TW200804082A - Thin film laminate and method for fabricating the same - Google Patents

Abstract

The present invention provides a transparent, weather-resistant, drug-resistant, durable and heat-resistant thin film laminate with high surface hardness and a method for fabricating the thin film laminate. The light-curable resin composition containing the cage-typed silsesquioxane resin is applied on one side of the transparent plastic thin film having a glass transition temperature ranged from 70 DEG C to 220 DEG C so as to light-cure the light-curable resin composition, so that the resin layer with the transmittance more than 90% at 550 nm of the wavelength and a heat-resisting capability of more than 250 DEG C is formed and the thin film laminate having the ratio of the thickness of the resin layer to the thickness of the transparent plastic thin film (thickness of the resin layer/thickness of the transparent plastic thin film) is ranged from 0.1 to 5.0.

Description

200804082 IX. Description of the invention: • Technical field to which the invention pertains -. The invention is a film market suitable for optical applications with excellent transparency, high surface hardness, weather resistance, tensile strength, durability and heat resistance. Body, and the method of its manufacture. θ [Prior Art] k is a polyethylene terephthalate (G), a ring-like polymer (G), and a ring-copolymer (_ represents a translucent film), which is a transparent pot for use. In recent years, it has been used for various optical materials used in liquid crystal displays, front panels and anti-reflection panels used in flat panel displays, etc. Transparent plastic films such as PET C0P and coc are excellent in transparency, but high in surface. The properties of hardness, weather resistance, chemical resistance, durability, and heat resistance are not sufficient. Here, a method of applying a photocurable resin electroformed material to the surface of the transparent plastic film to protect the surface is proposed. In the case of the above-described method, the above-described method has been proposed, and is proposed in Japanese Laid-Open Patent Publication No. Hei 9-131841 (Patent Literature!). A surface hardening layer is provided on the surface of the PET film by a laminate film containing a vinegar tree and a melamine-based crosslinking agent as a main constituent component, thereby improving the surface hardness. In the case of the surface hardness, the improvement of the surface hardness is not affected by the improvement of the chemical resistance, the durability, and the heat resistance. In addition, in Japanese Patent Publication No. 2_-130540 (Patent Document 2) It is proposed that the ultraviolet curable resin coating composition is transferred between a poly-carbonic acid-PC (PC) tree-formed sheet and a synthetic resin film, and after being pressed, the resin composition is cured by 329396 5 200804082, and the resin is cured. Laminar body. However, by = household, Na's π for transparency, _sheng, and resistance: although the film-laden layer can be found without special review. Furthermore, ::, promotion, but related In the heat resistance (Patent Document 3), the purpose of the invention is to improve the surface protection by the electron ^ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Obtaining the tempering;: The film is laminated. However, the improvement of the obtained film--the excellent poetic film is not touched. The quality, durability, and heat resistance of the film [Patent Document 1] Japanese Patent Publication No. 9-131841 (Patent Document 2) [Patent Document 3] Japanese Laid-Open Patent Publication No. 2003-261819. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) An object of the present invention is to provide a film laminate which is transparent and which is manufactured High surface hardness and weather resistance 1 1 1 1 1 1 1 1 1 1 口 口 口 口 口 口 口 口 口 & & & & & & & & & & & & & & & & & & & & & & & & & & & & & The surface of the transparent plastic film having a glass transition temperature is coated and cast with a photocurable resin composition containing a photo-curable cage-type sesquiterpene oxide resin, and the photocurable resin composition is photocured. The present invention can be obtained by obtaining a film laminate having a transparency, a high surface hardness, a weather resistance, a chemical resistance, a durability, and a heat resistance of 319396 6 200804082. • The invention is a thin film laminate which is composed of a resin layer having a light transmittance of 90% or more at a wavelength of 55 Å nm and a glass transition temperature of 250 ° C or more, and a glass transition temperature of ? (The rc is less than 2 inches of transparent enough to form a laminate. The characteristics of the laminate include: the resin layer is a photocurable resin composition containing a half-baked resin. #严声* Resin layer and transparent plastic film The thickness ratio (the thickness of the resin as long as the thickness of the transparent plastic film) is 0.1 or more and 5.0 or less. The second method:::=::: the manufacturing method of the layer body, which