JP2011072878A - Method of producing laminate, laminate, optical component, and method of producing coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a laminate comprising a functional film, for example, an antistatic film or the like and having excellent inter-layer adhesion, useful in an optical application, a building material application, or the like, according to a simple means, i.e., a one-component type coating method; a laminate produced by the method; an optical component including the laminate; and a method of producing a coating film including a phase separation structure. <P>SOLUTION: The method of producing a laminate comprising an ionic liquid layer and a hard coat layer using a one-component type coating liquid, includes the following processes 1 to 3 to be carried out in numerical order, the process 1: a process of mixing, (A1) a component curable by active energy rays for forming the hard coat layer, (A2) a solvent for use in a component of forming the hard coat layer, (B1) an ionic liquid, (B2) a matrix polymer for use in the ionic liquid, and (C) an intermediary solvent compatible with the components (A2) and (B2) both and having a boiling point lower than that of the component (A2), to prepare a one-component type coating liquid; the process 2: a process of applying the one-component type coating liquid prepared in the process 1 onto a substrate and subsequently evaporating the component (C) therefrom to produce a coating film including a phase separation structure; and the process 3: a process including a process of evaporating the component (A2) present in the coating film and a process of irradiating active energy rays onto the coating film, subsequent to the process 2. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a laminated structure, a laminated structure obtained by the production method, an optical member having the laminated structure, and a method for forming a coating film. More specifically, it is a laminated structure provided with a functional film such as an antistatic film, which is useful for optical and building materials, etc., by a simple one-component coating method using layer separation, The present invention relates to a method for producing a laminated structure with good adhesion, a laminated structure obtained by the production method, an optical member having the laminated structure, and a method for forming a coating film having a layer separation structure.

Conventionally, in order to form a laminated structure, various methods for forming a multilayer coating film have been developed. As a method for forming a multilayer coating film, (1) a tandem coating method in which coating and drying are repeated using a plurality of coating liquids, and (2) a method in which multilayer coating is simultaneously performed using a plurality of coating liquids (For example, refer to Patent Documents 1 and 2), and (3) A plurality of coating liquids are previously multilayered on an inclined slide surface, and the multilayer coating film is transferred onto a substrate to form a multilayer coating film. A forming method (see, for example, Patent Document 3) is known.
On the other hand, an antiglare film is known as a laminated structure in which a phase separation structure is formed by spinodal decomposition and unevenness is provided on the surface. For example, from a liquid phase containing one polymer, one curable resin precursor, and a solvent, a phase separation structure is formed by spinodal decomposition accompanying evaporation of the solvent, the resin precursor is cured, and an antiglare layer The anti-glare film which formed A is disclosed (for example, refer patent document 4). Moreover, as a technique using phase separation by spinodal decomposition, (A) active energy ray-curable polymerizable compound, (B) thermoplastic resin, (C) a good solvent for the component (A) and the component (B), And (D) a poor solvent for the component (B), and the content ratio of the component (A) and the component (B) [(A) :( B)], the component (C) and the component (D) ) The content ratio [(C) :( D)] of the component is within a specific range, and the material for forming an antiglare hard coat layer, and the active energy ray curable resin layer formed on the base film using the material. An anti-glare hard coat film having an anti-glare hard coat layer is disclosed (for example, see Patent Document 5).

Japanese Examined Patent Publication No. 62-51670 Japanese Patent Publication No.2-222711 JP 2003-62517 A JP 2004-126495 A JP 2006-137835 A

However, the above method (1) has a problem that operations are complicated and inferior in productivity because a plurality of coating liquids must be prepared separately and a plurality of coating and drying processes are required. . In the methods (2) and (3) described in Patent Documents 1 to 3, the coating method is improved and the productivity is improved as compared with the method (1). The problem that the liquids must be prepared separately remains.
Further, the methods (1) to (3) have a problem that the adhesion between layers is not always sufficient depending on the types of the plurality of coating liquids.
Further, the phase separation technique based on spinodal decomposition described in Patent Documents 4 and 5 is a technique for forming irregular irregularities on the surface, and is difficult to apply to a technique for forming a multilayer coating film.

  By the way, various optical members used in the display field, for example, protective films such as an antireflection film, an antiglare film, and a hard coat film, and various members used in the building material field, etc., an antistatic film for preventing charging. In addition, it is required to provide a functional film such as an antifouling film for preventing adhesion of dust, dust, fingerprints and the like on the surface of an optical member, a decorative board, and the like. However, high-performance antistatic materials are usually poor in solvent solubility and compatibility with other components such as hard coat materials, so when using a tandem coating method, etc., the interlayer adhesion is insufficient. There is a problem of becoming.

