KR20130113379A - Hard coating composition having antifouling - Google Patents

Abstract

PURPOSE: An antifouling imparting hardcoating composition provides a hardcoating surface with excellent anti-fingerprint and fingerprint-removing performance and prevents attached fingerprint, sebum, sweat, and cosmetics from standing out. CONSTITUTION: An antifouling imparting hardcoating composition comprises a hardcoating material, a fluorine-containing acrylate compound represented by chemical formula 1, and an acrylate compound which has a perfluoropolyether group represented by chemical formula 2. The hardcoating material is a UV-curable acrylic hardcoating material. The UV-curable acrylic hardcoating material includes a (meth)acrylic compound and a photopolymerization initiator.

Description

Antifouling imparting hard coating composition {HARD COATING COMPOSITION HAVING ANTIFOULING}

The present invention relates to a hard coating material imparting antifouling properties, more specifically, an antifouling imparting agent having a fluorine-containing organic group, a hydrocarbon group and a (meth) acryl group in the same molecule, and a perfluoropolyether group (meth) in the same molecule. The present invention relates to an antifouling imparting hard coating composition to which an antifouling imparting agent having an acrylic group is added.

Since the resin material has characteristics such as being lighter and less rust than metals, it is widely used in various telephone products, cases of electronic devices such as personal computers and mobile phones. Moreover, it is hard to be broken even compared with glass, The resin which has properties, such as high hardness and high transparency, such as an acrylic resin and a polycarbonate resin, is a single body or a hard coating material, such as a liquid crystal display or a touch panel. It is used for a display body.

In recent years, especially in the case of an electronic device, the surface which is high gloss is calculated | required in terms of a design. Moreover, the thing which has the specification of a touch panel also increases in the display for mobile phones and personal computers, and the hard outer coating materials, such as an acrylic resin and a silicone resin, are coated in the outermost surface for the purpose of a wound prevention.

They frequently come in contact with human hands and the like, and contaminants such as sebum, sweat, and fingerprints tend to adhere, and when they become traces, they often impair appearance or deteriorate visibility. In particular, in a capacitive touch panel, input by direct contact with a finger is essential, and this problem cannot be avoided. Therefore, the improvement of antifouling performances, such as a fingerprint-proof, is strongly calculated | required about these hard coat materials.

As a countermeasure thereof, various studies have been made so far, and the following two methods are largely distinguished. One is to use a silicone compound or a fluorine compound to form a water / oil repellent surface having low surface energy on the hard coat surface, and to perform a treatment that is difficult to adhere to stains such as fingerprints and is easy to remove.

For example, Japanese Patent Laid-Open No. 2004-250474: As disclosed in Patent Document 1, a silane compound having a perfluoropolyether group is treated on the outermost surface of a hard coating, or Japanese Patent No. 3963169: Patent As disclosed in Document 2, a perfluoropolyether urethane acrylate composition is added to a hard coating composition, and the antifouling performance is expressed by uncrosslinking on the surface thereof to form a water / oil repellent surface.

In this method, it is easy to wipe off the adhered contamination. However, due to its high water / oil repellency, the attached fingerprint or the like forms fine droplets and diffusely reflects light, resulting in deterioration of the transmittance and visibility, or because the fluorine compound has a low refractive index. The difference in refractive index with sebum, sweat, etc. which are the components of is large, and even a slight adhesion trace may stand out.

In addition, the attached fingerprint contains inorganic components such as water and salt, organic components such as proteins and fats and oils, etc., and its composition is complicated, and it is difficult to completely prevent their adhesion.

In addition, a hydrophilic / lipophilic surface having a high affinity for contaminants such as fingerprints is formed on the outermost surface of the hard coating, so that the adhered contaminants are melted and wet-diffused so as to be less noticeable.

For example, as disclosed in Japanese Patent Laid-Open No. 2001-353808: Patent Document 3, a silane compound having a long-chain alkylester group is treated on the outermost surface of a hard coating, or published in International Publication No. 2009/44912: Patent As disclosed in Document 4, colloidal silica is added to the acrylic polymer composition to form hydrophilic and lipophilic surfaces on the surface, thereby reducing the visibility of contamination.

In this method, even if contamination adheres to the hard coating surface, it is difficult to see the wet diffusion throughout. In addition, by lowering the refractive index of the hard coating to contaminants such as fingerprints, it is possible to further prevent the deterioration of visibility. However, since the affinity for contaminants is high and they gradually become difficult to deposit or wipe, the light transmittance of a display or the like is sometimes lowered.

In addition, Japanese Patent No. 4873666: Patent Document 5 describes an acrylate compound having a perfluoropolyether group. When the compound is added alone, fingerprint wiping properties are greatly improved, but fingerprints are noticeable. Difficult was insufficient.

Japanese Patent Laid-Open No. 2004-250474 Japanese Patent No. 3963169 Japanese Patent Laid-Open No. 2001-353808 International Publication No. 2009/44912 Japanese Patent No. 4873666

The present invention has been made in view of the above circumstances, and it is hard to be noticed even when fingerprints, sebum, sweat, etc., cosmetics, and the like are attached, and a hard coating surface having excellent wiping property is provided even when dirt is attached. An object of the present invention is to provide an antifouling imparting hard coating composition.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, and, as a result, the fluoro-containing acrylate compound represented by following General formula (1) and the perfluoropolyether represented by following General formula (2) to a hard-coating material The hard-coating surface obtained by using the antifouling imparting hard coating composition which added two kinds of antifouling additives of the acrylate compound which has a group improves the inconspicuous difficulty of a fingerprint, and finds that fingerprint wiping property is also favorable, It was completed.

Accordingly, the present invention provides the following antifouling imparting hard coating composition.