is a method of manufacturing the second product = thin film laminated body The manufacturer knows that the temperature is 70 in the glass transition. (: On the single side of the 220 type, it will contain a photohardenable cage * hardening extension: make the transmittance w 〇 into a wavelength of 550 nm. The sheep is top and the glass transfer temperature is 25 generations or more> 曰' and the thickness of the resin layer and the transparent plastic film 曰 + the thickness of the transparent plastic film becomes 01 or more and (# layer thickness is mentioned by the way, the so-called sheet The ratio of t ^ is small and thin and flat. The thickness of the system is extremely small and wide compared with the width and width; 7 is: (the thickness of the system is often referred to as the drum type. Therefore, the product It can also be called a film, because the thin film and the film are not thin. The difference between the two is that it is difficult to be a "film" in the present specification. The both sides of the λ film "binding film" are defined as 319396 7 200804082 (Effect of the invention) The film laminate according to the present invention and the method of manufacturing the same, Applying a photocurable resin composition containing a photocurable cage-type sesquiterpene oxide resin to a transparent plastic film, curing the photocurable resin composition, and laminating the resin layer in a transparent plastic film Since the film is provided, a film laminate which is excellent in transparency, high surface hardness, weather resistance, chemical resistance, durability, and heat resistance can be obtained. The film laminate system is particularly suitable for optical applications, and is suitable, for example, for a liquid crystal display. A touch panel, an optical film with a transparent electrode, an optical film such as a lens sheet, or a transparent substrate, etc. Therefore, the industrial use value of the present invention which is possible to obtain a ruthenium laminate of 2 is extremely high. [Embodiment] Hereinafter, a film laminate according to the present invention and a method for producing the same will be described in detail in a suitable embodiment. In the present invention, the layer is laminated. The resin layer of the plastic film must be heated to a temperature of 5ΓΓ5 (the light transmittance is 9n or more and the glass transition temperature is more than...^. When forming such a resin layer, use the cage containing: light=half The photocurable wax of the tender tree wax has a cage type sesquis oxide resin in the composition of the chemical resin composition, and is contained in an amount of 3% by weight or more, more preferably 5 to 30%. Heavy = not on the Wei Wei. If the light hard and pure cage type half-stone Xixia burning = less than 3 heavy, the obtained film laminate is important in touch panels and basin hair machines. The heat-resistance property will become insufficient. Therefore, even if the content of the halved stone-heating tree is the same, the glass transfer 319396 200804082 • ==!, the other resin used in the tree (four) is used, private; Degree and female movement, so it is appropriate to adjust the sesquiterpene oxygen resin, which contains. The resin layer laminated on the transparent (tetra) film has a light transmittance of 9 % or more at a wavelength of 55 Å. If the light transmittance is less than _, the obtained film laminate will have insufficient light transmittance in the use of a transparent film such as a touch panel or other electronic equipment, and there is a problem in the visibility of the surface. Further, the glass transition temperature of the resin layer is 25 or more. If the glass transition temperature is less than 25 (rc, the obtained film laminate is insufficient in heat resistance characteristics such as touch panels and other electronic devices. The higher the thermal temperature of the resin layer of the laminate, the better the transparency of the resin layer of the laminate, the high surface hardness, the weather resistance, the musicality, and the durability. As the photocurable cage type sesquiterpene oxide resin, for example, the following may be used. First, the first system is obtained by the following general formula (i) RSiXs (i) (however, R is ( a hydrazine compound represented by any one of a methyl propylene group, a propylene group or a vinyl group; and a hydrazide represented by a hydrolyzable group) is hydrolyzed in the presence of an organic polar solvent and a basic catalyst. After the partial condensation is carried out, the obtained hydrolyzate is subjected to recondensation in a nonpolar solvent and a basic catalyst to form a cage sesquioxane resin. Further, the second system is represented by the following formula (2). [RSi〇3/2]n (2) 319396 9 200804082 • (only 'R 4 has (曱Any of the organofunctional groups of any of the propylene-based, epoxy-propyl or ethylene-based groups; n is a cage-type sesqui-half, a naphthene resin as shown in 8, 1G, 12, or 14). (5) Further, 'the third system is in the general formula (1), and R is represented by the following general formulae (3) and (4).