  The present invention has been made under such circumstances, and a functional film such as an antistatic film, which is useful for optical and building materials, is provided by a one-part coating method which is a simple means. A laminated structure having good adhesion between layers, a laminated structure obtained by the production method, an optical member having the laminated structure, and a coating having a layer separation structure It is an object to provide a method for forming a film.

  The present inventor has paid attention to the fact that the ionic liquid has low compatibility with the hard coat layer forming component, and by using a mediating solvent capable of dissolving both the hard coat layer forming component and the ionic liquid, It has been found that a laminated structure can be produced by the method and the above-mentioned problems can be solved.

That is, the present invention relates to the following [1] to [7].
[1] A method for producing a laminated structure using a one-component coating liquid, comprising the following steps 1 to 3 in this order, and a method for producing a laminated structure having an ionic liquid layer and a hard coat layer.
Step 1: (A1) Active energy ray-curable hard coat layer forming component, (A2) Hard coat layer forming component solvent, (B1) ionic liquid, (B2) matrix polymer for ionic liquid, and (C) ( A step of mixing a solvent having a lower boiling point than the component (A2) having compatibility with both the component A2) and the component (B2) to obtain a one-component coating solution.
Process 2: The process of forming the coating film which has a layer-separation structure by volatilizing the said (C) component, after apply | coating the 1-component coating liquid obtained at the process 1 to the base material.
Process 3: The process which has the process of volatilizing the said (A2) component in a coating film after the process 2, and the process of irradiating an active energy ray to a coating film.
[2] The component (B1) is selected from the group consisting of an imidazolium cationic substance, a pyridinium cationic substance, a pyrrolidinium cationic substance, a quaternary ammonium cationic substance, and a quaternary phosphonium cationic substance Any of the cationic substances described above, halide, cyanide (CN ⁻ ), triflate (CF ₃ SO ₃ ⁻ ), tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), sulfonylamide ( SO ₂ NH ₂ ⁻ ), methyl sulfate (CH ₂ SO ₄ ⁻ ), ethyl sulfate (C ₂ H ₄ SO ₄ ⁻ ), bis (trifluoromethanesulfonyl) imide [(CF ₃ SO ₂ ) ₂ N ⁻ ], bis ( one of a is selected from the group consisting of ^- trifluoroethane sulfonyl) imide _{[(C 2 H 2 F 3} SO 2) 2 N] Is on and is bonded to salts, method of manufacturing the stacked structure according to [1].
[3] The method for producing a laminated structure according to [1] or [2], wherein the component (C) is at least one selected from the group consisting of acetone, tetrahydrofuran, and dichloromethane.
[4] A laminated structure obtained by the production method according to any one of [1] to [3].
[5] An optical member having the laminated structure according to [4].
[6] The optical member according to [5], which is an antistatic hard coat film.
[7] A method for forming a coating film using a one-component coating liquid,
(A1) Active energy ray-curable hard coat layer forming component,
(A2) Hard coat layer forming component solvent,
(B1) ionic liquid,
(B2) Mixing a matrix polymer for ionic liquid, and (C) a solvent having a lower boiling point than the component (A2), which is compatible with both the component (A2) and the component (B2), A method for forming a coating film having a layer separation structure by volatilizing the component (C) after obtaining a working solution and applying the obtained one-component coating solution to a substrate.

  According to the present invention, it is a laminated structure having a functional layer such as an antistatic layer provided on the surface, which is useful as an optical material or a building material by a simple one-component coating method. It is possible to provide a method for manufacturing a laminated structure having good properties. In the production method of the present invention, a laminated structure having good adhesion while using an antistatic material that has low solubility in a solvent for forming a hard coat layer and usually has low adhesion between layers is obtained. Therefore, it becomes possible to provide an optical member having a high antistatic function.

This invention is a manufacturing method of the laminated structure by 1 liquid type coating liquid, Comprising: It is the manufacturing method of the laminated structure which has the following processes 1-3 in this order, and has an ionic liquid layer and a hard-coat layer.
Step 1: (A1) Active energy ray-curable hard coat layer forming component, (A2) Hard coat layer forming component solvent, (B1) ionic liquid, (B2) matrix polymer for ionic liquid, and (C) ( A step of mixing a solvent having a lower boiling point than the component (A2) having compatibility with both the component A2) and the component (B2) to obtain a one-component coating solution.
Process 2: The process of forming the coating film which has a layer-separation structure by volatilizing the said (C) component, after apply | coating the 1-component coating liquid obtained at the process 1 to the base material.
Process 3: The process which has the process of volatilizing the said (A2) component in a coating film after the process 2, and the process of irradiating an active energy ray to a coating film.
Hereinafter, steps 1 to 3 will be described in order.