〔One〕

(A) hard coating material,

(B) a fluorine-containing acrylate compound represented by the following general formula (1),

(1)

(One)

[In formula, Rf is a C2-C16 fluoroalkylene group, Q is independently a single bond or a C1-C12 divalent organic group, R is independently C6-C20 which may contain an oxygen atom. Is an alkyl group or an aralkyl group having 7 to 20 carbon atoms, R ¹ is independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ² is a hydrogen atom or Methyl group, X is the following general formula

(Wherein R ¹² is a divalent hydrocarbon group having 1 to 12 carbon atoms)

Wherein m is an integer of 2 to 8, n is independently 1 or 2]

(C) An acrylate compound having a perfluoropolyether group represented by the following general formula (2)

(2)

(2)

[Wherein, Rf 'is independently a divalent perfluoropolyether group having a molecular weight of 500 to 30,000, and may include a branch in the middle, and X ¹ is independently of the following general formula (3)

(3)

(3)

{In formula (3), a and c are each 0 or an integer of 1 to 3, b is an integer of 1 to 4, except that a + b + c is 2, 3 or 4, and the arrangement of each repeating unit is random May be, and R ³ is independently the following formula (4):

(4)

(4)

(In formula (4), d, e, f, g are integers of 0 or 1 to 20 independently of each other in a range in which the molecular weight of R ³ becomes 45 to 600, and the arrangement of each repeating unit may be random, , R ⁵ is a saturated or unsaturated monovalent hydrocarbon group having 1 to 10 carbon atoms)

R ⁴ is a group represented by the following formula (5)

(5)

(5)

(In formula (5), R <^6> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group independently, and R <^7> is bivalent or trivalent which may contain the ether bond or ester bond of C1-C18. Connector, u is 1 or 2)

Is an acryl group or an α substituted acryl group-containing group, Q ¹ and Q ² independently represent a divalent linking group which may contain an ether bond, an ester bond, an amide bond or a urethane bond having 3 to 20 carbon atoms, May contain a ring or branch structure in the middle, and may be the same or different from each other}

X ² is independently a group represented by the following formula (6)

(6)

(6)

(In formula (6), R <^3> , R <^4> , Q <^1> , Q <^2> is as above, h, k are 0 or an integer of 1-3, j is an integer of 1-3, h + j + k is any value of 1 to 3, and the arrangement of each repeating unit may be random)

Z is a divalent group, Z is a divalent organic group which may contain an oxygen atom, a nitrogen atom, and a silicon atom independently of each other, and may also have a cyclic structure and an unsaturated bond, and v is 0 or 1 to Is an integer of 5]

Antifouling imparting hard coating composition containing a main component.

[2] The antifouling imparting hard coating composition according to [1], wherein the hard coating material of the component (A) is an ultraviolet curable acrylic hard coating material.

[3] The antifouling imparting hard coating composition as described in [2], wherein the ultraviolet curable acrylic hard coating material contains a (meth) acrylic compound and a photopolymerization initiator.

According to the antifouling imparting hard coating composition of the present invention, it is difficult to be noticed even when fingerprints, sebum, perception of sweat or the like, cosmetics, etc. are attached, and a hard coating surface excellent in wiping property can be provided even when contamination is attached.

Hereinafter, the present invention will be described in detail.

The antifouling imparting hard coating composition of the present invention,

(A) hard coating material,

(B) a fluorine-containing acrylate compound represented by the general formula (1),

(C) An acrylate compound having a perfluoropolyether group represented by the general formula (2)

It is based on the main component.

(A) hard  Coating material

Although it does not specifically limit as a hard coat material of (A) component of this invention, It hardens | cures by irradiation of the active energy ray which was excellent in the balance of solubility and surface exudation property with respect to the antifouling agent of (B) and (C) component mentioned later. Resin (active energy ray curable resin composition) is preferable, and the ultraviolet curable acrylic hard coating material containing a (meth) acrylic-type compound and a photoinitiator is especially preferable.

In the ultraviolet curing acrylic hard coating material, as a (meth) acrylic compound, for example, pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyl Alltetra (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- ( Meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-6 functional (meth) acryl compounds, such as dipentaerythritol hexa (meth) acrylate and sorbitol hexa (meth) acrylate, these (meth) acryl compounds Epoxyacrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- which are obtained by adding acrylic acid to a seed, a propylene oxide, epichlorohydrin, a fatty acid, an alkyl, a urethane modified product, and an epoxy resin. From (meth) acrylate having a hydroxyl group selected from acryloyloxypropyl methacrylate and pentaerythritol triacrylate, and from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate Polyfunctional (meth) acrylate mixtures, such as a urethane acrylate which reacted the selected polyisocyanate, and the copolymer which introduce | transduced the (meth) acryloyl group into the side chain of an acrylic acid ester copolymer, etc. can be used, and benzoin Photopolymerization, such as benzoin methyl ether, benzophenone, and 1-hydroxycyclohexylphenyl ketone An initiator is combined and used.

Moreover, a commercial item can be used as an ultraviolet curable acryl-type hard-coating material, As a (meth) acrylic-type compound, For example, EBECRYL40 (4-functional acrylate, the Daicel Cytec company make), Petia (PETIA) ( Trifunctional acrylate, manufactured by Daicel Cytec Co., Ltd., A-TMPT (trifunctional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), A-DPH (6-functional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H ( 6-functional acrylate, Kyoisha Chemical Co., Ltd.), UN-952 (15-functional acrylate, Negami Kogyo Co., Ltd.) etc. can be used. Moreover, as a photoinitiator, Irgacure 184, Irgacure 127, Irgacure 651, Darocure 1173 (made by BASF), etc. can be used, for example.

Here, it is preferable that it is 1-10 mass parts with respect to 100 mass parts of (meth) acrylic-type compounds, and, as for the usage-amount of a photoinitiator, it is more preferable that it is 1-5 mass parts. When there is too little compounding quantity, sclerosis | hardenability will become inadequate, hardened | cured material may become soft, and when too large, the impurity which does not participate in bridge | crosslinking in hardened | cured material may increase, and a physical property may fall.

