KR20170082596A - Surface treatment method - Google Patents

Abstract

The present invention provides a method of forming a functional film on a substrate, comprising the steps of: applying a matrix-forming composition on a substrate to form a film of a matrix-forming composition; and forming a composition comprising a functional sub- Containing functional group-containing polymerizable compound in the matrix-forming composition film and curing the matrix-forming composition film containing the obtained functional side-excitation-containing polymerizable compound to form a monolayer functional film.

Description

{SURFACE TREATMENT METHOD}

The present invention relates to a surface treatment method.

BACKGROUND ART [0002] Conventionally, surface treatment of a base material has been performed to impart various functions to a base material. For example, it has been known that certain types of fluorine-containing compounds can provide excellent water repellency, oil repellency, and antifouling property when used in the surface treatment of substrates, and a layer obtained from a surface treatment agent containing a fluorine-containing compound is a so- For example, glass, plastics, textiles, and building materials.

Especially recently, transparent plastic such as acrylic resin or polycarbonate has been widely used as a material replacing inorganic glass in that it is lightweight and hardly fragile and easy to be processed. Since a base material using such a resin material is liable to be easily scratched, a hard coat layer is formed in order to impart scratch resistance and abrasion resistance. Further, the surface of the hard coat layer is subjected to treatment for imparting functions such as water repellency, oil repellency, and antifouling property as described above, for example.

For example, in Patent Document 1, a hard coat composition is applied on a substrate, followed by drying to form a hard coat composition layer, a surface treatment material is formed on the hard coat composition layer to form a surface material layer, And a method of simultaneously curing these layers by irradiating active energy rays.

Patent Document 2 discloses a carbon-carbon double bond-containing composition comprising (A) a triisocyanate obtained by trimerizing a diisocyanate and (B) a combination of at least two active hydrogen- -1) a perfluoropolyether having at least one active hydrogen, and (B-2) a composition comprising an active hydrogen and a monomer having a carbon-carbon double bond in a hard coat agent, Lt; / RTI >

Japanese Patent Application Laid-Open No. 2003-260761 International Publication No. 2003/002628

In recent years, the use of touch panels has been expanding as smartphones and tablet-type handsets are rapidly spreading. In the use of the touch panel, durability against friction is required in that the user touches and operates the display panel with a finger.

However, when the function is developed especially in the hard coat agent, the above-mentioned requirement, which is increasingly required in the conventional treatment method, can not necessarily satisfy the demand for the friction durability.

It is an object of the present invention to provide a treatment method useful for forming a functional film having excellent friction durability in addition to a predetermined function on a substrate containing various materials.

As a result of intensive studies, the inventors of the present invention have found that by applying a matrix-forming composition (for example, hard coat agent) on a substrate to form a film of this composition and applying a composition containing a functional adherent- A functional film having high friction durability can be formed, and the present invention has been accomplished.

According to a first aspect of the present invention, there is provided a method for forming a functional film on a substrate, comprising: forming a matrix-forming composition film by applying a matrix-forming composition on a substrate; Containing functional group-containing polymerizable compound in the film of the matrix-forming composition and curing the film of the matrix-forming composition containing the obtained functional side-excited polymerizable compound to form a single functional layer by applying the composition containing the compound Is provided.

According to a second aspect of the present invention, there is provided a functional film formed by the method for forming a functional film of the present invention.

According to a third aspect of the present invention, there is provided an article comprising a substrate and the functional film of the present invention located on the substrate.

According to the present invention, a matrix-forming composition is applied to a substrate to form a film of a matrix-forming composition, and a functional sub-excitation-containing polymerizable compound is added to the film before drying, and then cured to form a functional film having excellent friction durability .

Hereinafter, the method of the present invention will be described.

First, a substrate is prepared.

The substrate usable in the present invention is not particularly limited and may be an organic material, an inorganic material, or a hybrid material thereof.

For example, the substrate that can be used in the present invention may be glass, sapphire glass, resin (natural or synthetic resin such as a general plastic material), metal (metal such as aluminum, copper, iron, Ceramics, semiconductors (silicon, germanium, etc.), fibers (fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, architectural members.

Preferably, the substrate used in the present invention is a substrate of an organic material, preferably a resin substrate. The resin constituting the resin substrate is not particularly limited and examples thereof include polycarbonate resin, poly (meth) acrylate resin, polyethylene terephthalate resin, triacetylcellulose resin, polyester resin, epoxy resin, polyimide resin, Novolak resins, phenol resins, polyurethane resins, fluororesins, vinylidene chloride resins and the like.

Examples of other organic materials include cellulose esters (e.g., triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamides, polystyrene (e.g., syndiotactic polystyrene), polyolefins For example, polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide and polyetherketone.

When the article to be manufactured is an optical member, the material constituting the surface of the substrate may be a material for an optical member, for example, transparent plastic or the like. The substrate may have an insulating layer, a pressure-sensitive adhesive layer, a protective layer, a decorative frame layer (I-CON), an acryl film layer, a polarizing film, a retardation film and a liquid crystal display module. In the present invention, these layers, films and the like are referred to as substrates.

The shape of the substrate is not particularly limited and may be, for example, a plate shape, a film, or other shapes. The surface area of the substrate on which the functional film is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the use of the article to be produced, the specific specification, and the like.

A matrix-forming composition is then applied to the surface of such a substrate to form a film of the matrix-forming composition.

The matrix-forming composition is not particularly limited as long as it contains a polymerizable compound. The polymerizable compound is not particularly limited as long as it has at least one polymerizable unsaturated bond. For example, a group having a carbon-carbon double bond such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, A phenyl group, an isopropenyl group, a vinyl ether group, etc., or a compound having a maleimide group or an epoxy group.

Preferably, the polymerizable compound is an acrylic material such as monofunctional and / or multifunctional acrylate and methacrylate (hereinafter also referred to as "(meth) acrylate" in combination of acrylate and methacrylate), monofunctional And / or polyfunctional urethane (meth) acrylate, monofunctional and / or polyfunctional epoxy (meth) acrylate.

Examples of the acrylic material include those synthesized from monofunctional or polyfunctional (meth) acrylate compounds such as acrylic acid or methacrylic acid esters of polyhydric alcohols, diisocyanates and polyhydric alcohols, and hydroxy esters of acrylic acid or methacrylic acid The same polyfunctional urethane (meth) acrylate compound can be used. In addition to these, a polyether resin, an acrylic resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin and the like having an acrylate functional group may be used as the polymerizable compound.

Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N- vinylpyrrolidone, tetrahydrofurfuryl acrylate (Meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (Meth) acrylate, phosphoric acid (meth) acrylate, (Meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, (Meth) acrylates such as ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol 2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (Meth) acryloyloxypropyl hydrogensphthalate, 2- (meth) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyl tetrahydrophthalate, 2- (Meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, Adamantane derivatives such as adamanthyl acrylate having a monovalent mono (meth) acrylate derived from octafluoropropyl (meth) acrylate 2-adamantane and adamantanediol mono (meth) acrylate And the like.

Examples of the bifunctional (meth) acrylate compound include ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) (Meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tripropylene glycol di Acrylate, di (meth) acrylate such as hydroxypivalic acid neopentyl glycol di (meth) acrylate, and the like.

Examples of the trifunctional or more (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) Tri (meth) acrylate such as 2-hydroxyethyl isocyanurate tri (meth) acrylate and glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (Meth) acrylate compounds such as ditrimethylolpropane tri (meth) acrylate and ditrimethylolpropane tri (meth) acrylate, and trifunctional (meth) acrylate compounds such as pentaerythritol tetra Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, di (Meth) acrylate compounds such as pentaerythritol hexa (meth) acrylate and ditrimethylol propane hexa (meth) acrylate, and polyfunctional (meth) acrylate compounds in which some of these (meth) acrylates are substituted with an alkyl group or ε-caprolactone Substituted polyfunctional (meth) acrylate compounds, and the like.

The acrylic material may be a polyfunctional urethane acrylate. The urethane acrylate is obtained by reacting a polyhydric alcohol, a polyvalent isocyanate and a hydroxyl group-containing acrylate. UA-306T, UA-306T and UA-306L manufactured by Kyowa Shagakuka Co., Ltd., Beam Set 575CB manufactured by Arakawa Chemical Industries, Ltd., UV-1700B, UV-6300B manufactured by Nippon Gosei Chemical Co., U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA and the like manufactured by Shin Nakamura Kagaku Co., Ltd., such as UV-7600B, UV-7605B, UV-7640B and UV- It is not.

In addition to these, a polyether resin, an acrylic resin, an epoxy resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin and the like having an acrylate functional group can be used as the polymerizable compound.

The matrix-forming composition is not particularly limited, but a composition generally considered to be a hard coating agent or an antireflective agent can be used. For example, a hard coating agent containing a polyfunctional (meth) acrylate or a fluorine-containing (meth) Based on the total weight of the composition. The hard coating agent is commercially available, for example, as a beam set 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (trade name) from Arakawa Kagaku Kogyo K.K., EBECRYL40 (Trade name) available from Yokohama Rubber. The antireflective agent is commercially available from Daikin Kogyo Co., Ltd., for example, as Optul AR-110 (trade name).

The matrix-forming composition may or may not contain a solvent. In one form, the matrix forming composition does not comprise a solvent. In another form, the matrix forming composition comprises a solvent.

The solvent is not particularly limited and may be appropriately selected depending on the polymerizable compound in the matrix-forming composition to be used. Examples of the solvent include, but are not limited to, hydrocarbon solvents such as hexane, heptane and octane; Chlorinated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane; Ether solvents such as diethyl ether, dimethoxyethane, diglyme and triglyme; Ethyl lactate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, ethyl acetate, ethyl acetoacetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, Ester solvents such as ethyl methoxypropionate, methyl 2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; Propylene glycol type solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether ; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and diacetone alcohol; Aromatic hydrocarbons such as benzene, toluene, xylene, and nitrobenzene; And cellosolve solvents such as hydrochlorofluorocarbons (Asahi Clean AK-225 (trade name) and the like), methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate. These solvents may be used alone or as a mixture of two or more thereof.

The concentration of the effective component (that is, the polymerizable compound) in the matrix-forming composition is not particularly limited, but may be, for example, 10 to 90 mass%, preferably 30 to 80 mass%.

The matrix forming composition may further comprise other components, for example, an active energy ray curing initiator.

As the active energy ray curing initiator, for example, radicals and cations are generated by irradiation with an electromagnetic wave in a wavelength range of 350 nm or less, that is, ultraviolet light, electron beam, X-ray or γ-ray, Carbon-carbon double bond) (that is, a cross-linking reaction). Generally, those which generate radicals or cations with ultraviolet light, in particular radicals, are used.

The active energy ray curing initiator in the composition is appropriately selected according to the kind of the polymerizable compound, the kind of the active energy ray to be used (wavelength range, etc.), the irradiation intensity, etc. In the case of using the active energy ray in general ultraviolet ray region, For example, the following can be exemplified.

· Acetophenone

Methyl-1- [4- (methylthio) phenyl] -2-morpholino (methoxy) acetophenone, diethoxyacetophenone, hydroxyacetophenone,? -Aminoacetophenone, Propan-1-one etc.

· Benzoin

Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

· Benzophenone

Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.

· Thioacetic acid

Thioxanthone, chlorothioxanthone, methylthioxanthone, diethylthioxanthone, dimethylthioxanthone, etc.

·Other

Benzyl,? -Acyloxime ester, acylphosphine oxide, glyoxyester, 3-ketocmarine, 2-ethyl anthraquinone, camphorquinone, anthraquinone, etc.

These active energy ray curing initiators may be used singly or in combination of two or more kinds.

The active energy ray curing initiator is not particularly limited, but is contained in an amount of 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymerizable compound.

The matrix-forming composition may contain other components such as an antioxidant, a thickener, a leveling agent, a defoaming agent, an antistatic agent, a fogging agent, an ultraviolet absorber, a pigment, an inorganic microfine particle such as silica, hollow silica, Fillers such as glass frit and metal powder, polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ), and the like.

In one form, the matrix-forming composition may contain the following functional subsidiary-containing polymerizable compound. By including the functional side-chain-containing polymerizable compound in the matrix-forming composition before application to the substrate, the functional side-effect-containing polymerizable compound can be dispersed throughout the film of the matrix-forming composition and the function of the resulting functional film can be further enhanced, Can be improved.

The method of applying the matrix-forming composition to a substrate is not particularly limited and may be, for example, immersion coating, spin coating, flow coating, spray coating, slit coating, roll coating, gravure coating, microgravure coating, Screen printing and similar methods may be used.

