JP5691713B2 - Antifouling agent and hard coat material with antifouling property - Google Patents

Description

  In the present invention, an antifouling property-imparting agent comprising a novel perfluoropolyether group-containing polyether-modified polysiloxane as an antifouling property-imparting component and the antifouling property-imparting agent are imparted. It relates to a hard coat material.

  Resin materials are widely used in various electrical appliances, electronic devices such as personal computers, mobile phones, and the like because they have features that do not rust and are lighter than metals. In addition, it has characteristics such as being hard to break even when compared with glass. Resins with properties such as acrylic resin and polycarbonate resin, such as high hardness and high transparency, can be used alone or as hard coating agents for liquid crystal displays and touch panels. It is used for display bodies.

  In recent years, particularly in the case of an electronic device casing or the like, a highly glossy surface is required from the viewpoint of design. In addition, the number of mobile phone and personal computer displays that have touch panel specifications is increasing, and hard coating materials such as acrylic resin and silicone resin are coated on the outermost surface for the purpose of scratch prevention. .

  Since these frequently touch human hands, dirt such as sebum, sweat, and fingerprints are likely to adhere to them, and when they become traces, the appearance is often impaired and the visibility is often lowered. In particular, in a capacitive touch panel, input by directly touching with a finger is essential, and this problem is unavoidable. Therefore, an improvement in antifouling performance such as fingerprint resistance has been strongly demanded for these hard coat materials.

  Various countermeasures have been studied so far, and roughly divided into the following two methods. One is to form a water- and oil-repellent surface with low surface energy on the hard coat surface using a silicone-based compound or a fluorine-based compound, and apply a treatment that makes it difficult to get dirt such as fingerprints and is easy to remove. Is.

  For example, as disclosed in JP-A-2004-250474 (Patent Document 1), a silane compound having a perfluoropolyether group is treated on the outermost surface of a hard coat, or Japanese Patent No. 3963169 (Patent Document 2). As shown in Fig. 2, anti-fouling performance is achieved by adding a perfluoropolyether urethane acrylate composition to the hard coat composition and forming a water- and oil-repellent surface on the surface by unevenly cross-linking the surface. Is intended to express.

  This method makes it easy to wipe off the attached dirt, but due to its high water and oil repellency, the attached fingerprints form fine droplets and diffusely reflect light, resulting in reduced transparency and visibility. In addition, since the fluorine compound has a low refractive index, there is a large difference in refractive index from sebum or sweat, which is a component of fingerprints, and even a slight adhesion trace may be noticeable.

  In addition, fingerprints include inorganic components such as moisture and salt, organic components such as proteins and fats and oils, and the composition thereof is complicated, and it is difficult to completely prevent such adhesion.

  The other is that it forms a hydrophilic / lipophilic surface with a high affinity for dirt components such as fingerprints on the outermost surface of the hard coat, so that the attached dirt becomes familiar and spreads thinly and becomes inconspicuous. That's it.

  For example, as disclosed in Japanese Patent Application Laid-Open No. 2001-353808 (Patent Document 3), a silane compound having a long-chain alkyl ester group is treated on the outermost surface of a hard coat, or International Publication No. 2009/44912 (Patent) As shown in Reference 4), the visibility of dirt is reduced by adding colloidal silica to an acrylic polymer composition to form a hydrophilic / lipophilic surface on the surface.

  In this method, even if dirt adheres to the surface of the hard coat, the entire surface is wet and spreads, making it difficult to see. Further, by reducing the refractive index of the hard coat to a stain component such as a fingerprint, it is possible to further prevent the visibility from being lowered. However, since the affinity for the dirt component is high, they gradually accumulate or are difficult to wipe off, so that the light transmittance of a display or the like may be lowered.

  Each of these two methods has advantages and disadvantages, and a technique for imparting antifouling properties having both adhesion prevention properties and good visibility has been demanded.

JP 2004-250474 A Japanese Patent No. 3963169 JP 2001-353808 A International Publication No. 2009/44912 Pamphlet

  The present invention has been made in view of the above circumstances, and provides an antifouling property imparting agent that imparts good antifouling properties, and a hard coat material imparted with antifouling properties by using the antifouling property imparting agent. The purpose is to do.

  As a result of intensive studies to achieve the above object, the present inventor has an antifouling agent containing a perfluoropolyether group-containing polyether-modified polysiloxane represented by the following general formula (1) as an antifouling property-imparting component. It has been found that by adding a property imparting agent to a hard coat material as, for example, a fingerprint resistance imparting agent, a hard coat film having a surface that is less noticeable of dirt such as fingerprints and easy to wipe can be obtained. It came to.