On. CKs CH, 丨ι_ —. ( g> (only, Hi is an integer of 1 to 3, and Ri represents a nitrogen atom or a methyl group) is an organofunctional group cage sesquiterpene oxide. In the clarification, the complex sesquiterpene oxide resin is preferably an organic compound having a (meth) propylene, a base, an epoxy propyl group or an ethylene group in which the molecular weight distribution and the molecular structure are controlled. a reactive sulphate-based sesquioxane resin composed of a base. The photocurable composition of the present invention may have such a cage-type sesquiterpene oxide resin, or The resin mixture contained in the main component or another component such as a component having a different number of n, and the cage sesquioxane resin may be an oligomer. Here, the cage-containing sesquiterpene oxide resin is mainly used. In the resin mixture of the component, the resin which is suitable for mixing is not particularly limited as long as it is compatible with the cage sesquioxane resin, but is a (fluorenyl) acrylate and a % oxyresin. If it is better, as long as it does not hinder the photohardenability, it is also hardened by light. A filler-based additive is added to the raw resin composition. 319396 10 200804082 Agent. Two ==== often used for photopolymerization initiation, but also can be used to remove the volatilization of the medium by using light hardening == when the solvent is used as a diluent. The step takes time and the production effect "(4) 2;: 4 exists in the inside of the resin layer obtained after hardening, resulting in a decrease in the characteristics of the melon thick boat, etc., and the content of the solvent is preferably limited to _ 5 skin ============================================================================================================ The thickness of the resin layer obtained by hardening the material in February: the thickness ratio of the transparent plastic film (the thickness of the resin layer thick transparent plastic film) becomes 〇} 曰 度. The ratio is less than 〇", the resin layer becomes the following. In the thickness of the furnace, the first layer of the furnace is passed through, and the south of the photocurable resin composition is not fully utilized. Therefore, it cannot be expected to be used in the base: the heat-resistant properties of the plastic-bonded film are improved. If the thickness is especially: "The layer becomes too thick' The lipid layer is easily broken, and the film layer is cracked, and the obtained skin is easily formed. At the same time, the heat resistance of the film laminate itself is lowered due to the generation of wheat in the resin layer. The photo-curable tree mb is coated on both sides of the transparent plastic film of the substrate, and is a film laminate composed of a three-layer structure of "tree wax layer_transparent plastic film_resin layer". : "Resin layer - transparent plastic film" in the early face, which can further reduce the bending or deformation of the film laminate. In addition, it is formed on both sides of the transparent plastic film; 319396 11 200804082 When the grease layer is made to satisfy the respective resin layers Ben Jia: That is, for example, the two conditions of the resin layer and the transparent plastic film are the ratio of the thickness of each resin layer to the thickness of the transparent plastic film: the ratio is preferably in the manner of. In addition, the two resin layers may be separated from each other: the photocurable resin composition applied to each surface in the above range may be different, or the transparent plastic film may have a transmittance of m or more. good. If the light transmission is 550nra, the light film accumulates the total π product, and the first transmittance is less than 80%, then the light transmission will be obtained in the use of transparent film such as other electronic devices. Becomes insufficient, ❿ : = Ming plastic film, using glass transfer temperature (four) = degree M 70C or more. If the glass transition temperature is not caught, it may be deformed or bent by heat in a southerly environment such as a vehicle. Then, the glass transition temperature is 22 (the transparent plastic film below rc has a failure. When the heat-resistant temperature of the transparent plastic film exceeds 2 2 0, the film has a heat resistance, and the laminate of the present invention is produced. The intention of the bulk structure is smaller. As a material of such a transparent plastic film, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PE, polyparaphenyl) can be exemplified. Butane dicarboxylate (PBT), cycloolefin polymer (c〇p), cyclic olefin co-support (C0C), polycarbonate (pc), acetate, acrylic acid, fluoroethylene, poly A film such as a phthalamide, a polyarylate, a cell 〇 e 、 聚醚 聚醚 聚醚 聚醚 聚醚 降 降 降 降 降 降 降 降 降 降 降 降 降 降 降 降 降 降 且 且 且 且 且 且 且 且 且 且 且 且It is preferred to obtain polyethylene terephthalate (PET), polyethylene naphthalate (pen), cycloolefin polymer (COP), and cyclic olefin copolymer (C0C) in which each characteristic is balanced. Adhesion with 12 319396 200804082 resin layer excellent adhesion, for example, thin surface: 隹二: Surface treatment with wire irradiation treatment of resin layer, electric treatment, electric discharge treatment, UV-free treatment, etc. About transparent plastic Μ胜 & @ _ heart to / - thickness 'must meet its The ratio of the thickness to the resin layer, but in the case of the individual acne _ Λ ^ early g degree, the thickness of the transparent plastic film is u5mm, and the π ^ 士早1 soil field does not reach 0.05πιιϊι, It may be hardened by the resin layer