(B) fluorine-containing Acrylate  compound

The fluorine-containing acrylate compound as the component (B) of the present invention is represented by the following general formula (1), and acts as an antifouling agent.

(1)

(One)

In general formula (1), Rf is C2-C16, Preferably it is C2-C10, More preferably, it is a C4-C8 linear or branched fluoroalkylene group, Water-repellent, oil-repellent, antifouling property, It is for providing a compound with characteristics, such as exudation to a hard coat surface. When carbon number in Rf exceeds the said upper limit, compatibility with a hard coat material will be impaired, and there exists a possibility of generating whitening, a hardening defect, etc ..

As an example of such a fluorine-containing group Rf, what is shown below is illustrated, for example.

-C _p F _2p- ,

-(CF ₂ ) _r -CH _2- (CF ₂ ) _s-

Wherein p is an integer of 2 to 10, preferably 4 to 8, r is 1 to 8, preferably 2 to 6, and s is 1 to 8, preferably 2 to 6 )

Among these, what is shown below can be used preferably.

-C _p F _2p-

(Wherein p is the same as above)

In General formula (1), Q is a single bond or a divalent organic group of C1-C12, Preferably C3-C8 independently. Specific examples of the divalent organic group include alkylene groups such as methylene group, ethylene group, propylene group (trimethylene group and methylethylene group), butylene group (tetramethylene group and methylpropylene group), hexamethylene group and octamethylene group. Arylene groups, such as a phenylene group, or 2 or more types of these groups (alkylene arylene group etc.) may be sufficient, or 1 type selected from these into an ether bond, an amide bond, an ester bond, a diorganosilylene group, etc. Or a divalent hydrocarbon group which may include two or more kinds of structures, and may contain a group containing one or two or more selected from an oxygen atom, a nitrogen atom, and a silicon atom in addition to the above.

As such a divalent organic group of Q, group represented by a following formula is mentioned.

-CH _2- ,

-CH ₂ CH _2- ,

-CH ₂ CH ₂ CH ₂ -,

-CH ₂ -O- (CH ₂ ) _t- ,

-CH ₂ CH ₂ -O- (CH ₂ ) _t- ,

-OCH _2- ,

-CO-NH-CH _2- ,

-CO-N (Ph) -CH _2- ,

-CO-NH-CH ₂ CH _2- ,

-CO-N (Ph) -CH ₂ CH ₂ CH _2- ,

-CO-N (CH ₃ ) -CH ₂ CH ₂ CH _2- ,

-CO-O-CH _2- ,

-CO-N (CH ₃ ) -Ph'-,

-CO-NR ¹¹ -Y'-,

-CO-NR ¹¹ -Y'-CH ₂ CH _2-

(Wherein, Ph is "and is a phenylene group, t is an integer from 1 to 10, Y, a phenyl group, Ph is -CH ₂ - or the following formula

Is a divalent group represented by: R ¹¹ is a hydrogen atom or an unsubstituted or substituted, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms)

Here, as the unsubstituted or substituted, preferably C 1 to C 10 monovalent hydrocarbon group of R ¹¹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl Alkyl groups, such as an alkyl group, such as a group, a pentyl group, a neopentyl group, a hexyl group, an octyl group, a cycloalkyl group, such as a cyclohexyl group, a vinyl group, an allyl group, and a propenyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group Aralkyl groups such as aryl groups such as aryl groups, benzyl groups, phenylethyl groups, and phenylpropyl groups; some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, chlorine, and cyano groups (N≡C-); Substituted with, for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group and the like.

In formula (1), R is independently an alkyl group having 6 to 20 carbon atoms, preferably having 8 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably having 8 to 14 carbon atoms. The group is introduced in order to make the contamination or fingerprints compatible with the oil component and make the contamination or fingerprints less noticeable. For example, as the alkyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tetradecyl group (myristol group), hexadecyl group (palmityl group), octa A decyl group (stearyl group), an acyl group, etc. are mentioned, As an aralkyl group, a benzyl group, a phenylethyl group, a tolylethyl group, etc. are mentioned. Moreover, it may also interpose these through 1 type (s) or 2 or more types, such as an ether bond oxygen atom (-O-), a carbonyl bond (-CO-), and an ester bond (-COO-), For example, Undecanoic acid An ethyl group, an octylate acid group, an ethoxy pentyl group, etc. are mentioned. The plurality of R may be the same group or different groups.

In formula (1), R ¹ is independently of each other an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably having 6 to 8 carbon atoms, or 7 to 10 carbon atoms, It is preferably an aralkyl group having 7 to 8 carbon atoms, which is introduced to impart lipophilic properties, compatibility with hard coating materials, and the like to the compound. For example, an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, aryl group such as phenyl group, benzyl group, etc. And an aralkyl group. Especially, it is preferable that they are a methyl group, n-butyl group, and a phenyl group, and a methyl group is especially preferable. R ¹ may be the same group or a heterogeneous group, respectively.

In addition, R ² is a hydrogen atom or a methyl group.

In Formula (1), X is represented by the following general formula.

(In formula, R <^12> is a C1-C12 divalent hydrocarbon group, such as alkylene groups, such as a methylene group, an ethylene group, and a propylene group, arylene groups, such as a phenylene group and a naphthylene group.)

In addition, in Formula (1), n is 1 or 2 independently, Preferably it is 2. m is an integer of 2-8, Preferably it is an integer of 2-6.

As a fluorine-containing acrylate compound represented by the said General formula (1), what is specifically shown below can be illustrated.

(Where x + y (average) = 5)

The fluorine-containing acrylate compound represented by the general formula (1) can be easily produced by a known method. For example, the following general formula (i)

(i)

(i)

(Wherein Rf, Q and R ¹ are the same as above)

A hydrosiloxy group-containing fluorine-containing compound, a C6-C20 alpha -olefin-based compound corresponding to a residue obtained by removing one hydrogen atom from the R group of formula (1), and alkenol, preferably platinum It can be manufactured by making a fluorine-containing organic group modified siloxane by hydrosilylation addition-reaction by the conventionally well-known method in presence of a system catalyst, and then making the said siloxane react with a (meth) acryl-group containing isocyanate compound.

