TW201400562A - Process for producing article having fluorine-containing silane-based coating - Google Patents

Abstract

The present invention provides a process for producing an article comprising a fluorine-containing silane-based coating on a coating surface of an organic base material, wherein the process comprises the steps of: (a) forming a precursor coating on a surface of the organic base material by using a composition comprising an unsaturated silane compound, a photocatalyst and a photocurable organic material; (b) forming a cured coating derived from the precursor coating on the surface of the organic base material by photo-irradiation to the precursor coating; and (c) forming a fluorine-containing silane-based coating on the cured coating directly or via an inorganic material layer by using a surface treatment agent comprising a fluorine-containing silane compound. The process can form the fluorine-containing silane-based coating having high friction durability is provided.

Description

Method for producing article having fluorine-containing decane-based coating layer Cross-references to related applications

The present application claims priority to and the benefit of U.S. Provisional Application Serial No. 61/620,690, filed on Apr. 5, 2012, the entire disclosure of which is incorporated herein by reference.

The present invention relates to a method for producing an article having a fluorine-containing decane-based coating layer, and more particularly to a method for producing an article having a fluorine-containing decane-based coating layer on the surface of a coating layer of an organic base material. The invention also relates to an article that can be manufactured by the method of manufacture.

Since transparent plastics (such as acrylate resins and polycarbonates) are lightweight and easy to process, their use as alternative inorganic glass materials has gradually expanded. Transparent plastics can be treated with a variety of different finishes depending on their application. For example, since transparent plastics have lower surface hardness than inorganic glass and are more susceptible to scratching, it may be necessary to undergo a hard coating treatment to prevent such problems.

Generally, in the use of an optical component, an antifouling coating layer is formed on a base material composed of inorganic glass as a surface treatment layer to prevent adhesion of, for example, fingerprints. A surface treatment agent as an antifouling coating agent is known, which comprises As the active ingredient, a perfluoropolyether group and a fluorine-containing decane compound having a hydroxyl group or a hydrolyzable group bonded to Si are used as an active ingredient (see Patent Documents 1 and 2).

When the above transparent plastic is applied to an optical component, it is desirable to perform a surface treatment to provide antifouling properties. In a common surface treatment method of an organic base material composed of a transparent plastic or the like, a surface containing an ultraviolet curable acrylic hard coater and a perfluoropolyether-containing compound having a carbon-carbon double bond as an antifouling additive is used. The treating agent forms a hard coat layer having antifouling properties as a surface treatment layer (see Patent Document 3), and is applied to the organic base material by this surface treatment agent, and cured by ultraviolet light.

Excerpt list

Patent document

Patent Document 1: WO 97/07155

Patent Document 2: JP 2008-534696 A

Patent Document 3: WO 03/002628

Patent Document 4: JP 2004-250474 A

Patent Document 5: JP 2007-332262 A

Patent Document 6: JP 2003-137944 A

The surface treatment layer (or coating layer) is required to have high durability to provide a base material having a desired function for a long period of time. In particular, when used in optical components (such as glasses) and touch panels that require light transmission or transparency, the surface treatment layer is required to have high antifouling properties and high abrasion resistance (in other words, to maintain initial properties, such as : anti-fouling properties, etc., against repeated friction).

However, conventional surface treatment methods for organic substrate materials are not sufficient to meet the requirements of high antifouling properties and high abrasion resistance. In particular, the problem is that the antifouling property (initial antifouling property) produced by a common surface treatment method in which an antifouling additive is added to a hard coating agent is lower than using a surface treatment agent containing a fluorine-containing decane compound. The antifouling property of the formed fluorine-containing decane-based coating layer.

The fluorine-containing decane-based coating layer has high adhesion strength to an inorganic base material (e.g., inorganic glass, etc.), that is, has high abrasion resistance. However, the fluorine-containing decane-based coating layer has low adhesion strength to the organic base material, and thus cannot have high abrasion resistance.

Therefore, it is proposed to form a hard coat layer having a hydrophilic group on the organic base material, and then to form a fluorine-containing decane-based coat layer thereon (see Patent Document 4). However, the friction resistance provided by such manufacturing methods is not always sufficient.

Alternatively, it is planned to form a ceria coating layer on the organic base material, and then form a fluorine-containing decane-based coating layer thereon. By this manufacturing method, high adhesion strength is achieved between the fluorine-containing decane-based coating layer and the cerium oxide coating layer, but the adhesion strength between the cerium oxide coating layer and the organic base material is still insufficient, so that it cannot be achieved. High abrasion resistance.

On the other hand, an organic-inorganic composite having excellent adhesion to a base material is known (see Patent Document 4). However, the organic-inorganic composite contains a functional material, so that the composite itself can provide a desired function, and it is not intended to form a surface treatment layer on the organic-inorganic composite, such as a fluorine-containing decane-based coating layer, etc. Wait.

An object of the present invention is to provide a method for producing an article comprising a fluorine-containing decane-based coating layer on a surface of a coating layer of an organic base material, wherein the production method can form a fluorine-containing decane-based coating layer having high abrasion resistance.

According to an aspect of the present invention, there is provided an organic substrate material A method for producing an article comprising a fluorine-containing decane-based coating layer (outermost layer) on a surface of a coating layer, wherein the method comprises the steps of: (a) using a composition comprising an unsaturated decane compound, a photocatalyst, and a photocurable organic material; Forming a precursor coating layer on the surface of the organic base material; (b) subjecting the precursor coating layer to light irradiation, thereby forming a cured coating layer derived from the precursor coating layer on the surface of the organic base material; (c) forming a fluorine-containing decane-based coating layer directly on the cured coating layer or via an inorganic material layer by using a surface treatment agent containing a fluorine-containing decane compound.

In the production method of the present invention, the order in which the steps (a) to (c) are carried out is not particularly limited. In particular, steps (b) and (c) can be carried out at any suitable point in time as long as a cured coating layer is formed and a fluorine-containing decane-based coating layer is formed on the cured coating layer (directly or through The inorganic material layer can be used.

According to the above method for producing the article of the present invention, a fluorine-containing decane-based coating layer having high abrasion resistance can be formed on the surface of the coating layer of the organic base material. Although the invention is not limited by any theory, the following factors can be considered. According to the above method for producing the article of the present invention, during the step (b), the photocatalyst is excited upon irradiation on the precursor coating layer, and acts on the surface of the organic substrate material to react the surface with the unsaturated decane compound, thereby A bond is formed therebetween. At the same time, an addition reaction with an unsaturated decane compound is carried out to cure the photocurable organic material. The resulting cured coating layer thus has a bond formation and addition reaction with high adhesion strength to the organic substrate material. Further, during the step (c), the fluorine-containing decane compounds react with each other to form a bond between the compounds, and react with the surface of the cured coating layer (or the underlayer) to form a bond therebetween. Knot. The obtained fluorine-containing decane-based coating layer itself has high coating layer strength and high adhesion strength to the cured coating layer. Resultable A fluorine-containing decane-based coating layer having high abrasion resistance is formed on the surface of the organic base material with the cured coating layer.