The amount to which the matrix-forming composition is applied to the substrate is not particularly limited and can be appropriately adjusted according to the thickness of the desired functional film.

Subsequently, by applying a composition containing the functional side-excluded polymerizable compound on the film of the matrix-forming composition formed above, the functional side-excluded polymerizable compound is contained in the film of the matrix-forming composition.

By applying a composition containing a functional side-excitable polymerizable compound to a liquid matrix-forming composition film, the functional side-excited polymerizable compound can be diffused from the surface of the matrix-forming composition film into the inside thereof or dissolved in the film of the matrix- . The composition comprising the matrix-forming composition film and the functional adherend-containing polymerizable compound by diffusion or dissolution of the functional partial-ion-containing polymerizable compound into the matrix-forming composition film forms one layer (single layer). That is, application of the composition containing the functional side-chain-containing polymerizable compound to the matrix-forming composition film can be replaced with the addition of the composition containing the functional side-chain-containing polymerizable compound to the matrix-forming composition on the substrate.

In the present specification, the term " single layer " means a layer which does not have an interface due to lamination in the layer and whose composition varies constantly or continuously over the entire thickness direction of the layer (or film). In the present invention, even if the composition of the upper part and the lower part of the layer is completely different from each other, if the composition of both layers changes continuously in the middle part of the layer, it is regarded as a single layer. The region where the composition continuously changes is 100 nm or more. For example, even if the composition at the top of the layer is A and the composition at the bottom is B, the composition A and the composition B are mixed in any one region of the layer, and the composition along the thickness direction is continuously If there is a region changing from A to B (or B to A), the layer is considered to be a single layer. The composition of the layer can be measured by elemental depth in the depth direction using ion beam ESCA measurement.

In one preferred form, the layer formed of the composition comprising the matrix-forming composition film and the functional side-excitation-containing polymerizable compound may contain only a composition (or a functional partial imine-containing polymerizable compound) containing a functional side-excited polymerizable compound And does not have a thickness portion to contain. Such a layer may have higher durability in that the functional partial-ion-containing polymerizable compound is dispersed and held in the matrix-forming composition.

In another preferred embodiment, the layer formed from the composition comprising the matrix-forming composition film and the functional side-excluded-containing polymerizable compound is a composition comprising a functional side-excluded polymerizable compound on the surface of the film (or a functional side- ). ≪ / RTI > The function imparted by the functional partial imine-containing polymerizable compound can be exhibited to the maximum by having a portion containing only the composition (or the functional side-chain-containing polymerizable compound) containing the functional side-chain-containing polymerizable compound on the surface.

In a preferred form, the matrix-forming composition film when applying the composition containing the functional partial-excited polymerizable compound is a liquid. A liquid phase is a state having fluidity. Specifically, it means that the viscosity of the composition containing the functional part-containing polymerizable compound is 1 Pa · s or less, for example, at 25 ° C. measured by a cone plate type viscometer (JIS K7117-2) .

In a preferred form, the matrix-forming composition film when applying the composition comprising the functional side-excited polymerizable compound may comprise a solvent. The concentration of the solvent in the film of the matrix-forming composition when applying the composition containing the functional side-chain-containing polymerizable compound is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more to be. By including the solvent-containing matrix-forming composition film, the diffusion or dissolution of the composition containing the functional side-excited-containing polymerizable compound into the matrix-forming composition film is further promoted.

The matrix-forming composition film when applying the composition containing the functional partial-ion-containing polymerizable compound may be subjected to a drying process or may not be subjected to a drying process. When the film is subjected to a drying process, the film is not completely dried, but is dried to some extent, for example, 10 mass% or more, preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 50 mass% It is preferable to leave it. The drying method is not particularly limited, and natural drying, air blow drying, heat drying, vacuum drying, freeze drying, and the like are preferred, and natural drying is preferable.

In a preferred form, the matrix-forming composition film when applying the composition comprising the functional side-excited polymerizable compound does not undergo a drying step. By not performing the drying step, the decrease of the solvent in the film of the matrix-forming composition can be suppressed and the diffusion or dissolution of the composition containing the functional side-excited polymerizable compound into the matrix-forming composition film can be prevented.

In a preferred form, the matrix-forming composition film when applying the composition comprising the functional side-excited polymerizable compound may be in an uncured state. The uncured state includes a state in which the polymerization of the polymerizable compound in the matrix composition does not proceed, and a state in which the polymerization does not progress partially, for example, the polymerization of the entire half polymerizable compound does not proceed. Preferably, the matrix-forming composition film when applying the composition containing the functional side-chain-containing polymerizable compound is a state in which the polymerization of the polymerizable compound does not substantially progress. Formulation of the matrix-forming composition Before the film is cured, the addition of a composition comprising a functional side-excited polymerizable compound further promotes diffusion or dissolution of the composition comprising the functional side-excited polymerizable compound into the matrix-forming composition film. In addition, since the film on which the diffusion or dissolution has progressed is a single layer and the both are cured simultaneously after the addition, the polymerizable compound in the matrix-forming composition and the functional subsidiary-containing polymerizable compound are polymerized with each other, so that a functional film having higher durability can be obtained.

The functional partial imine-containing polymerizable compound is a compound having at least one polymerizable unsaturated group and at least one functional group-imparting group in the molecule.

The polymerizable unsaturated group is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group and a vinyl ether group. From the viewpoint of excellent reactivity, acryloyl group, methacryloyl group and vinyl group are preferable, acryloyl group and methacryloyl group are more preferable, and acryloyl group is particularly preferable.

The functional property-imparting agent means a functional group having a function capable of imparting a desired surface property to a substrate.

The functional part is not particularly limited,

1) water-repellent and / or oleophilic group,

2) hydrophilic group,

3) refractive index fluctuator,

4) ultraviolet absorbing functional group,

5) Photostability Functional group,

6) Biological characteristic functional group,

7) Flame retardant group or

8) an antistatic group.

When the functional part-containing polymerizable compound is a water repellent and / or oil repellent group-containing polymerizable compound, that is, it has a water repellent and / or oil repellent group as a functional part excipient, the obtained functional film has a water repellent and / or oil repellent group.

Examples of the water repellent and / or oil repellent group include fluorine-containing groups, preferably perfluoro groups. The water repellent and / or oil repellent group is preferably a fluoroalkyl group or a fluoropolyether group, more preferably a perfluoroalkyl group or a perfluoropolyether group.

Wherein said perfluoroalkyl group has the formula:

F (C _n F _2n ) -

[Wherein n is an integer of 1 to 30, preferably an integer of 3 to 20, more preferably an integer of 3 to 15].

The perfluoroalkyl group may be a straight chain or branched chain.

In one form, the water repellent and / or oil repellent group is a bivalent group in which one fluorine atom is removed from the perfluoroalkyl group, a so-called perfluoroalkylene group:

- (C _n F _2n ) -

.

The perfluoropolyether group is represented by the following formula:

F (C _m F _2m ) -PFPE-

Wherein m is an integer of 1 to 16; PFPE is _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - represents; a, b, c, and d are each independently 0 or an integer of 1 or more, and the sum of a, b, c, and d is at least 1 and the existence order of each repeating unit enclosed in parentheses by attaching a, Is a group represented by any of the formulas.

Preferably, a, b, c, and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 to 200, and more preferably, an integer of 0 or more and 100 or less. The sum of a, b, c and d is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

Of the repeating units in parentheses attached with a, b, c or d, - (OC ₄ F ₈ ) - represents - (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)) - , And preferably - (OCF ₂ CF ₂ CF ₂ CF ₂ ) -. - (OC ₃ F ₆₎ - it is _{- (OCF 2 CF 2 CF 2} ) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - which is, but even during, preferably Is - (OCF ₂ CF ₂ CF ₂ ) -. Further, - (OC ₂ F ₄ ) - may be any of - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, preferably - (OCF ₂ CF ₂ ) -.

In one form, PFPE is - (OC ₃ F ₆ ) _b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less) (OCF ₂ CF ₂ CF ₂ ) b- wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less), or - (OCF (CF ₃ ) CF ₂ ) _b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, and more preferably - (OCF ₂ CF ₂ CF ₂ ) _b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less).

In a further aspect, PFPE is _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - ( wherein, a and b are independently 0, respectively And c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts a, b, c, optionally in the presence order of the repeating units of formula bound to Im), preferably _{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF 2) b - (OCF 2 CF 2) c - (OCF ₂ ) _d -. In one form, PFPE is - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d - wherein c and d are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit parenthesized by appending subscript c or d is optional in the formula).

In another form, PFPE is a group represented by - (OC ₂ F ₄ -R ¹¹ ) _{n "} -, wherein R ¹¹ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ Or a combination of two or three groups independently selected from these groups. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, For example, -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC _{3 F 6 OC 4 F 8 -,} -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ - , -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ - and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -, and the like, wherein n "is an integer of 2 to 100, preferably an integer of 2 to 50 . In the above formulas, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched chain, and preferably straight chain. In this form, PFPE is preferably - (OC ₂ F ₄ -OC ₃ F ₆ ) _{n "} - or - (OC ₂ F ₄ -OC ₄ F ₈ ) _n" -.

In one form, the water repellent and / or oleophilic group is a bivalent group:

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

It may be.

One specific water repellent and / or oil repellent group-containing polymerizable compound is

(a) a polyisocyanate which is a trimer of a diisocyanate

(b) a carbon-carbon double bond-containing compound (A) obtained by reacting a compound having an active hydrogen.

As used herein, "active hydrogen" means a hydrogen atom that can be donated as a proton in an isocyanate group. "Active hydrogen group-containing" refers to a group containing the active hydrogen, such as -OH groups, -C (= O) H group, a -SH group, a -SO ₃ H group, a -SO ₂ H group, and - SOH group, -NH ₂ group, -NH- group, -SiH group, and the like.

Component (a) is a polyisocyanate obtainable by trimerizing a diisocyanate. The triisocyanate polyisocyanate of the diisocyanate may be present as a polymer obtained by polymerizing these.

In a preferred form, the triisocyanate polyisocyanate of the diisocyanate of component (a) may be an isocyanurate type polyisocyanate. The isocyanurate type polyisocyanate may be present as a polymer obtained by polymerizing these isocyanurate type polyisocyanates. That is, the isocyanurate type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or a polycyclic compound obtained by polymerization of the monocyclic compound, or a mixture thereof. Such an isocyanurate type polyisocyanate is commercially available, for example, as Sumierum (registered trademark) N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

Examples of the diisocyanate used to obtain the polyisocyanate in the trimer of the (A) diisocyanate include, but are not limited to, diisocyanates having an isocyanate group bonded to an aliphatic group such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate; Diisocyanates in which isocyanate groups are bonded to aromatic groups such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylidine diisocyanate and naphthalene diisocyanate.

Specific examples of the triisocyanate polyisocyanate of the diisocyanate of component (a) include, but are not limited to, compounds having the following structures.

As described above, these polyisocyanates may be present as polymers, and, for example, in the case of isocyanurate type polyisocyanates of hexamethylene diisocyanate,

≪ / RTI >

Component (b)

(b1) perfluoropolyethers having active hydrogen and

(b2) a monomer having active hydrogen and at least one carbon-carbon double bond. In a preferred form, component (b) is

(b3) a silane compound having active hydrogen.

The perfluoropolyether having an active hydrogen of the component (b1) has, in addition to the perfluoropolyether group, one active hydrogen-containing group at one molecular end, for example, a hydroxyl group, or one Containing group is a compound having an active hydrogen-containing group-containing hydroxyl group.

The perfluoropolyether having an active hydrogen of the component (b1) is not particularly limited, but has a number average molecular weight of 500 to 12,000, preferably 1,000 to 10,000, and more preferably 1,500 to 8,000.

Preferably, component (b1) is any of the following formulas (b1-i) and (b1-ii)

Rf-PFPE-R < ₁ > -CH2OH (b1-i)

HOCH ₂ -R ¹ -PFPE-R ¹ -CH ₂ OH (b ¹ -ii)

Lt; / RTI >

In the formulas (b1-i) and (b1-ii), Rf represents an alkyl group having 1 to 16 carbon atoms (for example, a straight chain or branched chain) which may be substituted with one or more fluorine atoms, Is a straight or branched alkyl group of 1 to 3 carbon atoms which may be substituted by one or more fluorine atoms. Preferably, Rf is linear. The alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group whose terminal carbon atom is CF ₂ H- and all other carbon atoms are substituted by fluorine, More preferably a perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ or -CF ₂ CF ₂ CF ₃ .