（式中、Ｒｆは炭素数１〜１０の直鎖状又は分岐状パーフルオロアルキル基、Ｘはフッ素原子又はトリフルオロメチル基、Ｑは下記式
−ＣＨ₂−，
−ＣＨ₂ＣＨ₂−，
−（ＣＨ₂）_n−Ｏ−ＣＨ₂−，
−ＯＣＨ₂−，
−ＣＯ−ＮＨ−ＣＨ₂−，
−ＣＯ−Ｎ（Ｐｈ）−ＣＨ₂−，
−ＣＯ−ＮＨ−ＣＨ₂ＣＨ₂−，
−ＣＯ−Ｎ（Ｐｈ）−ＣＨ₂ＣＨ₂−，
−ＣＯ−Ｎ（ＣＨ₃）−ＣＨ₂ＣＨ₂ＣＨ₂−，
−ＣＯ−Ｏ−ＣＨ₂−，
−ＣＯ−Ｎ（ＣＨ₃）−Ｐｈ’−，又は
−ＣＯ−ＮＲ³−Ｙ’−
（式中、Ｐｈはフェニル基、Ｐｈ’はフェニレン基であり、ｎは１〜１０の整数である。Ｙ’は−ＣＨ₂−又は下記式

で表される二価の基であり、Ｒ³は水素原子、メチル基又はフェニル基である。）
で示される基、Ｒは水素原子又は炭素数１〜６のアルキル基もしくはアシル基であり、Ｒ¹、Ｒ²は互いに独立に炭素数１〜１０のアルキル基、アリール基又はアラルキル基であり、ａ、ｂ、ｃ、ｄは互いに独立に０〜２００の整数であり、但し、ａ＋ｂ＋ｃ＋ｄは１以上であり、ｅは０又は１であり、ｐ、ｑは互いに独立に０〜５０の整数であり、但し、ｐ＋ｑは２以上であり、ｋは１〜３の整数である。）
〔請求項２〕
防汚性付与成分が、下記一般式（２）：

（式中、Ｑ、Ｒ、ｐ、ｑ、ｐ＋ｑ及びｋは前記と同じである。ｆは２〜２００の整数である。）
で示されるパーフルオロポリエーテル基含有ポリエーテル変性ポリシロキサンである請求項１記載の防汚性付与剤。
〔請求項３〕
前記式中のＱが、
−ＣＨ₂−Ｏ−ＣＨ₂−，
−ＣＯ−ＮＨ−ＣＨ₂−，又は
−ＣＯ−Ｎ（ＣＨ₃）−Ｐｈ’−Ｓｉ（ＣＨ₃）₂−
（式中、Ｐｈ’はフェニレン基である。）
である請求項１又は２記載の防汚性付与剤。
〔請求項４〕
請求項１，２又は３記載の防汚性付与剤を０．０１〜１０．０質量％含有することを特徴とする防汚性が付与されたハードコート材料。
〔請求項５〕
ハードコート材料が、活性エネルギー線硬化型樹脂組成物からなることを特徴とする請求項４に記載の防汚性が付与されたハードコート材料。 Therefore, the present invention provides the antifouling property-imparting agent and hard coat material described below.
[Claim 1]
An antifouling agent containing a perfluoropolyether group-containing polyether-modified polysiloxane represented by the following general formula (1) as an antifouling agent.

(Wherein Rf is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, X is a fluorine atom or a trifluoromethyl group, Q is a group represented by the following formula —CH ₂ —,
—CH ₂ CH ₂ —,
_{- (CH 2) n -O-} CH 2 -,
-OCH ₂ -,
-CO-NH-CH ₂ -,
_{-CO-N (Ph) -CH 2} -,
_{-CO-NH-CH 2 CH 2} -,
_{-CO-N (Ph) -CH 2} CH 2 -,
_{-CO-N (CH 3) -CH} 2 CH 2 CH 2 -,
-CO-O-CH ₂ -,
_{-CO-N (CH 3) -Ph'-} , or -CO-NR ³ -Y'-
(In the formula, Ph is a phenyl group, Ph ′ is a phenylene group, and n is an integer of 1 to 10. Y ′ is —CH ₂ — or the following formula.

R ³ is a hydrogen atom , a methyl group or a phenyl group . )
R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, a, b, c and d are each independently an integer of 0 to 200, provided that a + b + c + d is 1 or more, e is 0 or 1, and p and q are integers of 0 to 50 independently of each other. However, p + q is 2 or more, and k is an integer of 1 to 3. )
[Claim 2]
Antifouling imparting component is represented by the following general formula (2):

(In the formula, Q, R, p, q, p + q and k are the same as described above. F is an integer of 2 to 200.)
The antifouling property-imparting agent according to claim 1, which is a perfluoropolyether group-containing polyether-modified polysiloxane represented by the formula:
[Claim 3]
Q in the above formula is
-CH ₂ -O-CH ₂ -,
-CO-NH-CH ₂ -, or _{-CO-N (CH 3) -Ph'} -Si (CH 3) 2 -
(In the formula, Ph ′ is a phenylene group.)
The antifouling property-imparting agent according to claim 1 or 2.
[Claim 4]
A hard coat material imparted with antifouling property, comprising 0.01 to 10.0% by mass of the antifouling agent according to claim 1, 2, or 3.
[Claim 5]
The hard coat material imparted with antifouling property according to claim 4, wherein the hard coat material comprises an active energy ray-curable resin composition.