Here, the (alpha) -olefin type compound is olefin which removed one hydrogen atom from R in Formula (1), Preferably the olefin which has a vinyl group at one terminal is preferable. If both terminal vinyl group-containing olefins are used, crosslinking reaction may occur between molecules at the time of hydrosilylation addition reaction, and it may polymerize and gelatinize a product, or the solubility to a hard coating material may fall. As a C6-C20 alpha-olefin type compound, 1-hexadecene, 1-dodecene, ethyl 10- undecenoic acid, ethoxy-1- pentene, etc. can be mentioned specifically ,.

Moreover, what is represented by a following formula can be illustrated as alkenol.

HO-R ¹³ -CH = CH ₂

(Wherein, R ¹³ is a single bond or an alkylene group such as methylene group, ethylene group, propylene group, butylene group having 1 to 6 carbon atoms)

The hydrosiloxy group-containing fluorine-containing compound and the C6-C20 α-olefin-based compound are reacted so that at least one SiH group of the hydrosiloxy group-containing fluorine-containing compound remains, specifically, SiH of the hydrosiloxy group-containing fluorine-containing compound The reaction is carried out such that the molar ratio (Vi / SiH ratio) of the terminal and the terminal vinyl group of the α-olefin compound is 0.167 to 0.833, more preferably 0.333 to 0.667, and has at least one SiH group, preferably 1 to 3 It is preferable to obtain a fluorine-containing organic group-modified siloxane. If the α-olefin-based compound is in excess, the turbidity may be generated when added to the hard coat material.

The alkenol is then reacted with all remaining SiH groups. The fluorine-containing organic group-modified siloxane which has at least one SiH group which made the said hydrosiloxy group containing fluorine-containing compound and the alpha-olefin type compound react, and alkenol are the SiH group of the said fluorine-containing organic group modified siloxane, and the vinyl group of alkenol The reaction is preferably carried out such that the molar ratio (Vi / SiH ratio) is 0.2 to 1.5, particularly 0.333 to 1.2, to obtain a fluorine-containing organic group-modified siloxane having no SiH group.

As the platinum-based catalyst in the above reaction, a conventionally known platinum group metal catalyst used in the hydrosilylation addition reaction can be used. Generally, a platinum or a platinum compound which is relatively easy to obtain is used because it is a compound of a precious metal and is expensive. As such a platinum compound, complexes of chloroplatinic acid or chloroplatinic acid with olefins such as ethylene, complexes of alcohols and vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon and the like can be used. As platinum group metal catalysts other than the platinum compound, rhodium, ruthenium, iridium, and palladium-based compounds can be used, for example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _4, and the like (wherein Ph is a phenyl group) can be used.

The amount of the platinum-based catalyst may be a catalytic amount, preferably an amount of 0.1 to 500 ppm (platinum mass equivalent) based on 100 parts by mass of the total amount of the hydrosiloxy group-containing fluorine-containing compound and the α-olefin-based compound or alkenol.

The reaction temperature is appropriately determined depending on the amount and type of the solvent, and may be usually room temperature to 200 ° C, preferably 40 to 100 ° C. There is no restriction | limiting in particular in reaction time, According to an individual reaction condition, reaction can fully be made to progress.

When performing the hydrosilylation addition reaction of each said step, you may use a solvent as needed. The solvent preferably dissolves all of the hydrosiloxy group-containing fluorine-containing compound, the α-olefin-based compound and the alkenol. However, even if only one is dissolved, the solvent is not particularly limited as long as it does not inhibit the hydrosilylation addition reaction. Although the usage-amount of a solvent is suitably selected according to the viscosity and the dosage of the hydrosiloxy-group containing fluorine-containing compound, the alpha-olefin type compound, and alkenol or the fluorine-containing organic group modified siloxane produced | generated, a hydrosiloxy group containing fluorine-containing compound, (alpha) 10-200 mass parts is preferable with respect to 100 mass parts of total amounts of -olefin type compound and alkenol, and it is especially preferable that it is 20-100 mass parts.

Examples of such a solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane and isododecane, aromatic hydrocarbon compounds such as toluene and xylene, and fluorine-containing aromatic hydrocarbons such as trifluorotoluene and hexafluoromethylene System compounds, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (tri Hydrofluoroether compounds such as fluoromethyl) pentane, chlorofluorocarbon compounds such as diproyl (manufactured by Daikin Kogyo Co., Ltd.), hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethyl Cyclic siloxanes such as chain siloxanes such as pentasiloxane and 2- (trimethylsiloxy) -1,1,1,2,3,3,3-heptamethyltrisiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, Pomblin, Galden (Solvay Solixis), Dempnum (Daikin High School) And perfluoropolyether compounds such as Crytox (manufactured by DuPont). Among them, toluene, xylene, and hexafluoromethxylene are preferred because of excellent solubility of the hydrosiloxy group-containing fluorine-containing compound, α-olefin-based compound, alkenol and the resulting fluorine-containing organic group-modified siloxane.

The (meth) acryl group-containing isocyanate compound is reacted with the obtained fluorine-containing organic group modified siloxane. At this time, it is preferable to quantify the amount of alcohol in the fluorine-containing organic group-modified siloxane and to react the (meth) acryl group-containing isocyanate compound in an amount of 1.2 to 3 times the molar amount, and preferably 1.5 to 2 times the molar amount thereof.

Here, what is represented by a following formula can be illustrated as a (meth) acryl group containing isocyanate compound.

Wherein R ² and R ¹² are the same as above.

The reaction between the fluorine-containing organic group-modified siloxane and the (meth) acryl group-containing isocyanate compound can proceed by mixing both under conditions of 0 to 120 ° C, preferably 25 to 80 ° C.