Among the above-mentioned formulas (b1-i) and (b1-ii), PFPE is the perfluoropolyether group described above,

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -

Lt; / RTI > Such a compound having a perfluoropolyether group can exhibit excellent water repellency, oil repellency and antifouling property (for example, preventing adhesion of contamination such as a fingerprint).

R ¹ in the formulas (b1-i) and (b1-ii) each independently represents the following formula:

- (Y) _f - (CF ₂ ) _g - (CH ₂ ) _h -

Lt; / RTI > In this formula, Y is a bivalent polar group. Examples of the divalent polar group include, but are not limited to, -COO-, -OCO-, -CONH-, -OCH ₂ CH (OH) CH ₂ -, -CH ₂ CH (OH) CH ₂ O-, and the like -SCO-, -O-, preferably _{-COO-, -CONH-, -CH 2 CH (} OH) CH a ₂ O-, -O-. F, g and h are each independently an integer of 0 to 50, preferably 0 to 20, such as 1 to 20, and the sum of f, g and h is at least 1, 10. It is more preferable that f, g and h are integers of 0 to 2, and it is further preferable that f = 0 or 1, g = 2, h = 0 or 1. In addition, the order of existence of each repeating unit parenthesized by appending subscripts f, g, and h is arbitrary in the formula.

In a preferred form, component (b1) is a compound represented by the above formula (b1-i).

Rf-PFPE-R < ₁ > -CH2OH (b1-i)

The monomer having at least one carbon-carbon double bond and active hydrogen of the component (b2) is preferably an active hydrogen-containing group, particularly a (meth) acrylate ester having a hydroxyl group and a vinyl monomer.

The monomer having the active hydrogen of the component (b2) and one carbon-carbon double bond is not limited, and for example, the following compounds:

HO (CH ₂ CH ₂ ) _i OCO (R) C = CH ₂

(Wherein, i = 2 to 10), for example, 2-hydroxyethyl (meth) acrylate, 4-fluoromethyl (meth) acrylate, Hydroxybutyl (meth) acrylate;

_{CH 3 CH (OH) CH 2} OCO (R) C = CH 2

(Wherein R is a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine), such as 2-hydroxypropyl (meth) acrylate;

_{CH 3 CH 2 CH (OH)} CH 2 OCO (R) C = CH 2

(Wherein R represents a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-hydroxybutyl (meth) acrylate;

C ₆ H ₅ OCH ₂ CH (OH) CH ₂ OCO (R) C = CH ₂

(Wherein R is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine) such as 2-hydroxy-3-phenoxypropyl (meth) acrylate;

HOCH ₂ C (CH ₂ OCO (R) C = CH ₂ ) ₃

(Wherein R is a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, pentaerythritol triacrylate

C (CH ₂ OCO (R) C = CH ₂ ) ₃ CH ₂ OCH ₂ C (CH ₂ OCO (R) C = CH ₂ ) ₂ CH ₂ OH

(Wherein R is a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, dipentaerythritol polyacrylate

HOCH ₂ CH ₂ OCOC ₆ H ₅ OCOCH ₂ CH ₂ OCO (R) C = CH ₂

(Wherein R is a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid

H (OCH ₂ CH ₂ ) _n OCO (R) C = CH ₂

(Wherein n is 1 to 30 and R is an alkyl group having 1 to 10 carbon atoms which may be substituted by a hydrogen atom, a chlorine atom, a fluorine atom or fluorine), for example, a poly (ethylene glycol) acrylate

_{H (OCH (CH 3) CH} 2) n OCO (R) C = CH 2

(Wherein n is 1 to 30, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom or fluorine), for example, poly (propylene glycol) acrylate

Allyl alcohol;

HO (CH ₂ ) _k CH = CH ₂

(k = 2 to 20);

_{(CH 3) 3 SiCH (OH} ) CH = CH 2; And

Styrylphenol.

The active hydrogen of the component (b2) and the monomer having two or more carbon-carbon double bonds are not limited, but the following groups as the group having a carbon-

^{-OC (O) -CR 2 = CH} 2

Lt; / RTI >

In the above formula, R ² is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom or fluorine, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen An atom or a methyl group. Here, a group in which R ² is a hydrogen atom or a methyl group, that is, -OC (O) -CH═CH ₂ or -OC (O) -CCH ₃ ═CH ₂ is collectively referred to as "(meth) acrylate group" It is called.

In a preferred form, the active hydrogens of component (b2) and the monomers having two or more carbon-

HO-CH ₂ -C (CH ₂ -OC (O) -CR ² = CH ₂ ) ₃ ; or

_{HO-CH 2 -C (CH 2} -OC (O) -CR 2 = CH 2) 2 -CH 2 OCH 2 -C (CH 2 -OC (O) -CR 2 = CH 2) 3

(Wherein R ² is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine).

In a more preferred form, the active hydrogen of the component (b2) and the monomer having two or more carbon-carbon double bonds are at least one selected from the group consisting of pentaerythritol triacrylate or dipentaerythritol hexaacrylate / RTI >

The active hydrogen-containing silane compound of the component (b3) may have one active hydrogen-containing group at one molecular end, for example, a hydroxyl group, or one active hydrogen-containing group at each of two terminals, .

The active hydrogen-containing silane compound of the component (b3) is not particularly limited, but has a number average molecular weight of 100 to 20,000, preferably 500 to 15,000, and more preferably 800 to 12,000.

Preferably, the component (b3) is a compound represented by the following formula (b3-i) and (b3-ii):

Lt; RTI ID = 0.0 > 1, < / RTI >

In the formula (b3-ⅰ) and ^{(b3-ⅱ), R 11} , R 12, R 13, R 14 and R ¹⁵ is each independently an alkyl group or an aryl group.

The alkyl group is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be straight chain or branched, but is preferably straight chain. Specific preferred examples are n-butyl groups for R ¹¹ and methyl groups for R ¹² to R ¹⁵ .

The aryl group is not particularly limited and includes an aryl group having 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is a phenyl group.

The alkyl group and the aryl group may contain a hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom in the molecular chain or ring, if desired.

The alkyl and aryl groups may also be optionally substituted with halogen; One or a C _{1- 6} alkyl group which may be substituted by more halogen, C _{2- 6} alkenyl, C _{2- 6} alkynyl, C _{3- 10} cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, a 5 to 10 A 5- to 10-membered unsaturated heterocyclyl group, a C _6-10 aryl group, and a 5- to 10-membered heteroaryl group.

In the formula (b3-ⅰ) and (b3-ⅱ) R ¹⁶ represents a divalent organic group. Preferably, R ¹⁶ is - (CH ₂ ) _r - (wherein r is an integer of 1 to 20, preferably an integer of 1 to 10).

In the formulas (b3-i) and (b3-ii), A is an active hydrogen-containing group. The group A is preferably -OH group, -C (= O) H group, -SH group, -SO ₃ H group, -SO ₂ H group, -SOH group, -NH ₂ group, -NH- group or -SiH More preferably an -OH group or -NH ₂ group, more preferably an -OH group.

Wherein l and n in the formulas (b3-i) and (b3-ii) are each independently 0 or 1; m is an integer of 1 to 500, preferably 1 to 200, more preferably 5 to 150; o is an integer of 0 to 20, for example an integer of 1 to 20, and p is 0 or 1.

Specific examples of the compound represented by the above formula (b3-i) include, for example, the following compounds.

The component (b3) may be an active hydrogen-containing group and a silane compound having an amino group. Examples of such compounds include, but are not limited to, the following compounds.

The ratio of the number average molecular weight of the component (b1) to the number average molecular weight of the component (b3) is not particularly limited, but may be, for example, from 1: 5 to 5: 1, preferably from 1: 3 to 3: To 3: 2. By setting the ratio of the number average molecular weight of the component (b1) to the number average molecular weight of the component (b3) within the above range, solubility in a fluorine-free solvent is further improved.

In the reaction between the component (a) and the component (b) of the present invention, the isocyanate group of the component (a) reacts with the hydroxyl group of the component (b) to form a urethane bond.

In the present invention, the number of moles of the total of the components (b1), (b2) and (b3) to be reacted with the component (a) is substantially equal to the number of moles of the isocyanate group in the component (a).

In a preferred form, when component (b) comprises components (b1), (b2) and (b3), component (b) reacting with 9 moles of isocyanate groups in component

0.1 to 2 moles of component (b1)

From 5 to 8.85 moles of component (b2) and

The component (b3) may be 0.05 to 2 moles.

By setting the amounts of the components (b1) to (b3) within the above range, the surface slip property, the friction durability and the solubility in the fluorine-free solvent are improved.

The method of reacting the components (a) and (b1) to (b3) is not particularly limited. For example, the reaction may be performed in one system (that is, one-port synthesis), or a separate reaction may be performed in two systems.

In the case of one-port synthesis, for example, they may be reacted simultaneously by simultaneously adding the components (b1) to (b3) to the component (a), or they may be sequentially reacted by sequentially adding the components (b1) to . In the case of the sequential addition (reaction), the order of the addition (reaction) is not particularly limited. For example, the components (b1) to (b3) may be separately added in any order and reacted. Alternatively, two components out of the components (b1) to (b3) May be added and reacted. Preferably, the components (b1) and (b3) are added and reacted, and then the component (b2) is added and reacted. Alternatively, the component (b1) And finally, the component (b2) may be added to carry out the reaction. In the case of sequential addition, an excess amount may be added to the finally added component.

The solvent used in this reaction is not particularly limited as long as the reaction proceeds, and various fluorine solvents, various general-purpose solvents, solvents obtained by mixing them in an arbitrary ratio, and the like can be used, and 1,1-dichloro- 1,2,2,3,3-pentafluoropropane (HCFC225) is used.

It is possible to simplify the process such that purification at each step becomes unnecessary by performing synthesis at the original port.

When the reaction is carried out in two systems, for example, the first composition is obtained by reacting the component (a) with the components (b1) and (b2) in one system, b2) and (b3) to obtain a second composition, and subsequently, the first composition and the second composition may be mixed to obtain the composition. In the composition thus obtained, the carbon-carbon double bond-containing compound having both of the perfluoropolyether derived from the component (b1) and the silane moiety derived from the component (b3) may be substantially absent. The order of the reaction in each system is not particularly limited. For example, the components (a) and (b1) (or the components (b3) The component (b1) (or the component (b3)) may be reacted and then the component (b2) may be reacted, or vice versa. It is preferable that the component (a) is reacted with the component (b1) (or the component (b3)) and subsequently the component (b2) is reacted.

As described above, the reaction of the component (a) and the component (b1) and the reaction of the component (a) and the component (b3) are carried out in separate systems to select conditions such as a more suitable solvent for each reaction It becomes possible. By selecting the appropriate conditions for each reaction in this way, it is possible to suppress the fluctuation of the product obtained in comparison with the one-port synthesis in the large-scale synthesis in particular. Specifically, the component (b1) is generally soluble in a fluorine-based solvent and is poorly soluble in a general-purpose solvent, while the component (b3) is soluble in a general-purpose solvent and is insoluble in a fluorine-based solvent. In the case of synthesis at one port, especially when the reaction is carried out on a large scale, the influence of the difference in solubility becomes significant, and any one of the components (b1) and (b3) does not completely dissolve in the solvent, (In other words, the reaction is performed with good reproducibility) becomes difficult. On the other hand, when the reaction is carried out in two systems, the optimum solvent can be selected for each reaction, so that it is easy to stably control the reaction. In other words, the reaction can be performed with good reproducibility, and further, it is easy to suppress fluctuation in the quality of the obtained product.

Another specific water repellent and / or oil repellent group-containing polymerizable compound is a fluorine-containing polymer (B) having a curable site.

In one embodiment, the fluorine-containing polymer (B) is any one of the following formulas (B1) and (B2)

(Hereinafter, the compounds represented by the respective formulas are also referred to as "fluorine-containing polymer (B1)" and "fluorine-containing polymer (B2)").

Another specific water repellent and / or oil repellent group-containing polymerizable compound is a fluorine-containing silicon-containing polymer (C) having a curable site.

In one form, the fluorine-containing silicon-containing polymer (C) is any one of the following formulas (C1) and (C2)

Containing silicon-containing polymer (hereinafter, the compound represented by each formula is also referred to as "fluorine-containing silicon-containing polymer (C1)" or "fluorine-containing silicon-containing polymer (C2)").

In the formulas (B1) and (C1), Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms is a straight or branched alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, Is a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms Alkyl group. Preferably, the alkyl group which may be substituted by one or more fluorine atoms is a fluoroalkyl group or a perfluoroalkyl group whose terminal carbon atom is CF ₂ H- and all other carbon atoms are substituted by fluorine, more preferably Is a perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ or -CF ₂ CF ₂ CF ₃ .