It may be deformed by shrinkage or may not be (4) Tension at the time of coating = It may be a flat surface, or a surface shape which does not hinder transparency of the processor H. * Since the photocurable resin composition is in a liquid form, a known coating device = coating can be used. However, if a hardening reaction is caused by using a coating head, the gel-like object may become a line or foreign matter. 'So it is ideal that the UV light is not irradiated onto the coating head. In terms of coating method, gravure coating 'roller coating, reverse coating, knife coating, die coating, up coat, blade coating can be used ( A known method such as d〇ct〇r blade coat), extrusion coating, slit coating, wire bar coating, curtain coating, extrusion coating, and spin coating. The photocurable resin composition is subjected to photocuring after being applied and cast on a transparent plastic film, and this photohardening is generally performed by an ultraviolet irradiation method. UV light is used to generate and illuminate ultraviolet light. In the ultraviolet lamp, there may be any one of a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a pulse type xenon lamp, an iSl/mercury mixed lamp, a low temperature germicidal lamp, an electrodeless lamp, or the like. Among these ultraviolet lamps, a metal halide lamp or a high pressure mercury lamp is preferred as 319396 13 200804082. Irradiation conditions vary depending on various lamp conditions, but the exposure amount may be about 20 to 10000 inj/cm2, preferably ^ to , , ' ι_(Χα„, and, in terms of efficient use of light energy, purple It is preferable that the lamp is provided with a reflector having an elliptical shape, a radiation type, a diffusion type, or the like, and a heat cut filter or the like may be provided as a cooling countermeasure. Further, the ultraviolet lamp is irradiated with a cooling crack. It is preferable that the device can suppress the thermal deformation of the transparent rear line temple caused by the heat generated by the ultraviolet rays. In terms of cooling method, there are known methods such as air cooling method and water cooling method. Since the radical reaction is carried out, the anti-2 is suppressed by the oxygen. Therefore, although the (four) curable resin composition is applied and k is extended to the transparent plastic film, photohardening is performed, but coating and casting are performed. After that, in order to prevent the suppression of positive oxygen, it is preferred to apply a vapor-recovery film on the photocurable resin composition and to make oxygen/oak on the wide surface of the liquid photocurable resin of the cast material. The degree is 1% or less, and more preferably the oxygen concentration is 0. 1% •, in order to reduce the oxygen concentration, it is necessary to use a transparent ruthenium film with no pores on the surface and an oxygen transmission rate. In the case of a transparent cover film, it can be suppressed (terephthalate PC (polycarbonate) Ester), Polypropylene, Polyethylene, Acetate, C-X-Difluoroethylene, Polyamide, Polyarylate, Raceway, Polyether, and Drop:: Film: Resin-based film, alone or in combination It is used in two or more types. However, the T-coated film must be peeled off from the photocurable resin composition. Therefore, "', and, on the surface of the specific transparent coating film, the coating is applied. [Examples] 14 319396 200804082 The following description of the film laminate and the method for producing the same according to the present invention will be described in detail by way of examples and comparative examples, but the present invention is not subjected to the following embodiments. In the examples or comparative examples, "parts" means "parts by weight". Further, the glass transition temperature of the transparent plastic film used in each of the examples and the comparative examples, and the respective resin layers formed. Light transmittance and glass transition temperature 茱 are not in the table 1 ° light transmittance system The wavelength range of 400 to 800nm in a spectrophotometer i outside the spectral transmission spectrum of visible light, the wavelength at

