness&gt; Using (Metric (10) company, film thickness-refractive index measuring device, Model 2010, 稜鏡 合(prism c〇Upier)), the antireflection layer and the hardened coating layer were measured for refractive index and film thickness under 594 nm laser light. &lt;Measurement method of film thickness&gt; The film thickness of the sample in which the refractive index was not measured was a sample having a thickness of 1 〇〇 nm cut by a microtome, and observed using a transmission electron microscope. The transmission electron microscope was measured using JEOL JEM-1010 manufactured by Sakamoto Electronics. [Experimental Example 1] • Anti-reflective transfer film (manufactured by Oikei Co., Ltd., trade name: STEP PAR-1, laminated film (pET film), release layer, anti-reflection layer, hard coating film) The adhesive layer side of the layer and the adhesive layer is coated with 35 parts by weight of TAS, 30 parts by weight of C6DA, 10 parts by weight of M305, and 25 parts by weight in a line perpendicular to the traveling direction of the film. M400 and 2 parts by weight of a coating material of an ultraviolet curable mixture composed of DAROCUR TPO, and a planar coating layer was formed using a bar coater (5 Å). Further, instead of directly using the anti-reflection transfer film which is wound into a roll shape, the anti-reflection transfer film is cut out in a planar shape by using an anti-reflection transfer film wound into a roll shape. . Next, on the acrylic resin substrate (Acrylite EX001) having a thickness of 2 mm (the thickness of 2 cm of TC), the coating layer of the antireflection transfer film on which the coating layer was formed was oriented toward the resin substrate side. The above transfer film is superposed on the film, and then passed through a fixed light JIS hardness of 4 〇β under the light weight (the traveling direction of the upper face) so as to be cured by ultraviolet rays.

The excess of the coating is extruded in the manner of the coating of the mixture, and the pressure is applied in such a manner that it does not contain bubbles. Further, the thickness of the coating film containing the ultraviolet curable mixture was calculated from the supply amount and the developed area of the ultraviolet curable mixture. Then, warm up to 60. In the state of €, after 120 seconds, the position of the 2G em under the metal toothed lamp of the power of 9 6 was passed through the transfer film at a speed of 2.5 m/min, and ultraviolet rays were irradiated to harden the ultraviolet curable mixture. The second hard coat layer is formed. Thereafter, after the transfer film is peeled off, the antireflection layer, the i-th hard coat film layer, and the adhesive layer are all transferred onto the second cured coating film layer to obtain an antireflection layer and a first hard coat layer. A resin laminate having a structure of a second layer, a second hardening coating, and a propylene oxide-based resin substrate. The film thickness of the first cured coating layer of the obtained resin laminate was 2 _, and the thickness of the second cured coating layer was 13 # m.

The anti-reflective laminate _ total light transmitting material is 94%, the haze is φ, and the second transparency is excellent, and the appearance accompanied by the optical distortion is poor. Moreover, there are no appearance defects, inclusion bubbles, etc. due to foreign matter, and there is a good 28 201012646 JZZ./Hpu surface layer. The anti-reflection layer has an increase in haze of 0.1% after scratching. The number of flaws is three. The minimum reflectance is 1% at a wavelength of 580 nm. Further, as a result of the adhesion test, the coating film was not peeled off and the adhesion was good. The results of the warpage test were as follows: the amount of warpage was less than 5 mm. The results are shown in Table 1. [Experimental Example 2] A resin laminated body was produced in the same manner as in Experimental Example 1 except that the film thickness of the second cured coating film layer was changed to that shown in Table 1. The results are shown in Table 1. Ο

[Experimental Example 3] A resin laminated body was produced in the same manner as in Experimental Example 1 except that the film thickness of the second cured coating film layer was changed to that shown in Table 1. The results are shown in Table 1. [Experimental Example 4] In Experimental Example 1, the resin laminate was produced in the same manner as in Experimental Example 1 except that the temperature of the resin substrate was changed to that shown in Table 1. The results are shown in Table 1. [Experimental Example 5] A resin laminate was produced in the same manner as in Experimental Example i except that the ultraviolet curable mixture was changed to the same as in Table 1. The results are shown in Table 1. [Experimental Example 6] In Experimental Example 1, the ultraviolet curable mixture was changed to the one shown in Table i, and the experimental example was given! The same object. The results are shown in Table 1. [Layer 29 201012646 32274pif [Experimental Example 7] A resin laminate was produced in the same manner as in Experimental