TWI703040B - Layered body - Google Patents

Abstract

The subject of the present invention is to suppress the peeling between the base material and the cured resin layer while ensuring the bending resistance. The solution of the present invention is a laminate (1) comprising a substrate (2) with a thickness of 5-24 µm and a hardened resin layer (3) laminated on the substrate (2). The base material (2) contains a cycloolefin resin, a metal (2M) of group 6 of the periodic table, and an alicyclic monomer (2P). The hardened resin layer (3) contains acrylic resin and an alicyclic monomer (3P).

Description

Layered body

The present invention relates to a laminate in which a hardened resin layer (hard coat layer) is laminated on a substrate.

In recent years, transparent touch panels have been used as input devices on displays of various electronic devices. As the form of the touch panel, a resistive film type or a capacitance type, etc. can be cited. The resistive touch panel is used in input devices such as home appliances, and can also be input with a dedicated pen. Capacitive touch panels are mostly used in mobile devices because they can be input by multi-touch.

In any form, the touch panel has a transparent conductive layer that serves as an electrode on the substrate. In recent years, in view of processability, light weight, economic efficiency, etc., as the above-mentioned base material, a transparent plastic film is used instead of a glass substrate. In addition, for the purpose of improving durability during pressing input, a cured resin layer is generally provided on a transparent plastic film (for example, refer to Patent Document 1).

Furthermore, in recent years, the flexibility of the device has been demanded, and with this, both the base material and the cured resin layer have been required to be thinned while ensuring the bending resistance. In particular, it is required to thin the substrate, which accounts for most of the thickness. However, if the base material is made into a thin film, the toughness (rigidity) of the base material becomes weak. Therefore, in order to form a transparent conductive layer on a laminate with a hardened resin layer laminated on the base material, if the laminate is transported, it will be transported. Minute wrinkles (before contact with the transfer roller, the cross section becomes a wavy state, equivalent to "wrinkle" in English), there is a concern that interlayer peeling may occur between the base material and the hardened resin layer.

Therefore, for example, in Patent Document 2, a (meth)acrylate having a phosphoric acid group is contained in a curable composition, and the curable composition is coated on a cycloolefin resin film as a substrate to make It hardens to improve the adhesion between the base material and the hardened resin layer. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-34207 (refer to claim 1, paragraph [0005], [0006], etc.) [Patent Document 2] JP 2014-189566 A (refer to Claims 1, 4, paragraphs [0008] to [0011], [0034], [0040], etc.)

[The problem to be solved by the invention]

However, in Patent Document 2, the thickness of the cycloolefin resin film used as the substrate is set to 50 to 200 µm from the viewpoint of suppressing curling. When the substrate is further thinned, the toughness of the substrate is weakened, and wrinkles are likely to occur during transportation. Therefore, in a state where the substrate is further thinned, even by the method of Patent Document 2, it is difficult to suppress the delamination.

The present invention was completed in order to solve the above-mentioned problems, and its object is to provide a laminated body that can reduce the occurrence of wrinkles during transportation even when a hardened resin layer is formed on a filmed substrate and transported. Ensure the bending resistance while suppressing delamination between the base material and the hardened resin layer. [Means to solve the problem]

The above object of the present invention is achieved by the following configuration.

1. A layered body characterized by: Substrates with a thickness of 5-24µm, and A hardened resin layer laminated on the aforementioned substrate; The aforementioned base material includes cycloolefin resin, metal of group 6 of the periodic table, and alicyclic monomer, The said hardening resin layer contains an acrylic resin and an alicyclic monomer.

2. The laminate as described in 1 above, wherein Take the thickness of the aforementioned substrate as d(µm), From the surface of the substrate opposite to the side in contact with the cured resin layer to a depth of d/5 (µm), it is regarded as the lower layer of the substrate, When the surface of the substrate on the side in contact with the cured resin layer to the depth of d/5 (µm) is regarded as the upper layer of the substrate, There is a difference in the concentration of the alicyclic monomer between the upper layer of the substrate and the lower layer of the substrate.

3. The layered product according to the above 2, wherein the concentration of the alicyclic monomer in the upper layer of the substrate is greater than that of the lower layer of the substrate.

4. The layered product according to the above 2, wherein the concentration of the alicyclic monomer in the upper layer of the substrate is lower than that of the lower layer of the substrate.

5. The layered product according to any one of 1 to 4 above, wherein in the cured resin layer, from the surface of the side in contact with the base material to the center in the thickness direction is regarded as a resin underlayer, When the surface on the side opposite to the side in contact with the substrate reaches the center in the thickness direction as the upper resin layer, the alicyclic monomer exists only in the lower resin layer.

6. The laminate according to any one of 1 to 5 above, wherein the alicyclic monomer contained in the base material is dicyclopentadiene or tetracyclododecene.

7. The layered product according to any one of 1 to 6, wherein the alicyclic monomer contained in the cured resin layer is the same as the alicyclic monomer contained in the substrate.

8. The laminate according to any one of 1 to 7, wherein the metal contained in the substrate is tungsten, molybdenum, or chromium. [Effects of the invention]

Even when transporting a laminate with a hardened resin layer formed on a substrate with a thickness of 5-24 µm, it can reduce wrinkles during transport. Therefore, it is possible to suppress interlayer peeling between the base material and the cured resin layer while ensuring the bending resistance of the laminate.

[The form of implementing the invention]

In an embodiment of the present invention, if it is described based on the drawings, it is as follows. In addition, when the numerical range is described as A to B in this specification, the value of the lower limit A and the upper limit B are included in this numerical range.

[The composition of the layered body] Fig. 1 is a cross-sectional view showing the schematic configuration of a laminate 1 of this embodiment. The laminate 1 includes a base 2 and a cured resin layer 3 laminated on the base 2. The thickness of the substrate 2 is 5-24 µm. The base material 2 includes a cycloolefin resin, a metal 2M of group 6 of the periodic table, and an alicyclic monomer 2P. The hardened resin layer 3 contains acrylic resin and an alicyclic monomer 3P.

With the above-mentioned configuration, it is possible to suppress interlayer peeling between the base material 2 and the cured resin layer 3 while ensuring the bending resistance of the laminate 1. As for the reason, the inventor of this case inferred as follows.

(1) First, the alicyclic monomer 2P contained in the base material 2 diffuses into the hardened resin layer 3 (the composition for forming the hardened resin layer) when the hardened resin layer 3 is formed, and passes through the base 2 The alicyclic monomer 2P interacts with the alicyclic monomer 3P in the hardening resin layer 3, and the adhesion between the base material 2 and the hardening resin layer 3 is improved.