The transmittance at 550 nm is used as a representative value. The glass transition temperature is measured by a tMA (thermo-mechanical analysis) method to determine the change in the amount of thermal expansion caused by heating by the thermal analysis apparatus, and the value obtained is shown. Further, in the measurement of each resin layer, except that the surface of the transparent plastic film was subjected to a release treatment in advance, it was produced under the same conditions as in the examples and the comparative examples, and then only the resin layer was peeled off, and the light transmittance and the glass transition were measured. temperature. [Example 1] 80 parts of bismethylmethylpropane triacrylate (KS-TMPA, manufactured by Nippon Kayaku Co., Ltd.), sesquiterpene oxide oligomer (structure formula 1 below) 2 parts, hydroxycyclohexylbenzene 2 parts of the ketones (IRGACURE 184, manufactured by Ciba Specialty Chefflicals Co., Ltd.) were uniformly stirred and mixed, and then defoamed to obtain a liquid photocurable resin composition #, and then the liquid photocurable resin composition was put into a coating device. The composition was simultaneously applied to a transparent film (PET/polyethylene terephthalate film) having a width of 3 Å by using a slit die coating method. 〇 _, thickness 〇 · 1mm, transmittance at a wavelength of 550nm on both sides). 319396 200804082 After the 'photo-curing resin coated with transparent cover film (polyethylene terephthalate thin boat, width 3_m, thickness 〇. lmra, transmittance _ above), press-bonded from both sides The photochemical lamp irradiates ultraviolet rays from both sides at a ratio of 5 〇 ^ iu / cm 2 . The early edges of the resin layers obtained by hardening were each made U5 mm. Then, the transparent cover film was peeled off and removed to obtain a three-layer structure of "resin layer (thickness: 〇〇 5 mm) _ transparent plastic film (thickness 1 coffee) - resin layer (thickness: 〇. 〇 5 touch)" Thin film laminate (total thickness: 〇. 2mm). Further, the results of measuring the respective resin ratios were 85% or more. Structure 1

[Example 2] The photocurable resin composition obtained in the above Example 投入 was placed in a coating apparatus, and the composition was simultaneously applied to a transparent film which was taken up in a minute by a slit die coating method ( The c〇c··cycloolefin copolymer film has a width of 300 mra, a thickness of 〇·mmm, and a transmittance of π% or more at a wavelength of 55 〇 nm). Then, after the photocurable resin which has been coated with a transparent cover film (polyethylene terephthalate film, 300 mm in width, thickness 〇 · imm, transmittance 90% or more) is pressed from both sides, metal halide is used. The object lamp illuminates the ultraviolet rays from both sides at a ratio of 500 m j / cm 2 . The thickness of the single side of the tree sap layer obtained by hardening is 〇· 〇5_. Then, the transparent cover thin film 16 319396 200804082 film was peeled off to obtain a three-layer structure of "resin layer (thickness: 0.05 mm) - transparent plastic thin film (thickness: G.lmnO-resin layer (thickness: n)" (four) • The film laminate (consistent itch, nn, 、, 曰 、, 寸 ' 子 2 2 2 mm). The result of measuring the reaction rate of each resin layer is 85% or more. Example 3] The photocurable resin composition obtained in the above Example 1 was placed in a coating apparatus, and the composition was simultaneously applied to a transparent film (PEN: rolled out per minute) by a slit die coating method. A film of polyethylene naphthalate film having a width of 300 mm and a thickness of 〇.lmm and a transmittance of 55 〇nm at both sides). Then, for a coated transparent cover film (poly(p-benzoic acid) After the photocurable resin having a thickness of 3 GGmm 'thickness 〇. lmm 'transmittance of 9 Q% or more) is pressed from both sides, the ultraviolet ray is irradiated from both sides at a ratio of 50 〇mJ 7 cm 2 using a metal halide lamp. And the thickness of the single side of the tree B layer obtained is 〇. 〇 5mm. The transparent cover film was peeled off and removed, and a three-layer structure of "resin layer (thickness: 0 05 mm)_transparent plastic ς thin film (thickness: 0.1 mm) - resin layer (thickness: 〇〇 5 mm)" was obtained. In the film laminate (total thickness: 0.2 mm), the reaction rate of each resin layer was measured to be 85% or more. 实施 [Example 4] The photocurable resin composition obtained in the above Example 1 was put into a coating device. The composition was simultaneously applied to a transparent film which was rolled out by a slit die coating method (PET: polyethylene terephthalate film, 1 300 mm 'thickness 〇. 2 mm' wavelength 550 nm The transmittance of the time is on both sides of the above. Then, for the transparent cover film (polyethylene terephthalate 319396 17 200804082 ethylene ester film, width 300roro, thickness 〇 · lmm, transmittance 9 〇 % or more) After the photocurable resin was pressure-bonded from both surfaces, the ultraviolet ray was irradiated from both surfaces at a ratio of 500 m j/cm 2 using a metal halide lamp, and the thickness of the single k of the eucalyptus layer obtained by hardening was 〇 2 mni. Then, peel off the transparent cover film A film laminate composed of a three-layer structure of "resin layer (thickness: 〇. 〇 2 mm) _ transparent plastic film (thickness: 0.2 mm) - resin layer (thickness: 〇〇 2_)" was obtained, (total thickness: 〇24 mm) Further, the result of measuring the reaction rate of each resin layer was 85% or more. [Example 5]