  The antifouling property-imparting agent of the present invention is useful for imparting antifouling property, fingerprint resistance, etc. to the hard coat layer surface by being blended with the hard coat material, thereby enabling fingerprints, sebum, sweat, etc. Even if human fats, cosmetics, etc. are attached, it becomes difficult to stand out, and even if dirt is attached, a hard coat surface excellent in wiping property is given.

Perfluoropolyether group-containing polyether-modified polysiloxane The perfluoropolyether group-containing polyether-modified polysiloxane that is the main component of the antifouling property-imparting agent of the present invention is represented by the following general formula (1) as described above. .

  In General formula (1), Rf is a C1-C10, Preferably it is a C1-C3 linear or branched perfluoroalkyl group. When the number of carbon atoms in Rf exceeds the upper limit, the flexibility of the perfluoropolyether chain is impaired, or harmful perfluorooctanoic acid (PFOA) is generated during thermal decomposition.

Examples of such a perfluoroalkyl group Rf include groups represented by the following formulae.
CF ₃ −,
CF ₃ CF ₂ −,
CF ₃ CF ₂ CF ₂ −,
(CF ₃ ) ₂ CF−,
(CF ₃ ) ₂ CFCF ₂ −

  In the formula (1), Q is a divalent organic group having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms. Specifically, methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group and other alkylene groups, phenylene group, etc. It may be an arylene group or a combination of two or more of these groups (alkylene / arylene group, etc.), or one of these groups selected from an ether bond, an amide bond, an ester bond, a diorganosilylene group, etc. Two or more types of structures may be interposed, and examples thereof include a divalent hydrocarbon group that may contain one or more selected from an oxygen atom, a nitrogen atom, and a silicon atom.

で表される二価の基であり、Ｒ³は水素原子又は非置換もしくは置換の、好ましくは炭素数１〜１０の一価炭化水素基である。） Examples of such Q include a group represented by the following formula.
-CH ₂ -,
—CH ₂ CH ₂ —,
_{- (CH 2) n -O-} CH 2 -,
-OCH ₂ -,
-CO-NH-CH ₂ -,
_{-CO-N (Ph) -CH 2} -,
_{-CO-NH-CH 2 CH 2} -,
_{-CO-N (Ph) -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 ³ -Y'-
(In the formula, Ph is a phenyl group, Ph ′ is a phenylene group, and n is an integer of 1 to 10. Y ′ is —CH ₂ — or the following formula.

R ³ is a hydrogen atom or an unsubstituted or substituted, preferably monovalent hydrocarbon group having 1 to 10 carbon atoms. )

  In the formula (1), R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyl group, and examples thereof include a methyl group, an ethyl group, an n-butyl group, and an acetyl group. Of these, a methyl group, an n-butyl group, and an acetyl group are preferable.

In the formula ^{(1), R 1, R} 2 is an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms, e.g., methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, Examples include isobutyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, 2-phenylpropyl group and the like. Among these, a methyl group, an n-butyl group, and a phenyl group are preferable, and a methyl group is particularly preferable. Incidentally, R ^1, R ² is, R ^1, R ² also each be the same group may be a group of heterogeneous, and R ¹ and R ² are different groups be the same group It may be.

In Formula (1), X is a fluorine atom or a trifluoromethyl group.
In the formula (1), a, b, c and d are each independently an integer of 0 to 200, preferably 20 to 100. However, a + b + c + d is 1 or more, preferably 2 to 200, more preferably 3 to 100, and further preferably 5 to 50. e is 0 or 1, and p and q are each independently an integer of 0 to 50, preferably 0 to 30. However, p + q is 2 or more, preferably 3 to 50, more preferably 6 to 40, and still more preferably 9 to 30. k is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

  The perfluoropolyether chain and the polyether chain in the compound of the formula (1) are preferably present at a ratio of 5 to 50% by mass of fluorine atoms in the molecule, more preferably 10 to 40% by mass. %. If it is less than the above lower limit value, it is difficult to exude to the hard coat surface, and desirable characteristics may not be obtained. Further, if the value exceeds the upper limit value, the affinity for the resin is impaired, so that the appearance may be whitened or the hardness may be lowered.

（式中、Ｑ、Ｒ、ｐ、ｑ、ｐ＋ｑ及びｋは前記と同じである。ｆは２〜２００、好ましくは３〜５０、より好ましくは４〜４０の整数である。） The perfluoropolyether group-containing polyether-modified polysiloxane represented by the general formula (1) is a perfluoro represented by the following general formula (2) from the viewpoint of easy availability of raw materials and ease of production. A polyether group-containing polyether-modified polysiloxane is preferred.

(In the formula, Q, R, p, q, p + q and k are the same as described above. F is an integer of 2 to 200, preferably 3 to 50, more preferably 4 to 40.)

Specific examples of the perfluoropolyether group-containing polyether-modified polysiloxane of the present invention include the following.

Process for Producing Perfluoropolyether Group-Containing Polyether-Modified Polysiloxane The perfluoropolyether group-containing polyether-modified polysiloxane, which is the main component of the antifouling agent of the present invention, is a vinyl represented by the following general formula (3). By subjecting a group-containing perfluoropolyether and a tetraorganocyclotetrasiloxane to a hydrosilylation reaction, preferably in the presence of a platinum-based catalyst, a part of the SiH group in the tetrasiloxane is perfluoropolyether-modified cyclotetra After making the siloxane, the remaining SiH groups present in the cyclotetrasiloxane and the allyl group-containing polyether compound represented by the following general formula (4) are preferably hydrosilylated in the presence of a platinum-based catalyst. Can be manufactured.