(2) By including the metal 2M in the base material 2, the hardness of the base material 2 increases. Furthermore, by selecting a specific metal (metal of Group 6 of the periodic table), the surrounding resin can be aggregated by the metal 2M, and therefore the resin density of the base material 2 is increased. Due to the synergistic effect of the increase in the hardness of the base material 2 and the increase in the density of the resin, even if the thickness of the base material 2 is as thin as 5-24 mm, the base material 2 itself can be made tough (rigid), which can prevent The cause of the peeling between the base material 2 and the cured resin layer 3 is wrinkles during transportation. Furthermore, by thinning the substrate 2, the laminate 1 becomes flexible, and the bending resistance of the laminate 1 can also be ensured.

(3) By adding the alicyclic monomer 2P and the specific metal 2M to the substrate 2 at the same time, it is inferred that it has the effect of promoting the diffusion of the alicyclic monomer 2P to the side of the hardened resin layer 3, thereby promoting the above (1) The adhesion is increased.

For the reasons (1) to (3) above, even if the substrate 2 is as thin as 5-24 mm in thickness, the adhesion between the substrate 2 and the cured resin layer 3 can be improved, and toughness can be imparted to the substrate 2. Therefore, while ensuring the bending resistance of the laminate 1 by thinning the substrate 2, it is possible to suppress the wrinkles of the laminate 1 during transportation and prevent the interlayer peeling of the substrate 2 and the cured resin layer 3.

Here, the thickness of the base material 2 is regarded as d (µm), and the surface of the base material 2 from the side opposite to the side in contact with the cured resin layer 3 to a depth of d/5 (µm) is regarded as the base material The lower layer 2a, the depth of d/5 (µm) from the side in contact with the hardened resin layer 3 in the substrate 2 is regarded as the upper substrate layer 2b, and the lower substrate layer 2a and the substrate in the substrate 2 will be removed When the part after the upper layer 2b (the part between the lower substrate layer 2a and the upper substrate layer 2b) is used as the substrate intermediate layer 2c, the upper substrate layer 2b and the lower substrate layer 2c should preferably have the concentration of the alicyclic monomer 2P difference. In this case, the effect of increasing the adhesion between the base material 2 and the cured resin layer 3 can be improved, thereby improving the effect of suppressing delamination between layers. In more detail, it is as follows.

For example, when the concentration of the alicyclic monomer 2P in the upper substrate layer 2b is greater than that in the lower substrate layer 2a, the amount of the alicyclic monomer 2P interacting with the alicyclic monomer 3P of the hardened resin layer 3 is increased. Big. Therefore, by the above-mentioned interaction, the adhesion between the base material 2 and the cured resin layer 3 can be further improved, and the effect of suppressing delamination between layers can be improved.

Also, for example, when the concentration of the alicyclic monomer 2P in the upper substrate layer 2b is lower than that in the lower substrate layer 2a, the alicyclic monomer 2P in the upper substrate layer 2b easily diffuses to the hardened resin layer 3 and the hardened resin layer The alicyclic monomer 3P is easy to interact. Therefore, by the above-mentioned interaction, the adhesion between the base material 2 and the curable resin layer 3 can be further improved, and the effect of suppressing delamination between layers can be improved.

In addition, in the cured resin layer 3, the surface from the side in contact with the substrate 2 to the center in the thickness direction is regarded as the lower resin layer 3a, and the surface from the side opposite to the side in contact with the substrate 2 When the center in the thickness direction is regarded as the upper resin layer 3b, the alicyclic monomer 3P may exist only in the lower resin layer 3a. Since the alicyclic monomer 3P is only present in the resin lower layer 3a, the content of the alicyclic monomer 3P in the hardened resin layer 3 can be kept low, and the adhesion to the substrate 2 can be improved. Since the content of the alicyclic monomer 3P in the cured resin layer 3 is kept low, it is possible to suppress the deterioration of the brittleness of the cured resin layer 3, and to suppress the deterioration of the bending resistance when it becomes a transparent conductive film.

In addition, the alicyclic monomer 2P contained in the substrate 2 may be dicyclopentadiene (DCP) or tetracyclododecene (TCD). In the structure using DCP or TCD as the alicyclic monomer 2P, the above-mentioned effects of this embodiment can be obtained.

In addition, the alicyclic monomer 3P contained in the cured resin layer 3 may be the same as the alicyclic monomer 2P contained in the substrate 2. In this case, since the interaction can be improved by the same type of monomer, the adhesion between the base material 2 and the curable resin layer 3 can be improved by the above-mentioned interaction, and the effect of suppressing delamination between layers can be improved.

In addition, the metal 2P system contained in the base material 2 may be tungsten (W), molybdenum (Mo), or chromium (Cr). By using any of these metals, the effect of increasing the hardness of the base material 2 and the effect of increasing the resin density can be reliably obtained. Therefore, with these synergistic effects, the base material 2 itself has toughness, which can ensure the bending resistance of the laminate 1 while suppressing wrinkles during transportation, and surely obtain the effect of suppressing delamination.

[Substrate] The base material 2 of the laminate 1 contains cycloolefin resin. Examples of cycloolefin resins include the following (co)polymers.

In the formula, R ¹ to R ⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an amide group, a silyl group or a polar group (ie, Halogen atom, hydroxyl group, ester group, alkoxy group, cyano group, amide group, amide group or silyl group) substituted hydrocarbon group.

However, two or more of R ¹ to R ⁴ may be combined with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond or form an aromatic ring. R ¹ and R ² , or R ³ and R ⁴ , can also form an alkylene group. m is an integer of 0 to 3, p is an integer of 0 to 3, preferably m+p=0 to 4, more preferably 0 to 2, particularly preferably m=0, p=1 to 2.

The specific single system with m=0 and p=1～2 is suitable because the obtained cycloolefin resin is excellent in mechanical strength and solvent resistance.

In the above general formula (1), the hydrocarbon group represented by R ¹ and R ³ is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2.

R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ may be a polar group having polarity other than a hydrogen atom and a hydrocarbon group.

Examples of the polar groups of the above-mentioned specific monomers include carboxyl groups, hydroxyl groups, alkoxycarbonyl groups, allyloxycarbonyl groups, amine groups, amide groups, cyano groups, etc. These polar groups may also be separated by methylene groups. The linking base is combined.

Moreover, the hydrocarbon group etc. which have a polar divalent organic group, such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group, become a linking group, and a polar group can be mentioned.

Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, at least one of R ² and R ⁴ is a monomer with a polar group represented by the formula -(CH ₂ ) _n COOR, which is based on the fact that the resulting cycloolefin resin has a high glass transition temperature and low hygroscopicity , It is more suitable for excellent adhesion with various materials. Furthermore, the glass transition temperature mentioned here is a value obtained by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).