Example 1 except that the ultraviolet curable mixture was changed to the same as in Table 1 in Experimental Example 1. The results are shown in Table 1. [Experimental Example 8] A resin laminate was produced in the same manner as in Experimental Example 7, except that the temperature of the resin substrate was changed to that shown in Table 1 in Experimental Example 7. The results are shown in Table 1 [Experimental Example 9] A resin laminate was produced in the same manner as in Experimental Example 1, except that the ultraviolet curable mixture was changed to the same as in Table 1 in Experimental Example 1. The results are shown in Table 1 [Experimental Example In Experimental Example 1, the antireflection transfer film was changed to (manufactured by Oike Industrial Co., Ltd., trade name. STEP PAR_2: film (PET film) was sequentially laminated, and peeled off) A resin laminate was produced in the same manner as in Experimental Example 1, except that the layer, the antireflection layer, the cured coating film layer, and the adhesive layer were used. The results are shown in Table 1. [Experimental Example] In Experimental Example 1, 'the resin substrate was changed to a polycarbonate resin of 2 mm thick (manufactured by Teijin Chemical Co., Ltd., trade name: panlite) The resin layer and the fruit of the material of the age class U are shown in Table i. [Experimental Example 12] 30 9 9 In Experimental Example 1, the second

As shown in 201012646 tHpn. 1, in addition to this, it is more like a surface layer with Experimental Example 2. Since the film thickness of the second hard coat layer is less than 3', the gambling stack is lower than that of Experimental Example 1. In addition, unlike the experimental example i, it was a hard defect. The results are shown in Table 2. 'Experimental Example 13> In the experimental weave, the first hardened coating medium layer 1 was shown as a surface layer in addition to the experimental example. Since the film thickness of the second hard coat layer is equal to or greater than that of the experiment 1, warpage is caused unlike the test example 1. The results are shown in Table 2 ^ m [Experimental Example 14] ' ° In the experimental example i, the base _ 岐 岐 蚊 成 成 成 , 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作 制作Degree is less than the thief, this is the secret of the New Zealand &amp; The results are shown in Table 2. [Experimental Example 15] A resin laminate was produced in the same manner as in Experimental Example i except that the surface temperature of the substrate was changed to that shown in Table i in Experimental Example 1. Since the surface temperature of the substrate is greater than or equal to 10 (rc, the hardness of the substrate is lower than that of the experimental example i due to excessive dissolution of the substrate. In addition, since the viscosity of the ultraviolet curable/kun compound is less than or equal to 15 mPa·s, The results were shown in Table 2. The results are shown in Table 2. [Experimental Example 16] In Experimental Example 1, 'the composition of the ultraviolet curable mixture was changed as shown in Table 31 201012646 /*tpu Table 1, except The resin laminate was produced in the same manner as in Experimental Example 1. Since the viscosity of the ultraviolet curable mixture was 120 mPa_s or more, the adhesion was lower than that of Experimental Example 1. Further, unlike Experimental Example 1, foreign matter defects were generated in the surface layer. The test results are shown in Table 2. [Experimental Example 17] A resin laminate was produced in the same manner as in Experimental Example 1 except that the viscosity of the ultraviolet curable mixture was changed to the same as in Table 2 except for the heating. Since the viscosity of the ultraviolet curable mixture is 15 mPa·s or less, optical distortion occurs unlike Experimental Example 1. [Experimental Example 18] In Experimental Example 1, the film was parallel to the traveling direction of the film and was formed into a line. A resin laminate was produced in the same manner as in Experimental Example 1 except that the coating layer was applied and a planar coating layer was formed using a No. 50 bar coater. When a planar coating layer was formed using a bar coater. A part of the uncoated portion was formed. Therefore, in the resin laminate, streak-like optical distortion occurred unlike Experimental Example 1. The results are not shown in Table 2. [Experimental Example 19] In Experimental Example 1, The resin laminate was produced in the same manner as in Experimental Example 1 except that the film thickness and composition of the cured coating layer were changed as shown in Table 3. The thickness of the second cured coating layer was 3 大于 or more. However, since the urethane macromonomer RESIN Sux-i) was used, no warpage occurred. The results are shown in Table 3. [Experimental Example 20] In Experimental Example 13, a resin laminate was produced in the same manner as the crucible except that the antireflection transfer film 32 201012646 was wound onto a paper tube to form a roll shape. . • Paper tube: 6 inches in diameter (inch) • PET substrate thickness. 