The unsaturated decane compound may be, for example, a compound of the formula: CH ₂ =CH-(R ¹² ) _y -SiT _x R ¹¹ _3-x wherein: T is a hydroxyl group or a hydrolyzable group; R ¹¹ is a hydrogen atom Or an alkyl group having 1 to 22 carbon atoms; x is an integer from 1 to 3; R ¹² is a divalent organic group; and y is 0 or 1.

The photocatalyst used in the present invention is preferably composed of a metal compound, but is not necessarily limited thereto.

Since the fluorine-containing decane-based coating layer contains a fluorine atom, it has water repellency, oil repellency, antifouling property, and the like in addition to the above-mentioned rubbing resistance. In particular, the fluorine-containing decane compound preferably has a perfluoropolyether group and a hydroxyl group or a hydrolyzable group bonded to Si. The fluorine-containing decane-based coating layer obtained by using the present compound has high abrasion resistance, water repellency, oil repellency, antifouling property (for example, prevention of adhesion stains such as fingerprints), surface slip properties (or lubricity, for example, wiping Stains (such as the nature of fingerprints), and so on.

Examples of the fluorine-containing decane compound having a hydroxyl group or a hydrolyzable group bonded to Si and a perfluoropolyether group include one or more compounds of any one of the following formulas (1a) and (1b): Wherein: Rf ¹ is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms; a, b, c and s are each independently an integer from 0 to 200, wherein the a, b The total number of c and s is at least 1, and the order of occurrence of each repeating unit in the brackets of the formula a, b, c or s is not limited; d and f are respectively 0 or 1; e and g respectively Independently an integer from 0 to 2; m and l are independently an integer from 1 to 10; X is a hydrogen atom or a halogen atom; Y is a hydrogen atom or a lower alkyl group; Z is a fluorine atom or a lower fluoroalkyl group; a hydroxyl group or a hydrolyzable group; R ¹ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; and n is an integer of 1 to 3.

Examples of other fluorine-containing decane compounds having a hydroxyl group or a hydrolyzable group bonded to Si and a perfluoropolyether group include one or more compounds of any one of the following formulas (2a) and (2b): Wherein: Rf ² is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms; a, b, c and s are each independently an integer from 0 to 200, wherein the a, b The total number of c and s is at least 1, and the order of occurrence of each repeating unit in the brackets of the formula a, b, c or s is not limited; d and f are independently 0 or 1; h and j are 1 or 2; i and k are each independently an integer 2 to 20; Z is a fluorine atom or a lower fluoroalkyl group; T is a hydroxyl group or a hydrolyzable group; R ² is a hydrogen atom or has 1 to 22 carbon atoms An alkyl group; and n is an integer from 1 to 3.

According to another aspect of the present invention, there is also provided an article comprising an organic base material, a coating layer formed on a surface of the organic base material, comprising a cured material of an unsaturated decane compound and a photocurable organic material, and a photocatalyst, And a fluorine-containing decane-based coating layer formed on the coating layer.

This article can be made by the manufacturing method of the present invention. In this item, even if organic As the base material, a fluorine-containing decane-based coating layer having high antifouling properties can be formed on the surface (or outermost layer) of the coating layer of the organic base material.

The organic substrate material can be transparent. The article according to the invention substantially maintains the transparency of the organic substrate material.

The fluorine-containing decane-based coating layer can provide antifouling properties (initial antifouling properties) by containing a fluorine atom, and thus is suitable as an antifouling coating layer.

The article made by the present invention may be, for example, an optical component, but is not particularly limited. The present invention is suitable for coating optical components because of its high degree of requirement for improved abrasion resistance.

According to the present invention, a fluorine-containing decane-based coating layer having high abrasion resistance is formed by a composition comprising an unsaturated decane compound, a photocatalyst, and a photocurable organic material in an organic base material and a fluorine-containing decane-based coating layer. A layer of cured coating is formed between them.

Fig. 1 is a graph showing the rub resistance of the antifouling layers produced in Examples 1 to 3 and Comparative Examples 1 to 4.

Hereinafter, a method of manufacturing the article of the present invention and an article manufactured by the manufacturing method will be described in detail through specific embodiments of the present invention, but the present invention is not limited thereto.

First, an organic base material is provided. The organic base material suitable for use in the present invention may be a base material in which at least the surface is composed of an organic material. The "organic material" used in the present invention may be a material containing an organic substance, typically a material composed of one or more organic substances, but may contain one or more organic substances and inorganic substances. A complex (mixture) or a mixture of materials.

The organic material can be any suitable organic material. For example, general plastic materials such as acrylate resin ((meth) acrylate polymer), polycarbonate, polyethylene terephthalate, polystyrene, polyethylene, polypropylene, polyvinyl chloride, AS resin, and ABS resin. Further, a polyoxyxylene resin, a fluororesin, a cycloolefin resin, an epoxy resin, a TAC resin, a fluororesin, an MS resin, a polyvinyl alcohol, a diallyl citrate, a polyimine, a phenol resin, or a melamine resin can be used. , urea resin, unsaturated polyester resin, polyurethane, diallyl citrate resin, alkyd resin, and the like. Further, an organic-inorganic hybrid resin can also be used.

The invention is applicable when the organic substrate material is transparent. The transparent organic base material is, for example, a transparent acrylate resin, a polycarbonate, a polyethylene terephthalate, a polyoxyl resin (for example, see Patent Document 6), or the like, or an alternative to inorganic glass. Commercial materials such as "SILPLUS" (registered trademark; manufacturer Nippon Steel Chemical Co., Ltd.) and "ORGA" (registered trademark; manufacturer Nippon Synthetic Chemical Industry Co., Ltd.) are sold. In the present invention, the "transparent" system is generally considered to be transparent, for example, representing a haze value of 5% or less.

For example, when the article to be manufactured is an optical component, any layer (or coating layer) composed of an organic material such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the base material. The antireflection layer may use a single antireflection layer or a multiple antireflection layer. When the article to be manufactured is an optical component for a touch panel, it may have a transparent electrode, for example, having indium tin oxide (ITO), indium zinc oxide or the like on a part of the surface of the organic base material (glass) Thin layer. In addition, the organic base material may have an antistatic layer, an insulating layer, an adhesive layer, a protective layer, a bezel decorative layer (I-CON), a spray layer, a hard coating layer, a polarizing film, a phase difference film, LCD module, and more.

The shape of the organic base material is not specifically limited, but may be in the form of a flat plate, a film, a compression body, or the like. The surface area of the base material which should form the cured coating layer and the fluorine-containing decane-based coating layer (outermost layer) may be at least a part of the surface of the base material, and may be appropriately determined depending on the use of the article to be manufactured, the specification, and the like.

The organic substrate material can accept any pretreatment. Examples of pretreatment include plasma treatment (e.g., corona discharge) or ion beam irradiation. The plasma treatment method is suitable for introducing or adding a hydroxyl group to the surface of the base material, and further cleaning the surface of the base material (removing foreign materials, etc.). Alternatively, other pretreatment examples include forming a single surface adsorbent having a carbon-carbon unsaturated bond group on the surface of the base material by the LB method (Langmuir-Blodgett method), or performing a chemical adsorption method first, followed by oxygen and The unsaturated bond is cleaved under a nitrogen atmosphere.