[Step 1]
Step 1 is a step of obtaining a one-component coating liquid. In the present invention, (A1) active energy ray-curable hard coat layer forming component, (A2) hard coat layer forming component solvent, (B1) ionic liquid, (B2) ionic liquid matrix Using a mediator solvent having a lower boiling point than the component (A2) having compatibility with both the polymer and the component (C2) and the component (A2) and the component (B2), these are mixed to form a one-component coating solution. obtain.
The mixing temperature is not particularly limited as long as it does not exceed the boiling point of any of the components (A2), (B2), and (C), but it is easy to operate and suppresses volatilization of each component. From the viewpoint, it is usually preferable to mix at room temperature (points at 15 to 30 ° C., the same applies hereinafter).
Hereinafter, each component of the coating liquid will be described.

((A1) Active energy ray-curable hard coat layer forming component)
The component (A1) is for imparting hard coat performance to the laminated structure and irradiates an active energy ray such as an ultraviolet ray or an electron beam having an energy quantum among electromagnetic waves or charged particle beams. Thus, it contains a compound that crosslinks and cures. As the active energy ray-curable compound, an active energy ray-curable oligomer and / or an active energy ray-curable monomer can be used.

Examples of the active energy ray-curable oligomer include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyether acrylate oligomers, polybutadiene acrylate oligomers, and silicone acrylate oligomers.
Here, as the polyester acrylate oligomer, for example, the hydroxyl group of the polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyhydric alcohol is esterified with (meth) acrylic acid, or the polyhydric carboxylic acid is alkylene. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an oxide with (meth) acrylic acid.
The epoxy acrylate oligomer can be obtained, for example, by reacting an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin with (meth) acrylic acid for esterification. A carboxyl-modified epoxy acrylate oligomer obtained by partially modifying this epoxy acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.
The urethane acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. It can be obtained by esterifying the hydroxyl group of ether polyol with (meth) acrylic acid.
The weight average molecular weight of the active energy ray-curable oligomer is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, preferably 500 to 100,000, more preferably 1,000 to 70,000, Preferably it is 3,000-40,000.
An active energy ray hardening-type oligomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the active energy ray-curable monomer include di (meth) acrylic acid 1,4-butanediol ester, di (meth) acrylic acid 1,6-hexanediol ester, di (meth) acrylic acid neopentyl glycol ester, di (Meth) acrylic acid polyethylene glycol ester, di (meth) acrylic acid neopentyl glycol adipate ester, di (meth) acrylic acid hydroxypivalic acid neopentyl glycol ester, di (meth) acrylic acid dicyclopentanyl, di (meth) Acrylic acid caprolactone-modified dicyclopentenyl, di (meth) acrylic acid ethylene oxide-modified phosphate ester, di (meth) acrylic acid allylated cyclohexyl, di (meth) acrylic acid isocyanurate, dimethylol tricyclodecane di (meth) a Relate, tri (meth) acrylic acid trimethylolpropane ester, tri (meth) acrylic acid pentaerythritol ester, tri (meth) acrylic acid dipentaerythritol ester, tri (meth) acrylic acid propionic acid modified dipentaerythritol ester, tri ( (Meth) acrylic acid pentaerythritol ester, tri (meth) acrylic acid propion oxide modified trimethylolpropane ester, isocyanuric acid tris (acryloxyethyl), penta (meth) acrylic acid propionic acid modified dipentaerythritol ester, hexa (meth) acrylic Examples include acid dipentaerythritol ester, hexa (meth) acrylic acid caprolactone-modified dipentaerythritol ester, and the like. An active energy ray hardening-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

The component (A1) may contain a photopolymerization initiator, a surface conditioner (leveling agent), an antiglare agent, an antiaging agent and the like.
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4, -(2- Droxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate , Oligo (2-hydroxy-2-methyl-1- [4- (1-propenyl) phenyl] propanone) and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. What is necessary is just to select the usage-amount of a photoinitiator suitably according to the kind of active energy ray-curable compound to be used.
As the leveling agent, known ones can be used, and examples thereof include various surfactants such as silicone, fluorine, polyether, acrylic and titanate. Among these, a fluorosurfactant is preferable, and a fluorosurfactant containing a perfluoroalkyl group [for example, trade name “MCF-350-5” (manufactured by DIC Corporation)]. ] Is more preferable.
As an anti-glare agent, a well-known thing can be used and a silica particle etc. are mentioned.
Known antiaging agents can be used, and examples thereof include metal oxides such as zinc oxide, calcium oxide, and magnesium oxide.