The formula (B1), (B2), (C1) and (C2) of the R ⁴¹ is the above-mentioned poly-perfluoroalkyl ether group:

_{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - a.

- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) - (OC ₃ F ₆ ) _{b in the} above formulas (B1) The lower limit of the number average molecular weight of the perfluoro (poly) ether group represented by _d - is preferably about 1,000, more preferably about 1,500, and even more preferably about 2,000 from the viewpoint of obtaining high oil repellency and water repellency, The upper limit is preferably about 100,000, more preferably about 50,000, and even more preferably about 10,000 from the viewpoint of obtaining high solubility in a general solvent (fluorine-free organic solvent).

R ⁴² in each of the formulas (B1), (B2), (C1) and (C2) represents 2 to 10 valent organic groups in each occurrence independently. The R ⁴² is a linker connecting the perfluoropolyether moiety (R ⁴¹ ) and the moiety having a curable moiety (R ⁴⁴ ) in the compounds represented by the formulas (B1), (B2), (C1) Is interpreted as part of. Accordingly, the R ⁴² group may be any two to ten valent organic groups provided that the compounds represented by the formulas (B1), (B2), (C1) and (C2) can be stably present. According to the valence of the R ⁴² group,? Is an integer of 1 to 9, and when? ⁴² is a divalent organic group,? Is 1 and R ⁴² is a 7-valent organic group,? Is 6 to be.

In a preferred form, R ⁴² is a 2 to 4-membered organic group, a is 1 to 3, more preferably R ⁴² is a divalent organic group, and a is 1.

In a more preferred form, R ⁴² is a group represented by the formula: - (Q) _d - (CFZ) _e - (CH ₂ ) _f -. Here, d, e and f are each independently an integer of 0 to 50, the sum of d, e and f is at least 1, and the order of existence of each repeating unit in parentheses is arbitrary in the formula.

Wherein Q represents an oxygen atom, phenylene, carbazolylene, -NR ^a - (wherein R ^a represents a hydrogen atom or an organic group) or a divalent polar group, preferably an oxygen atom or a divalent A polar group, and more preferably an oxygen atom.

The "bivalent polar group" in the above Q is not particularly limited, and -C (O) -, -C (═NR ^b ) - and -C (O) NR ^b - wherein R ^b is a hydrogen atom Or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, which may be substituted by one or more fluorine atoms.

In the formula, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.

The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, and more preferably a trifluoromethyl group.

R ⁴² is preferably a group represented by the formula: - (O) _d - (CF ₂ ) _e - (CH ₂ ) _f - wherein d, e and f are as defined above and the presence of each repeating unit parenthesized And the order is arbitrary in the formula).

The _{formula: - (O) d - (} CF 2) e - (CH 2) f - as the group represented by, for example, _{- (O) d '- (} CF 2) e' - (CH 2) f '- O -, and _{[(CH 2) f ''} -O-] f '''( in the formula, "and is 0 or 1, e, d, f' and f '' is independently an integer from 1 to 10, f '" is 0 or 1).

In another preferred aspect, R < ⁴² > is a group of the formula:

- (R ⁶¹ ) _{p '} - (X ^a ) _q' -R ⁶² -

^Wherein R ⁶¹ represents a single bond, - (CH ₂ ) _{s '} - or an o-, m- or p-phenylene group, preferably - (CH ₂ ) _s'

R ⁶² represents a single bond, - (CH ₂ ) _{t '} - or o-, m- or p-phenylene group, preferably - (CH ₂ ) _t'

s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2,

t 'is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3,

X ^a represents - (X ^b ) _{r '} -,

X ^b is independently in each occurrence -O-, -S-, o-, m- or p- phenylene group, -C (O) O-, -CONR 64 -, -O-CONR 64 -, - ^{NR 64 -, -Si (R 63} ) 2 -, - (Si (R 63) 2 O)) m '-Si (R 63) 2 - and - (CH _{2) n'} - group is selected from the group consisting of And,

R ⁶³ are each independently a phenyl group, C _{1- 6} alkyl or C _{1- 6} represents an alkoxy, preferably a C _1-6 alkyl group, more preferably a methyl group, in each occurrence,

R ⁶⁴ represents each independently a hydrogen atom, a phenyl group or a C _{1- 6} alkyl group (preferably methyl group), in each occurrence,

m 'each independently represent an integer of 1 to 100, preferably an integer of 1 to 20 in each occurrence,

n 'each independently represent an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3 in each occurrence,

r 'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,

p 'is 0 or 1,

q 'is 0 or 1,

Wherein at least one of p 'and q' is 1 and the order of existence of each repeating unit in parentheses with p 'or q' attached is arbitrary.

And the like.

Preferably, R < ⁴² >

_1- C ₂₀ alkylene group,

-R ⁶¹ -X ^c -R ⁶² - or

-X ^d R ⁶² -

[Wherein R ⁶¹ and R ⁶² are as defined above].

More preferably, R < ⁴² >

_1- C ₂₀ alkylene group,

- (CH ₂ ) _s' -X ^c -,

- (CH ₂ ) _{s '} - X ^c - (CH ₂ ) _t' -

-X ^d - or

^{_{-X d - (CH 2) t}} '-

[Wherein s 'and t' have the same meanings as defined above].

Wherein X < ^c >

-O-,

-S-,

-C (O) O-,

-CONR ⁶⁴ -,

-O-CONR ⁶⁴ -,

-Si (R < ⁶³ >) ₂ -,

- (Si (R ⁶³ ) ₂ O) _{m '} -Si (R ⁶³ ) ₂ -,

_{-O- (CH 2) u '-} (Si (R 63) 2 O) m' -Si (R 63) 2 -,

-CONR ⁶⁴ - (CH ₂ ) _{u '} - (Si (R ⁶³ ) ₂ O) _m' -Si (R ⁶³ ) ₂ -

-CONR ⁶⁴ - (CH ₂ ) _{u '} -N (R ⁶⁴ ) - or

-CONR ⁶⁴ - (o-, m- or p-phenylene) -Si (R ⁶³ ) ₂ -

^Wherein R ⁶³ , R ⁶⁴ and m 'are as defined above, and u' is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. X ^c is preferably -O-.

Wherein X ^d is

-S-,

-C (O) O-,

-CONR ⁶⁴ -,

^{_{-CONR 64 - (CH 2) u}} '- (Si (R 63) 2 O)) m' -Si (R 63) 2 -,

-CONR ⁶⁴ - (CH ₂ ) _{u '} -N (R ⁶⁴ ) - or

-CONR ⁶⁴ - (o-, m- or p-phenylene) -Si (R ⁶³ ) ₂ -.

More preferably, R < ⁴² >

_1- C ₂₀ alkylene group,

- (CH ₂ ) _{s '} -X ^c - (CH ₂ ) _t' - or

^{_{-X d - (CH 2) t}} '-

[Wherein each symbol is as defined above].

More preferably, R < ⁴² > is

_1- C ₂₀ alkylene group,

- (CH ₂ ) _{s '} -O- (CH ₂ ) _t' -,

- (CH ₂ ) _{s '} -Si (R ⁶³ ) ₂ - (CH ₂ ) _t' -,

- (CH ₂ ) _s' - (Si (R ⁶³ ) ₂ O) _{m '} -Si (R ⁶³ ) ₂ - (CH ₂ ) _t'

_{- (CH 2) s '-O-} (CH 2) u' - (Si (R 63) 2 O) m '-Si (R 63) 2 - (CH 2) t' - or

- (CH ₂ ) _{s '} -O- (CH ₂ ) _t -Si (R ⁶³ ) ₂ - (CH ₂ ) _u' -Si (R ⁶³ ) ₂ - (C _v H _2v )

[Wherein each symbol is as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3].

In the _{formula, - (C v H 2v)} - is straight even even branched, for example _{-CH 2 CH 2 -, -CH 2} CH 2 CH 2 -, -CH (CH 3) -, -CH ( CH ₃₎ CH ₂ - can be.

The R ⁴² group is an alkyl group with fluorine atom, C _{1- 3} alkyl and C _{1- 3} fluoro is optionally substituted by one or more substituents selected from (preferably _1- C ₃ perfluoroalkyl group).

Specific examples of R ⁴² include, for example,

-CH ₂ O (CH ₂ ) ₂ -,

-CH ₂ O (CH ₂ ) ₃ -,

-CH ₂ O (CH ₂ ) ₆ -,

-CH ₂ O (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ -

_{-CH 2 O (CH 2) 3} Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,

_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,

_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,

_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH3) 2 (CH 2) 2 -,

_{-CH 2 O (CH 2) 3} Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,

-CH ₂ OCF ₂ CHFOCF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ -,

-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ -,

-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF ₂ -

_{-CH 2 OCH 2 (CH 2)} 7 CH 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 Si (OCH 3) 2 OSi (OCH 3) 2 (CH 2) 2 -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₂ (CH ₂ ) ₂ -,

-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSi (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₂ -

- (CH ₂ ) ₂ -,

- (CH ₂ ) ₃ -,

- (CH ₂ ) ₄ -,

- (CH _{2) 5} -,

- (CH ₂ ) ₆ -,

- (CH ₂ ) ₂ -Si (CH ₃ ) ₂ - (CH ₂ ) ₂ -

-CONH- (CH ₂ ) ₃ -,

-CON (CH ₃ ) - (CH ₂ ) ₃ -,

-CON (Ph) - (CH ₂ ) ₃ - (wherein Ph stands for phenyl),

-CONH- (CH ₂ ) ₆ -,

_{-CON (CH 3) - (CH} 2) 6 -,

-CON (Ph) - (CH ₂ ) ₆ - (wherein Ph means phenyl),

-CONH- (CH ₂ ) ₂ NH (CH ₂ ) ₃ -,

-CONH- (CH ₂ ) ₆ NH (CH ₂ ) ₃ -,

-CH ₂ O-CONH- (CH ₂ ) ₃ -,

-CH ₂ O-CONH- (CH ₂ ) ₆ -,

-S- (CH ₂ ) ₃ -,

- (CH ₂ ) ₂ S (CH ₂ ) ₃ -,

-CONH- (CH ₂ ) ₃ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ (CH ₂ ) ₂ -,

_{-CONH- (CH 2) 3 Si (} CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,

_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 2 Si (CH 3) 2 (CH 2) 2 -,

_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 3 Si (CH 3) 2 (CH 2) 2 -,

_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 10 Si (CH 3) 2 (CH 2) 2 -,

_{-CONH- (CH 2) 3 Si (} CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,

-C (O) O- (CH ₂ ) ₃ -,

-C (O) O- (CH ₂ ) ₆ -,

_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 2 -,

_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -,

_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 - (CH 2) 3 -,

_{-CH 2 -O- (CH 2) 3} -Si (CH 3) 2 - (CH 2) 2 -Si (CH 3) 2 -CH (CH 3) -CH 2 -,

-OCH ₂ -,

-O (CH ₂ ) ₃ -,

-OCFHCF ₂ -,

And the like.

Examples of other R < ⁴² > groups include, for example, the following groups:

[Wherein, R ⁴¹ each independently represent an alkyl group or a C _{1- 6} alkoxy group, a hydrogen atom, a phenyl group, having 1 to 6 carbon atoms, preferably a methyl group;

D is

-CH ₂ O (CH ₂ ) ₂ -,

-CH ₂ O (CH ₂ ) ₃ -,

-CF ₂ O (CH ₂ ) ₃ -,

- (CH ₂ ) ₂ -,

- (CH ₂ ) ₃ -,

- (CH ₂ ) ₄ -,

-CONH- (CH ₂ ) ₃ -,

-CON (CH ₃ ) - (CH ₂ ) ₃ -,

-CON (Ph) - (CH ₂ ) ₃ - (wherein Ph stands for phenyl) and

(Wherein R ⁴² is each independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group)

E is - (CH ₂ ) _n - (n is an integer from 2 to 6)

D binds to the PFPE of the molecular backbone and E binds to the opposite group to PFPE)

Examples of other R < ⁴² > groups include the following groups:

Wherein R ⁴¹ is each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or a C _1-6 alkoxy group, preferably a methyl group;

For each R < ⁴² > group, any of T is any of the following groups bonded to the PFPE of the molecular backbone:

-CH ₂ O (CH ₂ ) ₂ -,

-CH ₂ O (CH ₂ ) ₃ -,

-CF ₂ O (CH ₂ ) ₃ -,

- (CH ₂ ) ₂ -,

- (CH ₂ ) ₃ -,

- (CH ₂ ) ₄ -,

-CONH- (CH ₂ ) ₃ -,

-CON (CH ₃ ) - (CH ₂ ) ₃ -,

-CON (Ph) - (CH ₂ ) ₃ - (wherein Ph means phenyl) or

[Wherein R ⁴² is each independently a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group]

, And some of the other T's are - (CH ₂ ) _{n "} - (n" is an integer from 2 to 6) bonded to the opposite group of the PFPE of the molecular backbone and, if present, the rest are each independently a methyl group or a phenyl group .