1〇〇 • Winding length: 500 m. Winding direction of the transfer layer: Winding even if the transfer layer is inside The thickness of the hard coat layer is 3 Å or more, and the resin laminate does not cause warpage. The results are shown in Table 3.实验• [Experimental Example 21] In Experimental Example 20, 'Acrylite MR100 was used as a resin substrate, and a second hard coat layer having a film thickness and composition as shown in Table 3 was formed on the surface on which the hard coat layer was not formed. A resin laminate was produced in the same manner as in Experimental Example 20 except that the transfer layer was transferred. The warpage of the MR100 itself, that is, the warpage of the inner side of the arc of the antireflection layer formation side, was successfully eliminated. The results are shown in Table 31. [Experimental Example 22] A resin laminate was produced in the same manner as in Experimental Example 21 except that the winding direction of the transfer layer was set to the outside of the roll. The difference from Experimental Example 21 is the suppression effect of the uninteresting song, and the layer body is warped. The results are shown in Table 3. [Experimental Example 23] A resin laminate was produced in the same manner as in Experimental Example 1 except that the antireflection transfer film in Experimental Example 1 was changed to the following single-layer antireflection film having only the low refractive index layer. . 33 201012646 ό22Ί^ρη (Preparation of low-refractive-index paint) MIBK (methyl isobutyl net)'_ is a solid content concentration of 1% by weight relative to 100 weight of Optool AR (solid content concentration: 15% by weight) A low refractive index coating was prepared by adding a weight fraction of Irgacure 184 ' to the solid component of 0ptool AR. (Preparation of high refractive index coating) Add MIBK to OGSOLEA-F5010 towel (N-isobutyl butyl is diluted to a solid concentration of 50% by weight, relative to

: A test of LEA-F5_, a high refractive index coating was prepared by adding 5 parts by weight of 184 '. (Preparation of layer-forming coating material) ^ 50 parts by weight of yttrium oxide sol (manufactured by Sumitomo Osaka Cement Co., Ltd., manufactured by Sumitomo Osaka Cement Co., Ltd., 50% by weight) Methyl ethyl ketone dispersion sol) "'Addition of MIBK (methylisobutyl ketone) and system = degree U mesh for Di secret (four) and lead oxide solid content

(Production of single-layer anti-reflection transfer film) = Coating on _(4) with melamine peeling layer film (manufactured by Reiko Co., Ltd., product name AC-J) using a No. 4 bar coater The above low refractive index coating was dried at 8 Torr and then passed through a position of 2 〇 cm under a 9.6 kw high waste water silver lamp at a speed of 2.5 m/min to form a low refractive index layer. Its refractive index is 1%. Next, after coating the above-mentioned high-fold 34 201012646 table on the low refractive index layer using a No. 4 bar coater, a high refractive index paint was formed at a position of cm of 2.5 m/min, and dried at 8 Torr for 5 minutes. After the lack of speed, the speed is passed through a 9.6kW high-pressure mercury lamp with a 2% coffee rate of hard coating. Its refractive index is 16 〇. Next, a subsequent layer forming coating was applied on the high refractive index layer using a No. 4 bar coater to dry at 8 GC for 5 minutes to form an adhesive layer. As a result of measuring the thickness of the obtained resin laminate, the film thickness of the low refractive index layer was 100 rnn, and the film thickness of the high refractive index hard coat layer was 4 _, and the subsequent layer

The film thickness is 200 nm. Μ ;; paper main, 丄w β 1 p ^ [Comparative Example 1] The back layer side of the anti-reflective transfer film (manufactured by Oikei Co., Ltd., trade name: STEPPAR-1) The base material (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite EX001) was bonded to the side, and then pressed with a hydraulic forming machine (made by Zhuangsi Iron and Steel Co., Ltd.) to set the upper and lower set temperatures. Set to 12 (rc and apply a pressure of 10 MPa for 10 minutes. A thermocouple was attached to the surface of the film, and the surface temperature of the film was measured. As a result, the surface temperature after 10 minutes was 1 Torr. 匸. Thereafter, the pressure was cooled under application of pressure. After the temperature is 30° C., the film is peeled off. Since the obtained resin laminate does not have the second cured coating layer, the hardness is insufficient. Further, the surface layer is foreign matter-defective, and the first cured coating layer and the resin substrate are The results are shown in Table 2. [Comparative Example 2] In Experimental Example 1 t, an antireflection transfer film having no adhesive layer was used (trade name manufactured by Oike Industrial Co., Ltd.: STEP PAR- 1 in C _ 35 201012646 32274pif (aceto A resin laminate was produced in the same manner as in Experimental Example 1 except that the adhesion layer was removed for 10 minutes, and the adhesion was insufficient. .