（式中、Ｒｆ、Ｘ、Ｑ、ａ、ｂ、ｃ、ｄ、ａ＋ｂ＋ｃ＋ｄ及びｅは前記と同じである。）
で示されるビニル基含有パーフルオロポリエーテル（ｉ）中のビニル基を、下記式：

（式中、Ｒ⁴は互いに独立に炭素数１〜１０のアルキル基、アリール基又はアラルキル基であり、上記Ｒ¹、Ｒ²で例示したものと同様のものが例示できる。）
で示されるテトラオルガノシクロテトラシロキサン（ｉｉ）中の４個のＳｉＨ基に対して、好ましくは白金系触媒の存在下で、部分的にヒドロシリル化付加反応させることによって、１分子中にパーフルオロポリエーテル変性シロキサン単位を１〜３個、好ましくは１個又は２個有すると共に、分子中にＳｉＨ基が残存した下記一般式：

（式中、Ｒｆ、Ｘ、Ｑ、Ｒ¹、Ｒ²、ａ、ｂ、ｃ、ｄ、ａ＋ｂ＋ｃ＋ｄ、ｅ及びｋは前記と同じである。）
で示されるＳｉＨ基含有パーフルオロポリエーテル変性シクロテトラシロキサン（ｉｉｉ）を得る。 That is, as a method for producing the perfluoropolyether group-containing polyether-modified polysiloxane of the present invention, a method having the following two-stage production steps is adopted.
<First stage reaction>
The following general formula (3):

(In the formula, Rf, X, Q, a, b, c, d, a + b + c + d and e are the same as described above.)
A vinyl group in the vinyl group-containing perfluoropolyether (i) represented by the following formula:

(Wherein, R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, the R ^1, the same ones as exemplified for R ² can be exemplified.)
Perhydropolysiloxane in one molecule is obtained by subjecting the four SiH groups in the tetraorganocyclotetrasiloxane (ii) represented by the following formula to a partial hydrosilylation addition reaction, preferably in the presence of a platinum-based catalyst. The following general formula having 1 to 3, preferably 1 or 2, ether-modified siloxane units and having SiH groups remaining in the molecule:

(In the formula, Rf, X, Q, R ¹ , R ² , a, b, c, d, a + b + c + d, e and k are the same as above.)
A SiH group-containing perfluoropolyether-modified cyclotetrasiloxane (iii) represented by

（式中、Ｒ、ｐ、ｑ及びｐ＋ｑは前記と同じである。）
で示されるアリル基含有ポリエーテル化合物（ｉｖ）中のアリル基とを、好ましくは白金系触媒の存在下でヒドロシリル化付加反応させることにより、一般式（１）で示されるパーフルオロポリエーテル基含有ポリエーテル変性ポリシロキサン（ｖ）を得る。 <Second stage reaction>
Subsequently, the remaining SiH group in the obtained cyclotetrasiloxane (iii) and the following general formula (4):

(In the formula, R, p, q and p + q are the same as described above.)
A perfluoropolyether group-containing compound represented by the general formula (1) is preferably reacted with an allyl group in the allyl-group-containing polyether compound (iv) represented by formula (1) in the presence of a platinum-based catalyst. A polyether-modified polysiloxane (v) is obtained.

  In the above two-stage production process, the reaction of vinyl group-containing perfluoropolyether (i) and tetraorganocyclotetrasiloxane (ii), which is the first stage reaction, is [siloxane (ii)] / [perfluoro The molar ratio of the molecules of the polyether (i)] is 2.0 or more, more preferably 3.0 or more. By using an excess of tetraorganocyclotetrasiloxane (that is, at a ratio of the above molar ratio ≧ 2.0), the perfluoropolyether-modified cyclotetrasiloxane of k = 1 represented by the general formula (1) is preferentially used. Can be obtained. Although there is no restriction | limiting in particular about the upper limit of this molar ratio, From points, such as manufacturing efficiency (the yield of a target product), it is usually preferable to set it as 10.0 or less especially about 5.0 or less. As described above, k = 1 is a particularly preferable value in the present invention, and the polysiloxane of the present invention has a structure exhibiting the highest surface activity. Excess tetraorganocyclotetrasiloxane can be easily removed by distillation under reduced pressure after completion of the reaction.

  In the two-stage production process, the reaction of the SiH group-containing perfluoropolyether-modified cyclotetrasiloxane (iii) and the allyl group-containing polyether compound (iv), which is the second stage reaction, is an allyl group-containing polyether. SiH group-containing perfluoropolyether-modified cyclotetrasiloxane (iii) has a molar ratio (SiH / allyl ratio) of 0.8 to 1.2, particularly 0.9 to allylic groups in compound (iv). It is preferable to subject the reaction to 1.1, especially 0.9 to 1.0. If the SiH group in the cyclotetrasiloxane is excessive, the affinity with other materials may be impaired, or the SiH group may cause a dehydrogenation reaction to generate hydrogen gas. On the other hand, if the allyl group in the polyether compound is more than the above, the characteristics as a perfluoropolyether may be impaired.