In the formulas (B1), (B2), (C1) and (C2), R ⁴³ represents a divalent organic group.

The R ⁴³ group is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, and is -C (R ^43a ) (R ^43b ) -. Here, R ^43a and R ^43b each independently represent a hydrogen atom or an alkyl group, and preferably one of R ^43a and R ^43b is an alkyl group.

R ⁴⁴ In the formula (B1), (B2), (C1) and (C2) are each independently selected from R ^44a or R ^44b, in each occurrence. Provided that at least one R ⁴⁴ is R ^44a .

And R < ^44a > represents a divalent organic group having a curable site independently at each occurrence.

The "curable part" is not particularly limited, and examples thereof include an allyl group, a cinnamic acid group, a sorbic acid group, an acryloyl group and a methacryloyl group (hereinafter referred to as "(meth) acryl" Quot; diary ").

When the material is an amorphous synthetic resin (e.g., an acrylic resin), the preferable curing site is preferably an allyl group, a cinnamic acid group, a sorbic acid group, ^{_{CH 2 = CX 1 -C (O}} ) - ( wherein, X ¹ represents an alkyl group having 1 to 10 carbon atoms that may be substituted by a hydrogen atom, a chlorine atom, a fluorine atom or fluorine) (e.g., (meth) acrylic ), More preferably an acryloyl group and a methacryloyl group.

R ^44a is preferably a group of the formula:

Lt; / RTI >

In the formula, R ³¹ represents, independently at each occurrence, a hydrogen atom or an alkyl group. This R ³¹ is preferably a hydrogen atom.

In the above formulas, R ³² represents, independently at each occurrence, a hydrogen atom or an alkyl group. R ³² is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom.

In the formula, R ³³ represents an organic group having a curable site independently at each occurrence.

Such a curing site may be the same as mentioned above. However, it is preferable that CH ₂ ═CX ¹ -C (O) - (wherein X ¹ represents a hydrogen atom, a chlorine atom, a fluorine atom or a fluorine atom, is the preferable, and specifically refers to an alkyl group of 10) is _{CH 2 = C (CH 3)} -C (O) - may be mentioned - or _{CH 2 = CH-C (O} ).

Wherein Y ¹ represents -O-, -N (R ^c ) -, phenylene or carbazolylene. Wherein R ^c represents an organic group, preferably an alkyl group.

Y ¹ is preferably -O-, phenylene or carbazolylene, more preferably -O- or phenylene, more preferably -O-.

Wherein Y ² represents a linker whose atomic number of the main chain is 1 to 16 (more preferably 2 to 12, still more preferably 2 to 10).

The Y ² is not particularly limited, but, for example,

- (CH ₂ -CH ₂ -O) _p 1 - (p 1 represents an integer of 1 to 10),

- (CHR ^d) -O- _p2 (p2 is an integer from 1 to 40, R ^d represents hydrogen or a methyl group),

- (CH ₂ -CH ₂ -O) _{p 3} -CO-NH-CH ₂ -CH ₂ -O- (p3 represents an integer of 1 to 10),

_{-CH 2 -CH 2 -O-CH 2} -CH 2 -,

_{- (CH 2) p4 - (} p4 is an integer of 1 to 6),

_{- (CH 2) p5 -O-} CONH- (CH 2) p6 - (p5 represents an integer of 1 to 8, preferably 2 or 4, p6 is preferably an integer of one to six represents a 3) or

-O- (provided that Y < ¹ > is not -O-).

Preferred ^{_{Y 2 - (CH 2 -CH 2}} -O) p1 - (p1 is an integer of 1 to 10) or - (CHR ^d) -O- _p2 (p2 is an integer from 1 to 40, R ^d is Hydrogen or a methyl group), specifically, -CH ₂ -CH ₂ -O-. These groups have the left end bonded to the molecular main chain side (Y ¹ side) and the right end bonded to the curable side (R ³³ side).

R ^44a is more preferably a group represented by the formula:

Lt; / RTI >

X ¹ represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom or fluorine, and is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, for example, a methyl group . Q1 is an integer of 1 to 10, preferably an integer of 1 to 5, for example, 1 or 2. q2 is an integer of 1 to 10, preferably an integer of 1 to 5, for example, 2.

R ^44b is a divalent organic group having no curable moiety at each occurrence independently.

R ^44b is preferably - (CHR ^44c -CR ^44d R ^44e ) _s -. Wherein R ^44c and R ^44d each independently represent a hydrogen atom or an alkyl group, s is an integer of 0 to 50, and the R ^44e group is -Q'-R ^44f . Wherein Q 'is the same as Q, R ^44f is an organic group having no curing site, and the group R ^44g described later is a group bonded to Q' via a linker or directly to Q '.

The linker is preferably

(a) - (CH ₂ -CH ₂ -O) s ₁ - (s 1 is an integer of 1 to 10, for example an integer of 2 to 10)

(b) - (CHR) _s2- O- (s2 represents a repeating number of 1 to 40, and R represents hydrogen or a methyl group),

_{(c) - (CH 2 -CH} 2 -O) s1 -CO-NH-CH 2 -CH 2 -O- (s1 is Im and the same significance),

_{(d) -CH 2 -CH 2 -O} -CH 2 -CH 2 -,

(e) - (CH ₂ ) _{s 3} - (s 3 represents an integer of 1 to 6) or

_{(f) - (CH 2)} s4 -O-CONH- (CH 2) s5 - (s4 is an integer of 1 to 8, preferably represents a 2 or 4, s5 is an integer from 1 to 6, preferably 3 ) Or

(g) -O- (Q 'is not -O-).

R ^44g is preferably the following group.

(I) an alkyl group

Examples include methyl, ethyl

(Ii) a chain containing an alkyl group substituted with fluorine

Yes:

(Iii) a group containing at least one cyclic moiety selected from the group consisting of a monocyclic carbon ring, a bicyclic carbon ring, a tricyclic carbon ring and a tetracyclic carbon ring

Yes:

(Iv) a group containing one or more (preferably one or two) hydrocarbon groups substituted with a carboxyl group

Yes:

(V) a group containing at least one (preferably one) amino group

(Vi) hydrogen

(Iii) a group containing an imidazolium salt

Yes:

R ^44g is more preferably a hydrogen atom or an alkyl group which may be fluorinated or bonded through an ethylene chain, more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group or R-CF ₂ - (CF ₂ ) _{s6 - (CH 2) s7 -O-} (CH 2) 2 - is the (R is a fluorine atom or a hydrogen atom, s6 is an integer from 0 to 6, and s7 is an integer of 1 to 6), more preferably 3- (perfluoroethyl) propoxy group [rational _{formula: CF 3 - (CF 2)} - (CH 2) 3 -O- (CH 2) 2 -] a.

The structural unit R ^44a and the structural unit R ^44b in R ⁴⁴ may form a block or may be bonded at random.

In the formulas (B1), (B2), (C1) and (C2), n1 is an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 50 or less, more preferably an integer of 2 or more and 30 or less.

In the formulas (B1), (B2), (C1) and (C2), R ⁴⁵ represents -O-, -S-, -NH- or a single bond, preferably -O-.

In the formulas (B1), (B2), (C1) and (C2), R ⁴⁶ represents Rf-R ⁴¹ -R ⁴² wherein Rf, R ⁴¹ and R ⁴² are as defined above, Or a hydrogen atom.

R ⁴⁶ is preferably an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl.

In one embodiment, the fluorine-containing polymers (B1) and (B2) are represented by the following formulas (B1a) and (B2a)

Wherein, Rf, R ^41, R ^43, R ^46, X ^1, Z and n1 is the the same significance, g is 0 or 1, h is 1 or 2, q1 is an integer of 1 to 5 (Hereinafter, the compounds represented by the respective formulas are also referred to as "fluorine-containing polymer (B1a)" and "fluorine-containing polymer (B2a)").

The fluorine-containing polymer (B) is not particularly limited, but may have a number average molecular weight of about 5 × 10 ² to 1 × 10 ⁵ . Among these ranges, a number average molecular weight of about 2,000 to 10,000 is preferable from the viewpoint of friction durability. The number average molecular weight can be determined by ¹⁹ F-NMR.

Examples of the fluorine-containing polymer (B) contained in the composition include a perfluoroalkyl group-containing curable fluoropolymer and a fluorine-modified acrylic-containing curable fluoropolymer in addition to the compounds represented by the above-mentioned (B1) and (B2). Such compounds are available, for example, as Megaface RS (trade name) series from DIC Corporation.

In the formulas (C1) and (C2), R ⁴⁷ is independently an organic group of 2 to 10 in each occurrence. This R ⁴⁷ is interpreted as a part of a linker connecting the R ⁴⁴ moiety having a curable moiety to the siloxane moiety in the compounds represented by the formulas (C1) and (C2). Accordingly, the R ⁴⁷ group may be any two to ten valent organic groups provided that the compounds represented by the formulas (C1) and (C2) can be stably present. Also, depending on the valency of the R ⁴⁷ group,? Is an integer of 1 to 9, and when? ⁴⁷ is a divalent organic group,? Is 1 and ^R47 is a 7-valent organic group,? Is 6 to be.

In a preferred form, R ⁴⁷ is a 2 to 4-membered organic group, β is 1 to 3, more preferably R ⁴⁷ is a divalent organic group, and β is 1.

In a preferred form, R < ⁴⁷ > may be a bivalent organic group as described above for R < ^{42 &} gt ;.

In a more preferred form, R ⁴⁷ is - (CH ₂ ) _{r "} -, wherein r" is an integer of 1 or more and 20 or less, more preferably - (CH ₂ ) _{r "} , r '''is an integer of 1 or more and 10 or less), and is, for example, a methylene group, an ethylene group or a propylene group.

In the formulas (C1) and (C2), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are each independently an alkyl group, an alkoxy group or an aryl group, preferably an alkyl group.

Examples of the alkyl group is not particularly limited and there may be mentioned a cycloalkyl group having 1 to 10 carbon atoms and an alkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, in particular with regard to R ¹³ is n- butyl And R ⁷ to R ¹² are methyl groups.

The alkoxy group is not particularly limited, but an alkoxy group having 1 to 10 carbon atoms can be enumerated, and alkoxy having 1 to 6 carbon atoms is preferable.

The aryl group is not particularly limited and includes an aryl group having 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is a phenyl group.

The alkyl group, the alkoxy group and the aryl group may contain a hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom in the molecular chain or ring thereof, if desired.

Further, the alkyl group, the alkoxy group and the aryl group may be optionally substituted with halogen; One or a C _{1- 6} alkyl group which may be substituted by more halogen, C _{2- 6} alkenyl, C _{2- 6} alkynyl, C _{3- 10} cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, a 5 to 10 A 5- to 10-membered unsaturated heterocyclyl group, a C _6-10 aryl group, and a 5- to 10-membered heteroaryl group.

N3 and n4 in the formulas (C1) and (C2) are each independently an integer of 0 to 50, and the sum of n3 and n4 is at least one. n3 and n4 are preferably each independently an integer of 5 to 30.

N2, n5 and n6 in the formulas (C1) and (C2) are each independently an integer of 0 to 500. n2, n5 and n6 are preferably each independently an integer of 1 to 200, more preferably an integer of 10 to 200. [

In one form, the fluorine-containing silicon-containing polymer represented by the above formulas (C1) and (C2) is a fluorine-containing silicon-containing polymer represented by the following formulas (C1-a) and (C2-

[Wherein:

^{Rf, R 41, R 43,} R 45, R 51, R 52, R 53, R 54, R 55, R 56, R 57, Z, n1, n2, n3, n4, n5 and n6 are the formula (C1 ) And (C2);

R ^{46 '} is an organic group of the formula (2) corresponding to R ⁴⁶ in the formulas (C1) and (C2);

X ¹ is a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine;

f 'are each independently 0 or 1 at each occurrence;

g ' is independently at each occurrence 1 or 2;

and q1 is independently an integer of 1 to 10 in each occurrence in the presence of a fluorine-containing silicon-containing polymer.