In addition, an appropriate catalyst may be added to increase the speed of the reaction. As the catalyst, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, and dioxanate tin 1 Alkyl tin ester compounds such as tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol, etc. Titanic acid ester or titanium chelate compound, zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetyl Although acetonate, a zirconium chelate compound, etc. are illustrated, these are not limited to the 1 type, It can also be used as a mixture of 2 or more types. The reaction rate can be increased by adding these catalysts at 0.01 to 2% by mass, preferably 0.05 to 1% by mass relative to the total mass of the reactants.

If necessary, the reaction may be carried out by diluting with a suitable solvent. As such a solvent, any solvent that does not react with isocyanate and hydroxyl groups can be used without particular limitation. Specifically, ethers such as tetrahydrofuran, diisopropyl ether and dibutyl ether, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketones, such as ethyl acetate, esters, such as butyl acetate, aromatic hydrocarbon solvents, such as toluene and xylene, etc. are illustrated.

(B) component of this invention can be manufactured with the solution melt | dissolved in the organic solvent uniformly. In this case, the concentration of the fluorine-containing acrylate compound in the solution is not particularly limited as long as it is a range where a homogeneous solution is obtained, but is usually 1 to 50% by mass, preferably 5 to 30% by mass, more preferably about 5 to 20% by mass. Can be.

As an organic solvent which melt | dissolves a fluorine-containing acrylate compound, it is selected from what does not react with the hard coat material of (A) component, For example, aliphatic hydrocarbon solvents, such as hexane, heptane, isooctane, isododecane, toluene, Aromatic hydrocarbon solvents such as xylene, alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethylene glycol monoethyl ether and ethylene glycol mono-t Glycol solvents such as -butyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. Among these, isododecane, isopropanol, methyl isobutyl ketone, etc. are used preferably.

The addition amount of the fluorine-containing acrylate compound which is (B) component is 0.1-3 mass parts (in solid content in the said solution) with respect to 100 mass parts of hard coat materials which are (A) component, Preferably it is the ratio of 0.2-2 mass parts When added, good surface properties are obtained. If it is less than the said lower limit, the exudation to a hard-coat surface is difficult and there exists a possibility that a preferable characteristic may not be obtained. Moreover, since the affinity for resin is impaired if it is the said upper limit, there exists a possibility that whitening of an external appearance, a fall of hardness, etc. may arise.

(C) Perfluoropolyether group  Have Acrylate  compound

The acrylate compound which has a perfluoropolyether group which is (C) component of this invention is represented by following formula (2), and acts as an antifouling agent.

(2)

(2)

In Formula (2), Rf 'is a bivalent perfluoropolyether group of the molecular weight 500-30,000 independently, and may contain the branch in the middle.

Rf 'is a divalent perfluoropolyether moiety comprising 1 to 500 repeating units represented by the general formula -C _i F _2i O- (i is independently an integer from 1 to 6 per unit), preferably It is a perfluoro polyether residue represented by following formula (7)-(9).

(7)

(7)

In formula (7), each Y is independently an F or CF ₃ group, A is an integer of 2 to 6, preferably an integer of 1 to 3, B and C are each an integer of 0 or 1 to 200, preferably Integer of 2-100, B + C is 2-200, Preferably it is 4-100. D is 0 or an integer of 1-6, Preferably it is an integer of 1-4, and each repeating unit may be combined at random.

(8)

(8)

In formula, E is an integer of 1-3, G is an integer of 1-200, Preferably it is an integer of 1-100.

(9)

(9)

Wherein Y is an F or CF ₃ group, E is an integer of 1 to 3, H, J are each 0 or an integer of 1 to 200, preferably an integer of 1 to 100, provided that H + J is 2 to 200, Preferably it is 4-100, and each repeating unit may be combined at random.

In Formula (2), X <^1> is group represented by following formula (3) each independently.

(3)

(3)

In formula (3), a and c are each 0 or an integer of 1 to 3, b is an integer of 1 to 4, preferably 2 or 3, provided that a + b + c is any of 2, 3, and 4 One, preferably 3 or 4, and the arrangement of each repeating unit may be random.

In Formula (3), R <^3> is group represented by following formula (4) independently.

(4)

(4)

In formula (4), d, e, f, and g are each independently an integer of 0 or 1-20, Preferably it is 1--20 in the range whose molecular weight of R <^3> is 45-600, Preferably it is 60-300. It is an integer of 10, It is preferable that d + e + f + g is 1-20, and it is more preferable that it is 2-15. In addition, the propylene group and butylene group in Formula (4) may be branched, and the arrangement of each repeating unit may be random.

In formula (4), R <^5> is a C1-C10 saturated or unsaturated monovalent hydrocarbon group, A methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, a pentyl group, a hexyl group, 2-ethylhexyl group, cyclo Alkyl groups, such as an alkyl group, such as a hexyl group, and an aryl group, such as a phenyl group, and a benzyl group, etc. are mentioned. Especially preferably, they are a methyl group and an ethyl group.

As such R <^3> , group represented by a following formula is preferable.

-(C ₂ H ₄ O) _{f '} (C ₃ H ₆ O) _e ' CH ₃

(In formula, f ', e' is 0 or an integer of 1-20, f '+ e' is 1-40, The propylene group in a formula may be branched and each repeating unit may be couple | bonded at random. has exist)

R ⁴ has at least one acryl group or an α-substituted acrylic group represented by the following formula (5), and is preferably a monovalent organic group having 1 to 21 carbon atoms.

(5)

(5)

In formula (5), R <^6> is any one of a hydrogen atom, a fluorine atom, a methyl group, and a trifluoromethyl group independently, Especially preferably, it is a hydrogen atom and a methyl group. R <^7> is a C1-C18, Preferably it is a C2-C10 divalent or trivalent coupling group, may contain the ether bond oxygen atom and ester structure, Preferably what is shown below is mentioned.