((A2) Hard coat layer forming component solvent)
The solvent of the component (A2) is a solvent that can dissolve the component (A1). For example, an aliphatic organic solvent such as hexane, heptane, and cyclohexane; an aromatic organic solvent such as toluene and xylene; methylene chloride, ethylene chloride Halogenated hydrocarbons such as: alcohol organic solvents such as methanol, ethanol, propanol, butanol and 1-methoxy-2-propanol; ketone organic solvents such as methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, cyclohexanone and isophorone; acetic acid Examples include ester organic solvents such as ethyl and butyl acetate; cellosolve organic solvents such as ethyl cellosolve, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them. From the viewpoint of ease of operation, a solvent capable of dissolving the component (A1) at room temperature is preferable. Among these, from the viewpoint of preferential volatilization of the component (C) described later, a solvent having a boiling point of more than 100 ° C is preferable, and a solvent having a boiling point of more than 110 ° C is more preferable.
Although there is no restriction | limiting in particular in the usage-amount of (A2) component, Usually, it is preferably 20-100 mass parts with respect to 100 mass parts of (A1) component, More preferably, it is 30-80 mass parts, More preferably. 30 to 60 parts by mass. Within this range, the component (A1) can be sufficiently dissolved and sufficient hard coat properties can be imparted to the laminated structure.

((B1) ionic liquid)
The component (B1) is an ionic liquid that can impart high antistatic properties to the laminated structure.
An “ionic liquid” generally refers to a liquid that exhibits a liquid state at room temperature and in a relatively low temperature region. Further, the ionic liquid usually exhibits high ionic conductivity, high thermal stability, relatively low viscosity, etc., has almost no vapor pressure, does not exhibit flammability and flammability, and has a wide liquid temperature range. It has the characteristics.
The ionic liquid is preferably a cationic substance. The cationic substance is usually present as a salt with an anion which is a counter ion. Specific examples of the ionic liquid are selected from the group consisting of imidazolium cationic substances, pyridinium cationic substances, pyrrolidinium cationic substances, quaternary ammonium cationic substances, and quaternary phosphonium cationic substances. Any of the above cationic substances, halide, cyanide (CN ⁻ ), triflate (CF ₃ SO ₃ ⁻ ), tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), sulfonylamide (SO ₂ NH ₂ ⁻ ), methyl sulfate (CH ₂ SO ₄ ⁻ ), ethyl sulfate (C ₂ H ₄ SO ₄ ⁻ ), bis (trifluoromethanesulfonyl) imide [(CF ₃ SO ₂ ) ₂ N ⁻ ], bis (tri tetrafluoroethane) imide _{[(C 2 H 2 F 3} SO 2) 2 N -] one selected from the group consisting of Include salts and anions are bonded.
Examples of the halide include chloride (Cl ⁻ ), bromide (Br ⁻ ), and iodide (I ⁻ ).

  Specific examples of a salt of an imidazolium-based cationic substance and an anion (counter ions in the brackets of the exemplified substance indicate counter ions) include 1,3-dimethylimidazolium “chloride”, 1,3-dimethylimidazolium “dimethyl” Phosphate, 1-ethyl-3-methylimidazolium “chloride”, 1-ethyl-3-methylimidazolium “bromide”, 1-ethyl-3-methylimidazolium “iodide”, 1-ethyl-3-methyl Imidazolium “trifluoromethanesulfonate”, 1-ethyl-3-methylimidazolium “p-toluenesulfonate”, 1-ethyl-3-methylimidazolium “ethylsulfate”, 1-ethyl-3-methylimidazolium “ 2-methyl (2-methoxyethoxy) ethyl sulfate ", 1-ethyl- -Methylimidazolium "tetrafluoroborate", 1-ethyl-3-methylimidazolium "hexafluorophosphate", 1-ethyl-3-methylimidazolium "bis (trifluoromethanesulfonyl) imide", 1-methyl- 3-propylimidazolium “iodide”, 1-butyl-3-methylimidazolium “chloride”, 1-butyl-3-methylimidazolium “bromide”, 1-butyl-3-methylimidazolium “iodide”, 1-butyl-3-methylimidazolium “chloride” Butyl-3-methylimidazolium “trifluoromethanesulfonate”, 1-butyl-3-methylimidazolium “tetrafluoroborate”, 1-butyl-3-methylimidazolium “hexafluorophosphate”, 1-butyl- 3-methylimidazolium “bis (trifluoro Tansulfonyl) imide ", 1-hexyl-3-methylimidazolium" chloride ", 1-hexyl-3-methylimidazolium" hexafluorophosphate ", 1-hexyl-3-methylimidazolium" tetrafluoroborate " 1-butyl-2,3-dimethylimidazolium “chloride”, 1-butyl-2,3-dimethylimidazolium “tetrafluoroborate”, 1-butyl-2,3-dimethylimidazolium “hexafluorophosphate” Or the like.