The fluorine-containing silicon-containing polymer (C1) is not particularly limited, but may have a number average molecular weight of about 2 x 10 ² to 1 x 10 ⁵ . Among these ranges, a number average molecular weight of about 1 x 10 ³ to 1 x 10 ⁵ is preferable from the viewpoint of friction durability. The fluorine-containing silicon-containing polymer (C2) is not particularly limited, and may have a number average molecular weight of about 2 x 10 ² to 1 x 10 ⁵ . Among these ranges, a number average molecular weight of about 1 x 10 ³ to 1 x 10 ⁵ is preferable from the viewpoint of friction durability. The number average molecular weight can be determined by gel permeation chromatography (GPC).

In one form, the composition comprising the carbon-carbon double bond-containing compound (A), the fluorine-containing polymer (B) or the fluorine-containing silicon-containing polymer (C) has, in addition to these compounds, Or a silicon-containing polymer (S).

The silicon-containing polymer (S) may be any of the following formulas (S1) and (S2)

At least one silicon-containing polymer represented by the following formula (1).

In the formulas (S1) and (S2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ and R ⁷⁷ independently represent an alkyl group, an alkoxy group or an aryl group;

Examples of the alkyl group is not particularly limited, but there may be mentioned a cycloalkyl group having 1 to 10 carbon atoms and an alkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, specifically, as to the carbon number of R ⁷¹ is n- Butyl group, and R ⁷² to R ⁷⁷ are methyl groups.

The alkoxy group is not particularly limited, but an alkoxy group having 1 to 10 carbon atoms can be enumerated, and alkoxy having 1 to 6 carbon atoms is preferable.

The aryl group is not particularly limited and includes an aryl group having 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is a phenyl group.

The alkyl group, the alkoxy group and the aryl group may contain a hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom in the molecular chain or ring thereof, if desired.

Further, the alkyl group, the alkoxy group and the aryl group may be optionally substituted with halogen; One or a C _{1- 6} alkyl group which may be substituted by more halogen, C _{2- 6} alkenyl, C _{2- 6} alkynyl, C _{3- 10} cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, a 5 to 10 A 5- to 10-membered unsaturated heterocyclyl group, a C _6-10 aryl group, and a 5- to 10-membered heteroaryl group.

In the formulas (S1) and (S2), R ⁷⁸ represents a divalent organic group.

R ⁷⁸ is preferably - (CH ₂ ) _{r "} -, wherein r" is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less, more preferably - (CH ₂ ) _{r ''} - wherein r '' is an integer of 1 or more and 10 or less.

In the formulas (S1) and (S2), X ¹ represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom or fluorine. Preferable X ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, for example, a methyl group.

In the formulas (S1) and (S2), n7 and n8 are each independently an integer of 1 or more and 500 or less. N4 and n5 are preferably 1 or more and 200 or less, and more preferably 10 or more and 200 or less.

The silicon-containing polymer (S) is not particularly limited, but has a number average molecular weight of about 500 to 20,000. In order to provide excellent surface slip and friction durability to the surface treatment layer, it is preferable that the number average molecular weight is at least about 500, for example, at least about 1,000. From the viewpoint of compatibility with the fluorine-containing polymer or the solvent, it is preferable that the number average molecular weight is about 20,000 or less, preferably about 15,000 or less.

The silicon-containing polymer (S) can be obtained by a commercially available product or by a known method. Examples of commercially available silicon-containing polymer (S) include, but are not limited to, X-22-164, X-22-164AS, X22-164A, X-22-164A, X- FM-7721, FM-7725, and X-22-2475 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164E, X- , DMS-R18, DMS-R22, DMS-R31 and DMS-U21 (manufactured by Gelest Co., Ltd.) .

The weight ratio of the carbon-carbon double bond-containing compound (A), the fluorine-containing polymer (B) or the fluorine-containing silicon-containing polymer (C) to the silicon-containing polymer (S) in the composition is from 10: 1 to 1:10, Preferably from 10: 1 to 2: 1, for example from 10: 1 to 3: 1, specifically about 10: 1. By the ratio in this range, it is possible to provide a surface treatment layer excellent in fingerprint wiping property, surface slip property and appearance.

(A), the fluorine-containing polymer (B) or the fluorine-containing silicon-containing polymer (C) is preferably 50 mass% or more based on the sum of these compounds and the silicon-containing polymer (S) % Or more, more preferably 60 mass% or more. By setting the content of the carbon-carbon double bond-containing compound (A), the fluorine-containing polymer (B) or the fluorine-containing silicon-containing polymer (C) within this range, a surface treatment layer with higher transparency can be provided. The term " transparent " means any material that can be generally recognized as transparent, but means that it has a haze value of 3% or less, for example.

Other specific examples of the water repellent and / or oil repellent group-containing polymerizable compound include at least one fluorine-containing compound selected from the group consisting of (D), (E), (F), (G) And polymerizable unsaturated compounds.

CH ₂ = CR ₁ COOR ₂ Rf ... (D)

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is -C _P H _2P -, -C (C _P H _{2P + 1} ) H-, -CH ₂ C (C _P H _{2P + 1} ) -CH ₂ CH ₂ O-, Rf is -C _n F _{2n +1} , - (CF ₂ ) _n H, -C _n F _2n -CF ₃ , - (CF ₂ ) _p OC _n F _2n C _j H _{2j + 1, - (CF 2) p} OC m H 2m C i H 2i H, -N (C P H2 P + 1) COC n F 2n +1, -N (C P H 2P + 1) SO 2 C n F _{2n + 1} , wherein p is 1 to 10, n is 1 to 16, m is 0 to 10, i is 0 to 16, and j is an integer of 0 to 10,

CF ₂ = CFOR _g ... (E)

[Wherein R _g represents a fluoroalkyl group having 1 to 20 carbon atoms]

CH ₂ = CHR _g ... (F)

[Wherein R _g represents a fluoroalkyl group having 1 to 20 carbon atoms]

CH ₂ = CR ₃ COOR ₅ R _j R ₆ OCOCR ₄ = CH ₂ ... (G)

Wherein R ₃ and R ₄ are each a hydrogen atom or a methyl group and R ₅ and R ₆ are -C _q H _2q- , -C (C _q H _{2q + 1} ) H-, -CH ₂ C (C _q H _{2q 1} ) H- or -CH ₂ CH ₂ O-, R _j is -C _t F _2t , with q being an integer from 1 to 10 and t being an integer from 1 to 16,

CH ₂ = CHR ⁷ COOCH ₂ (CH ₂ R _k ) CHOCOCR ₈ = CH ₂ ... (H)

Wherein R ⁷ and R ⁸ are each a hydrogen atom or a methyl group and R _k is -C _y F _{2y +1} with the proviso that y is an integer of 1 to 16,

Examples of the fluorine-containing polymerizable unsaturated compound include the following specific examples.

Examples of the monomer represented by the formula (D) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH═CH ₂ , CF ₃ CH ₂ OCOCH═CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ OCOC _{CH 3) = CH 2, C} 7 F 15 CON (C 2 H 5) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) CH 2 CH 2 OCOCH = CH _{2, CF 3 (CF 2)} 7 SO 2 N (C 3 H 7) CH 2 CH 2 OCOCH = CH 2, C 2 F 5 SO 2 N (CF 2) 7 CH 2 CH 2 OCOC (CH 3) = CH _{2, (CF 3) 2 CF} (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC (CH 3) = CH 2, CF 3 _{(CF 2) 4 CH (CH} 3) OCOC (CH 3) = CH 2, CF 3 CH 2 OCH 2 CH 2 OCOCH = CH 2, C 2 F 5 (CH 2 CH 2 O) 2 CH 2 OCOCH = CH 2 _{, (CF 3) 2 CFO (} CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 4 OCH 2 CH 2 OCOC (CH 3) = CH 2, C 2 F 5 CON (C 2 H 5) CH 2 _{OCOCH = CH 2, CF 3 (} CF 2) 2 CON (CH 3) CH (CH 3) CH 2 OCOCH = CH 2, H (CF 2) 6 C (C 2 H 5) OCOC (CH 3) = CH 2 _{, H (CF 2) 8 CH} 2 OCOCH = CH 2, H (CF 2) 4 CH 2 OCOCH = CH 2, H (CF 2) CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) ═CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH═CH ₂ , _{C 2 F 5 SO 2 N (} C 2 H 5) CH 2 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 4 OCOCH = CH 2, C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH = CH ₂ .

Examples of the fluoroalkylated olefins represented by the formulas (E) and (F) include C ₃ F ₇ CH═CH ₂ , C ₄ F ₉ CH═CH ₂ , C ₁₀ F ₂₁ CH═CH ₂ , C ₃ F ₇ OCF = CF ₂ , C ₇ F ₁₅ OCF = CF _2, and C ₈ F ₁₇ OCF = CF ₂ .

Formula (G), and as the monomer represented by (H), for example _{CH 2 = CHCOOCH 2 (CF 2} ) 3 CH 2 OCOCH = CH 2, CH 2 = CHCOOCH 2 CH (CH 2 C 8 F 17) OCOCH = CH ₂ , and the like.

Examples of the water-repellent and / or oil repellent group-containing polymerizable unsaturated compound include a polymerizable unsaturated compound having a Si-CH ₃ group or -O-Si-CH ₃ group. Specific examples thereof include acrylate and methacrylate having a polysiloxane chain (which may have a branched structure), and commercially available products include, for example, "Silaplane FM-0711", "Silaplane FM-0721", "Silaplane FM- 0725 " (all manufactured by JNC).

(J): < RTI ID = 0.0 >

^{Rf 1 -PFPE-Rf 2 (J} )

At least one kind of fluorine-containing oil represented by the following formula

Rf ¹ in the formula (J) represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, and Rf ² is a hydrogen atom, a fluorine atom or a Or an alkyl group having 1 to 16 carbon atoms which may be substituted. Preferably, the alkyl group which may be substituted by one or more fluorine atoms is a fluoroalkyl group or a perfluoroalkyl group whose terminal carbon atom is CF ₂ H- and all other carbon atoms are substituted by fluorine, more preferably Is a perfluoroalkyl group. More preferably Rf ¹ and Rf ² are each independently a perfluoroalkyl group having 1 to 3 carbon atoms.

Among the above formula (J), PFPE has the following chemical formula:

- (OC ₄ F ₈ ) _{a '} - (OC ₃ F ₆ ) _b' - (OC ₂ F ₄ ) _{c '} - (OCF ₂ ) _d'

(A), b ', c' and d 'each represent the number of four repeating units of perfluoro (poly) ether and are each independently an integer of 0 to 300, preferably 0 to 200 The sum of a ', b', c 'and d' is at least 1, preferably from 1 to 300, and subscripts a ', b', c 'or d' of attaching the presence order of the repeating units in brackets it is optional in the formula, these repeating units - (OC ₄ F ₈₎ - is _{- (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 )) - which is, but even during, preferably _{- (OCF 2 CF 2 CF 2} CF 2) - a _{-. (OC 3 F 6)} - is _{- (OCF 2 CF 2 CF 2} ) -, - (OCF ( CF ₃₎ CF ₂₎ - and _{- (OCF 2 CF (CF 3} )) - may be any of, preferably _{- (OCF 2 CF 2 CF 2} ) - a _{-. (OC 2 F 4)} - it is - (OC F ₂ CF ₂₎ - and _{- (OCF (CF 3))} - , but which is of the least, preferably - (OCF ₂ CF ₂₎ - a.

In a preferred form, the fluorine-containing oil (J) is any of the following formulas (J1) to (J3)

Rf ¹ - (OCF ₂ CF ₂ CF ₂ ) _{b '} - Rf ² (J 1)

[Wherein Rf ¹ and Rf ² are as defined in formula (J); b 'is an integer of 1 to 300;

Rf ¹ - (OCF (CF ₃ ) CF ₂ ) _{b '} - Rf ² (J ² )

[Wherein Rf ¹ and Rf ² are as defined in formula (J); b 'is an integer of 1 to 300;

or

^{_{Rf 1 - (OCF 2 CF 2}} CF 2 CF 2) a '- (OCF 2 CF 2 CF 2) b' - (OCF 2 CF 2) c '- (OCF 2) d' -Rf 2 (J3)

[Wherein Rf ¹ and Rf ² are as defined in formula (J); a 'and b' are each independently 0 or an integer of 1 to 30, c 'and d' are each independently an integer of 1 to 300, and subscripts a ', b', c 'or d' And the order of existence of each repeating unit to be bound is arbitrary in the formula].

The fluorine-containing oil (J) may have a number average molecular weight of about 1,000 to 30,000. As a result, a high surface slip property can be obtained. Typically, the compounds represented by the formulas (J1) to (J3) preferably have a number average molecular weight of about 1,500 or more. A high surface slip property can be obtained in the range of the number average molecular weight.