U is 1 or 2.

As group represented by Formula (5), Preferably it is group represented by the following formula, Especially preferably, it is group containing an ethylene group as R <^7> .

In Formula (3), Q <^1> and Q <^2> are the bivalent coupling groups which may contain the C3-C20 ether bond, ester bond, amide bond, or urethane bond independently of each other, On the other hand, a cyclic structure or a branched structure It may include, may be the same or different. As Q <^1> and Q <^2> , group represented by a following formula is preferable.

In Formula (2), X <^2> is a bivalent group represented by following formula (6) independently.

(6)

(6)

In formula (6), R <^3> , R <^4> , Q <^1> , Q <^2> are the same as the above, h and k are each 0 or an integer of 1-3, j is an integer of 1-3, h + j + k is a value of any one of 1, 2, and 3, and the arrangement of each repeating unit may be random.

In Formula (2), Z is a bivalent organic group which may contain the silicon atom, such as an oxygen atom, a nitrogen atom, and a diorganosilylene group, respectively independently, and Z may be a group which has a cyclic structure and an unsaturated bond. The structure is not particularly limited as long as it does not inhibit the polymerization of the acrylic group. As an example of Z, group represented by a following formula is mentioned.

Especially, group represented by a following formula is preferable.

v is 0 or an integer of 1-5, Preferably it is 0, 1 or 2, More preferably, it is 0 or 1.

As a perfluoro polyether group containing acrylate compound represented by the said General formula (2), what is specifically shown below can be illustrated.

(Wherein Rf 'is as defined above)

(C) component of this invention can be manufactured with the solution melt | dissolved in the organic solvent uniformly. In this case, the concentration of the perfluoropolyether group-containing acrylate compound in the solution is not particularly limited as long as it is a range where a homogeneous solution is obtained, but is usually 1 to 50% by mass, preferably 5 to 30% by mass, more preferably 5 To about 20 mass%.

As an organic solvent which melt | dissolves a perfluoropolyether group containing acrylate compound, it is selected from what does not react with the hard coat material of (A) component, For example, aliphatic hydrocarbons, such as hexane, heptane, isooctane, isododecane, etc. Solvents, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethylene glycol monoethyl ether, Ester solvents such as glycol ether solvents such as ethylene glycol mono-t-butyl ether and propylene glycol monomethyl ether, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate esters; Among these, methyl ethyl ketone, methyl isobutyl ketone, isopropanol and the like are preferably used.

The addition amount of the perfluoropolyether group containing acrylate compound which is (C) component is 0.1-3 mass parts (with solid content in the said solution) with respect to 100 mass parts of hard-coating materials which are (A) component, Preferably it is 0.1- If it adds in the ratio of 2 mass parts, favorable surface characteristics will be obtained. If it is less than the said lower limit, the exudation to a hard-coat surface is difficult and there exists a possibility that a preferable characteristic may not be obtained. Moreover, since the affinity for resin is impaired when the said upper limit is exceeded, there exists a possibility that whitening of an external appearance, a fall of hardness, etc. may arise.

In order to disperse | distribute each component uniformly, the hard coat composition of this invention can be diluted suitably with the solvent etc. which were illustrated as a solvent which can melt | dissolve the said (B) and (C) component. Moreover, additives, such as a leveling agent and a thickener, can also be mix | blended in the range which does not impair the objective of this invention.

The hard coating composition of this invention can provide antifouling property, anti-fingerprint, etc. to the hard-coating surface by mix | blending the above-mentioned two antifouling agents ((B), (C) component) with a hard coating material. Accordingly, it becomes difficult to be noticed even when fingerprints, sebum, perception of sweat or the like, cosmetics, or the like are attached, and provides a hard coating surface having excellent wiping property even when dirt is attached. For this reason, the hard coating composition of the present invention is useful as a curable composition used to form a coating film or a protective film that is impregnated on the surface of an article which may be contaminated by human body by contact with human body or cosmetics. . As such an article, For example, optical recording media represented by optical disks, such as a magneto-optical disk, CD, LD, DVD, Blu-ray disk, hologram recording, etc .; Optical components and optical devices such as spectacle lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers; Various screen display devices such as CRTs, liquid crystal displays, plasma displays, electroluminescent displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, toner-based displays, in particular PCs, mobile phones, portable information terminals, game machines , Digital cameras, digital video cameras, automated teller machines, cash dispensers, vending machines, navigation devices for automobiles, image display devices such as security system terminals, and touch panels (touch sensors, touches) that perform their operations. Screen) image display input device; Input devices such as a mobile phone, a portable information terminal, a portable music player, a portable game machine, a remote controller, a controller, a keyboard, and a panel switch for a vehicle-mounted device; Case surfaces, such as a mobile telephone, a portable information terminal, a camera, a portable music player, and a portable game machine; Paintings and surfaces of automobile exteriors, pianos, luxury furniture, marble, etc .; Made of transparent glass or transparent plastics such as protective glass for exhibitions of art, show windows, showcases, covers for advertisements, covers for photo stands, wrist watches, windshields for automobiles, window glass for trains, aircraft, automobile headlights, tail lamps, etc. Acrylic, polycarbonate, etc.) member, various mirror members, etc. are mentioned.

The hard coat composition (cured film) is formed by applying the hard coat composition of the present invention to the outer surface of the article and curing the ultraviolet ray.

Examples of the coating method include spin coating, immersion coating, and hair coating.

Moreover, as ultraviolet curing conditions, it can harden | cure by irradiating the ultraviolet-ray of wavelength 100-400 nm, Preferably about 200-400 nm about irradiation amount 200-2,000 mJ / cm <^2> , Preferably about 400-1,600 mJ / cm <^2> .

In addition, the thickness of the hard coat cured film may be about 0.1 to 30 µm, preferably about 1 to 10 µm.

[Example]

Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example.