In the formula of the aforementioned specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group.

Specific examples of the copolymerizable monomer include cycloolefin resins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.

The carbon number of the cycloolefin is preferably 4-20, more preferably 5-12.

Cycloolefin resins may also have crystallinity. Cycloolefin resins having crystallinity are preferable in terms of excellent heat resistance, mechanical properties, and solvent resistance.

The cycloolefin resin system may be used alone or in combination of two or more.

The preferred molecular weight of cyclic olefin resin is 0.2-5 dl/g, preferably 0.3-3 dl/g, especially 0.4-1.5 dl/g in terms of intrinsic viscosity [h]inh, by gel permeation chromatography. The number average molecular weight (Mn) measured in terms of polystyrene by (GPC) is 8000-100000, preferably 10000-80000, particularly preferably 12000-50000, and weight average molecular weight (Mw) is preferably 20000-300,000, preferably 30000～250,000, particularly preferably the range of 40,000～200,000.

Since the intrinsic viscosity [h]inh, number average molecular weight and weight average molecular weight are within the above range, the heat resistance, water resistance, chemical resistance, mechanical properties of the cycloolefin resin and the molding processability of the optical film of this embodiment are good .

The glass transition temperature (Tg) of the cycloolefin resin is usually 110°C or higher, preferably 110 to 350°C, more preferably 120 to 250°C, particularly preferably 120 to 220°C. When the Tg is above 110°C, it is not easy to deform due to use under high temperature conditions or secondary processing such as coating and printing, so it is more suitable.

On the other hand, since the Tg is 350°C or less, it is possible to avoid the difficulty of molding and suppress the possibility of resin degradation due to heat during molding.

In the cycloolefin resin, within a range that does not impair the effects of the present embodiment, for example, a specific hydrocarbon resin described in Japanese Patent Application Laid-Open No. 9-221577, Japanese Patent Application Laid-Open No. 10-287732, or Well-known thermoplastic resins, thermoplastic elastomers, rubber polymers, organic microparticles, inorganic microparticles, etc., specific wavelength dispersants, sugar ester compounds, antioxidants, peeling promoters, rubber particles, plasticizers, and ultraviolet absorbers can also be added And other additives.

In addition, the cycloolefin-based resins can preferably use commercially available products. As examples of commercially available products, JSR (Stock) uses Arton (registered trademark) G, Arton F, Arton R, and Arton RX. It can be sold under the trade name of Zeonor (Zeonor: Registered Trademark) ZF14, ZF16, Zeonex (Zeonex: Registered Trademark) 250 or Zeonex 280 by Zeonor of Japan. Use this.

[Hardened resin layer] The cured resin layer 3 of the laminated body 1 contains acrylic resin. As the acrylic resin, a cured product of an acrylic active line-curable compound (for example, ultraviolet curing resin) can be used. For example, polyfunctional (meth)acrylate type, urethane (meth)acrylate type, epoxy (meth)acrylate type, polyester (meth)acrylate type active thread curing can be used Hardened substance of sex compound. In addition, a cured polymer of acrylate can also be used.

The cured resin layer 3 is formed by using, for example, a composition for forming a cured resin layer containing the aforementioned ultraviolet curing resin and a photopolymerization initiator, and after the coating film is formed, the ultraviolet curing resin is cured by irradiation with ultraviolet rays. The photopolymerization initiator is not particularly limited, and well-known ones can be used. For example, as the photopolymerization initiator, acetophenones, diphenylketones, and Michler benzyl benzoate can be mentioned. , A-pentyl oxime ester, thioxanthones, phenylacetones, diphenylethylenediones, benzoin, phosphine oxides. Moreover, it is preferable to mix and use a photosensitizer, and as a specific example, n-butylamine, triethylamine, poly-n-butylphosphine etc. are mentioned, for example.

As the photopolymerization initiator, when the ultraviolet curable resin is a resin system with radically polymerizable unsaturated groups, it is preferable to use acetophenones, benzophenones, thioxanthones, and benzidines alone or in combination. Inin, benzoin methyl ether, etc. In addition, when the ultraviolet curable resin is a resin system having a cationically polymerizable functional group, it is preferable to use an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, and a sulfonium salt alone or in combination as the photopolymerization initiator Metal compounds, benzoin sulfonate, etc.

As the photopolymerization initiator, when it is an ultraviolet curable resin having a radically polymerizable unsaturated group, it is preferably 1-hydroxy-cyclohexyl-benzene for the reason that compatibility with the ultraviolet curable resin and yellowing are also low Base-ketone (trade name: IRGACURE 184, manufactured by BASF Japan).

烷、四氫呋喃、丙二醇單甲基醚、丙二醇單甲基醚乙酸酯等)、脂肪族烴類(例如，己烷等)、脂環式烴類(例如，環己烷等)、芳香族烴類(例如，甲苯、二甲苯等)、鹵化碳類(例如，二氯甲烷、二氯乙烷等)、酯類(例如，醋酸甲酯、醋酸乙酯、醋酸丁酯等)、水、醇類(例如，乙醇、異丙醇、丁醇、環己醇等)、溶纖劑類(例如，甲基溶纖劑、乙基溶纖劑等)、溶纖劑乙酸酯類、亞碸類(例如，二甲亞碸等)、醯胺類(例如，二甲基甲醯胺、二甲基乙醯胺等)等，亦可使用此等之混合溶劑。特別地，於酮類之溶劑，至少包含甲基乙基酮、甲基異丁基酮、環己酮中的任一者、或此等的混合物者，基於與紫外線硬化樹脂的相溶性、塗佈性優異之理由而較宜。The composition for forming a cured resin layer may contain a solvent. The solvent can be appropriately selected and used according to the type and solubility of the ultraviolet curable resin component used. For example, as the solvent, ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc.), ethers (for example, two

Alkane, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), aliphatic hydrocarbons (for example, hexane, etc.), alicyclic hydrocarbons (for example, cyclohexane, etc.), aromatic hydrocarbons Types (for example, toluene, xylene, etc.), halogenated carbons (for example, dichloromethane, dichloroethane, etc.), esters (for example, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohol Types (for example, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (for example, methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sludge (For example, dimethylsulfide, etc.), amides (for example, dimethylformamide, dimethylacetamide, etc.), etc., and these mixed solvents can also be used. In particular, the ketone-based solvent contains at least any one of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a mixture of these, based on the compatibility with the ultraviolet curable resin, coating It is more suitable for the reason of excellent cloth property.