On the other hand, a composition comprising an unsaturated decane compound, a photocatalyst and a photocurable organic material (hereinafter referred to as "the composition forming the underlayer") is provided. As used herein, "underlayer" means a layer that is coated with a surface treatment agent (or a layer of an inorganic material layer formed thereon when there is an inorganic material layer between the cured coating layer and the fluorine-containing decane-based coating layer) . In this embodiment, the bottom layer is a cured coating layer derived from the composition forming the underlayer.

The unsaturated decane compound may have a carbon-carbon double bond and a hydroxyl group or a hydrolyzable group bonded to Si. Examples of the unsaturated decane compound include a compound of the following formula (which may be one compound or a mixture of two or more compounds).

CH ₂ =CH-(R ¹² ) _y -SiT _x R ¹¹ _3-x wherein: T and R ¹¹ are groups bonded to Si, and if R ^{12 is} present, it is between vinyl and decyl The spacer.

T represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (wherein A is substituted or unsubstituted and has 1 to 3 A linear or branched alkyl group of a carbon atom, and the like, preferably -OA (alkoxy). Examples of A include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl; and substituted alkyl groups such as chloromethyl. Among them, an alkyl group (specifically, an unsubstituted alkyl group) is preferred. The hydroxyl group may be produced by hydrolysis of a hydrolyzable group, but is not specifically limited.

R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

x is an integer from 1 to 3.

R ¹² represents a divalent organic group. The divalent organic group may be a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, which may have an ester bond, an ether bond, a guanamine bond, a sulfide bond, Or similar.

y is 0 or 1. When y is 0, R ¹² is absent, and the vinyl group and the decyl group are directly bonded to each other.

As used herein, the term "photocatalyst" means that the material is excited when exposed to light (excitation light) having an energy higher than the energy gap between the crystalline conductive band and the valence band (ie, shorter wavelength). (Photoexcited) electrons in the valence band that produce conductive electrons and holes. The photocatalyst may be, for example, a metal compound containing a metal such as titanium, zinc, tin, iron, ruthenium, tungsten, or the like. More specifically, examples of the metal compound include titanium oxide, zinc oxide, tin oxide, iron oxide, antimony trioxide, tungsten trioxide, and barium titanate. It is known that a general photocatalyst is titanium oxide, more specifically an anatase or rutile type titanium oxide. Titanium oxide can have an average primary particle size of 0.1 μm or less. Fine particle type.

The photocatalyst is preferably a photosensitive compound (specifically, a metal compound) and/or a derivative thereof which is sensitive to light having a wavelength of 400 nm or less. The photosensitive compound may be at least one selected from the group consisting of a metal chelate compound, a metal organic acid salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensation product therewith, preferably The hydrolyzate and/or its condensation product is more preferably a hydrolyzate and/or a condensation product of the metal chelate compound. The derivative of the photosensitive compound may be, for example, a derivative obtained by further condensing a condensation product or the like of a metal chelate compound. The photosensitive compound and/or its derivative may be chemically bonded to the unsaturated decane compound, dispersed in a non-bonded state, or in a mixed state thereof.

The photocurable organic material may be any material as long as it can be hardened after being irradiated with light. The photocurable organic material may be a photocurable resin, and particularly preferably an ultraviolet curable resin. For example, ultraviolet curable acrylate and methacrylate (urethane type, epoxy type, polyester type, polybutadiene type, polyfluorene type, amine type resin type, polyether type) can be used. A polyhydric alcohol type, a fluorine type, a decane type) or the like, and a commercially available ultraviolet curable hard coater or the like can be used. The photocurable organic material may be monofunctional, but is preferably polyfunctional.

The unsaturated decane compound may be contained in the composition for forming the underlayer, for example, from about 0.1 to 90 parts by weight, preferably from about 1 to 50 parts by weight, per 100 parts by weight of the photocurable organic material, and The photocatalyst may be, for example, about 0.01 to 20 parts by weight, preferably about 0.1 to 2.0 parts by weight, per 100 parts by weight of the photocurable organic material.

The composition forming the bottom layer may contain any suitable additives in addition to these components. Examples of the additive include a polymerization initiator, a photosensitizer, and polymerization inhibition Agents, solvents, hardeners, crosslinkers, ultraviolet light shielding agents, ultraviolet light absorbers, surface conditioning agents (leveling agents), defoamers, and the like.

A precursor coating layer is formed on the surface of the organic base material by the composition forming the underlayer. The method of forming the precursor coating layer is to apply the composition forming the underlayer on the surface of the organic base material, thus being coated on the surface. The coating method is not particularly limited. Examples of the coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like.

The composition forming the underlayer may be applied to the surface of the substrate material after being diluted with a solvent. The solvent may be appropriately selected depending on the stability of the composition forming the underlayer and the volatile matter of the solvent, but it is preferred to use the following solvents: ketones (for example, methyl ethyl ketone, acetone, methyl isobutyl ketone, etc.) Alcohols (for example: monovalent alcohols such as: ethanol and propanol, polyvalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol (specifically, di-tetravalent alcohols)), esters (eg, acetic acid B) Ester), ether (for example: diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate), fluorine-containing alcohol, fluorine-containing ether, and the like. These solvents may be used singly or as a mixture of two or more of them.

Then, if the composition is diluted with a solvent, after a drying step is appropriately performed to remove the solvent, the precursor coating layer is irradiated with light, and a precursor coating layer is derivatized on the surface of the organic base material to form a cured coating layer. The cured coating layer is a coating layer comprising a cured material of an unsaturated decane compound and a photocurable organic material and a photocatalyst. The resulting cured coating layer thus has a high adhesion strength to the organic substrate material and a reactive portion on the surface of the cured coating layer.

Although the present invention is not limited by any theory, it is considered that the following phenomenon occurs when it is irradiated with light. The photocatalyst is excited by light irradiation, and the surface of the organic base material is hydrolyzed by the action of the photocatalyst to be generated on the surface of the organic base material. Hydroxyl and / or free radicals. Further, the hydrolyzable group which may be present in the unsaturated decane compound may be hydrolyzed by a photocatalyst to produce a hydroxyl group and/or a radical. The dehydration-condensation and/or radical reaction between the hydroxyl group and/or the radical of the unsaturated decane compound and the hydroxyl group and/or the radical on the surface of the organic base material forms a bond therebetween. At the same time, the photocurable organic material is hardened by light irradiation, during which the carbon-carbon double bond of the unsaturated decane compound undergoes an addition reaction between the unsaturated decane compounds and/or simultaneously with the photocurable organic material. The resulting cured coating layer has high adhesion strength to the organic base material due to the formation of bonding and addition reactions. Further, the surface of the cured coating layer becomes a reactive portion. The reactive moiety may be a hydroxyl group or a hydrolyzable group originally possessed by the unsaturated decane compound, a hydroxyl group and/or a radical generated by the photocatalytic action of the unsaturated decane compound, or hydrolyzed by the photocatalyst on the surface of the cured coating layer. Hydroxyl groups and/or free radicals produced.