36 201012646

1 Experimental example ii 1 ο Ο ΓΊ o SO § &lt;N m 00 d &lt;sd »Λ - 100/100 〇〇〇1 Experimental example ίο 1 •Λ Ο cn ο ο *Τί (Ν o Ν s v-&gt a\ oo ο 100/100 〇〇〇Experimental Example 9 I Ο ο g Ο o &lt;S s «S cs o 1 0.05 I &lt;«Ν 100/100 〇〇〇Experimental Example 8 Ο ο &lt;s ο ο go &lt;N Os % cs 茇is o 0.05 100/100 〇〇〇 Experimental Example 7 ο ο ο go (S CM % (N m &lt;so 0.05 «Μ 100/100 〇〇〇|Experimental Example 6 I ο ο ο ο Ο 卜 o iS 116 ov〇&lt;S cn &lt;so I 0.05 I — 1 loo/ioo 1 〇〇〇Experimental Example 5 1 ο ο 100 ο ο o rs § (S o 0.05 100/100 〇〇 〇1 Experimental Example 41 V) ο ο &lt;r&gt; (S og \T\ CM z fN oom *-Μ 100/100 〇〇〇1 Experimental Example 3 1 IT) m 沄ο ο V-) &lt;S ov 〇&lt;s S CM rs o I 0.05 I 100/100 〇〇〇1 Experimental Example 2 1 Vi ο ο ο cs o cs V〇(S % n tn &lt;N 〇dm ***&lt;Ν 100/100 〇〇〇1 Experimental Example 11 »r&gt; CO ο ο ο »r&gt; fS on VO s (N &lt;sod 100/100 〇〇〇TAS (parts by weight) C6DA (parts by weight) Μ305 (parts by weight) Μ309 (Heavy Dong) M400 (parts by weight) ART RESIN SUX-1 (Heavy Dong) DAROCURE TPO (Parts by weight) Viscosity (mPa's) P Thickness of the first hardened coating layer (&quot;m) Thickness (μm) of the second hardened coating layer Total light transmittance (%) Haze (%) Scratch resistance △ Haze (%) Number of scratch-resistant scratches (bar) Anti-reflection performance Evaluation (%) Appearance Evaluation Surface Appearance Defect Evaluation Light Distortion Resin Lamination "1 Warpage 201012646 kie &lt;N&lt; I Comparative Example 2 1 〇c&gt; • ο ΓΊ Ο ts cs s &lt;sm &lt; s 〇d «Μ 0/100 〇〇〇1Comparative example 1丨1 1 I 1 I 1 1 1 &lt;N Ο &lt;s ο Ο (S — 20/100 XX 〇1 powder example 18 ί % Ο ο CM CM Ό fS § &lt;S mdd CO — 100/100 〇X 〇 Experimental example 17 % Ο ο fS ο &lt;S o CS rs dom — ;100/100 〇X 〇L Experimental example I6 I o Ο Ο 宕g ο &lt;N so &lt;N § &lt;N m &lt;sdo co Μ4 30/100 &lt; 〇〇 验 验 15 , •r» Ο ο &lt;s ο &lt;S •r&gt; 110 CS m &lt ;N 〇00 o 〇100/100 〇X 〇1 real Example 14 j Vi Ο ο ίΝ ο CS § o iS m Cv| oom 30/100 〇〇〇 1 Poor Example 13 | »r&gt; Ο ο *&lt;Μ ο &lt;s ο ΓΊ fS sc**&gt; cn Dd cn 100/100 〇〇X Experimental Example 12 ο ο \η fS ο \〇ts o CS o 00 d 〇100/100 &lt; 〇〇TAS (parts by weight) C6DA (parts by weight) Μ305 (parts by weight) Μ309 ( Parts by weight Μ400 (replacement) ART RESIN SUX-1 (parts by weight) DAROCURE TPO (parts by weight) Viscosity (mPa_s) Surface temperature of the substrate (°c) Thickness of the first hardened coating layer (/irn) 2 Thickness of hardened coating layer (;um) Total light transmittance (%) Haze (%) Scratch resistance Δ haze (%) Number of scratch-resistant flaws (bar) Anti-reflection performance evaluation (%) Evaluation of appearance defects of the evaluation surface layer Warpage of the optical distortion resin laminate 201012646 Αν ❹ 1 Experimental example 23 1 〇〇«η cs ο &lt;s § inch ms; 〇w-&gt; d 00 卜 d 100/100 〇〇〇 Experimental Example 22 〇〇〇〇§ fS ΓΛ s; (N 〇d — 100/100 〇〇X 1 Experimental Example 21 1 〇〇〇〇§ &lt;s ΓΛ (S od co 100/10 0 〇〇〇|Experimental Example 20 I «Λ ΓΛ 〇〇〇*n &lt;s ο &lt;S fS s cn ΓΛ od ί Λ 100/100 〇〇〇1 Experimental Example 19 | Ο 〇〇ο &lt;S o SO fN ΓΛ Λ Λ On N od ΓΛ 100/100 〇〇〇TAS . (Heavy Dong) C6DA (parts by weight) M305 (parts by weight) M309 (parts by weight) Μ400 (parts by weight) ART RESIN SUX-1 (parts by weight) DAROCURE TPO (parts by weight) Viscosity (mPa-s) Surface temperature of the substrate (°c) Thickness of the first hard coat layer (Aim) Thickness of the second hard coat layer (#m) Total light transmittance (%) Haze (%) Scratch resistance △ Haze (%) Number of scratch-resistant scratches (bar) Evaluation of anti-reflection performance (%) Appearance of the adhesion evaluation surface defect Evaluation of warpage of optical distortion resin laminated ship 201012646 32274pit' [Industrial Applicability] The resin laminate of the present invention can be preferably used for CRT, liquid crystal display, organic EL (electroluminescence) display, plasma display, projection television Front panel of various displays, as well as mobile phones, portable digital music Set (portable music Player), the front panel and other information significant action is not part of the computer (Mobile rc) and other personal digital assistants. The present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. Anyone having ordinary knowledge in the art can make some changes and _ without departing from the inside. Among them, the patent is defined by Fan Gu. None [Main component symbol description] None