In addition, in the composition for forming the cured resin layer, the purpose is to increase the hardness of the cured resin layer, suppress curing shrinkage, prevent blocking, control the refractive index, impart anti-glare properties, control the properties of particles or the surface of the cured resin layer, etc. , Conventional organic particles, inorganic particles, dispersants, surfactants, antistatic agents, silane coupling agents, tackifiers, anti-colorants, colorants (pigments, dyes), defoamers, and leveling agents can also be added Agents, flame retardants, adhering agents, polymerization inhibitors, antioxidants, surface modifiers, etc. In addition, the composition for forming a cured resin layer may include a photosensitizer, and specific examples thereof include n-butylamine, triethylamine, and poly-n-butylphosphine.

The method for preparing the composition for forming the cured resin layer is not particularly limited as long as the constituent components can be uniformly mixed. For example, well-known equipment such as paint shaker, bead mill, kneader, and mixer can be used for mixing. Or prepare by dissolving each component.

In addition, the method for applying the composition for forming a cured resin layer to the substrate 2 is not particularly limited, and examples include spin coating, dipping, spraying, die coating, and bar coating. , Roll coating method, meniscus coating method, flexographic printing method, screen printing method, liquid coating method and other well-known wet coating methods.

[Alicyclic monomer] As the alicyclic monomer contained in the base material 2 and the cured resin layer 3, the monomer represented by the above-mentioned general formula (1) can be used. Here, in the general formula (1), R ¹ to R ⁴ are each independently a hydrogen atom, a hydrocarbon group, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amido group, an imino group, or a silyl group. Or a hydrocarbon group substituted with a polar group (ie, a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an amide group or a silyl group).

However, two or more of R ¹ to R ⁴ may be combined with each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond or form an aromatic ring. R ¹ and R ² , or R ³ and R ⁴ , can also form an alkylene group. m is an integer of 0 to 3, p is an integer of 0 to 3, preferably m+p=0 to 4, more preferably 0 to 2, particularly preferably m=0, p=1 to 2.

The alicyclic mono-system with m=0 and p=1 to 2 is suitable from the viewpoint of excellent diffusibility in cycloolefin resin and acrylic resin.

[Making method of base material] (Solution casting method) FIG. 2 is an explanatory diagram showing the schematic configuration of the manufacturing apparatus 10 of the optical film constituting the substrate 2 of the present embodiment. Moreover, FIG. 3 is a flowchart showing the flow of the manufacturing steps of the optical film. The manufacturing method of the optical film of this embodiment is shown in FIG. 3, including a stirring preparation step (S1), a casting step (S2), a peeling step (S3), a stretching step (S4), a drying step (S5), and cutting The breaking step (S6), the embossing step (S7), and the winding step (S8). Hereinafter, each step will be described with reference to FIGS. 2 and 3.

(S1; stirring and preparation step) In the stirring preparation step, in the stirring tank 11a of the stirring device 11, at least the resin and the solvent are stirred to prepare a dope cast on the support 13 (endless belt). As the above-mentioned resin, the above-mentioned cycloolefin resin can be used. As the above solvent, a mixed solvent of a good solvent and a weak solvent can be used. Furthermore, the so-called good solvent refers to an organic solvent that has the property of dissolving resin (solubility), 1,3-dioxolane, THF (tetrahydrofuran), methyl ethyl ketone, acetone, methyl acetate, Dichloromethane (dichloromethane, methylene chloride), toluene, etc. are equivalent. On the other hand, the so-called weak solvent refers to a solvent that does not dissolve the resin when alone, and methanol or ethanol is equivalent to it.

(S2; Casting step) In the casting step, the dope prepared in the stirring preparation step is passed through a pressurized quantitative gear pump or the like, and the liquid is sent to the casting die 12 through a pipe, and the dope is flowed from the casting die 12 It extends at the casting position on the support body 13 composed of an endless endless belt made of stainless steel which is rotated and driven indefinitely. Then, the support 13 is conveyed while supporting the cast dope (casting dope). Thereby, a web 15 as a casting film is formed on the support 13.

The support body 13 is held by a pair of rollers 13a, 13b and a plurality of rollers (not shown) between them. One or both of the rollers 13a and 13b are provided with a drive device (not shown) that applies tension to the support 13, whereby the support 13 is used in a tensioned state by applying tension.

In the casting step, the web 15 is heated on the support 13 to evaporate the solvent until the web 15 can be peeled from the support 13 by the peeling roller 14. In order to evaporate the solvent, there is a method of blowing air from the side of the net, or a method of transferring heat from the back of the support 13 through a liquid, a method of transferring heat from the surface and back by radiant heat, etc., which can be appropriately singly or combined use.

(S3; Peeling step) In the above-mentioned casting step, the web 15 is dried and solidified or cooled and solidified on the support 13 until it becomes a peelable film strength. In the peeling step, the web 15 is made self-supporting by the peeling roller 14 Peel off. The peeled net 15 constitutes a film substrate.

Furthermore, the residual solvent amount of the net 15 on the support 13 at the time of peeling depends on the strength of the drying conditions, the length of the support 13, etc., and is preferably in the range of 25 to 120% by mass. When peeling at a time when the amount of residual solvent is greater, if the web 15 is too soft, the flatness during peeling will be impaired, and wrinkles or vertical streaks are likely to occur due to peeling tension. Therefore, both economic speed and quality are considered to determine the residual solvent during peeling. the amount. In addition, the amount of residual solvent is defined by the following formula.

The amount of residual solvent (mass%) = (the quality of the net before heat treatment-the quality of the net after heat treatment) / (the quality of the net after heat treatment) ´ 100 Here, the heat treatment at the time of measuring the residual solvent amount means heat treatment at 115°C for 1 hour.

(S4; Extension step) In the stretching step, the web 15 (film base material) peeled from the support 13 is stretched in the conveying direction and/or the width direction by the tenter 16. In the stretching step, a tentering method in which the edges on both sides of the net 15 are fixed by a clip or the like is suitable for improving the flatness or dimensional stability of the film. Furthermore, in the tenter 16, drying can be performed in addition to stretching.

(S5; drying step) The web 15 stretched by the tenter 16 is dried in a drying device 17. In the drying device 17, the web 15 is conveyed by a plurality of conveying rollers arranged in a staggered shape from the side, and the web 15 is dried in the meantime. The drying method of the drying device 17 is not particularly limited. Generally, hot air, infrared rays, heating rollers, microwaves, etc. are used to dry the web 15. From the viewpoint of simplicity, a method of drying the net 15 with hot air is preferred.

After the web 15 is dried by the drying device 17, it is conveyed to the winding device 20 as an optical film.