The photocurable resin composition obtained in the above Example 1 was placed in a coating device. The slit film coating method was applied to the transparent film (PET: poly pair). A film of ethylene phthalate, a width of 300 coffee, a thickness of l.lmm, and a transmittance of 9 (10) or more at a wavelength of 55 〇 nm). Then, after the photocurable resin coated with the transparent cover film (polyethylene terephthalate film, width 300, thickness 〇 1 leg, transmittance: 9% by weight or more) is pressed from both sides, metal is used. The functional lamp illuminates the outer line from both sides at a ratio of 500 m j/cm 2 . The private ones obtained by hardening: the thickness of the single side of the moon layer is 〇. 5 coffee. Then, the transparent cover film was peeled off and removed to obtain a three-layer structure of "resin layer (thickness: G. 5·) - transparent plastic thin plate (thickness: G.lmm) - resin layer (thickness: Q 5 mm)" Thin film laminate (total thickness: h lmm). Further, the result of measuring the reaction rate of each resin layer was 85% or more. [Example 6] 80 parts of dihydroxydecylpropane triacrylate (319396 18 200804082 KS-ΤΜΡΑ, manufactured by Nippon Kayaku Co., Ltd.), sesquioxane oligomer (the following structural formula 2), 2 parts, 2.5 parts of mercaptohexyl phenyl ketone (IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was uniformly stirred and mixed, and then defoamed to obtain a liquid photocurable resin composition, and then this liquid photocurable resin composition was obtained. In the coating apparatus, the composition was simultaneously applied to a transparent film (pET: polyethylene terephthalate film), which was rolled out by a slit die coating method, and was 3 Å wide. The thickness 〇·, the transmittance at a wavelength of 55〇nm is 90% or more) on both sides. Then, the photocurable resin coated with a transparent cover film (polyethylene terephthalate film, width 3 〇〇, thickness 〇·1 mm, transmittance 90% or more) is pressed from both sides, and then used. The metal halide lamp irradiates ultraviolet rays from both sides at a ratio of 500 mj/cm2. The thickness of one side of the resin layer obtained by hardening was made 0. 05 mm. Then, the transparent cover film was peeled off to obtain a three-layer structure of an r resin layer (thickness: 〇.05 mm) - a transparent plastic film (thickness: 0.1 mm) - a resin layer (thickness: 〇 · 〇 5 mm). Thin film laminate (total thickness: _ 〇. 2mm). Further, the result of measuring the reaction rate of each resin layer was 85% or more. Structure 2