Light irradiation may be performed on the exposed surface side of the precursor coating layer (opposite to the surface contacting the surface of the organic substrate material). The wavelength of the illuminating light can be any wavelength as long as the photocurable organic material can be cured and the photocatalyst is excited. Generally, it may be ultraviolet light (wavelength: about 10 to 400 nm), but is not limited thereto. The amount of light irradiation may be appropriately selected depending on the type of the photocurable organic material to be used and the like and the photocatalyst to be used, for example, the cumulative amount of light may be 200 to 2,000 mJ/cm ² , but is not limited thereto.

The thickness of the cured coating layer is not specifically limited. When used for an optical component, the thickness of the cured coating layer is preferably in the range of 1 to 30 nm based on optical properties and adhesion strength.

Then, the cured coating layer is used as a primer layer, and a fluorine-containing decane-based coating layer is formed thereon by using a surface treatment agent containing a fluorine-containing decane compound. The fluorine-containing decane compound clearly has a hydroxyl group or a hydrolyzable group bonded to Si. Thus income The fluorine-containing decane-based coating layer itself has high coating strength and high adhesion strength to the cured coating layer (underlayer).

While the invention is not limited by theory, the following factors should be considered. The Si-bonded hydroxyl group or hydrolyzable group in the fluorine-containing decane compound can be interactively reacted to form a bond between the compounds. Further, a hydroxyl group or a hydrolyzable group bonded to Si in the fluorine-containing decane compound reacts with a reactive group present on the surface of the cured coating layer to form a bond between the fluorine-containing decane compound and the underlayer.

The fluorine-containing decane compound may have a perfluoropolyether group and a hydroxyl group or a hydrolyzable group bonded to Si. The perfluoropolyether group causes water repellency, oil repellency, and antifouling properties of the fluorine-containing decane-based coating layer.

Examples of the fluorine-containing decane compound having a perfluoropolyether group and a Si-bonded hydroxyl group or a hydrolyzable group include any of the following compounds of the formulae (1a) and (1b) (may be one compound or two or more a mixture of compounds).

In the formula: Rf ¹ is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms, preferably with or without one or more fluorine atoms. An alkyl group of 1 to 3 carbon atoms. The above alkyl group which may or may not be substituted by one or more fluorine atoms is preferably a perfluoroalkyl group.

The subscripts a, b, c and s represent the number of repetitions of the four perfluoropolyether repeating units constituting the polymer backbone, and represent integers 0 to 200, respectively, wherein the total number of a, b, c and s is at least 1 Preferably, it is an integer from 1 to 100. There is no limitation on the order in which the repeating units in the parentheses in the formula are a, b, c or s. In these repeating units, the -(OC ₄ F ₈ )- group may be any of the following: -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )- , -(OCF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF _{3 2} )-, -(OCF(CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-, preferably Is -(OCF ₂ CF ₂ CF ₂ CF ₂ ). The -(OC ₃ F ₆ )- group can be any of the following: -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ )) -, preferably -(OCF ₂ CF ₂ CF ₂ )-. The -(OC ₂ F ₄ )- group may be any of the following: -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

The subscripts d and f are independently 0 or 1.

The subscripts e and g are independent of integers 0 to 2, respectively.

The subscripts m and l are independent of integers 1 to 10, respectively.

X is a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom.

Y is a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms.

Z is a fluorine atom or a low carbon number fluoroalkyl group. The lower carbon number fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group. Also preferred is trifluoromethyl. Typically, Z is a fluorine atom, and d and f are 1.

T and R ¹ are groups bonded to Si.

T is a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (wherein A is substituted or unsubstituted having 1 to 3 carbon atoms Alkyl), and so on. The hydroxyl group may be a group produced by hydrolysis of a hydrolyzable group, but is not specifically limited.

R ¹ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

The subscript n is an integer from 1 to 3.

Examples of other fluorine-containing decane compounds having a perfluoropolyether group and a Si-bonded hydroxyl group or a hydrolyzable group include any of the following compounds of the formulae (2a) and (2b) which may be one compound or two or more. a mixture of various compounds).

In the formula: Rf ² is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms, preferably with or without one or more fluorine atoms. An alkyl group of 1 to 3 carbon atoms. The above alkyl group which may or may not be substituted by one or more fluorine atoms is preferably a perfluoroalkyl group.

The subscripts a, b, c and s represent the number of repetitions of the four perfluoropolyether repeating units constituting the polymer backbone, which are integers from 0 to 200, respectively, wherein the total number of a, b, c and s is at least 1 Preferably, it is an integer from 1 to 100. There is no limitation on the order in which the repeating units in the parentheses in the formula are a, b, c or s. In these repeating units, the -(OC ₄ F ₈ )- group may be any of the following: -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )- , -(OCF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF _{3 2} )-, -(OCF(CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-, preferably Is -(OCF ₂ CF ₂ CF ₂ CF ₂ ). The -(OC ₃ F ₆ )- group can be any of the following: -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ )) -, preferably -(OCF ₂ CF ₂ CF ₂ )-. The -(OC ₂ F ₄ )- group may be any of the following: -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

The subscripts d and f are independently 0 or 1.

The subscripts h and j are independently 1 or 2.

The subscripts i and k are independent of integers 2 to 20, respectively.

Z is a fluorine atom or a low carbon number fluoroalkyl group. The lower carbon number fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group. It is also preferred that the trifluoromethyl group represents Z as a fluorine atom, and d and f are 1.

T and R ² are groups bonded to Si.

T is a hydroxyl group or a hydrolyzable group. Examples of hydrolyzable groups include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (wherein A is substituted or unsubstituted having 1 to 3 carbon atoms Substituted alkyl), and so on. The hydroxyl group may be a group produced by hydrolysis of a hydrolyzable group, but is not specifically limited.

R ² is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

The subscript n is an integer from 1 to 3.

Examples of such fluorine-containing decane compounds may have an average molecular weight of, for example, 1,000 to 12,000. Within this range, the compound preferably has an average molecular weight of from 2,000 to 10,000 based on the abrasion resistance. As used herein, "average molecular weight" refers to the number average molecular weight.

Surface treatment agent (or surface) containing the fluorine-containing decane compound The treatment compound) can provide water repellency, oil repellency, antifouling properties, surface slip properties (or lubricity), or the like.

The composition having the surface treating agent used in the present invention can be appropriately selected depending on the function required for the fluorine-containing decane-based coating layer.

For example, the surface treatment agent may contain a fluoropolyether compound, which is also known as a fluorine-containing oil (for distinction from a fluorine-containing decane compound, hereinafter referred to as "fluorine-containing oil"), except for the fluorine-containing decane compound exemplified. Further, a perfluoropolyether compound is preferred. The fluorine-containing oil can improve the surface slip properties of the fluorine-containing decane-based coating layer.

The fluorine-containing oil may be contained in the surface treatment agent, for example, from 0 to 80 parts by weight, preferably from 0 to 40 parts by weight, per 100 parts by weight of the fluorine-containing decane compound.

Examples of the fluorine-containing oil include a compound of the following formula (3) (perfluoropolyether compound).

R ²¹ -(OC ₄ F ₈ ) _s' -(OC ₃ F ₆ ) _a' -(OC ₂ F ₄ ) _b' -(OCF ₂ ) _c' -R ²² . . . (3) In the formula: R ²¹ is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms, preferably with or without one or more fluorine atoms. An alkyl group having 1 to 3 carbon atoms. The above alkyl group which may or may not be substituted by one or more fluorine atoms is preferably a perfluoroalkyl group.