Specific examples of the salt of a pyridinium-based cationic substance and an anion (counter ions in the brackets of the exemplified substance indicate counter ions) include 1-ethylpyridinium “chloride”, 1-ethylpyridinium “bromide”, 1-butylpyridinium “ Chloride ",), 1-butylpyridinium" bromide ", 1-butylpyridinium" hexafluorophosphate ", 1-butyl-4-methylpyridinium" bromide ", 1-butyl-4-methylpyridinium" hexafluorophosphate " 1-ethyl-3-methylpyridinium “ethyl sulfate”, 1-ethyl-3- (hydroxymethyl) pyridinium “ethyl sulfate”, and the like.
Specific examples of the salt of a pyrrolidinium-based cationic substance and an anion (counter ions in the brackets of the exemplified substance indicate counter ions) include 1-butyl-1-methylpyrrolidinium “bis (trifluoromethanesulfonyl) imide” and the like. Can be mentioned.
Specific examples of a salt of a quaternary ammonium-based cationic substance and an anion (counter ions in the brackets of the exemplified substance indicate counter ions) include N, N-dimethyl-N-ethyl-N- (2-methoxyethyl) Ammonium “tetrafluoroborate”, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium “tetrafluoroborate”, N, N-dimethyl-N-ethyl-N- (2-methoxy Ethyl) ammonium “bis (trifluoroethanesulfonyl) imide”, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium “bis (trifluoroethanesulfonyl) imide” and the like.
Specific examples of the salt of a quaternary phosphonium cationic substance and an anion (counter ions in the brackets of the exemplified substance indicate counter ions) include tetraethylphosphonium “tetrafluoroborate”, tetraphenylphosphonium “chloride” and the like. It is done.
Among these, the component (B1) is preferably a salt of a quaternary ammonium-based cationic substance and an anion, and N, N-dimethyl-N-ethyl-N- (2-methoxyethyl) ammonium and More preferred is a salt with an anion. In particular, tetrafluoroborate and bis (trifluoroethanesulfonyl) imide are preferable as the anion in this combination.

Since the ionic liquid has low compatibility with the component (A2), when the ionic liquid is used as an antistatic material, a conventional method cannot form a laminated structure efficiently. According to this, it is possible to efficiently manufacture a laminated structure having high adhesion between layers (hereinafter simply referred to as adhesion).
The amount of component (B1) used is usually preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 10 to 25 parts by mass with respect to 100 parts by mass of component (A1). If it is this range, hard coat property will not be impaired, providing sufficient antistatic property to a laminated structure.

((B2) Matrix polymer for ionic liquid)
The component (B1) is mixed with the matrix polymer for ionic liquid as the component (B2) to form an ionogel, and functions as a high-performance antistatic layer having high conductivity in the laminated structure.
The component (B2) is not particularly limited as long as it is a film-forming polymer material that has high compatibility with the ionic liquid and does not inhibit ionic conductivity. From the known matrix polymer for ionic liquid, ( What has good compatibility with the ionic liquid selected as B1) component should just be selected suitably. Specific examples of the component (B2) include polystyrene, polyethylene, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyurethane, polyvinyl chloride, polyvinylpyrrolidone, cellulose, cellulose acetate, glucose oxidase, Examples include peroxidase, polyallylamine hydrochloride, polyorganosiloxane, and sulfonic acid polymers such as sodium polystyrene sulfonate and sodium polyethylene sulfonate. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, when a salt of a quaternary ammonium cationic substance and an anion is used as the component (B1), polyethylene oxide, polypropylene oxide, and sulfonic acid polymer are preferable, and polyethylene oxide is more preferable.
The weight average molecular weight of the component (B2) is usually preferably from 500 to 1,000,000, preferably from 1,000 to 700, from the viewpoint of compatibility with the component (B1) and incompatibility with the component (A2). 000 is more preferable, and 2,000 to 500,000 is more preferable. Here, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
Although there is no restriction | limiting in particular in the usage-amount of (B2) component, Usually, it is preferably 70-200 mass parts with respect to 100 mass parts of (B1) component, More preferably, it is 80-150 mass parts, More preferably. 90 to 130 parts by mass. If it is this range, it will fully be compatible with (B1) component, and high antistatic property can be provided to a laminated structure.