The amount of the fluorine-containing oil (J) in the composition is, for example, from 0 to 100 parts by mass relative to the total 100 parts by mass of the carbon-carbon double bond-containing compound (A), the fluorine-containing polymer (B) 80 parts by mass, preferably 0 to 40 parts by mass.

The composition may contain other components than the above, for example silicone oil.

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The straight-chain silicone oil may be a so-called straight silicone oil or a modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil. Examples of the modified silicone oils include those obtained by modifying a straight silicone oil with a polyether, a higher fatty acid ester, a fluoroalkyl, a (meth) acrylate, an amino, an epoxy, a carboxyl and an alcohol. The cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil and the like.

Such a silicone oil in the composition of the present invention may be used in an amount of, for example, from 0 to 50 mass parts per 100 parts by mass of the total amount of the carbon-carbon double bond containing compound (A), the fluorine containing polymer (B) or the fluorine containing silicon containing polymer Part, preferably 0 to 10 parts by mass.

When the functional partial imine-containing polymerizable compound is a hydrophilic group-containing polymerizable compound, the obtained functional film has a hydrophilic group.

Examples of the hydrophilic group include acid groups such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group; Betaine structure-containing groups such as carboxybetaine, sulfobetaine, and phosphobetaine;

Polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxyalkylene group including both oxyethylene group and oxypropylene group;

A hydroxyl group, an amide;

Tertiary amino groups, quaternary ammonium salts and the like.

Examples of the hydrophilic group-containing polymerizable unsaturated compound include (meth) acrylic acid or its alkali metal salts, amine salts and ammonium salts; Itaconic acid or its alkali metal salts, amine salts and ammonium salts; (Meth) acrylate, 2-acrylamide-2-methylpropanesulfonic acid, 3-sulfopropyl (meth) acrylate, 4-styrenesulfonic acid alkali metal salts, amine salts and 2-acryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, alkali metal salts of these phosphoric acid, 2-acryloyloxyethyl acid phosphate, Amine salts and ammonium salts; Methacryloyloxyethyl-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, methacryloyloxyethyl-N, N-dimethylammonium-a-methylcarboxybetaine; Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate; 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone, acrylamide, N, N-dimethylacrylamide; N-hydroxyalkyl (meth) acrylamides such as hydroxyethyl acrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, Acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, 2- 2- (meth) acryloyloxyethyl-2 '- (trimethylammonium) ethyl phosphate, 2- (methacryloyloxy) ethyltrimethylammonium dimethylphosphate, and the like.

Examples of the alkali metal salt in the hydrophilic group-containing polymerizable unsaturated compound include a lithium salt, a sodium salt, and a potassium salt.

When the functional partial-ion-containing polymerizable compound is a refractive-index-variable-group-containing polymerizable compound, the obtained functional film can impart a refractive index fluctuation.

The refractive index fluctuation factor is a functional group having a high or low incremental refraction, for example, a benzyl group, a partially or fully halogenated benzyl group, or a partially or fully halogenated alkyl, alkenyl or alkynyl group, Examples of the unsaturated compound include benzyl acrylate, pentabromobenzyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H-heptafluorobutyl acrylate and trifluoroethyl acrylate And the like.

When the functional partial-ion-containing polymerizable compound is an ultraviolet-absorbing functional group-containing polymerizable compound, the resulting functional film has ultraviolet absorption properties.

Examples of the ultraviolet absorbing functional group-containing polymerizable unsaturated compound include 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy- Hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, and the like are reacted with .

When the functional partial imine-containing polymerizable compound is a polymerizable compound having a light-stabilizing functional group, the resulting functional film has optical stability.

Examples of the polymerizable unsaturated compound having a light-stable functional group include 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloylpiperidine, 4-cyano- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano- 2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethyl Piperidin, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like.

When the functional partial-ion-containing polymerizable compound is a biopolymer-containing functional group-containing polymerizable compound, the obtained functional film has biological characteristics.

Examples of the functional group imparting biological characteristics include a group having an antifouling property and a group promoting the growth of the biological system.

Examples of the polymerizable unsaturated compound containing a group having an antifouling property include copper (II) diacrylate, copper (II) dimethacrylate, dibutyltin maleate, tin (II) diacrylate, Dimethacrylate, trialkyltin methacrylate, zinc dimethacrylate, and the like.

Examples of the group that promotes the growth of the living system include succinimide, glucoside and pull group. Examples of polymerizable unsaturated compounds having a group that promotes growth of the biological system include N-acyloxysuccinimide and 2-methacryloxyethyl glucoside.

When the functional part-containing polymerizable compound is a flame retardant group-containing polymerizable compound, the obtained functional film has flame retardancy.

Examples of the flame retarding group include a completely or partially chlorinated or brominated alkane or a nitrogen or phosphorus containing group.

Examples of the flame retardant group-containing polymerizable unsaturated compound include tribromoneopentyl methacrylate, bis (2-methacryloxyethyl) phosphate, monoacryloxyethyl phosphate, and the like.

When the functional partial-ion-containing polymerizable compound is an antistatic group-containing polymerizable compound, the resulting functional film has antistatic properties.

Examples of the antistatic group include tertiary amino, ethoxylated amino, alkanolamide, glycerol stearate, sorbitan, and sulfonate groups.

Examples of the antistatic group-containing polymerizable unsaturated compound include 2-diisopropylaminoethyl methacrylate, 3-dimethylamino neopentyl acrylate or oleyl bis (2-hydroxyethyl) amine, stearyl acrylate, Vinyl stearate and the like.

The composition containing the functional partial-excited polymerizable compound preferably includes a solvent.

The solvent is not particularly limited and may be appropriately selected depending on the functional group-containing polymerizable compound to be used. Examples of the solvent include, but are not limited to, hydrocarbon solvents such as hexane, heptane and octane; Chlorinated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane; Ether solvents such as diethyl ether, dimethoxyethane, diglyme and triglyme; Ethyl lactate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxyacetate, ethyl acetate, ethyl acetoacetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, Ester solvents such as ethyl methoxypropionate, methyl 2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; Propylene glycol type solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether ; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, and diacetone alcohol; Aromatic hydrocarbons such as benzene, toluene, xylene, and nitrobenzene; Perfluoro aliphatic hydrocarbons having 5 to 12 carbon atoms (e.g., perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); Polyfluoroaromatic hydrocarbons such as bis (trifluoromethyl) benzene; Polyfluoroaliphatic hydrocarbons; (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl methyl ether F ₉ OC ₂ H _5), perfluoro hexyl ether _{(C 2 F 5 CF (OCH} 3) C 3 F 7) with alkyl perfluoroalkyl ether (a perfluoroalkyl group and an alkyl group such as is may be a straight or branched And cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, and the like can be used as the solvent (for example, a solvent such as methyl ethyl ketone) and hydrochlorofluorocarbon (Asahi Clean AK-225 . These solvents may be used alone or as a mixture of two or more thereof.

In a preferred form, the concentration of the functional side-excluded polymerizable compound in the composition containing the functional side-excitation-containing polymerizable compound is 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 To 3% by mass. By setting the concentration range to this range, diffusion or dissolution of the composition including the functional side-excited polymerizable compound into the matrix-forming composition film is further promoted.

The composition containing the functional side-chain-containing polymerizable compound may or may not contain a solvent. In one form, a composition comprising a functional sub-excitable polymerizable compound does not comprise a solvent. In another form, the composition comprising the functional sub-excitation-containing polymerizable compound comprises a solvent.

The method for applying the composition containing the functional side excitation-containing polymerizable compound is not particularly limited, and examples of the method include a method of applying the functional side excitation-containing polymerizable compound to a substrate, such as an immersion coating, a spin coating, a flow coating, a spray coating, a slit coating, a roll coating, a gravure coating, Bar coating, die coating, screen printing, and the like.

The application amount of the composition containing the functional side-chain-containing polymerizable compound is not particularly limited, but is preferably about the same as that of the matrix-forming composition previously applied.

In a preferred form, the composition comprising the matrix-forming composition and the functional side-excipient-containing polymerizable compound may be compatible with each other. It is preferable that the functional side-chain-containing polymerizable compound is compatible or dissolvable with the matrix composition. The diffusion or dissolution of the functional side-excited polymerizable compound into the matrix-forming composition film is promoted by the compatibility of the matrix-forming composition and the composition containing the functional side-excited polymerizable compound.

Subsequently, the film of the matrix-forming composition containing the functional subsidiary-containing polymerizable compound thus obtained is cured.

The curing method is not particularly limited, and can be performed, for example, by irradiating an active energy ray, for example, an electromagnetic wave having a wavelength range of 350 nm or less, that is, ultraviolet rays, electron rays, X rays,? Rays or the like. The curing of the polymerizable compound in the film is initiated by the irradiation of the electromagnetic wave, and a bond is formed between the compound and the substrate, and a functional film is obtained.

The time from the application of the composition containing the functional side-chain-containing polymerizable compound to the initiation of curing is particularly limited as long as the time for the applied functional side-chain-containing polymerizable compound to diffuse or dissolve in the matrix- It does not. Preferably, the time from application of the composition containing the functional partial-excited polymerizable compound to initiation of curing is from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

The functional film of the present invention is obtained as a single layer film in which the functional partial imine-containing polymerizable compound is localized near the surface of the film. Therefore, the functional partial-ion-containing polymerizable compound is firmly bonded to the polymerizable compound of the matrix-forming composition inside the functional film, and thereby has excellent friction durability. Further, since the composition containing the functional side-excited polymerizable compound is applied after forming the matrix-forming composition film, the localization near the surface becomes larger, and the function can be exerted more highly.

The method of manufacturing the functional film of the present invention has been described above, but the present invention is not limited thereto. For example, the substrate may be pretreated prior to application of the matrix-forming composition to the substrate.

The present invention also relates to a functional film obtained by the above production method, and a substrate and a product comprising the functional film of the present invention on the surface of the substrate.

The article of the present invention may be an optical member having the above-mentioned functional film, particularly a film having water repellency and oil repellency, in the outermost layer.

As the optical member, a variety of optical members other than the optical member related to a display and the like as exemplified later may be preferably used. For example, a lens such as a spectacle lens; A field emission display (FED), a cathode ray tube (CRT), a liquid crystal display (LCD), a plasma display, an organic EL display, an inorganic thin film EL dot matrix display, a rear projection display, Display or the like, or a front protective plate, a scattering prevention film, an antireflection plate, a polarizing plate or an antiglare plate of these displays, or a surface thereof subjected to antireflection film treatment; A touch panel sheet of a device such as a cellular phone, a portable information terminal, and the like; A disc surface of an optical disc such as a Blu-ray (registered trademark) disc, a DVD disc, a CD-R, or an MO; Optical fiber and so on.

The present invention also relates to an apparatus for carrying out the production method of the present invention.

The apparatus for producing a functional film of the present invention comprises a matrix forming composition film forming section for supplying a matrix forming composition on a substrate to form a matrix forming composition film and a composition containing a polymerizable functional group- Containing functional group-containing polymerizable compound supply unit.

The matrix-forming composition film-forming portion and the functional side-excipient-containing polymerizable compound supply portion have a mechanism for supplying each composition to the substrate, preferably a spray nozzle.

In one form, the matrix forming composition film forming portion and the functional side excitation-containing polymerizable compound supplying portion may be the same portion. For example, one chamber may serve as a matrix-forming composition film-forming section and a functional side-excluded-containing polymerizable compound supply section. In the method for producing a functional film of the present invention, it is not necessary to apply the matrix forming composition to a substrate and then dried, and since the functional partial imine-containing polymerizable compound can be applied as it is, The above two operations can be performed in the same chamber. Therefore, the manufacturing apparatus of the present invention can have a simple structure.

In a preferred form, the production apparatus of the present invention has a chamber having a spray nozzle for providing a matrix-forming composition on a substrate, and another spray nozzle for providing a composition comprising a functional side-excited polymerizable compound on the substrate, , A matrix-forming composition film is formed by applying a matrix-forming composition on a substrate, and then a composition containing a functional side-excipient-containing polymerizable compound is applied onto the matrix-forming composition film.

Although the method for producing a functional film of the present invention, the functional film obtained therefrom, the article having the same, and the apparatus for carrying out the production method of the present invention have been described in detail, the present invention is not limited to those exemplified above.