Claims (1)

201012646 VII. Patent application: 1. A method for manufacturing a resin laminate comprising: 2 steps: forming a separation layer, an antireflection layer, and a first hard coating film sequentially on one surface of a transparent film The layer and the subsequent layer are coated with a solvent-free active energy ray-curable mixture, and the second step of attaching the coating layer side to the resin substrate is carried out in the step 1 2 to make the activity in the coating layer The energy ray-curable mixture is cured to form a second cured coating film layer; and in the fourth step, the transparent film is peeled off to leave the second cured coating film layer on the resin substrate, the adhesive layer, and the The second hard coat layer and the antireflection layer described above. 2. If you apply for a patent scope! In the method for producing a resin laminate according to the above aspect, the film thickness of the first cured coating film layer is 〇5 #m~1〇A m, and the film thickness of the second cured coating film layer is 〇5 to melon Take melon. 1. The method for producing a resin laminate according to the above aspect of the invention, wherein the surface temperature e of the resin substrate is again 40 C 100 100 X in the second step, at the same temperature as the surface temperature. The method of producing the resin laminate according to the above-mentioned first aspect of the invention, wherein the active energy ray-curable mixture of the second hard coat layer is formed to have a viscosity of 15 mPa·s to 120 mPa·s. The antireflection layer has a structure of two or more layers. 5. The method for producing a resin laminate according to the above aspect, wherein the antireflection layer has a single layer structure, and a refractive index of the first cured coating film 201012646 32274pif layer is higher than a refractive index of the antireflection layer. . Reference 42 201012646 IV. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: None. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: No. 201012646 is the 98128893 咐 page &quot; The sputum molecule has at least two (meth) propylene oxime groups. For example, it can be exemplified by trimethylolpropane toluene diisocyanate per gram of monomole. Methyl diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dinonyl diisocyanate, 4,4,-methylene bis(cyclohexyl isocyanate), isophorone diisocyanate, trimethyl Polyisocyanate obtained by trimerization of diisocyanate such as hexamethylene diisocyanate vinegar, and (meth)acrylic acid _2_ethyl ester, (meth) acrylic acid _2 _ via vinegar, (mercapto)acrylic acid 2-hydroxy-3-methoxypropyl ester, N-hydroxymethyl (fluorenyl) acrylamide, hydrazine hydroxy (meth) acrylamide, 1, 2 , 3-propanetriol-1,3-di(meth)acrylate, (mercapto)acrylic acid-3-propene a urethane (mercapto) acrylate obtained by reacting an acrylic monomer having an active hydrogen such as a nonyloxy-2-hydroxypropyl ester; and a tris(2-hydroxyethyl)isocyanuric acid (fluorenyl) acrylate or tris(meth)acrylate, etc., polymethyl) propylene oxime extended ethyl] isomeric cyanate; epoxy poly(fluorenyl) acrylate; (fluorenyl) acrylate and the like. Here, "(mercapto)acrylic acid" means "mercaptoacrylic acid" or "acrylic acid". Further, the ultraviolet curable mixture forming the second hard coat layer is preferably a micro monomer, more preferably a urethane macromonomer. By using these giant monomers, the warpage of the laminate can be reduced. Examples of the photoinitiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acet〇in, butyroin, dimethylbenzoin ( T〇lu〇in), benzil, benzhydrazine, p-nonoxybenzophenone, 2,2-diethoxyacetophenone, a, α-dimethoxy_ α-Phenylacetophenone, methyl benzhydrazide 11 201012646 32274pifl (methyl phenylglyoxylate ), ethyl phenylglyoxylate, 4,4′-bis(dimethylamino) dioxin , Wei-based compound such as cyclohexyl-phenyl ketone, 2-carbyl-2-mercapto-1-phenylpropanone-y-one, tetramethylthiuram monosulfide, a sulfur compound such as tetrakis-based thiuram; 2,4,6-tridecylbenzamide-diphenylphosphine oxide, bis(2,4,6-trimethyl adenyl)phenylphosphine oxide A phosphorus compound such as benzamidine diethoxy phosphine oxide. ❹ The amount of the photoinitiator to be added is preferably 0.1% by weight or more based on the curing property of the ultraviolet ray curable mixture, and is preferably 0.1% by weight or more based on 1% by weight of the ultraviolet curable mixture. From the viewpoint of maintaining a good color tone of the cured coating film layer, it is preferably equal to or less than the weight %. Further, the photoinitiator may be used in combination of two or more kinds. It is possible to add smoothness to the ultraviolet curable mixture as needed, such as a lifting agent, a leveling agent, an inorganic fine particle, a light stabilizer (external suction (four), a Hinder (Hindered Ami) Light Stabilizer), etc. ) and other ingredients. The transparency of the laminate ί. Further, the amount of the above-mentioned component of L is preferably 1% by weight or less based on the amount of the ultraviolet curable mixture. A better film thickness is better. Is the surface of °·5~0 _ hard, ~7 in this _, with charge: also good. The film thickness of the film layer 5 is also less, and the film thickness of the outer layer I is preferably a thickness of 3 (10) to 4 g. In this model, there is a charge or a temperature of 12 201012646 to achieve the above _ degree Fan®. In addition, there is no surface appearance defect due to inclusion of air bubbles. Further, the viscosity can be adjusted in accordance with the composition of the above-described hardenable mixture or the like. /tt,Q After attaching the transfer film to the mold in the second step, the third step is performed by irradiating the active energy ray through the transfer film to cure the active energy ray-curable mixture in the coating layer to form the second step. Harden the coating layer. The viability line is preferably an ultraviolet ray as described above. In the case of ultraviolet light, use an ultraviolet lamp. Examples of the ultraviolet lamp include a south pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp. The curing by ultraviolet irradiation may be performed in one stage via the transfer film, or may be performed in two stages, that is, the first stage of hardening via the transfer film (third step), and the transparent film is peeled off (fourth) Step), and then hardening is performed by irradiating the ultraviolet rays to the second stage of hardening or the like. When a curable resin other than the ultraviolet curable mixture is used, for example, an active energy ray such as an electron beam or an ray is appropriately selected and irradiated through the transfer film to be cured. In the present invention, after the curable mixture is cured in the third step to form the second cured coating film layer, the fourth step is performed: the transparent film of the transfer film is peeled off, and the second hardening provided on the resin substrate is left. A coating layer, an adhesive layer, a first cured coating film layer, and an antireflection layer. That is, a resin laminate in which an adhesive layer of the transfer film, the i-th hard coat film layer, and the antireflection layer are transferred onto the second cured coating film layer on the resin substrate is formed. Further, the release layer remains on the transparent film side. The resin laminate obtained by the above method is suitable for use in a front panel or the like of a display. 