[Comparative Example 1] The photocurable resin composition obtained in the above Example 1 was applied to a coating apparatus. 19 319396 200804082 In the apparatus, the composition was simultaneously coated by a slit die coating method to be wound out at a per minute. A transparent film (PET: polyethylene terephthalate film, width 300 mm 'thickness 〇 · 1 leg, transmittance at a wavelength of 55 〇, 9 % or more) on both sides. Then, the photocurable resin which has been coated with a transparent cover film (polyethylene terephthalate film, width 300 Å, thickness 〇·1 匪, transmittance: 9〇% or more) is pressed from both sides, and then used. The metal toothed lamp irradiated the purple=line at a ratio of 500 mj/cm2 from both sides. The one side of the tree sap layer obtained by hardening is each 〇 · (10) 5 _. Then, the transparent cover film was peeled off and removed, and the "resin layer (thickness: 〇〇〇5 匪) - transparent film (thickness: ο·ι匪) - resin layer (thickness: 〇〇〇 5 mm)" was obtained. A film laminate composed of a layer structure (total thickness: 〇· Umm). Further, the result of measuring the reaction rate of each resin layer was 85% or more. [Comparative Example 2] The photocurable resin composition obtained in the above Example 1 was placed in a coating-coating method. The slit-die coating method was applied to the composition at the same time. Film (PET: : polyethylene terephthalate film,

·. 6mro ) - Transparent plastic thin • 6mm)" three-layer structure 319396 20 200804082 Thin waist laminate (total thickness: 1 · 3mm). Further, the % reaction rate of each resin layer was measured and found to be 85 % or more. ^ [Comparative Example 3] 90 parts of sesquioxane-enriched polymer of di-light methyltricyclic terpene diacrylate (Light-acrylate DCP_A, manufactured by Kyoeisha Chemical Co., Ltd.) (with the above structural formula 1) The same) ιο parts, hydroxycyclohexyl phenyl ketone (1 RGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were uniformly stirred and mixed, and then defoamed to obtain a liquid photocurable resin composition, which was then subjected to liquid photohardening. The resin composition was placed in a coating apparatus, and the composition was simultaneously applied to a transparent film (PET/polyethylene terephthalate film), which was rolled out at a per minute, using a slit die coating method. 〇〇匪, the thickness 〇 · 1mm, the transmittance at a wavelength of 550nm is 90% or more) on both sides. However, the photocurable resin which has been coated with a transparent cover film (polyethylene terephthalate film) having a width of '300_, a thickness of 〇1 mm and a transmittance of 9% by weight or more) is pressed from both sides, and then used. The metal halide lamp irradiates ultraviolet rays from both sides at a ratio of 500 mj. The resin layers obtained by hardening are each uniformed to 2 单. Then, the transparent cover film is peeled off and removed to obtain a "resin layer ( Thickness: 0·05 mm) - a thin film laminate composed of a three-layer structure of a transparent plastic film (thickness: 〇lmm) and a = fat = (thickness: 0. 05 liter) (10 dryness · 〇 · 2 mm). Further, the knot of the reaction rate of each resin layer was measured to be 85% or more. For the film laminate obtained in the above examples and comparative examples, as in 319396 21 200804082 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Light transmittance of resin layer (%) 91 91 91 91 91 Tg(〇C) >300 >300 >300 >300 >300 Transparent Plastic Film TgCC ) 72 170 120 72 72 Thickness of Resin Layer / Thickness of Transparent Plastic Film " 0. 5 0. 5 0.5 0 · 1 0.5 Example 6 Light transmittance of resin layer (%) 91 Tg (°C) > 300 Transparent plastic film Tg (°C) 72 Thickness of resin layer / Thickness of transparent plastic film 0· 5 Comparative example 1 Comparison Example 2 Comparative Example 3 Light transmittance of resin layer (%) 91 91 91 Tg (°C) >300 > 300 210 Transparent plastic film Tg (°C) 72 72 72 Thickness of resin layer / thickness of transparent plastic film" 0.05 6. 0 0· 5 *ι : "Thickness of Resin Layer / Thickness of Transparent Plastic Film" means "the thickness of the resin layer on one side" and "in the resin layer of the two layers of each film laminate" The thickness of the transparent plastic film is compared to the value. [Evaluation method: surface hardness measurement test] According to the pencil hardness method (JIS-K5400), pencils of various hardnesses are drawn at a load of lkg on the surface (resin layer) of the obtained film laminate at an angle of 90 degrees. Pencil hardness at the time of injury. The results are shown in Table 2. [Evaluation method: financial evaluation test]