[Examples 1 to 4 and Comparative Example 1]

Preparation of antifouling agent

2.0 g of any of the following antifouling additives (B) and (C) and 8.0 g of methyl isobutyl ketone (MIBK) were weighed into a 10 ml glass sample bottle, sealed with a stopper, and shaken for 30 minutes. It was confirmed that the antifouling additive was completely dissolved, and filtered with a membrane filter made of PTFE (polytetrafluoroethylene) having a pore diameter of 0.45 µm, and the antifouling property containing 20% by mass of the component (B) or the component (C) as an antifouling imparting component. Each imparting agent was prepared.

Antifouling additive of (B) component

B-1

B-2

B-3

Antifouling additive of (C) component

C-1

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _G1 (OCF ₂ ) _H1 OCF _2-

(G1 / H1 = 0.9, G1 + H1 ≒ 45)

C-2

Rf ': -CF ₂ (OCF ₂ CF ₂ ) _G1 (OCF ₂ ) _H1 OCF _2-

(G1 / H1 = 0.9, G1 + H1 ≒ 45)

hard  Preparation of coating compositions

A hard coating composition was prepared in the formulation as shown in Table 1 below.

Evercryl 40: tetrafunctional acrylate, manufactured by Daicel Cytec

Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by Ciba Japan

hard  Preparation of Coating Coating Materials

Each solution (hard coating composition) containing an antifouling agent was spin-coated on a black polymethyl methacrylate plate (5 × 5 × 0.2 cm), and a nitrogen atmosphere with a conveyor type ultraviolet irradiation device (manufactured by Panasonic Denkosha) Ultraviolet rays of 1.6 J / cm ² were irradiated to form a cured film. The film thickness of the hard coat film after hardening was 7 micrometers. The material which coated this hard coat film was used as the test piece, and was used for the following tests.

1. Appearance test

The appearance (color tone, transparency, smoothness) of the hard coat film was visually evaluated. The results are shown in Table 2.

2. Contact angle measurement test

The contact angles of water and oleic acid on the surface of the hard coat film were measured using a contact angle meter (manufactured by Kyowa Chemical Co., Ltd.). The results are shown in Table 2.

3. Fingerprint test

Fingerprint test (fingerprint visibility, fingerprint wiping) was performed by the following method. The test was conducted by five panelists. The evaluation result was made into the evaluation result which was the largest evaluation value among five evaluation values. When two or more evaluation values were the same number, evaluation value was determined by consultation of five people. The results are shown in Table 2.

Fingerprint visibility

The index finger was pressed against the surface of the hard coating film for 3 seconds and then released. The visibility of the attached fingerprint was visually observed from just above the coating film under a three-wavelength fluorescent lamp, and evaluated in the following four steps.

◎ ... Fingerprint could not be recognized.

○ ... Almost no fingerprints were recognized.

△ ... I could recognize some fingerprints.

× ... The fingerprint could be recognized with certainty.

Fingerprint Wipes

The fingerprint attached to the surface of the hard coat film was reciprocated in one direction with a nonwoven fabric (Bencott M-3II (manufactured by Asahi Kasei Co., Ltd.)) to wipe the fingerprint. The state after wiping was visually observed on a 45 ° inclination of the coating film under a three-wavelength fluorescent lamp, and the number of round trips until the fingerprint could not be visually confirmed was evaluated in the following three steps.

 ◎ ... Fingerprints could be wiped less than 3 round trips.

 ○ ... Fingerprints could be wiped over 3 round trips and less than 5 round trips.

 × ... Wipe more than 5 round trips could not wipe fingerprints.

[Examples 5 and 6 and Comparative Examples 2 to 4]

In the same manner as in Example 1, a hard coating composition was prepared in the formulation of Table 3 below.

A hard coat coating material was produced in the same manner as in Example 1, and the properties were measured in the same manner, and the results shown in Table 4 below were obtained.

The synthesis example of B-1-B-3 component is shown below.

Synthesis Example 1

Preparation of the B-1 Component

In a flask equipped with a reflux condenser and thermometer, 43.1 g (0.050 mol) of fluorine-containing hydrosiloxane represented by the following formula (I), 21.1 g of toluene, and 0.04 g of platinum / vinylsiloxane complex toluene solution (containing 0.2 mg of platinum) Input. After heating internal temperature to 60 degreeC, 44.9 g (0.20 mol) of 1-hexadecenes were dripped by the dripping funnel so that internal temperature might not be 70 degreeC or more. After heating at 60 to 70 ° C for 1 hour, 17.2 g (0.20 mol) of 4-pentanol was added dropwise by adjusting the dropping rate so that the internal temperature did not become 70 ° C or higher. After confirming that the absorption derived from the SiH group of the fluorine-containing hydrosiloxane (I) was lost by measurement of the IR spectrum, hexafluoromethaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure, and the following formula (II) was used. 93.8 g of fluorine-containing siloxane represented was obtained.

Next, 44.8 g (0.030 mol) of fluorine-containing siloxane (II) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and 53.7 g of methyl isobutyl ketone were put into the flask equipped with the reflux cooling tube and the thermometer. After heating internal temperature to 50 degreeC, 0.02 g of dibutyltin dilaurate was added, and it was made to react at 50-60 degreeC for 2 hours. After the reaction, 0.90 g of ethanol was added, and after confirming that absorption of NCO was lost by measurement of the IR spectrum, the solvent was distilled off at 25 ° C, whereby 49.9 g of a transparent paste-like product was obtained.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and was a fluorine-containing acrylate compound represented by the following formula.