[Example]

Synthetic example

In a 1 L four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, SUMIJUL (registered trademark) N3300 (manufactured by Sumika Bayer Urethane Co., Ltd., content ratio of NCO group: 21.8%, 36.6 g) was dissolved in 219.4 g of HCFC225 , And dibutyltin dilaurate (0.30 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and while stirring at 40 캜 in an atmosphere of nitrogen, an average composition of CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₁₄ CF _{A solution of} perfluoropolyether-containing alcohol (60.0 g) represented by ₂ CF ₂ CH ₂ OH dissolved in HCFC 225 (60.0 g) was added dropwise and stirred. Hydroxyethyl acrylate (19.6 g) was added dropwise and stirred. IR showed that the absorption of NCO was completely lost. 0.05 g of dibutylhydroxytoluene was added and the HCFC 225 was completely removed. The composition (2 g) thus obtained was dissolved in 190 g of Irgacure 184 (manufactured by BASF Japan, 0.1 g), Aurora (registered trademark) H (manufactured by Nippon Zeon), 5 g of propylene glycol monomethyl ether (3 g) and methyl isobutyl ketone , And dissolved to obtain a surface treatment composition A.

The composition (2 g) obtained above was mixed with Irgacure 184 (manufactured by BASF Japan, 0.1 g), trimethylolpropane triacrylate (148.5 g) and polyethylene glycol diacrylate (49.5 g) .

Example 1

(10.0 g) of a hard coat agent (Beam Set 575CB (trade name), Arakawa Chemical Industries, Ltd.) was dissolved in methyl isobutyl ketone (15 g) to obtain a curable composition of 40 mass%. The viscosity of the curable composition was 0.4 Pa · s. The curable composition was applied to a polycarbonate substrate (Stera, manufactured by Nippon Test Panel Co., Ltd.) using Barcoat No. 20. Subsequently, the surface treatment composition A (32 g / m ² ) prepared in the above Synthesis Example was sprayed on the curable composition film. Subsequently, the film was dried at 70 DEG C for 5 minutes, and irradiated with ultraviolet rays of 600 mJ / cm < ² > to cure the film to obtain a functional film.

Trimethylolpropane triacrylate (100 g) and Irgacure 184 (manufactured by BASF Japan, 5 g) were mixed and dissolved to obtain a curable composition. The viscosity of the obtained curable composition was 0.1 Pa · s. The curable composition was applied to a polycarbonate substrate (Stera, manufactured by Nippon Test Panel Co., Ltd.) using Barcoat No. 20. Subsequently, the surface treatment composition B (32 g / m ² ) prepared in the above Synthesis Example was sprayed on the curable composition film. Subsequently, ultraviolet light of 600 mJ / cm ² was irradiated to cure the film to obtain a functional film.

Comparative Example 1

(10.0 g) of a hard coat agent (Beam Set 575CB (trade name), Arakawa Chemical Industries, Ltd.) was dissolved in methyl isobutyl ketone (15 g) to obtain a curable composition of 40 mass%. The curable composition was applied to a polycarbonate substrate (Stera, manufactured by Nippon Test Panel Co., Ltd.) using Barcoat No. 20. Followed by drying at 70 DEG C for 5 minutes. The solid content concentration of the matrix-forming composition film after drying at 70 占 폚 for 5 minutes was 99% by mass and the viscosity thereof was 1.5 Pa · s. After drying, the surface treatment composition (32 g / m ² ) prepared in the above synthesis example was sprayed on the film of the matrix-forming composition. Subsequently, the film was dried at 70 DEG C for 5 minutes, and irradiated with ultraviolet rays of 600 mJ / cm < ² > to cure the film to obtain a functional film.

Comparative Example 2

(10.0 g) of a hard coat agent (Beam Set 575CB (trade name), Arakawa Chemical Industries, Ltd.) was dissolved in methyl isobutyl ketone (15 g) to obtain a curable composition of 40 mass%. The curable composition was applied to a polycarbonate substrate (Stera, manufactured by Nippon Test Panel Co., Ltd.) using Barcoat No. 20. And then dried at 70 캜 for 15 minutes. The solid content concentration of the matrix-forming composition film after drying at 70 占 폚 for 15 minutes was 100% by mass, and the viscosity thereof was 1.6 Pa · s. After drying, the surface treatment composition (32 g / m ² ) prepared in the above synthesis example was sprayed on the film of the matrix-forming composition. Subsequently, the film was dried at 70 DEG C for 5 minutes, and irradiated with ultraviolet rays of 600 mJ / cm < ² > to cure the film to obtain a functional film.

The viscosity measurement of the above-mentioned matrix-forming composition film was also obtained by measuring the viscosity of the matrix-forming composition having the corresponding solid concentration. The viscosity of the matrix-forming composition films (Comparative Examples 1 and 2) subjected to the drying step was determined by calculating the solid content concentration of the membrane from the difference in weight before and after drying and by measuring the viscosity of the matrix-forming composition membrane at the solid concentration thereof. The viscosity of the matrix-forming composition was measured at 30 rpm for 180 seconds using a CP-20 cone at 25 占 폚, and a stable value was adopted. The measuring device was a cone plate type viscometer CV-1E manufactured by Tokai Yagami Co., Ltd.

(evaluation)

Eraser endurance test

The friction durability of the functional films formed on the substrate surface was evaluated by the eraser friction endurance test in Examples 1 and 2 and Comparative Examples 1 and 2. Specifically, the sample article on which the functional film was formed was placed horizontally, and an eraser (KESHI-70, manufactured by Kokuyo Corporation) was brought into contact with the surface of the functional film, a load of 500 gf was applied thereon Thereafter, the eraser was reciprocated at a speed of 20 mm / sec in a state where a load was applied. The static contact angle (degree) of water was measured every 100 reciprocations. Evaluation was stopped when the contact angle measurement value became less than 90 degrees. The results are shown in Table 1.

From the above results, it was confirmed that Examples 1 and 2, in which the composition for forming a matrix was applied on a substrate and were not subjected to a drying process, were more excellent in friction durability than Comparative Examples 1 and 2 which had been subjected to a drying process.

[Industrial applicability]

The present invention can be suitably used for forming a surface treatment layer on the surface of various various substrates.

Claims (21)

A method for forming a functional film on a substrate,
Forming composition on a substrate to form a matrix-forming composition film,
By applying a composition containing the functional side-excluded polymerizable compound on the film of the matrix-forming composition, the functional side-excluded polymerizable compound is contained in the film of the matrix-
And curing the film of the matrix-forming composition containing the obtained functional component-containing polymerizable compound to form a single functional layer. The method of claim 1, wherein the matrix forming composition is compatible with a composition comprising a functional side-excited polymerizable compound. The method according to claim 1 or 2, wherein the matrix-forming composition film when applying the composition containing the functional partial-excited polymerizable compound is liquid. The method according to any one of claims 1 to 3, wherein the matrix-forming composition film when applying the composition containing the functional partial-excited polymerizable compound contains 20 mass% or more of solvent. The method according to any one of claims 1 to 4, wherein the matrix-forming composition film when applying the composition containing the functional partial-excited polymerizable compound is not subjected to a drying step. The method according to any one of claims 1 to 5, wherein the matrix-forming composition film when applying the composition containing the functional partial-excited polymerizable compound is in an uncured state. 7. The composition according to any one of claims 1 to 6, wherein the matrix-forming composition is a monofunctional and / or polyfunctional (meth) acrylate, a monofunctional and / or polyfunctional urethane (meth) acrylate, a monofunctional and / Polyfunctional epoxy (meth) acrylate. 8. The compound according to any one of claims 1 to 7, wherein the functional group
1) water-repellent and / or oleophilic group,
2) hydrophilic group,
3) refractive index fluctuator,
4) ultraviolet absorbing functional group,
5) Photostability Functional group,
6) Biological characteristic functional group,
7) Flame retardant group or
8) A method of antistatic nature. 9. The method according to any one of claims 1 to 8, wherein the concentration of the functional side-excitation-containing polymerizable compound in the composition containing the functional side-chain-containing polymerizable compound is 0.01 to 5% by mass. 10. The method according to any one of claims 1 to 9, wherein the functional partial imine-containing polymerizable compound is a carbon-carbon double bond-containing perfluoropolyether compound. 11. The composition according to any one of claims 1 to 10, wherein the composition comprising the functional partial-excluded polymerizable compound is obtained by (a) reacting a triisocyanate polyisocyanate of diisocyanate with (b) a compound having active hydrogen, - a carbon double bond-containing compound (A)
Component (b)
(b1) perfluoropolyethers having active hydrogen and
(b2) a monomer having active hydrogen and at least one carbon-carbon double bond. The method according to claim 11, wherein component (b) further comprises (b3) a silane compound having active hydrogen. 11. The method according to any one of claims 1 to 10, wherein the functional partial imine-containing polymerizable compound is a fluorine-containing polymer (B) having at least one curing site. 14. The fluorine-containing polymer according to claim 13, wherein the fluorine-containing polymer (B) is any one of the following formulas (B1) and (B2)

[Wherein:
Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
R ⁴¹ is a group represented by the formula:
- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -
Wherein a, b, c and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and d is at least 1, and the order of existence of each repeating unit enclosed in parentheses is And R < 2 >
R ⁴² represents, independently at each occurrence, 2 to 10 organic groups,
R ⁴³ independently represents a divalent organic group at each occurrence,
R ⁴⁴ for each occurrence independently represents R ^44a or R ^44b , provided that at least one R ⁴⁴ is R ^44a ,
R ^44a represents a divalent organic group having a curable site independently at each occurrence,
R ^44b independently represent a divalent organic group having no curing site at each occurrence,
R ⁴⁵ represents -O-, -S-, -NH- or a single bond,
R ⁴⁶ represents Rf-R ⁴¹ -R ⁴² (wherein Rf, R ⁴¹ and R ⁴² are as defined above), a monovalent organic group or a hydrogen atom,
n1 is an integer of 1 or more and 50 or less,
is at least one fluorine-containing polymer represented by the following general formula (1): " (1) " 11. The method according to any one of claims 1 to 10, wherein the functional partial imine-containing polymerizable compound is a fluorine-containing silicon-containing polymer (C) having at least one curing site. The fluorine-containing silicon-containing polymer (C) according to claim 15, wherein any one of the following formulas (C1) and (C2)

[Wherein:
Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms,
R ⁴¹ is a group represented by the formula:
- (OC ₄ F ₈ ) _a - (OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d -
Wherein a, b, c and d are each independently an integer of 0 or more and 200 or less, the sum of a, b, c and d is at least 1, and the order of existence of each repeating unit enclosed in parentheses is And R < 2 >
R ⁴² represents, independently at each occurrence, 2 to 10 organic groups,
R ⁴³ independently represents a divalent organic group at each occurrence,
R ⁴⁴ for each occurrence independently represents R ^44a or R ^44b , provided that at least one R ⁴⁴ is R ^44a ,
R ^44a represents a divalent organic group having a curable site independently at each occurrence,
R ^44b independently represent a divalent organic group having no curing site at each occurrence,
R ⁴⁵ represents -O-, -S-, -NH- or a single bond,
R ⁴⁷ is independently an organic group of 2 to 10 in each occurrence,
R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are each independently an alkyl group, an alkoxy group or an aryl group,
n1 is an integer of 1 to 50,
n3 and n4 are each independently an integer of 0 to 50, the sum of n3 and n4 is at least 1,
n2, n5 and n6 are each independently an integer of 0 to 500;
? are each independently an integer of 1 to 9;
is a fluorine-containing silicon-containing polymer represented by the following general formula (1). 17. The positive working photoresist composition according to any one of claims 11 to 16, wherein the composition comprising the functional side-chain-containing polymerizable compound further comprises one of the following formulas (S1) and (S2):

[Wherein:
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ and R ⁷⁷ each independently represent an alkyl group, an alkoxy group or an aryl group,
R ⁷⁸ represents a divalent organic group,
X ¹ represents a hydrogen atom, a chlorine atom, a fluorine atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine,
and n7 and n8 are each independently an integer of 1 or more and 500 or less]. A functional film formed by the method according to any one of claims 1 to 17. 18. An article comprising a substrate and a functional film according to claim 18 located on the substrate. An apparatus for use in a method for forming a functional film according to any one of claims 1 to 17,
A matrix forming composition film forming unit for forming a matrix forming composition film by supplying a matrix forming composition onto a substrate,
And a functional side-excited polymerizable compound supply part for supplying a composition containing the functional side-excluded polymerizable compound to the matrix-forming composition film. 21. The method of claim 20, further comprising providing a chamber having a spray nozzle providing a matrix-forming composition to the substrate and another spray nozzle providing a composition comprising a functionalized,
Applying a matrix forming composition on a substrate in the chamber to form a matrix forming composition film and subsequently applying a composition comprising a functional side excitable polymerizable compound on the matrix forming composition film.