R ²² is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms, preferably a fluorine atom or may or may not have one or more fluorine atoms Substituting an alkyl group having 1 to 3 carbon atoms. The above alkyl group which may or may not be substituted by one or more fluorine atoms is preferably a perfluoroalkyl group.

The subscripts a', b', c' and s' represent the number of repetitions of the four perfluoropolyether repeating units constituting the polymer backbone, which are integers from 0 to 300, respectively, where a', b', c' The sum with s' is at least 1, preferably an integer from 1 to 100. There is no restriction on the order in which the subscripts in the parentheses in the formula are a', b', c' or s'. In these repeating units, the -(OC ₄ F ₈ )- group may be any of the following: -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )- , -(OCF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF _{3 2} )-, -(OCF(CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-, preferably Is -(OCF ₂ CF ₂ CF ₂ CF ₂ ). The -(OC ₃ F ₆ )- group can be any of the following: -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ )) -, preferably -(OCF ₂ CF ₂ CF ₂ )-. The -(OC ₂ F ₄ )- group may be any of the following: -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

Examples of the perfluoropolyether compound of the above formula (3) include any of the following compounds of the formulae (3a) and (3b) which may be one compound or a mixture of two or more compounds.

R ²¹ -(OCF ₂ CF ₂ CF ₂ ) _{a "} -R ²² (3a)

R ²¹ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _{s "} -(OCF ₂ CF ₂ CF ₂ ) _{a "} -(OCF ₂ CF ₂ ) _{b "} - ( OCF ₂ ) _{c "} -R ²² . . . (3b) In the equation: R ²¹ and R ^{22 are} as defined above; in the formula (3a), a" is an integer from 1 to 100; and in the formula (3b), s" and a" are independently from 1 to 30, respectively. The integers, and b" and c" are each independently an integer from 1 to 300. The order in which the subscripts in the brackets of the a", b", c", or s" are in the formula is not limited.

The compound of the formula (3a) and the compound of the formula (3b) may be used singly or in combination. When used in combination, it is preferred to use a compound of the formula (3a) and a formula (3b). The compounds are combined in a weight ratio of 1:1 to 1:30. With such ratios, a surface treatment agent having a good balance between surface slip properties and abrasion resistance can be obtained.

From other viewpoints, the fluorine-containing oil may be a compound of the formula: Rf ¹ -F (wherein Rf ^{1 is} as defined above). The compound Rf ¹ -F is preferably a compound having a high affinity for any of the above compounds of the formulae (1a) and (1b) and for the compound of any of the above formulas (2a) and (2b).

The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. High surface slip properties are obtained at this average molecular weight. Typically, the compound of the formula (3a) preferably has an average molecular weight of from 2,000 to 6,000. The average molecular weight of the compound of the formula (3b) is preferably from 8,000 to 30,000. Within this average molecular weight range, high surface slip properties are obtained.

Further, in addition to the fluorine-containing decane compound exemplified, the surface treatment agent may further contain a polyoxonium compound, which is also known as a polysiloxane oil (hereinafter simply referred to as "polyoxygenated oil"). The polyoxygenated oil can improve the surface slip properties of the fluorine-containing decane-based coating layer.

The polyoxyxylene oil may be contained in the surface treatment agent, for example, in an amount of from 0 to 80 parts by weight, preferably from 0 to 40 parts by weight, per 100 parts by weight of the fluorine-containing decane compound.

Examples of the polyoxygenated oil include, for example, a linear or cyclic polyoxyxene oil having a oxane bond of 2,000 or less. The linear polyoxygenated oil may be a so-called straight-run polyoxyl oil and a modified eucalyptus oil. Examples of straight-run polyoxyxene oils include dimethyl polyphthalide oil, methyl phenyl polyoxyxene oil, and methyl hydrogen polyoxyxene oil. Examples of modified polyoxyxides include alkyl ethers, aralkyl groups, polyethers, higher carbon number fatty acid esters, fluoroalkyl groups, amine groups, epoxy groups, carboxyl groups, alcohols, or the like. Analogs are modified. Cyclic polyoxylized oil Examples include, for example, cyclic dimethyl siloxane oil.

In the fluorine-containing decane-based coating layer, the polyoxygenated oil and/or the fluorine-containing oil are fixed or captured by affinity with a fluorine-containing decane compound.

The fluorine-containing decane-based coating layer is formed by forming a coating layer of a surface treating agent on the surface of the underlayer, and if necessary, post-treating the coating layer, but the present invention is not limited thereto.

The surface treatment agent coating layer is formed by coating a surface treatment agent on the surface of the underlayer, thus coating the surface. The coating method is not specifically limited. For example, a wet coating method or a dry coating method can be employed.

Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like.

Examples of dry coating methods include vacuum deposition, sputtering, CVD, and the like. Clear examples of the vacuum deposition method include a resistance heating method, an electron beam method, a high frequency heating method, an ion beam method, and the like. Clear examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and the like.

Further, the coating can be carried out by a normal piezoelectric slurry method.

When the wet coating method is employed, the surface treatment agent is diluted with a solution and then applied to the surface of the underlayer. Based on the stability of the surface treatment agent and the volatile nature of the solvent, it is preferred to use the following solvents: aliphatic perfluorocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and Fluorine-1,3-dimethylcyclohexane); aromatic polyfluorocarbons (eg bis(trifluoromethyl)benzene); aliphatic polyfluorocarbons; hydrofluoroethers (HFE) (eg alkyl groups) Fluoroalkyl ethers such as perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) with perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ ) C ₃ F ₇ ) (perfluoroalkyl and alkyl groups may be straight or branched), and the like. These solvents may be used singly or as a mixture of two or more. Among them, hydrofluoroether is preferred, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) are particularly preferred.

It is preferred to carry out a coating layer forming method of the surface treating agent so that the surface treating agent can be present in the coating layer together with the catalyst for hydrolysis and dehydration-condensation. In short, when the wet coating method is employed, after the surface treatment agent is diluted with a solvent, a catalyst may be added to the dilution of the surface treatment agent just before application to the surface of the underlayer. When the dry coating method is used, a surface treatment agent to which a catalyst has been added may be used in a vacuum deposition method, or a porous metal (for example, iron or the like may be used in a vacuum deposition method using a surface treatment agent to which a catalyst has been added. Granules obtained on copper).

Any suitable acid or base can be used as the catalyst. For example, acetic acid, formic acid, trifluoroacetic acid or the like can be used as the acid catalyst. For example, ammonia, an organic amine, or the like can be used as the base catalyst.

Then, if necessary, the coating layer of the surface treatment agent can be post-treated. This post-treatment is not specifically limited, but for example, when the surface treatment agent contains the fluorine-containing decane compound exemplified, the method of supplying water and dry heating can be continued. In particular, the approach is as follows. When it is exemplified that the fluorine-containing decane compound does not contain a hydrolyzable group (when all T in the formula are hydroxyl groups), it is not necessary to add water.