(S6; cutting step, S7; embossing processing step) Between the drying device 17 and the winding device 20, the cutting portion 18 and the embossing portion 19 are arranged in this order. In the cutting section 18, while conveying the formed optical film, a cutting step of cutting both ends in the width direction with a cutter is performed. In the optical film, after cutting both ends, the remaining part constitutes a product part as a film product. On the other hand, the part cut from the optical film is recovered by a chute, and then used as a part of the raw material again for film production.

After the cutting step, at both ends in the width direction of the optical film, embossing processing (knurling processing) is applied by the embossing processing portion 19. The embossing process is performed by pressing the heated embossing roll to the both ends of the optical film. Fine concavities and convexities are formed on the surface of the embossing roller, and the embossing roller is pressed to the two ends of the optical film to form concavities and convexities on the two ends. Through such embossing processing, it is possible to minimize winding deviation or adhesion (attachment of films to each other) in the next winding step.

(S8; winding step) Finally, the optical film after the embossing process is wound by the winding device 20 to obtain the original roll (film roll) of the optical film. That is, in the winding step, the optical film is rolled up on the core while being transported, thereby manufacturing a film roll. The winding method of the optical film, as long as the generally used winder is used, there are methods of controlling tension such as constant torque method, constant tension method, taper tension method, and program tension control method with constant internal stress, which can be used flexibly Them. The roll length of the optical film is preferably 1000 to 7200 m. Moreover, the width at that time should be 500-3200mm wide, and the film thickness should be 30-150µm.

(Melt casting film forming method) The base material 2 (optical film) of this embodiment can also be manufactured by a melt casting film forming method. The melt casting film forming method is a method in which a resin composition containing additives such as a resin and a plasticizer is heated and melted to a temperature showing fluidity, and then the fluidized melt is cast to produce a film. The method of forming by melt casting can be classified into a melt extrusion (forming) method, a pressure forming method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these, a melt extrusion method that can obtain a film having excellent mechanical strength and surface accuracy is preferred. In addition, the plural raw materials used in the melt extrusion method are usually preferably pre-kneaded and pelletized.

The granulation can be performed by a well-known method. For example, dry resin, plasticizer, and other additives can be fed to the extruder through a feeder, and a single-shaft or double-shaft extruder can be used for kneading, and the strips can be extruded from a die and cooled by water or air. Cut and granulate.

The additive system may be mixed with the resin before being supplied to the extruder, or the additive and the resin may be supplied to the extruder by respective feeders. In addition, small amounts of additives such as particles or antioxidants are preferably mixed in the resin in advance in order to be uniformly mixed.

In order to suppress the shearing force, the extruder system does not deteriorate the resin (low molecular weight, coloring, gel formation, etc.), and is preferably processed at the lowest possible temperature that can be pelletized. For example, in the case of a twin-shaft extruder, it is preferable to use a deep groove type screw to rotate in the same direction. From the viewpoint of the uniformity of kneading, the bite type is preferred.

Using the particles obtained as described above, a thin film is formed. Of course, the raw material powder may be directly fed to the extruder through a feeder without being pelletized, and the film may be formed as it is.

For the above pellets, use a uniaxial or biaxial extruder, set the melting temperature during extrusion to about 200-300°C, filter with a leaf disc filter etc. to remove foreign matter, and then flow from the T-die The film is stretched into a film shape, the film is sandwiched between a cooling roll and an elastic touch roll, and the film is solidified on the cooling roll.

When the pellets are introduced from the supply hopper to the extruder, it is preferable to prevent oxidative decomposition and the like under vacuum or reduced pressure or in an inert gas environment.

It is preferable that the extrusion flow rate is stable introduction by a gear pump. In addition, it is better to use a stainless steel fiber sintered filter as a filter for removing foreign matter. The stainless steel fiber sintered filter is formed by making the stainless steel fiber body into a complicated entangled state and then compressing and sintering the contact area to integrate it. Therefore, the density can be changed by the fiber thickness and the amount of compression to adjust the filtration accuracy. .

Additives such as plasticizers and particles can be pre-mixed with the resin, or can be mixed in the extruder. In order to add uniformly, it is preferable to use a mixing device such as a static mixer.

The film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg (glass transition temperature) or more of the film and Tg+110°C or less. The roller having an elastomer surface used for this purpose may be a well-known roller.

The elastic contact roller is also called a pinching rotating body. As the elastic touch roller, a commercially available one can also be used.

When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

In addition, the optical film system formed by each of the above-mentioned film forming methods may be a single-layer or two-layer or more laminated film. The laminated film can be obtained by well-known methods such as co-extrusion molding, co-casting molding, film lamination, and coating. Among these, co-extrusion molding method and co-casting molding method are preferable. Moreover, when the co-extrusion molding method (co-extrusion T-die method) is used, there are feed block method and multi-manifold method in the co-extrusion T-die method, which can reduce thickness deviation , Especially preferred is the multi-manifold method.

[Example] Hereinafter, specific examples of the present invention will be described together with comparative examples. In addition, the present invention is not limited by the following examples. In addition, in the following description, "parts" means "parts by mass" or "parts by weight".

<Example 1> (Substrate) <Production of cycloolefin resin 1> Into a glass pressure-resistant reaction vessel replaced with nitrogen after drying, add 40 parts of a 75% cyclohexane solution of dicyclopentadiene (endo content 99% or more) (amount of dicyclopentadiene) 30 parts), 3.50 parts of allyltrimethoxysilane, and 75 parts of cyclohexane, followed by 0.50 parts of 19% hexane solution of diethyl aluminum ethoxide and stirring.

Next, a solution in which 0.15 parts of tetrachlorotungstophenylimine (tetrahydrofuran) complex was dissolved in 2 parts of toluene was added, and the mixture was heated to 50°C to start the ring-opening polymerization reaction. After 3 hours, a small amount of isopropanol was added, and after stopping the polymerization reaction, the polymerization reaction solution was poured into a large amount of isopropanol to solidify the ring-opening polymer. The coagulated ring-opening polymer was separated and recovered from the solution by filtration, and then dried under vacuum at 40°C for 20 hours. The yield of the obtained ring-opening polymer was 29 parts (yield 97%). In addition, the molecular weight and ¹ H-NMR of the obtained ring-opening polymer were measured.

Next, add 10 parts of the obtained ring-opening polymer and 44 parts of cyclohexane to a pressure-resistant reaction vessel and stir to dissolve the ring-opening polymer in cyclohexane, and then add 6 parts of toluene with hydrogen chloride dissolved in it. A hydrogenation catalyst solution made of 0.0065 parts of carbonyl ginseng (triphenylphosphine) ruthenium is hydrogenated at a hydrogen pressure of 4MPa and 160°C for 5 hours. The obtained hydrogenation reaction liquid was poured into a large amount of isopropanol to completely precipitate the polymer, and after filtration, separation and washing, it was dried under reduced pressure at 60° C. for 24 hours to obtain cycloolefin resin 1.