((C) Mediator solvent)
The component (C) is a solvent having a lower boiling point than the component (A2), which is compatible with both the component (A2) and the component (B2), so as to obtain a “one-component” coating solution. Is an essential ingredient.
In addition, the component (C) is preferentially volatilized from the one-component type coating solution, so that the two layers with poor compatibility or incompatibility, that is, the component layer (A2) containing the component (A1) [A2] Hard coat layer] and (B2) component layer (ionic liquid layer) containing component (B1) can be separated into layers, so that it plays an important role in the formation of a laminated structure having a layer separation structure. It is a mediator solvent.
As described above, the component (C) is a solvent having a lower boiling point than the component (A2). However, from the viewpoint of forming a layer separation structure more easily, the boiling point of the component (A2) is preferably 5 ° C. or higher. More preferably, it is a solvent having a boiling point of 10 ° C. or higher, more preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and still more preferably 40 ° C. or higher.
Examples of the component (C) include ketone-based mediating solvents such as acetone and tetrahydrofuran (THF); halogen-based mediating solvents such as dichloromethane. Solvents having a boiling point of 100 ° C. or lower are preferable, and boiling points of 80 ° C. The following solvents are more preferable, and solvents having a boiling point of 70 ° C. or lower are more preferable. Among these, acetone, tetrahydrofuran, and dichloromethane are preferable, and acetone and tetrahydrofuran are more preferable from the viewpoint of efficiently forming a laminated structure with high adhesion and a difference in boiling point from the component (A2).
Although there is no restriction | limiting in particular in the usage-amount of (C) component, from a viewpoint which obtains a uniform 1 liquid type coating liquid, and the viewpoint which forms a laminated structure with high adhesiveness efficiently, said (A2) component and (B2) It is usually preferably 100 to 600 parts by mass, more preferably 150 to 500 parts by mass, more preferably 200 to 400 parts by mass, and further preferably 250 to 350 parts by mass with respect to 100 parts by mass of the total amount of components.

[Step 2]
In step 2, the one-component coating liquid obtained in step 1 is applied to a substrate, and then the component (C) is volatilized to contain (A1) component (A2) component layer [hard coat This is a step of forming a coating film having a layer separation structure of (layer) and (B2) component layer [ionic liquid layer] containing the component (B1).
According to the study by the present inventors, in Step 2, the component (C) having the effect of making all the components uniform is preferentially volatilized, so that the remaining incompatible or poorly compatible components are gradually added. It was considered that the layers were separated, and thus a layer separation structure could be formed. Although there is no restriction | limiting in particular in the method of volatilizing (C) component, The method heated more than the boiling point of (C) component and less than the boiling point of (A2) component is simple and preferable. The heating is preferably performed by means such as an oven that can uniformly heat the one-component coating solution. Further, the heating time is not particularly limited as long as the component (C) is sufficiently volatilized, but is usually preferably 20 seconds to 5 minutes, more preferably 30 seconds to 4 minutes, and even more preferably 40 seconds. ~ 2 minutes.

(Base material)
There is no restriction | limiting in particular in the said base material, What is necessary is just to select suitably with the member for optics, the member for building materials, etc., for example. In the case of an optical member, it can be appropriately selected from plastic films known as base materials for optical films.
Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, acetyl cellulose butyrate films, polychlorinated films. Vinyl film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyetherimide film , Polyimide film, fluororesin film, Amide film, acrylic resin film, norbornene resin film, cycloolefin resin films or the like.
These substrates may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. For example, when used for protecting a liquid crystal display, a colorless and transparent film is suitable.
There is no restriction | limiting in particular in the thickness of a base material, Although what is necessary is just to select suitably according to a condition, Usually, it is preferably 15-250 micrometers, More preferably, it is 30-200 micrometers.

Moreover, the base material can be surface-treated by an oxidation method, an uneven | corrugated method, etc. as needed for the purpose of improving the adhesiveness with the layer provided in the surface. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include a sand blast method and a solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.
There is no particular limitation on the method of applying the one-component coating liquid to the substrate, and conventionally known methods such as bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating are used. Coating method.

  According to the above steps 1 and 2, a method for forming a coating film using a one-pack type coating liquid, comprising (A1) an active energy ray-curable hard coat layer forming component and (A2) hard coat layer formation Component solvent, (B1) ionic liquid, (B2) matrix polymer for ionic liquid, and (C) compatible with both (A2) component and (B2) component, lower boiling point than component (A2) Coating having a layer separation structure by volatilizing the component (C) after mixing a medium solvent to obtain a one-component coating solution, applying the obtained one-component coating solution to a substrate A method for forming a film can be provided.