After the coating layer of the surface treating agent is formed on the surface of the underlayer as described above, water is added to the coating layer (to be distinguished from the above-mentioned underlying precursor coating layer, hereinafter referred to as "second precursor coating layer"). The method of adding water may be, for example, a method of causing condensation or a method of spraying water vapor (steam) by using a difference in temperature between the second precursor coating layer (and the base material and the bottom layer) and the surroundings, but is not specifically limited.

Salt believes that when water is added to the second precursor coating, the water will A hydrolyzable fluorine-containing decane compound is rapidly hydrolyzed by a hydrolyzable group bonded to Si in a fluorine-containing decane compound.

The water addition process can be carried out under atmospheric conditions, for example, between 0 and 500 ° C, preferably between 100 ° C and 300 ° C. Hydrolysis can be carried out by adding water at these temperature ranges. The pressure at this time is not clearly limited, but the surrounding pressure can be carried out.

Then, the second precursor coating layer was heated on the surface of the underlayer in a dry atmosphere at over 60 °C. The dry heat method allows the second precursor coating layer to be placed with the base material and the bottom layer at a temperature of more than 60 ° C, preferably more than 100 ° C, for example, 500 ° C or below, preferably 300 ° C or less, and Unsaturated water vapor pressure in the atmosphere, but there is no clear limit. The pressure at this time is not clearly limited, but the surrounding atmosphere can be carried out.

Under such atmospheres, between the fluorine-containing decane compounds, the group bonded to the Si after hydrolysis (when all T in the formula is a hydroxyl group, the group refers to a hydroxyl group; this also applies to the following) is rapid Dehydration - condensation with each other. As a result, a bond is formed between the fluorine-containing decane compounds.

While the invention is not limited by any theory, between the fluorine-containing decane compound and the underlayer, the group bonded to the Si will rapidly react with the reactive moiety present on the surface of the underlayer after hydrolysis of the compound. As a result, a bond is formed between the compound and the underlayer.

The above water addition and dry heat processes can be carried out continuously using super hot water steam.

The super hot water steam is a gas obtained by heating the saturated steam to a temperature exceeding a boiling point, wherein the gas is heated to a temperature exceeding 100 ° C under ambient pressure, usually 500 ° C or below, for example, 300 ° C or below. And when the boiling point is exceeded, Will turn into an unsaturated water vapor pressure. When the base material on which the second precursor coating layer has been formed on the underlayer is exposed to the super hot water vapor, firstly due to a temperature difference between the super hot water vapor and the relatively low temperature second precursor coating layer, Condensation occurs on the surface of the second precursor coating layer, thereby providing water to the second precursor coating layer. At present, when the temperature difference between the super hot water vapor and the second precursor coating layer is reduced, the water on the surface of the second precursor coating layer evaporates in a dry atmosphere due to the super hot water vapor, and the second precursor The amount of water on the surface of the coating layer is gradually reduced. During the reduction of water on the surface of the second precursor coating layer, that is, while the second precursor coating layer is in a dry atmosphere, the second precursor coating layer is in contact with the super hot water vapor, resulting in The second precursor coating layer is heated by the temperature of the super hot water vapor (temperature exceeding 100 ° C under ambient pressure). Therefore, water and dry heat can be continuously supplied by exposing the base material which has formed the precursor coating layer on the underlayer to the super hot water vapor by using super hot water vapor.

Post treatment can be carried out as described above. The post-treatment method is carried out in order to further improve the rubbing resistance, but it should be noted that the post-treatment method is not a necessary condition for the manufacture of the article of the present invention. For example, after applying a surface treatment agent on the surface of the bottom layer, it can be simply left to stand.

As described above, the underlayer is formed on the surface of the organic base material, and the fluorine-containing decane-based coating layer is formed on the underlayer to produce the article of the present invention. Among the obtained articles, the fluorine-containing decane-based coating layer has high antifouling properties and high abrasion resistance, and thus the fluorine-containing decane-based coating layer is suitably used as an antifouling coating layer. Specifically, by using a surface treatment agent containing the fluorine-containing decane compound, it is formed to have water repellency, oil repellency, antifouling properties (for example, prevention of adhesion such as fingerprints), surface slip properties (or lubricity). , for example: wiping such as: the nature of fingerprints), etc., fluorine-containing decane coating Also suitable for functional thin coatings.

The articles of the invention are not specifically limited, but may be optical components. Examples of optical components include the following: glass lenses, or the like; front surface protection panels, anti-reflection panels, polarizing panels or anti-glare panels on displays (eg, PDPs and LCDs); instruments (eg, cell phones or personal digital assistants) (PDA)) touch panel; disc (such as Blu-ray Disc, DVD, CD-R or MO); optical fiber, and so on.

The thickness of the fluorine-containing decane-based coating layer is not specifically limited. The fluorine-containing decane-based coating layer of the optical component has a thickness in the range of 1 to 30 nm, preferably 1 to 15 nm, based on optical properties, abrasion resistance and antifouling properties.

In the above, the method of producing the article of the present invention and the articles produced by the method of the present invention have been described in detail through the specific embodiments of the present invention, but the specific embodiments may be variously modified.

For example, although in the above specific embodiment, the fluorine-containing decane-based coating layer is directly coated on the underlayer, it may be formed on the underlayer by using an inorganic material layer. In the modified specific embodiment, also because of the presence of a reactive moiety on the surface of the underlying layer (cured coating layer), the inorganic material layer has a high adhesion strength to the underlayer, and by applying a fluorine-containing decane in the inorganic material layer The surface treatment agent of the compound forms a fluorine-containing decane-based coating layer having high adhesion strength to the inorganic material layer. As a result, a fluorine-containing decane-based coating layer having abrasion resistance can be formed. The inorganic material layer may be a single layer or multiple layers. Further, if necessary, an inorganic material layer having an antireflection function may be used as the inorganic material layer, and a single antireflection layer or a multiple antireflection layer may be used. The inorganic material layer is not specifically limited, but may include, for example, SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , A layer of MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , and the like. These inorganic materials may be used singly or in combination of two or more kinds (for example, in a mixture). When a multiple antireflection layer is used, it is preferred to use SiO ₂ and/or SiO in the outermost layer. These layers may be formed by a known method such as a vapor deposition method, a sol-gel method or the like. The thickness of the inorganic material layer is not specifically limited, but may be, for example, in the range of 1 to 300 nm.