  Further, this production process is not a two-step reaction, but a vinyl group-containing perfluoropolyether (i) of the formula (3), a tetraorganocyclotetrasiloxane (ii) and an allyl group-containing polyether compound of the formula (4) (iv) ) Are subjected to the reaction at once, depending on the reactivity of the vinyl group-containing perfluoropolyether (i) and the allyl group-containing polyether compound (iv) with respect to the SiH group, the vinyl group-containing perfluoropolyether (I) or a cyclotetrasiloxane modified only with the allyl group-containing polyether compound (iv), or the modification ratio of the vinyl group-containing perfluoropolyether (i) and the allyl group-containing polyether compound (iv) Since many different compounds are produced, the product may become turbid.

As a platinum-type catalyst used in the said manufacturing process, the conventionally well-known thing used for hydrosilylation can be used. Generally, platinum or platinum compounds that are relatively easily available are often used because they are precious metal compounds and are expensive. As such a platinum compound, chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinyl siloxane, and metal platinum supported on silica, alumina, carbon or the like can be used. . Examples of platinum group metal catalysts other than platinum compounds include rhodium, ruthenium, iridium, and palladium compounds, such as RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ or the like (wherein Ph is a phenyl group) can be used.

  The platinum catalyst may be used in a catalytic amount. Specifically, the vinyl group-containing perfluoropolyether (i) and tetraorganocyclotetrasiloxane (ii), or the SiH group-containing perfluoropolyether-modified cyclotetrasiloxane ( The amount of 0.1 to 500 ppm (in terms of platinum mass) is preferable with respect to the total mass of iii) and the allyl group-containing polyether compound (iv).

  When performing the said hydrosilylation reaction, you may use a solvent as needed. It is desirable that the solvent dissolves both reaction substrates in the reaction of each stage in both the first and second stage reactions, but even if only one of them is dissolved, hydrosilyl There is no particular limitation as long as it does not inhibit the chemical reaction.

  Examples of such solvents include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane and isododecane, aromatic hydrocarbon compounds such as toluene and xylene, trifluorotoluene, hexafluorometaxylene and the like. Fluoroaromatic hydrocarbon compounds, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- ( Hydrofluoroether compounds such as trifluoromethyl) pentane, chlorofluorocarbon compounds such as Daifroyl (made by Daikin Industries), Fomblin, Galden (made by Solvay Solexis), Demnam (made by Daikin Industries), Krytox (made by DuPont) Perfluoropolyether compounds such as And the like. Among these, hexafluorometaxylene is a vinyl group-containing perfluoropolyether (i) of formula (3), a SiH group-containing perfluoropolyether-modified cyclotetrasiloxane (iii), or an allyl group-containing polyether compound of formula (4). (Iv) and the final product (perfluoropolyether group-containing polyether-modified polysiloxane (v) of the formula (1)) are excellent in solubility and suitable.

  Although the usage-amount of a solvent is suitably selected by the viscosity and preparation amount of each reaction substrate, 10-200 mass parts is preferable with respect to 100 mass parts of total amounts of each reaction substrate, and it is 20-100 mass parts. Is particularly preferred.

  The reaction temperature in the above production process is appropriately determined depending on the amount and type of the solvent, and the reaction in the first stage and the second stage is usually room temperature (25 ° C.) to 140 ° C., preferably 70 to 120 ° C. It is. When the temperature is higher than the specified range, the polyether chain and the cyclic siloxane chain may be thermally decomposed, which is not preferable. The time is not particularly limited, and the reaction may be sufficiently advanced according to the individual reaction conditions.

Antifouling imparting agent The antifouling imparting agent of the present invention can be prepared, for example, as a solution in which the above-mentioned perfluoropolyether group-containing polyether-modified polysiloxane is uniformly dissolved in an organic solvent as an antifouling imparting component. it can. In this case, the concentration of the antifouling property-imparting component in the antifouling property-imparting agent is not particularly limited as long as a uniform solution can be obtained. It may be about 20% by mass, more preferably about 1 to 10% by mass.

  The organic solvent that dissolves the perfluoropolyether group-containing polyether-modified polysiloxane is selected from those that do not react with the hard coat material. For example, aliphatic hydrocarbon solvents such as hexane, heptane, isooctane, and isododecane, toluene , Aromatic hydrocarbon solvents such as xylene, alcohol solvents such as methanol, ethanol, isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether, ethylene glycol mono-t-butyl ether , Glycol ether solvents such as propylene glycol monomethyl ether, ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, etc. And the like. Of these, isododecane, isopropanol, methyl isobutyl ketone and the like are preferably used.

Hard coat material The antifouling property-imparting agent of the present invention is mainly added to a hard coat material and used as an anti-fingerprint agent or the like. The hard coat material is not particularly limited as long as it has transparency, appropriate hardness, and mechanical strength, and can be mixed and cured with the perfluoropolyether group-containing polyether-modified polysiloxane of the present invention.