23 201012646 022/4pm [Experimental Example] The following is a detailed description of the present invention by way of experimental examples. Here, the abbreviations of the compounds in the experimental examples and comparative experiments are as follows. TAS". The molar ratio of butyric acid/dimethylolethane/acrylic acid is 1:5:4 condensation mixture (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_3〇5 (manufactured by Toagosei Co., Ltd.) "M309": trimethylol Propane triacrylate M_3〇9 (manufactured by Toagosei Co., Ltd.) "M400": dipentaerythritol hexaacrylate M_4〇〇 (manufactured by Toagosei Co., Ltd.) "ART RESIN SUX-1": Amino phthalate macromonomer (manufactured by Gensei Sangyo Co., Ltd.) "Optool AR": fluorine-based low refractive index acrylate, solid content concentration: 15% by weight, decyl isobutyl Ketone solution (manufactured by Daikin Chemicals Sales Co., Ltd.) "OGSOL EA-F5010": acrylate containing ruthenium skeleton (manufactured by 〇saka Gas Chemicals Co., Ltd.) "Dianal BR-80": acrylic resin (Mitsubishi Rayon) Co., Ltd.). 24 201012646 A resin laminate was produced in the same manner as in Experimental Example 13, except that it was wound up on a paper tube to form a roll. • Paper tube: 6 inches in diameter • PET substrate thickness: 1 〇〇 • • Winding length: 500 m • Winding direction of the transfer layer: Winding even if the transfer layer is inside 2 The thickness of the hardened coating layer is greater than or equal to 3 〇 to the sister, and the fat is not produced. The results are shown in Table 3. [Experimental Example 21] In Experimental Example 20, Acrylite MRIOO was used as a resin, and the surface on which the hard coat layer was not formed was transferred by transferring the transfer layer via the film thickness of the composition 2 as shown in Table 3 In addition to this, a resin laminate was produced in two. Successfully eliminated the A-te distortion. The meaning of the station ί, that is, the surface on which the antireflection layer is formed becomes the inner side of the arc, is shown in Table 3. _ [Experimental Example 22] Lateral body. Surface curl, it: 21, medium', the winding direction of the transfer layer was set to the outside of the drum, and the same effect as in the experimental example 21 was made to produce the group 矗js. A resin laminate was produced in the same manner as in Experimental Example 1 except that the antireflection transfer film in the layer 1 of the [Experimental Example 23] was changed to have a low refractive index. 33 201012646 ^^/4pm (Preparation of low refractive index coating) Adding MIBK (methyl isobutyl ketone) to Optool AR (solid content concentration: 15% by weight) is diluted to a solid concentration of 丨% by weight, relative to A low refractive index coating was prepared by adding 100 parts by weight of Irgacure 184 to 100 parts by weight of the solid component of 〇pt〇〇1 AR. (Preparation of high refractive index coating) MIBK (nonylisobutyl ketone) was added to OGSOLEA-F5010, and diluted to have a solid concentration of 50% by weight. /. A high refractive index coating was prepared by adding 5 parts by weight of ?jgacure® 184 ' to 1 part by weight of the solid component of OGSOL EA-F5010. (Preparation of layer-forming coating material) 50 parts by weight of Dianal BR-80 and 166 parts by weight of zirconia sol (manufactured by Sumitomo Osaka Cement Co., Ltd., solid content concentration (oxidation error) of 30% by weight of methyl ethyl group) Ketone dispersion sol) mixed 'further added MIBK (fluorenyl isobutyl ketone) and prepared to a solid concentration (100 parts by weight relative to the total solid content of Dianal BR-80 and Oxidation Record) is 2 weight 碜 (single layer anti-reflection) Production of transfer film) The above film was coated on a PET film (manufactured by Reik Co., Ltd., manufactured under the name AC-J) of 111 with a melamine peeling layer of 111 using a No. 4 bar coater. The low refractive index coating was dried at 5 〇〇c for 5 minutes and then passed through a position of 9.6 kW of high pressure mercury 卞 2 cm at a rate of 2.5 m/min to form a low refractive index layer. Its refractive index is 138. Next, the above high fold is applied to the low refractive index layer using a No. 4 bar coater.