Further, for example, in the above specific embodiment, a composition for forming an underlayer is applied on the surface of the organic base material to form a precursor coating layer; (when the composition for forming the underlayer is diluted with a solvent, it is moving After removing the solvent, the precursor coating layer is subjected to light irradiation to completely cure to obtain a cured material as a primer layer; then a surface treatment agent containing a fluorine-containing decane compound is applied thereon to form a fluorine-containing decane-based coating layer. However, the time for forming the cured coating layer and forming the fluorine-containing decane-based coating layer is not limited thereto. More specifically, the composition for forming the underlayer is applied on the surface of the organic base material to form a precursor coating layer; the precursor coating layer (which should be removed after solvent removal in the previous example) can be used as the bottom layer. And then applying a surface treatment agent containing a fluorine-containing decane compound thereon; the precursor coating layer is irradiated with light through the surface treatment agent layer to form a cured coating layer; thereby, the surface treatment agent containing the fluorine-containing decane compound is A fluorine-containing decane-based coating layer is formed on the cured coating layer. Alternatively, the composition for forming the underlayer is coated on the surface of the organic base material to form a precursor coating layer; the precursor coating layer (previously, after removing the solvent) is subjected to light irradiation to obtain a semi-cured coating layer in which partial curing is performed; the semi-cured coating layer is used as a primer layer, and a surface treatment agent containing a fluorine-containing decane compound is applied thereon; the semi-cured coating layer is permeable to the surface treatment agent The layer is irradiated with light to obtain a fully cured coating layer; thereby, a fluorine-containing decane-based coating layer is further formed on the cured coating layer formed of a surface treatment agent containing a fluorine-containing decane compound. According to such modified specific embodiments, the precursor coating layer or the semi-cured coating layer is transmitted through the surface The layer of the agent is irradiated with light to obtain a cured coating layer, and thus the surface of the coating layer (including the precursor coating layer or the state from the semi-cured coating layer to the cured coating layer) is subjected to the photocatalyst during this period. While hydrolyzing on the surface of the coating layer to generate hydroxyl groups and/or radicals, and in the surface treatment agent, the Si-bonded hydroxyl group or hydrolyzable group in the fluorine-containing decane compound is easily contacted with the coating layer. The hydroxyl group and/or the radical generated on the surface of the coating layer reacts, so that a high adhesion strength can be produced between the fully cured coating layer and the fluorine-containing decane compound (the inorganic material layer in the above modified specific embodiment), and as a result A fluorine-containing decane-based coating layer having high abrasion resistance can be formed.

Hereinafter, the method of producing the article of the present invention will be described in detail using the examples, but the present invention is not limited by the examples.

Example 1

. Method for producing TiO ₂ nanoparticle solution (A-1)

First, diisopropanol bis(acetylthiopyruvate) titanium (manufacturer Nippon Soda Co., Ltd.; T-50, titanium oxide-equivalent solid content = 16.5% by weight) (70 g) was dissolved. The alcohol (134.9 g) was denatured, and then ion-exchanged water (26.0 g) (10 times mol/mol of TiO ₂ ) was slowly added dropwise to hydrolyze diisopropanol bis(acetylthiopyruvate) titanium. After one day, the solution was filtered to obtain 5.0 wt% (titanium oxide-equivalent solid content) of a yellow-brown transparent TiO ₂ nanoparticle solution (A-1). It is a hydrolysis product of a chelate compound of titanium.

. Manufacturing method for forming a composition of the underlayer (S-1)

The manufacturing method for forming the composition of the underlayer (S-1) is to add the TiO ₂ nanoparticle solution (A-1) (74.0 g) prepared as described above (as a photocatalyst) to the polyfunctional urethane urethane ( The manufacturer is Arakawa Chemical Industries, Ltd.; Beam Set 575 CB) (37.0 g) (as photocurable organic material), vinyl trimethoxy decane (manufacturer is Dow Corning Torav Co., Ltd.; DOW CORNING TORAY SZ6300) SILANE) (18.5g) and γ-methacryloxypropyltrimethoxysilane (manufacturer of Dow Corning Toray Co., Ltd.; DOW CORNING TORAY SZ6030 SILANE) (18.5g) (as a photocurable organic material and A composition for forming the underlayer (S-1) was prepared by using an unsaturated decane compound) and methyl isobutyl ketone (46.3 g) as a solvent.

. Bottom layer formation

As the organic base material, an acrylic plate (manufacturer: Mitsubishi Rayon Co., Ltd.; Acrylite, thickness: 1.0 mm) was used. The acrylic sheet (pull-out rate: 15 mm/sec) was treated with a Dip Coater (manufacturer SDI Company) using the composition for forming the underlayer (S-1). The composition forming the underlayer thus coated on the acrylic plate was dried in a dryer at 60 ° C for 30 minutes, and then subjected to ultraviolet light irradiation (wavelength: 200 to 400 nm; cumulative light amount: 600 mJ/cm ² ) to form an underlayer. (P-1) as its cured coating layer.

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A composition (80 mg) mainly containing a compound of the following formula (molecular weight: about 4,000) was added to a copper cup, and then a compound was deposited by a resistance heating method using a deposition apparatus (manufactured by Shincron Co., Ltd.). On the surface of the underlayer (P-1) formed as described above, a fluorine-containing decane-based coating layer was formed. This produces a sample of the item.

Wherein: n is an integer from 20 to 30, and m is an integer from 1 to 5.

Example 2

. Manufacturing method for forming a composition of the underlayer (S-2)

The manufacturing method for forming the composition of the underlayer (S-2) is to add the TiO ₂ nanoparticle solution (A-1) (75.0 g) prepared in Example 1 (as a photocatalyst) to the polyfunctional amide group. Acid ester (manufactured by Arakawa Chemical Industries, Ltd.; Beam Set 575 CB) (50.0 g) (as a photocurable organic material), vinyl trimethoxy decane (manufacturer of Dow Corning Toray Co., Ltd.; DOW) CORNING TORAY SZ6300 SILANE) (12.5g) and γ-methacryloxypropyltrimethoxydecane (manufacturer Dow Corning Toray Co., Ltd.; DOW CORNING TORAY SZ6030 SILANE) (12.5g) (as light) The organic material and the unsaturated decane compound were cured, and methyl isobutyl ketone (46.9 g) was used as a solvent.

. Bottom layer formation

In the same manner as in Example 1, the underlayer (P-2) was formed on the surface of the acrylic sheet, but the composition forming the underlayer (S-2) was used instead of the composition forming the underlayer (S-1).

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer (as an antifouling layer), but in which a compound was deposited on the surface of the underlayer (P-2) instead of the surface of the underlayer (P-1).

Example 3

. Bottom layer formation

Similar to the method of Example 1, the underlayer (P-1) was formed on the surface of the acrylic plate.

. Formation method of inorganic material layer (cerium oxide coating layer)

Using a electron beam method of a deposition apparatus (manufactured by Shincron Co., Ltd.), cerium oxide was deposited on the surface of the underlayer (P-1) to form a cerium oxide coating layer having a thickness of 7 mm.

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer as an antifouling layer, but in which a compound was deposited on the surface of the ceria coating layer instead of the surface of the underlayer (P-1).

Comparative example 1

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer as an antifouling layer, but in which an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd.; Acrylite; thickness: 1.0 mm) was used as an organic base material. And without forming a bottom layer, the compound is deposited on the surface of the acrylic sheet.

Comparative example 2

. Formation method of inorganic material layer (cerium oxide coating layer)

As the organic base material, an acrylic plate (manufacturer: Mitsubishi Rayon Co., Ltd.; Acrylite; thickness: 1.0 mm) was used. The cerium oxide coating layer was formed by depositing cerium oxide on the surface of the acryl plate by a electron beam method and using a deposition apparatus (manufactured by Shincron Co., Ltd.) to a thickness of 7 mm.

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer (as an antifouling layer), but in which a compound was deposited on the surface of the ceria coating layer instead of the surface of the underlayer (P-1).