混合上述後，將混合物投入至具備4個內徑3mm的模孔之雙軸擠壓機(東芝機械公司製：TEM-37B)中，藉由熱熔融擠出形成，得到條狀的成形體後，以條料切粒機切細，得到顆粒。雙軸擠壓機之運轉條件係如以下。 ・機筒設定溫度：270～280℃ ・模頭設定溫度：250℃ ・螺桿旋轉數：145rpm ・進料器旋轉數：50rpm＜Production of base film 1＞

After mixing the above, the mixture is put into a biaxial extruder (Toshiba Machine Co., Ltd.: TEM-37B) equipped with 4 die holes with an inner diameter of 3 mm, and formed by hot melt extrusion to obtain a strip-shaped molded body , Use a strip pelletizer to cut finely to obtain pellets. The operating conditions of the twin-shaft extruder are as follows.・Cylinder set temperature: 270～280℃ ・Die head set temperature: 250℃ ・Screw rotation number: 145rpm ・Feeder rotation number: 50rpm

The obtained pellets were formed into a film with a thickness of 50 mm and a width of 120 mm using a hot melt extrusion film forming machine (manufactured by Optical Control Systems: Measuring Extruder Type Me-20/2800V3) with a T-die. The speed is wound into a roll shape. The operating conditions of the film forming machine are as follows. ・Cylinder temperature setting: 280～290℃ ・Die temperature: 270℃ ・Screw rotation number: 30rpm

Then, cut the above-mentioned film into a size of 100mm x 100mm, and use a small biaxial stretching machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to grasp the ends of the four sides of the film with a clip at a stretching temperature of 110°C and a stretching ratio of 3.3 times , The fixed-end uniaxial stretching is continuously performed to obtain a base film 1 with a film thickness of 15 µm.

(Hardened resin layer) <Preparation of coating solution 1> The coating liquid 1 of the following composition was prepared. ・Acrylic 1 (urethane acrylate oligomer "UV-7640B (Nippon Gosei Chemical Industry Co., Ltd.)" 　　　　 50.0 parts ・Acetone　　　　　　　　　　　　　　　　　 45.0 parts ・Propyl acetate　　　　　　　　　　　　　　　 20.0 parts ・Acrylic particles "Techpolymer SSX-101 (Sekisui Chemical Co., Ltd.)" 　　　　　　　　　　　　　　　　　　　　 0.1 part ・Leveling agent "GRANDIC PC11-6204L (DIC Corporation)" 0.2 part

<Formation of the hardened resin layer> Apply the coating solution 1 on one surface of the base film 1, and after drying at 80°C for 1 minute, immediately use an ozone-type high-pressure mercury lamp (16W/cm, 15cm condensing type, cumulative light quantity 200mJ/ cm ² ) is irradiated with ultraviolet rays to form a hardened resin layer (hard coat layer) with a thickness of 1.0 µm, which is used as a laminate 1.

<Example 2> Except that 0.01 part of dicyclopentadiene was additionally added to the coating liquid 1, a laminate 2 was produced in the same manner as in Example 1.

<Example 3> Except that the amount of tungsten nano particles in the base film 1 was changed to 0.1 part, a laminate 3 was produced in the same manner as in Example 1.

<Example 4> Except that the alicyclic monomer in the base film 1 was changed to tetracyclododecene, a laminate 4 was produced in the same manner as in Example 1.

<Example 5> Except for changing the tungsten nano particles in the base film 1 to molybdenum nano particles (particle size: 20 nm), a laminate 5 was produced in the same manner as in Example 1.

<Example 6> A laminate 6 was produced in the same manner as in Example 1, except that the tungsten nano particles in the base film 1 were changed to chromium nano particles (particle size: 20 nm).

<Example 7> The laminate 7 was produced in the same manner as in Example 1, except that the stretching ratio during the production of the base film 1 was changed to 2.1 times and the thickness of the base film 1 was changed to 24 μm.

<Example 8> The laminate 8 was produced in the same manner as in Example 1, except that the stretching ratio during the production of the base film 1 was changed to 10 times and the thickness of the base film 1 was changed to 5 μm.

<Example 9> The coating liquid 2 of the following composition was prepared. ＜Preparation of coating liquid 2＞ ・Acrylic 2 (Polymer acrylate "Unidic V6840 (DIC Corporation)") 20.0 parts ・1-Methoxy-2-propanol 　　　　　　　　　　　　 80.0 parts ・Acrylic particles "Techpolymer SSX-101 (Sekisui Kasei Co., Ltd.)" 0.1 part ・Leveling agent "GRANDIC PC11-6204L (DIC Corporation)" 0.2 part

＜Formation of hardened resin layer＞ Then, a layered body 9 was produced in the same manner as in Example 1, except that the coating liquid 2 was used instead of the coating liquid 1 to form a cured resin layer.

<Example 10> Except that the amount of tungsten nanoparticles was changed to 0.0001 part, a laminate 10 was produced in the same manner as in Example 1.

<Example 11> A laminated body 11 was produced in the same manner as in Example 1, except that the base film 1 was changed to the base film 11 obtained by the following method (solution casting film forming method).

(Substrate) <Preparation of tungsten particle dispersion> ・Tungsten particles (particle size 20nm) 　　　4.0 parts ・Dichloromethane　　　　　　　48.0 parts ・Ethanol 　　　　　　　　　48.0 parts The above-mentioned constituent materials were stirred and mixed in a dissolver for 50 minutes, and then dispersed with a homogenizer. It is filtered with Finemet NF manufactured by Nippon Seiki Co., Ltd. to prepare a tungsten particle dispersion with a tungsten particle content of 4.0% by mass.

<Production of base film 11> The main paste 1 of the following composition was prepared. That is, first, dichloromethane and ethanol are added to the pressurized dissolution tank. Next, in the pressurized dissolution tank, ARTON-G7810, which is a cycloolefin-based resin, is put in while stirring. Next, the alicyclic monomer dicyclopentadiene and the tungsten nanoparticle dispersion liquid were put in, heated to 60°C, and completely dissolved while stirring. The heating temperature was raised at 5°C/min from room temperature, and after 30 minutes of dissolution, the temperature was lowered at 3°C/min. The viscosity of the obtained solution was 7000cp, and the water content was 0.50%. Use SHP150 manufactured by ROKI TECHNO to filter with a filtration flow rate of 300L/m ² ·h and a filtration pressure of 1.0´10 ⁶ Pa to obtain the main paste 1.・Cycloolefin resin 2 (ARTON-G7810 (JSR Corporation)) 100 parts・Dichloromethane 270 parts・Ethanol 20 parts・Alicyclic monomer (dicyclopentadiene) 0.05 parts・Tungsten nanoparticle dispersion 0.25 Share

Next, using an endless endless belt casting device, the main glue 1 was uniformly cast on the stainless steel belt support at a temperature of 31°C and a width of 1800 mm. The temperature of the stainless steel strip is controlled at 28°C. The conveying speed of the stainless steel belt is 20m/min.