[Step 3]
Step 3 includes the step of volatilizing the component (A2) from the coating film having the layer separation structure obtained in Step 2, and the component (A1) in the layer separation structure by irradiating the coating film with active energy rays. And a step of curing.
In the step 3, the step of volatilizing the component (A2) from the coating film may be included before or after the irradiation with the active energy ray, but before the irradiation with the active energy ray. It is simpler and preferable.
Examples of the active energy rays include ultraviolet rays and electron beams. Ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like. On the other hand, an electron beam is obtained by an electron beam accelerator or the like. Among these active energy rays, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a cured film can be obtained without using the said photoinitiator.
(A2) Although there is no restriction | limiting in particular in the method of volatilizing a component, For example, the method of heating at about 70-120 degreeC etc. are mentioned. It is preferable to use a means that can uniformly heat the coating film, such as an oven.
Thus, the thickness of the coating film formed is about 0.5-20 micrometers normally, Preferably it is 1-10 micrometers.
In addition, the presence or absence of the layer separation structure in the coating film can be confirmed using, for example, an interfacial ultraviolet-visible spectroscopic measurement apparatus using slab type optical waveguide spectroscopy. Moreover, it can also confirm with the scanning electron microscope (SEM) and optical microscope of a cross section.
The optical member having the laminated structure obtained as described above has a high antistatic function, and is particularly useful as an antistatic hard coat film.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
In addition, the investigation of the presence or absence of the layer separation structure of the coating film obtained in each example, and the measurement of the surface resistivity and adhesion of the laminated structure obtained in each example were performed according to the following methods.

(1) Presence / absence of layer separation structure A quartz optical waveguide substrate (manufactured by System Instruments Co., Ltd.) is in close contact with the coated film side and the back side thereof, and interfacial ultraviolet using slab type optical waveguide spectroscopy. The evanescent wave absorption characteristics were investigated using a visible spectroscopic measurement apparatus “SIS-50 type” (manufactured by System Instruments).
When a large difference was obtained in the evanescent wave absorption characteristics between the coated surface side and the back surface (base material side), it was determined that the layer separation structure was effectively formed.
(2) Antistatic property (2-1) Using a high resistivity meter “HIRESTA (registered trademark) UP” (manufactured by Mitsubishi Chemical Corporation), the surface resistivity (Ω / □) can be obtained at an applied voltage of 100 V for 10 seconds. Measurement was performed and used as an antistatic index. In an optical member or a building material, a surface resistivity of 10 ¹⁰ Ω / □ or less is required as an antistatic function.
(2-2) After leaving each laminated structure in a 90 ° C. oven for 250 hours, the surface resistance value was measured by the same method as in (2-1) above and placed in a high-temperature environment. It was used as an index of antistatic property in the case (hereinafter referred to as high temperature antistatic property).
(3) Adhesiveness Based on JIS K5600-5-6, the adhesiveness of an ionic liquid layer and a hard-coat layer was evaluated. In addition, the remainder after peeling was expressed in percentage. The closer the remaining after peeling is to 100%, the better the adhesion between the ionic liquid layer and the hard coat layer.

<Production Example 1> Coating liquid 1
All components were mixed as shown in Table 1 below at room temperature to prepare a coating liquid 1.

<Production Example 2> Coating liquid 2
In Production Example 1, N, N-dimethyl-N-ethyl-N- (2-methoxyethyl) ammonium tetrafluoroborate as component (B1) was mixed with N, N-dimethyl-N-ethyl-N- (2- In place of methoxyethyl) ammonium bis (trifluoroethanesulfonyl) imide (manufactured by Kanto Chemical Co., Inc.), all components were mixed in the same manner except that acetone of component (C) was replaced with tetrahydrofuran, and coating solution 2 was Obtained.

<Manufacture examples 3 and 4> Coating liquid for formation sequentially The coating liquid which mixes (A1) component and (A2) component of Table 1 in manufacture example 1 with the compounding quantity of Table 1 at room temperature. The component (B1) and the component (B2) were separately mixed at room temperature in the amounts shown in Table 1 to obtain a coating solution 4.

<Production Example 5>
In Production Example 1, all components were mixed in the same manner except that the component (C) was not used, and separated into a propylene glycol monomethyl ether layer (upper layer) and an ionic liquid layer (lower layer), and homogeneous in one liquid It was not possible to obtain a coating solution that could be applied to the surface.

<Example 1>
On the base material (Toyobo Co., Ltd. PET film, product name “A-4100”, thickness 100 μm), the coating liquid 1 obtained in Production Example 1 was applied by bar coating, and then in an oven at an internal temperature of 60 ° C. And kept for 1 minute to volatilize the component (C). Here, it was confirmed by the above method that the coating film had a layer separation structure [(A1) · (A2) layer / (B1) · (B2) layer]. Subsequently, (A2) component in a coating film was volatilized by hold | maintaining for 30 second in oven with an internal temperature of 80 degreeC. Thereafter, ultraviolet rays were applied (accumulated light amount: 100 mJ / cm ² ) to cure the coating film, and a laminated structure 1 having a thickness of 1 μm was obtained.
Table 2 shows the results of measurement of antistatic properties, high-temperature antistatic properties and adhesion of the laminated structure 1 obtained.