Comparative example 3

. Manufacturing method for forming a composition of the underlayer (S-3)

The manufacturing method for forming the composition of the underlayer (S-3) is to add IRGACURE 907 (manufactured by Ciba Specialty Chemicals Inc.) (2.4 g) (as an ultraviolet curing initiator) to vinyltrimethoxydecane (manufacture) Dow Corning Toray Co., Ltd.; DOW CORNING TORAY SZ6300 SILANE) (40.0 g) and γ-methacryloxypropyltrimethoxydecane (manufacturer Dow Corning Toray Co., Ltd.; DOW) CORNING TORAY SZ6030 SILANE) (40.0g) (as light The organic material was cured with an unsaturated decane compound) and methyl isobutyl ketone (120.0 g) as a solvent.

. Bottom layer formation

The bottom layer (P-3) was formed in a manner similar to that of Example 1, except that the composition forming the underlayer (S-3) was used instead of the composition forming the underlayer (S-1).

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer (as an antifouling layer), but in which a compound was deposited on the surface of the underlayer (P-3) instead of the underlayer (P-1) surface.

Comparative example 4

. Method for producing a composition for forming a bottom layer (S-4)

The composition for forming the underlayer (S-4) was prepared by adding the TiO ₂ nanoparticle solution (A-1) (58.0 g) prepared in Example 1 (as a photocatalyst) to a polyfunctional urethane urethane ( The manufacturer was Arakawa Chemical Industries, Ltd.; Beam Set 575CB) (59.0 g) (as a photocurable organic material) and methyl isobutyl ketone (37.8 g) (as a solvent).

. Bottom layer formation

The bottom layer (P-4) was formed in a manner similar to that of Example 1, except that the composition forming the underlayer (S-4) was used instead of the composition forming the underlayer (S-1).

. Formation method of antifouling layer (fluorine-containing decane-based coating layer)

A method similar to that of Example 1 was carried out to form a fluorine-containing decane-based coating layer (as an antifouling layer), but in which a compound was deposited on the surface of the underlayer (P-4) instead of the underlayer (P-1) surface.

Evaluation method

The static water contact angle of the antifouling layer (fluorine-containing decane-based coating layer) formed in the above examples and comparative examples was measured. Use automated contact angle meter (manufacturer is KYOWA) INTERFACE SCIENCE Co., LTD.) measured the static water contact angle of 1 μL of water.

Analytical method 1. Initial evaluation method

First, after the antifouling layer is formed, the static water contact angle (zero number of rubbing) of the surface on which the substance has not been contacted is measured.

Analytical method 2. Friction resistance evaluation method

The eraser is then evaluated for abrasion resistance. Specifically, the sample of the article on which the antifouling layer has been formed is horizontally arranged, and then the eraser (manufacturer is Kokuyo Co., Ltd.; KESHI-70; plane size: 1 cm x 1.6 cm) and the antifouling layer The exposed surface was exposed and a load of 500 gf was applied. Then let the eraser move back and forth at a rate of 20 mm/sec under the applied load. The static water contact angle (degrees) was measured after moving 50, 100, 250, 500, 750 and 1,000 times back and forth. When the measured value of the contact angle is less than 100, the evaluation method is stopped.

The results of Test Examples 1 and 2 are shown in Table 1 and Figure 1. The symbol "-" stands for "not measured".

As can be seen from Table 1 and Figure 1, compared to Comparative Example 1 in which the underlayer was not formed, Comparative Example 2 (in which the ruthenium dioxide coating layer was replaced by the underlayer), Comparative Example 3 (in which the composition of the photocatalyst was changed) The substance forms the bottom layer) and Comparative Example 4 (where the use does not contain The fluorine-containing decane-based coating layer of the composition of the unsaturated decane compound forms the underlayer), and the fluorine-containing decane-based coating layer of Examples 1 to 3 of the present invention has high abrasion resistance.

Industrial utilization

The present invention is applied to the surface treatment of organic substrate materials, and is particularly suitable for obtaining optical components requiring high antifouling properties and high abrasion resistance.

Claims (11)

A method for producing an article comprising a fluorine-containing decane-based coating layer on a surface of a coating layer of an organic base material, wherein the manufacturing method comprises the steps of: (a) using an unsaturated decane-containing compound, a photocatalyst, and a photocurable organic material. a composition, a precursor coating layer is formed on a surface of the organic base material; (b) the precursor coating layer is irradiated with light, whereby the precursor coating is formed on the surface of the organic base material a cured coating layer of the coating; and (c) forming a fluorine-containing decane-based coating layer directly on the cured coating layer or via an inorganic material layer by using a surface treatment agent containing a fluorine-containing decane compound. The method for producing an article according to claim 1, wherein the unsaturated decane compound is a compound of the formula: CH ₂ =CH-(R ¹² ) _y -SiT _x R ¹¹ _3-x wherein: T is a hydroxyl group or a hydrolyzable group; R ¹¹ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; x is an integer of 1 to 3; R ¹² is a divalent organic group; and y is 0 or 1 . The method of producing an article according to claim 1 or 2, wherein the photocatalyst is composed of a metal compound. The method for producing an article according to any one of claims 1 to 3, wherein the fluorine-containing decane compound has a perfluoropolyether group and a hydroxyl group or a hydrolyzable group bonded to Si. The method for producing an article according to claim 4, wherein the fluorine-containing decane compound comprises one or more compounds of any one of the following formulas (1a) and (1b): Wherein: Rf ¹ is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms; a, b, c and s are each independently an integer from 0 to 200, wherein the a, b The total number of c and s is at least 1, and the order of occurrence of each repeating unit in parentheses in which a subscript is a, b, c or s is not limited; d and f are independently 0 or 1; e and g, respectively Separately, the integers are 0 to 2; m and l are each independently an integer of 1 to 10; X is a hydrogen atom or a halogen atom; Y is a hydrogen atom or a lower alkyl group; and Z is a fluorine atom or a lower fluoroalkyl group; T is a hydroxyl group or a hydrolyzable group; R ¹ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms; and n is an integer of 1 to 3. The method for producing an article according to claim 4, wherein the fluorine-containing decane compound comprises one or more compounds of any one of the following formulas (2a) and (2b): Wherein: Rf ² is an alkyl group having 1 to 16 carbon atoms which may or may not be substituted by one or more fluorine atoms; a, b, c and s are each independently an integer from 0 to 200, wherein the a, b The total number of c and s is at least 1, and the order of occurrence of each repeating unit in parentheses in which a subscript is a, b, c or s is not limited; d and f are independently 0 or 1; h and j, respectively Is 1 or 2; i and k are each independently an integer 2 to 20; Z is a fluorine atom or a lower fluoroalkyl group; T is a hydroxyl group or a hydrolyzable group; R ² is a hydrogen atom or has 1 to 22 carbons An alkyl group of atoms; and n is an integer from 1 to 3. An article comprising: an organic base material; a coating layer formed on a surface of the organic base material, and comprising a cured material of an unsaturated decane compound and a photocurable organic material, and a photocatalyst; A fluorine-containing decane-based coating layer formed on the coating layer. An article manufactured by the manufacturing method according to any one of claims 1 to 6. The article of claim 7 or 8, wherein the organic base material is transparent. The article of any one of claims 7 to 9, wherein the fluorine-containing decane-based coating layer is an anti-fouling coating layer. The article of any one of claims 7 to 10, wherein the article is an optical component.