On the stainless steel belt support, the solvent is evaporated so that the amount of residual solvent in the cast (cast) film becomes 30% by mass. Next, the cast film was peeled from the stainless steel tape support with a peeling tension of 128 N/m.

Next, the peeled cast film was evaporated at 35°C and the solvent was stretched with a tenter, and was dried at a drying temperature of 160°C while being stretched 1.25 times in the width direction (TD direction). The residual solvent amount after stretching at the start of the zone stretching was 10.0% by mass, and the residual solvent amount after starting the stretching of the tenter was 5.0% by mass.

After being stretched by the tenter, a relaxation treatment was applied at 160°C for 5 minutes, and the drying was completed while conveying the 120°C drying zone with a large number of rollers. The obtained film was cut into a width of 1.5 m, knurled with a width of 10 mm and a height of 5 µm was applied to both ends of the film, and then wound on the core to obtain a base film 11. The film thickness of the base film 11 is 40 µm, the roll length is 4000 m, and the width is 1500 mm.

Then, cut the above-mentioned film into a size of 100mm x 100mm, and use a small biaxial stretching machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to grasp the ends of the four sides of the film with a clamp. The stretching temperature is 210°C and the stretching ratio is 2.7 times. , The fixed-end uniaxial stretching is continuously performed to obtain a base film 11 with a thickness of 15 µm.

<Comparative example 1> The alicyclic monomer (dicyclopentadiene) is not added to the base film 1. Except for this, in the same manner as in Example 1, a layered body 21 was produced.

＜Comparative example 2＞ No tungsten nano particles are added to the base film 1. Otherwise, in the same manner as in Example 1, a laminate 22 was produced.

<Comparative Example 3> The laminate 23 was produced in the same manner as in Example 1, except that the stretching ratio during the production of the base film 1 was changed to 1.7 times and the thickness of the base film 1 was changed to 29 µm.

<Comparative Example 4> Except that the resin of the base film 1 was changed to a polyethylene terephthalate resin "TRN-8580FH (Teijin Corporation)", a laminate 24 was produced in the same manner as in Example 1.

＜Monomer concentration ratio and quantification of metals＞ (Quantification of alicyclic monomer concentration ratio) The thickness of the base film is set to d (µm), and the surface of the base film from the side opposite to the side in contact with the cured resin layer to the depth of d/5 (µm) is regarded as the lower layer of the base material. When the base film is used as the upper layer of the base material from the surface in contact with the hardened resin layer to the depth of d/5 (µm), the lower base layer and the upper base layer of the alicyclic single Quantification of body concentration ratio. That is, the cross-sections of the films of the laminates 1 to 11 and 21 to 24 were measured by TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) to perform the above-mentioned quantification. The measurement of TOF-SIMS uses, for example, the TRIFTII type TOF-SIMS manufactured by Phi Evans, and can be observed by detecting fragments caused by the presence of alicyclic monomers on the cross-section of the film. The TOF-SIMS method is described in detail in Maruzen Co., Ltd. (published in 1999) in the "Selected Book of Surface Analysis Technology, Secondary Ion Mass Analysis Method," edited by the Japanese Society of Surface Science.

In addition, in the cured resin layer, the surface from the side in contact with the base material to the center in the thickness direction is regarded as the lower resin layer, and the surface from the side opposite to the side in contact with the base material to the thickness direction When the center is regarded as the upper resin layer, the quantification of the concentration ratio of the alicyclic monomer in the lower resin layer and the upper resin layer is also performed in the same manner as described above.

(Quantification of metal in base material) In a closed microwave decomposition device, 500 mg of the substrate film was decomposed by nitric acid, and the metal was quantified by ICP-MS (inductively coupled plasma mass analyzer).

＜Evaluation＞ (Adhesion) After the layered bodies 1-11, 21-24 are humidified for 12 hours in an environment of 23°C and 55%RH, in accordance with JIS K 5400, on the surface of the hardened resin layer of each layered body, the vertical and horizontal are introduced at intervals of 1mm 11 slits, make a 1mm square, 100 checkerboard grids, attach transparent tape, and quickly peel off at an angle of 90 degrees. While exchanging the scotch tape every time it is peeled off, after performing the peeling operation of the tape 6 times, the area of the grid that has never peeled off is used to evaluate the adhesion (not easy to peel off between layers) using the following criteria . Furthermore, JIS is an abbreviation of Japanese Industrial Standards (Japanese Industrial Standards) that represents Japanese Industrial Standards. "Evaluation Standards" 5: The checkerboard (hardened resin layer) is not peeled off at all. 4: The area ratio of the stripped checkerboard is less than 2%. 3: The area ratio of the stripped checkerboard is 2% or more and less than 5%. 2: The area ratio of the stripped checkerboard is 5% or more and less than 10% (poor adhesion). 1: The area ratio of the peeled checkerboard is 10% or more (poor adhesion).

(Bending resistance when making transparent conductive film) ITO (Indium Tin Oxide) electrodes were formed on the cured resin layers of the laminates 1 to 11 and 21 to 24 to produce ITO laminates 1 to 11 and 21 to 24. The ITO laminates 1 to 11, 21 to 24 were set on the MIT flexural fatigue tester (Toyo Seiki Co., Ltd.) at 25°C and 60%RH. The bending speed was 170rpm, the bending angle was 135°, and the chuck tip radius ( The tip radius of the bending jig) is 0.35mm and the load is 4.9N. When the increase rate of the resistance value of the ITO becomes 10% or more under the condition of bending, the bending resistance of the laminate is evaluated using the following criteria. "Evaluation Standards" 3: The number of bending is 300 times or more (very good bending resistance). 2: The number of bending times is 200 to 299 times (good bending resistance). 1: The number of bending is less than 200 times (poor bending resistance).

Table 1 shows the evaluation results of layered bodies 1-11 and 21-24. In addition, in Table 1, "COP" refers to cycloolefin resin, "PET" refers to polyethylene terephthalate, "DCP" refers to dicyclopentadiene, "TCP" refers to tetracyclododecene, and "W "Refers to tungsten, "Mo" refers to molybdenum, and "Cr" refers to chromium.