[Synthesis Example 2]

Preparation of the B-2 Component

In a flask equipped with a reflux cooling tube and a thermometer, 43.1 g (0.050 mol) of fluorine-containing hydrosiloxane represented by the formula (I), 18.8 g of toluene, 0.04 g of a platinum / vinylsiloxane complex toluene solution (containing 0.2 mg as platinum) Was added. After heating internal temperature to 60 degreeC, 33.6 g (0.20 mol) of 1-dodecenes were dripped by the dropping funnel by adjusting the dropping rate so that internal temperature might not be 70 degreeC or more. After heating at 60 to 70 ° C for 1 hour, 17.2 g (0.20 mol) of 4-pentanol was added dropwise by adjusting the dropping rate so that the internal temperature did not become 70 ° C or higher. After confirming that the absorption derived from the SiH group of the fluorine-containing hydrosiloxane (I) was lost by measurement of the IR spectrum, hexafluoromethaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure, and the following formula (III) was used. 80.4 g of fluorine-containing siloxane represented was obtained.

Subsequently, 31.4 g (0.030 mol) of fluorine-containing siloxane (III) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and 40.3 g of methyl isobutyl ketones were charged to the flask equipped with the reflux cooling tube and the thermometer. After heating internal temperature to 50 degreeC, 0.02 g of dibutyltin dilaurate was added, and it was made to react at 50-60 degreeC for 2 hours. After the reaction, 1.55 g of ethanol was added, and after confirming that absorption of NCO was lost by measurement of the IR spectrum, the solvent was distilled off at 25 ° C, whereby 36.4 g of a transparent paste-like product was obtained.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and was a fluorine-containing acrylate compound represented by the following formula.

[Synthesis Example 3]

Preparation of B-3 Ingredients

In a flask equipped with a reflux condenser and a thermometer, 43.1 g (0.050 mol) of fluorine-containing hydrosiloxane represented by the formula (I), 20.6 g of toluene, and 0.04 g of platinum / vinylsiloxane complex toluene solution (containing 0.2 mg of platinum) Input. After heating internal temperature to 60 degreeC, 42.5 g (0.20 mol) of 10-undecenoic acid ethyls were dripped by the dropping funnel by adjusting the dropping rate so that internal temperature might not be 70 degreeC or more. After heating at 60 to 70 ° C for 1 hour, 17.2 g (0.20 mol) of 4-pentanol was added dropwise by adjusting the dropping rate so that the internal temperature did not become 70 ° C or higher. After confirming that the absorption derived from the SiH group of the fluorine-containing hydrosiloxane (I) was lost by measurement of the IR spectrum, hexafluoromethaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure, and the following formula (IV) was used. 93.4 g of fluorine-containing siloxane represented was obtained.

Subsequently, 30.9 g (0.030 mol) of fluorine-containing siloxane (IV) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and 39.8 g of methyl isobutyl ketone were added to the flask equipped with a reflux cooling tube and a thermometer. After heating internal temperature to 50 degreeC, 0.02 g of dibutyltin dilaurate was added, and it was made to react at 50-60 degreeC for 2 hours. After the reaction, 1.58 g of ethanol was added, and after confirming that absorption of NCO was lost by measurement of the IR spectrum, the solvent was distilled off at 25 ° C, whereby 34.2 g of a transparent paste-like product was obtained.

The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum, and was a fluorine-containing acrylate compound represented by the following formula.

Claims (3)

(A) hard coating material,
(B) a fluorine-containing acrylate compound represented by the following general formula (1),

(One)
[In formula, Rf is a C2-C16 fluoroalkylene group, Q is independently a single bond or a C1-C12 divalent organic group, R is independently C6-C20 which may contain an oxygen atom. Is an alkyl group or an aralkyl group having 7 to 20 carbon atoms, R ¹ is independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and R ² is a hydrogen atom or Methyl group, X is the following general formula

(Wherein R ¹² is a divalent hydrocarbon group having 1 to 12 carbon atoms)
Wherein m is an integer of 2 to 8, n is independently 1 or 2]
(C) An acrylate compound having a perfluoropolyether group represented by the following general formula (2)

(2)
[Wherein, Rf 'is independently a divalent perfluoropolyether group having a molecular weight of 500 to 30,000, and may include a branch in the middle, and X ¹ is independently of the following general formula (3)

(3)
{In formula (3), a and c are each 0 or an integer of 1 to 3, b is an integer of 1 to 4, except that a + b + c is 2, 3 or 4, and the arrangement of each repeating unit is random May be, and R ³ is independently the following formula (4):

(4)
(In formula (4), d, e, f, g are integers of 0 or 1 to 20 independently of each other in a range in which the molecular weight of R ³ becomes 45 to 600, and the arrangement of each repeating unit may be random, , R ⁵ is a saturated or unsaturated monovalent hydrocarbon group having 1 to 10 carbon atoms)
R ⁴ is a group represented by the following formula (5)

(5)
(In formula (5), R <^6> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group independently, and R <^7> is bivalent or trivalent which may contain the ether bond or ester bond of C1-C18. Connector, u is 1 or 2)
Is an acryl group or an α substituted acryl group-containing group, Q ¹ and Q ² independently represent a divalent linking group which may contain an ether bond, an ester bond, an amide bond or a urethane bond having 3 to 20 carbon atoms, It may contain an annular structure or a branched structure in the middle, and may be the same or different from each other}
X ² is independently a group represented by the following formula (6)

(6)
(In formula (6), R <^3> , R <^4> , Q <^1> , Q <^2> is as above, h, k are 0 or an integer of 1-3, j is an integer of 1-3, h + j + k is any value of 1 to 3, and the arrangement of each repeating unit may be random)
Z is a divalent group, Z is a divalent organic group which may contain an oxygen atom, a nitrogen atom, and a silicon atom independently of each other, and may have a cyclic structure, an unsaturated bond, and v is 0 or 1 to 5 Is an integer of]
Antifouling imparting hard coating composition containing a main component. The antifouling imparting hard coating composition according to claim 1, wherein the hard coating material of component (A) is an ultraviolet curable acrylic hard coating material. The antifouling imparting hard coating composition according to claim 2, wherein the ultraviolet curable acrylic hard coating material comprises a (meth) acrylic compound and a photopolymerization initiator.