  The concentration of the antifouling imparting agent added to the hard coat material is not particularly limited, but is usually 0.01 to 10.0% by mass, preferably 0.05 to 8.0% by mass, and more. Preferably, it may be about 0.1 to 5.0% by mass.

  Here, as the hard coat material, a resin curable by irradiation with active energy rays (active energy ray curable resin composition) or a thermosetting resin (thermosetting resin composition) can be used. Consists of a thermosetting silicone hard coat material composed of a partially hydrolyzed oligomer of an alkoxysilane compound, a thermosetting polyurethane hard coat material composed of a thermosetting polyurethane resin, or an acrylic compound having an unsaturated group. An ultraviolet curable acrylic hard coat material is preferred. In particular, for the antifouling property imparting agent of the present invention, an active energy ray-curable resin composition having an excellent balance between solubility and surface exudation property, particularly an ultraviolet curable acrylic hard coat material is preferable.

As the thermosetting silicone hard coat material, a partially hydrolyzed oligomer of an alkoxysilane compound synthesized by a known method can be used. A curing catalyst such as acetic acid and maleic acid is added to this and dissolved in an alcohol or glycol ether organic solvent to obtain a thermosetting silicone hard coat solution. And this is apply | coated to the outer surface of a transparent plastic molding by the coating method in a normal coating material, and a hard-coat coating film is formed by heat-hardening at the temperature of 80-140 degreeC. However, in this case, the setting of the curing temperature below the heat distortion temperature of the plastic molded product is a prerequisite.
Examples of such thermosetting silicone hard coat materials include materials described in WO 2010/110389 pamphlet, JP 2000-273394 A, JP 10-218995 A, and the like. Can do.

The thermosetting polyurethane hard coat material includes, as polyoxyalkylene polyol, polyhydric alcohols having 2 to 3 hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, bisphenol A, trimethylol ethane, trimethylol propane, glycerin, etc., ethylene oxide and other alkylene oxides such as propylene oxide, Polyoxyalkylene polyols to which styrene oxide or the like is added alone or in combination of two or more thereof are used, and organic diisocyanates include, for example, 2,4-tolylene diisocyanate, 2, -Tolylene diisocyanate, 2,4 / 2,6 isomer ratio 65/35 (mass ratio) tolylene diisocyanate, 2,4 / 2,6 isomer ratio 80/20 (mass ratio) tolylene diisocyanate, 4,4 -Diphenylmethane diisocyanate, hexamethylene diisocyanate, metaxylylene diisocyanate, phenyl diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, terminal diisocyanate prepolymer, etc., alone or as a mixture It is possible to use organic metal salts known as catalysts for the urethanization reaction, such as organic lead compounds such as lead naphthenate, lead octylate, lead stearate, tin naphthenate, and octylic acid. A mixture of organic tin compounds such as tin laurate, tetra-n-butyltin, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, etc. By diluting, a thermosetting polyurethane hard coat liquid is prepared. And this is apply | coated to the outer surface of a transparent plastic molding by the coating method in a normal coating material, and a hard-coat coating film is formed by heat-hardening at the temperature of 70-100 degreeC. However, in this case as well, the setting of the curing temperature below the heat distortion temperature of the plastic molded product is a prerequisite.
Examples of such a thermosetting polyurethane hard coat material include materials described in Japanese Patent No. 3650988, Japanese Patent No. 3583073, Japanese Patent No. 4498850, Japanese Patent Application Laid-Open No. 2006-182904, and the like. be able to.

Examples of the ultraviolet curable acrylic hard coat material include an acrylic compound having an unsaturated group such as pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra ( (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 , Dipentaerythritol hexa (meth) acrylate, bifunctional to hexafunctional (meth) acrylic compounds such as sorbitol hexa (meth) acrylate, and these (meth) acrylic compounds are ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, urethane Modified product, epoxy acrylate obtained by adding acrylic acid to epoxy resin, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and hydroxyl group selected from pentaerythritol triacrylate Polyisocyanate selected from (meth) acrylate and hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate Polyfunctional (meth) acrylate mixtures such as urethane acrylates that have been reacted with acrylate, copolymers in which (meth) acryloyl groups are introduced into the side chain of the acrylate copolymer, and the like can be used. In addition, a photopolymerization initiator such as benzoin methyl ether or benzophenone is used in combination. And this is apply | coated to the outer surface of a transparent plastic molding, and a hard-coat coating film is formed by carrying out ultraviolet curing.
Incidentally, curing the ultraviolet curing conditions, wavelength 100 to 400 nm, preferably ultraviolet of about 200 to 400 nm, dose 200~2,000mJ / cm ^2, can be applied, preferably by irradiation of about 400~1,600mJ / cm ² can do.