<Example 2>
A laminated structure 2 was obtained in the same manner as in Example 1, except that the coating liquid 2 obtained in Production Example 2 was used instead of the coating liquid 1. In Example 2 as well, the coating film obtained by volatilizing the component (C) had a layer separation structure.
Table 2 shows the results of measurement of antistatic property, high-temperature antistatic property and adhesion of the laminated structure 2 obtained.

<Comparative Example 1> Tandem coating method The coating liquid 4 obtained in Production Example 4 was applied by bar coating on a base material (PET film manufactured by Toyobo Co., Ltd., product name “A-4100” thickness 100 μm). After coating the coating liquid 3 obtained in Production Example 3 on the coating liquid 4 by bar coating, the coating liquid 4 is dried in an oven at an internal temperature of 80 ° C. for 30 seconds, and then the total amount of ultraviolet light is 100 mJ / cm ² . In this way, the coating film was cured to obtain a laminated structure 3 having a thickness of 3 μm.
Table 2 shows the results of measurement of antistatic properties, high-temperature antistatic properties and adhesion of the laminated structure 3 obtained.

  From Table 2, the laminated structure obtained by the method of the present invention (Examples 1 and 2) was compared with the laminated structure (Comparative Example 1) produced by the conventional tandem coating method using the same material. It can be seen that the adhesion is high. Further, it can be seen that even though the same ionic liquid is used, the initial antistatic property and the antistatic property when placed in a high temperature environment are improved. Therefore, according to the method of the present invention, it can be seen that an antistatic hard coat film having higher reliability and performance can be produced by a simple one-component coating method.

  The production method of the present invention can be used as a production method of a laminated structure provided with a functional film such as an antistatic film, which is useful for optics, building materials, and the like. The laminated structure obtained by the present invention is useful as an optical member such as a protective film such as an antireflection film, an antiglare film, or a hard coat film used in the display field.

Claims (7)

A method for producing a laminated structure using a one-component coating liquid, comprising the following steps 1 to 3 in this order: an ionic liquid layer and a hard coat layer.
Step 1: (A1) Active energy ray-curable hard coat layer forming component, (A2) Hard coat layer forming component solvent, (B1) ionic liquid, (B2) matrix polymer for ionic liquid, and (C) ( A step of mixing a solvent having a lower boiling point than the component (A2) having compatibility with both the component A2) and the component (B2) to obtain a one-component coating solution.
Process 2: The process of forming the coating film which has a layer-separation structure by volatilizing the said (C) component, after apply | coating the 1-component coating liquid obtained at the process 1 to the base material.
Process 3: The process which has the process of volatilizing the said (A2) component in a coating film after the process 2, and the process of irradiating an active energy ray to a coating film. The component (B1) is selected from the group consisting of an imidazolium cationic substance, a pyridinium cationic substance, a pyrrolidinium cationic substance, a quaternary ammonium cationic substance, and a quaternary phosphonium cationic substance Cationic substances such as halide, cyanide (CN ⁻ ), triflate (CF ₃ SO ₃ ⁻ ), tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), sulfonylamide (SO ₂ NH) ₂ ^-), methyl sulphate (CH ₂ SO ₄ ^-), ethylsulfate (C ₂ H ₄ SO ₄ ^-), bis (trifluoromethanesulfonyl) imide _{[(CF 3 SO 2) 2} N -], bis (trifluoro ethane sulfonyl) imide _{[(C 2 H 2 F 3} SO 2) 2 N -] one of anion selected from the group consisting of There is bound salts, method for producing a laminated structure according to claim 1.   (C) The manufacturing method of the laminated structure of Claim 1 or 2 which is at least 1 sort (s) selected from the group which consists of acetone, tetrahydrofuran, and a dichloromethane.   The laminated structure obtained by the manufacturing method in any one of Claims 1-3.   An optical member having the laminated structure according to claim 4.   The optical member according to claim 5, which is an antistatic hard coat film. A method for forming a coating film using a one-component coating liquid,
(A1) Active energy ray-curable hard coat layer forming component,
(A2) Hard coat layer forming component solvent,
(B1) ionic liquid,
(B2) Mixing a matrix polymer for ionic liquid, and (C) a solvent having a lower boiling point than the component (A2), which is compatible with both the component (A2) and the component (B2), A method for forming a coating film having a layer separation structure by volatilizing the component (C) after obtaining a working solution and applying the obtained one-component coating solution to a substrate.