Using a hot air oven, the change in the physical property value of the obtained film laminate after heating at 201 ° 22 22 319396 200804082 for 1 hour was evaluated based on the following criteria. 〇. After the heat test, the physical property values are not reduced. • X. After the heat resistance test, the physical property values are lowered. The results are shown in Table 2. [Evaluation method: Appearance evaluation] The appearance evaluation after the production of the obtained film laminate was evaluated based on the following criteria. _〇: There is no appearance abnormality such as cracks on the surface of the laminate. X: Appearance abnormalities such as cracks on the surface of the laminate. The results are shown in Table 2. [Table 2]

Example 1 Example 2 Example 3 Example 4 Example 5 Surface hardness measurement 4H 4H 4H 4H 4H Heat resistance evaluation 〇〇 - 〇〇〇 Appearance evaluation 〇〇〇〇〇 Example 6 Surface hardness measurement B Heat resistance evaluation X Appearance evaluation 〇Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface hardness measurement B 4H ~ 4H Heat resistance evaluation XXX Appearance evaluation 〇 XX

[Industrial Applicability] The present invention provides a film laminate using a photocurable resin composition and provides a method for producing the same. The obtained film laminate system is suitable for the optical field of 319396 23 200804082 which has transparency, high surface hardness, weather resistance, chemical resistance, durability and t ^ heat, and in particular, can be applied to various types including liquid crystals. A display substrate, a touch panel, a film with a transparent electrode, a lens sheet, an optical waveguide, a solar cell substrate, a optical disc, and various transparent substrates used for the display are used.

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Claims (1)

200804082 X. Patent application scope: L A film laminate consisting of a resin layer having a light transmittance of 9 〇/° or more at a wavelength of 550 nm and a glass transition temperature of 250 ° C or higher, and a glass transition temperature of 70 t: A thin film laminated body formed by laminating a transparent plastic film of 22 Å or less, characterized in that the resin layer is composed of a photocurable resin containing a cage type sesquiterpene oxide resin containing / and a light 11 The material is hardened, and the thickness of the resin layer and the transparent plastic film is less than 5 · 0 or less than the thickness of the leather (1⁄4 fat layer thickness + transparent plastic film thickness). 2. For example, a film laminate having a range of μ in the application range, wherein the layer of the tree layer is laminated on both sides of the transparent plastic film of the enamel laminate. 3. \Applicable to the film laminate of item 1 or 2 of the patent scope, wherein the dragon type double-cut oxygen (four) fat fine-off type (2) is a cage type sesquito compound: mouth L RS i 〇 3/2 ] η (2) (R, R is an organic functional group having either (meth)acrylic, propyl or vinyl; 11 is 8, 1 (), 12 or 14) . For example, the film laminate of the first or second aspect of the patent application, ", == semi-nen resin, by the following general formula (1), shows the stone: the organic polar solvent and the organic touch After the hydrolysis reaction is carried out in the presence of the medium and a part of the condensation is carried out, the hydrolyzed product of the Μ ^ ^ ^ ^ ^ 于 于 于 于 于 于 人 人 人 人 人 人 人 人 人 人 人 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解 水解倍半石夕(1) RSiXs 319396 25 200804082 (only 'R is an organic functional group having either (meth)acrylonitrile, epoxypropyl or vinyl, or the following formula (3) , (4) or (5) (However, 'm is an integer of 1 to 3, R1 represents a hydrogen atom or a fluorenyl group; and X represents a hydrolyzable group). 5. A method for producing a multilayered membrane layer comprising a resin layer and a transparent plastic film, wherein the glass transition temperature is 70° C. or more and 22 CTC or less. On one side of the film, a photocurable resin composition containing a photocurable cage type sesquiterpene oxide resin is applied and cast, and the photocurable resin composition is photocured to form a wavelength of 55 〇. In the case of a resin layer having a light transmittance of at least % and a heat-resistant temperature of 25 CTC or more, the thickness ratio of the resin layer to the transparent plastic film (thickness of the resin layer + thickness of the transparent plastic film) is not less than 5 Å. 6. The method for producing a film laminate according to claim 5, wherein the photocurable resin composition (four) is cast on the remaining one side of the transparent plastic film, so that the light hard pure tree is frequently formed. The material is photohardened to form a resin layer. 319396 26 200804082 VII. Designation of the representative figure··β (1) The representative representative of the case is: (). - (2) A brief description of the symbol of the representative figure: 10 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: RSiXs (1) 319396