The antifouling property imparting agent of the present invention is useful for imparting antifouling property, fingerprint resistance and the like to the surface of the hard coat layer by being blended with the hard coat material. As a result, even if human fats such as fingerprints, sebum and sweat, cosmetics, etc. are attached, it becomes inconspicuous, and even if dirt is attached, a hard coat surface excellent in wiping properties is provided. For this reason, the antifouling agent of the present invention is used to form a coating film or a protective film applied to the surface of an article that may be touched by the human body and contaminated by human fat, cosmetics, etc. It is useful as an additive for curable compositions. Such articles include, for example, magneto-optical discs, optical discs such as CD / LD / DVD / Blu-ray discs, optical recording media represented by hologram recording, etc .; glasses lenses, prisms, lens sheets, pellicle films, polarizing plates, Optical components, optical devices such as optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes (VFDs), fields Various screen display devices such as emissive projection display and toner display, especially PCs, mobile phones, personal digital assistants, game machines, digital cameras, digital video cameras, automatic cash withdrawal and deposit devices, automatic cash payments , Vending machines, navigation devices for automobiles, image display devices such as security system terminals, and touch panel (touch sensors, touch screen) type image display input devices that also perform operations thereof; cellular phones, portable information terminals, portable music players , Portable game consoles, remote controllers, controllers, keyboards, input devices such as panel switches for in-vehicle devices; mobile phone, portable information terminals, cameras, portable music players, portable game consoles, etc .; automobile exteriors, pianos Painting and surface of high-quality furniture, marble, etc .; protective glass for exhibition of artworks, show windows, showcases, advertising covers, covers for photo stands, watches, windshields for automobiles, window glass for trains, aircraft, etc., automobile heads Transparent glass such as lights and tail lamps Ltd. or transparent plastic (such as acrylic and polycarbonate) member, various mirrors member, and the like.
In addition, the thickness of the hard coat cured film is usually about 0.1 to 30 μm, preferably about 1 to 10 μm.

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

[Examples 1-3, Comparative Examples 1-3]
Preparation of antifouling property-imparting agent In a 10 ml glass sample bottle, 1.0 g of perfluoropolyether group-containing polyether-modified polysiloxane shown in Table 1 and 9.0 g of 2-propanol were weighed, sealed, and sealed for 30 minutes. Shake. After confirming that the polysiloxane is completely dissolved, the polysiloxane is filtered through a PTFE (polytetrafluoroethylene) membrane filter having a pore diameter of 0.45 μm, and the perfluoropolyether group-containing polyether-modified polysiloxane is added to the antifouling property. As an antifouling property-imparting agent, 10% by mass was prepared.

Preparation of Hard Coat Composition A hard coat composition was prepared using the above-described antifouling property-imparting agent with the following composition. In addition, the composition which does not add an antifouling property imparting agent was also prepared as a blank.
Tetrafunctional acrylate (EBECRYL 40 [manufactured by Daicel Cytec)]: 100 parts by mass propylene glycol monomethyl ether: 137 parts by mass 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan): 3 parts by mass antifouling agent ( Antifouling imparting component concentration: 10% by mass): 10.0 parts by mass

Preparation of hard coat coating material Each solution mixed with an antifouling property imparting agent is spin-coated on a black polycarbonate plate (5 × 5 × 0.2 cm), and a conveyor type ultraviolet irradiation device (manufactured by Panasonic Electric Works Co., Ltd.). Then, a cured film having a thickness of 7 μm was formed by irradiation with 1.6 J / cm ² ultraviolet rays in a nitrogen atmosphere. A polycarbonate plate having a cured film of this hard coat composition was used as a test piece and subjected to the following test.

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

3. Fingerprint resistance test A fingerprint resistance test was performed by the following method. The test was conducted by five panelists. As the evaluation result, the evaluation value that was the highest among the five evaluation values was taken as the evaluation result. When the two evaluation values were the same number, the evaluation result was determined by discussion of five people.
-Fingerprint visibility The index finger was pressed against the hard coat film surface and held for 3 seconds, and then the finger was gently released. The visibility of the attached fingerprint was visually observed from directly above the coating film under a three-wavelength fluorescent lamp and evaluated in the following four stages.
◎… The fingerprint could not be recognized.
○: Almost no fingerprints were recognized.
Δ: Some fingerprints could be recognized.
X: The fingerprint was clearly recognized.

-Fingerprint wiping property The fingerprint adhered to the hard coat film surface was reciprocated in one direction with a non-woven fabric (Bencot M-3II [manufactured by Asahi Kasei Corporation)] to wipe the fingerprint. The state after wiping was visually observed from a 45 ° oblique angle above the coating film under a three-wavelength fluorescent lamp, and the number of reciprocations until the fingerprint could not be viewed was evaluated in the following three stages.
A: The fingerprint could be wiped out in less than 3 round trips.
○: The fingerprint could be wiped off at 3 or more round trips and less than 5 round trips.
×: Fingerprints could not be wiped off even if wiped 5 times or more.