According to Table 1, in Comparative Examples 1 to 4, adhesion or bending resistance was poor. In Comparative Example 1, alicyclic monomers are not contained in both the base film and the cured resin layer. Since the alicyclic monomers in each layer do not interact, it is considered that the base film and the cured resin layer are closely adhered Sexual decrease. In Comparative Example 2, although the alicyclic monomer is contained in both the base film and the cured resin layer, since the base film does not contain a specific metal (tungsten), it is considered that no promoting base material can be obtained. The effect of diffusing the alicyclic monomer in the film to the side of the hardened resin layer results in insufficient adhesion enhancement. In Comparative Example 3, the thickness of the base film is 29 µm. Since the base film is easily broken when a force in the bending direction is applied to the base film, it is considered that the bending resistance is reduced. In Comparative Example 4, although the base film contains polyethylene terephthalate resin, when this resin is used, the effect of diffusing the alicyclic monomer of the base film to the hardened resin layer cannot be obtained. However, it is considered that the effect of increasing the adhesion due to the interaction between the alicyclic monomer of the base film and the alicyclic monomer of the hardened resin layer is not obtained.

In contrast, in Examples 1 to 11, good results were obtained in both the adhesion and the bending resistance. In Examples 1-11, the thickness of the base film is 5-24 µm, the base film contains cycloolefin resin, metal from group 6 of the periodic table, and alicyclic monomer, and the hardened resin layer contains acrylic resin and ester Cyclic monomers, because of the interaction between the alicyclic monomers of the base film and the alicyclic monomers of the hardened resin layer, the adhesion is improved. Therefore, it is considered that the base film and the hardened resin layer are separated Department is suppressed. In particular, since the above-mentioned metal is contained in the base film, the diffusion of the alicyclic monomer of the base film to the side of the hardened resin layer can be promoted, and therefore, it is considered to further promote the increase in adhesion. In addition, it is thought that by thinning the base film, the laminate becomes flexible and the bending resistance is improved.

In addition, according to the comparison of Example 4 with Examples 1 to 3, 5 to 11, from the viewpoint of improved adhesion (from the viewpoint of suppressing interlayer peeling), the alicyclic monocyclic monomer on the upper layer of the substrate in the substrate film It can be said that the concentration of the body is different from the concentration of the alicyclic monomer in the lower layer of the substrate. As in Examples 1 to 2, 5 to 11, when the concentration of the alicyclic monomer in the upper layer of the substrate is greater than that in the lower layer of the substrate, the resin of the substrate film interacts with the alicyclic monomer of the hardened resin layer. The amount of the cyclic monomer is increased. Therefore, compared with Example 4, it is believed that the effect of increasing the adhesion caused by the above-mentioned interaction is increased. Also, as in Example 3, when the concentration of the alicyclic monomer in the upper layer of the substrate is lower than that in the lower layer of the substrate, the alicyclic monomer in the upper layer of the substrate easily diffuses to the hardened resin layer, due to the fact that it is Cyclic monomers tend to interact easily, so compared to Example 4, it is believed that the effect of increasing the adhesion caused by the above interaction is increased.

In addition, compared to Example 2, Example 1 has a higher effect of improving the bending resistance. In Example 1, in the coating solution 1 for forming the hardened resin layer, although the alicyclic monomer does not exist, after coating the coating solution 1 on the substrate film, the alicyclic monomer in the substrate film The body diffuses into the coating solution 1, and it is considered that as a result, the alicyclic monomer exists only in the resin lower layer of the hardened resin layer. Since the alicyclic monomer only exists in the lower layer of the resin, it can reduce the content of the alicyclic monomer in the hardened resin layer while improving the adhesion. As the content of the alicyclic monomer in the hardened resin layer is reduced, Since the brittleness deterioration of the cured resin layer is suppressed, it is estimated that the bending resistance is improved. [Industrial use possibility]

The build-up system of the present invention can be used for, for example, a thin film of a touch panel on which electrodes are formed.

1‧‧‧Layered body 2‧‧‧Substrate 2a‧‧‧Bottom layer of substrate 2b‧‧‧Upper substrate 2M‧‧‧Metal 2P‧‧‧Alicyclic monomer 3‧‧‧Hardened resin layer 3a‧‧‧Resin lower layer 3b‧‧‧Resin upper layer 3P‧‧‧Alicyclic monomer

Fig. 1 is a cross-sectional view showing the schematic configuration of a laminate according to an embodiment of the present invention. Fig. 2 is an explanatory diagram showing a schematic configuration of a manufacturing apparatus of an optical film constituting the substrate of the laminate. FIG. 3 is a flowchart showing the flow of the manufacturing steps of the above-mentioned optical film.

1‧‧‧Layered body

2‧‧‧Substrate

2a‧‧‧Bottom layer of substrate

2b‧‧‧Upper substrate

2c‧‧‧Substrate intermediate layer

2M‧‧‧Metal

2P‧‧‧Alicyclic monomer

3‧‧‧Hardened resin layer

3a‧‧‧Resin lower layer

3b‧‧‧Resin upper layer

3P‧‧‧Alicyclic monomer

Claims (6)

A laminated body characterized by comprising: a substrate with a thickness of 5-24 μm, and a hardened resin layer laminated on the substrate; the substrate includes a cycloolefin resin, a metal of Group 6 of the periodic table, and an alicyclic ring The hardened resin layer includes an acrylic resin and an alicyclic monomer, and the alicyclic monomer contained in the substrate and the hardened resin layer is dicyclopentadiene or tetracyclododecene. The laminate of claim 1, wherein the thickness of the substrate is taken as d (μm), and the surface of the substrate opposite to the side in contact with the cured resin layer is d/5 (μm) When the depth of the base material is regarded as the lower layer of the base material, and the depth of d/5 (μm) from the surface of the base material in contact with the cured resin layer is regarded as the upper layer of the base material, the upper layer of the base material is The lower layer of the substrate has a concentration difference of the alicyclic monomer. The laminate of claim 2, wherein the concentration of the alicyclic monomer in the upper layer of the substrate is greater than that of the lower layer of the substrate. The laminate of claim 2, wherein the upper layer of the substrate is the alicyclic ring The concentration of the formula monomer is smaller than the lower layer of the aforementioned substrate. The laminate according to any one of claims 1 to 4, wherein in the cured resin layer, from the surface of the side in contact with the base material to the center in the thickness direction as the lower resin layer, When the surface on the side opposite to the contact side of the substrate reaches the center in the thickness direction as the upper resin layer, the alicyclic monomer exists only in the lower resin layer. The laminate according to any one of claims 1 to 4, wherein the metal contained in the base material is tungsten, molybdenum or chromium.

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