で示されるビニル基含有パーフルオロポリエーテル４３２．２ｇ（［シロキサン］／［パーフルオロポリエーテル］＝４．０（モル比））、白金／ビニルシロキサン錯体トルエン溶液０．３２ｇ（白金として１．６ｍｇ含有）、及びヘキサフルオロメタキシレン５２．８ｇを混合した溶液を仕込んだ。内温を８０℃まで加熱したのち、前述の溶液を内温１１０℃以下で滴下した。９０〜１００℃で１時間加熱し、ＩＲスペクトルでパーフルオロポリエーテル（５）のビニル基由来の吸収が消失していることを確認した後、減圧下でヘキサフルオロメタキシレンと過剰のシクロテトラシロキサンを溜去して、下記式（６）：

で示されるパーフルオロポリエーテル変性ＳｉＨ基含有シクロテトラシロキサン４５５．２ｇを得た。 [Reference Example 1] Production of perfluoropolyether group-containing polyether-modified polysiloxane used in Example 1 Into a flask equipped with a reflux condenser and a thermometer, 1,3,5,7-tetramethylcyclotetrasiloxane 96 was added. .2 g and 105.7 g of hexafluorometaxylene are added, and the following formula (5):

432.2 g of vinyl group-containing perfluoropolyether ([siloxane] / [perfluoropolyether] = 4.0 (molar ratio)), platinum / vinylsiloxane complex toluene solution 0.32 g (1.6 mg as platinum) Containing) and 52.8 g of hexafluorometaxylene were charged. After heating the internal temperature to 80 ° C., the above solution was added dropwise at an internal temperature of 110 ° C. or lower. After heating at 90 to 100 ° C. for 1 hour and confirming the disappearance of the vinyl group-derived absorption of perfluoropolyether (5) by IR spectrum, hexafluorometaxylene and excess cyclotetrasiloxane under reduced pressure The following formula (6):

455.2 g of a perfluoropolyether-modified SiH group-containing cyclotetrasiloxane represented by the formula:

で示されるアリル基含有ポリエーテル化合物１４３．８ｇ（シロキサン（６）中のＳｉＨ基／ポリエーテル化合物（７）中のアリル基＝０．９５（モル比））を８０〜９０℃で滴下した。滴下終了後、８０℃で１時間加熱した後、減圧下でヘキサフルオロメタキシレンを溜去し、白色ペースト状の生成物を２９０．８ｇ得た。 Next, 150.0 g of the cyclotetrasiloxane (6) obtained above and 146.9 g of hexafluorometaxylene were added to a flask equipped with a reflux condenser and a thermometer. After heating the internal temperature to 80 ° C., 0.18 g of platinum / vinylsiloxane complex toluene solution (containing 0.9 mg of platinum) is added, and the following formula (7):

143.8 g of the allyl group-containing polyether compound (SiH group in siloxane (6) / allyl group in polyether compound (7) = 0.95 (molar ratio)) was added dropwise at 80 to 90 ° C. After completion of dropping, the mixture was heated at 80 ° C. for 1 hour, and then hexafluorometaxylene was distilled off under reduced pressure to obtain 290.8 g of a white paste product.

で示される分子中のフッ素原子の質量割合が３１．７％の化合物であった。 The product obtained above was analyzed by ¹ H-NMR (manufactured by JEOL Ltd., JNM-NS50, the same applies below) and IR spectrum (KBr method, manufactured by Horiba, Ltd., FT-730, applies hereinafter). As a result of analysis by measurement, the following formula (8):

The mass ratio of the fluorine atom in the molecule | numerator shown by 31.7% was a compound.

で示されるビニル基含有パーフルオロポリエーテル４３４．１ｇ（［シロキサン］／［パーフルオロポリエーテル］＝４．０（モル比））、白金／ビニルシロキサン錯体トルエン溶液０．３２ｇ（白金として１．６ｍｇ含有）、及びヘキサフルオロメタキシレン５３．０ｇを混合した溶液を仕込んだ。内温を８０℃まで加熱したのち、前述の溶液を内温１１０℃以下で滴下した。９０〜１００℃で１時間加熱し、ＩＲスペクトルでパーフルオロポリエーテル（９）のアリル基由来の吸収が消失していることを確認した後、減圧下でヘキサフルオロメタキシレンと過剰のシクロテトラシロキサンを溜去して、下記式（１０）：

で示されるパーフルオロポリエーテル変性ＳｉＨ基含有シクロテトラシロキサン４５６．３ｇを得た。 Reference Example 2 Production of perfluoropolyether group-containing polyether-modified polysiloxane used in Example 2 1,3,5,7-tetramethylcyclotetrasiloxane 96 was placed in a flask equipped with a reflux condenser and a thermometer. .2 g and 106.1 g of hexafluorometaxylene are added, and the following formula (9):

434.1 g of vinyl group-containing perfluoropolyether represented by ([siloxane] / [perfluoropolyether] = 4.0 (molar ratio)), 0.32 g of platinum / vinylsiloxane complex toluene solution (1.6 mg as platinum) Containing) and 53.0 g of hexafluorometaxylene were mixed. After heating the internal temperature to 80 ° C., the above solution was added dropwise at an internal temperature of 110 ° C. or lower. After heating at 90 to 100 ° C. for 1 hour and confirming that allyl group-derived absorption of perfluoropolyether (9) has disappeared by IR spectrum, hexafluorometaxylene and excess cyclotetrasiloxane under reduced pressure The following formula (10):

456.3 g of a perfluoropolyether-modified SiH group-containing cyclotetrasiloxane represented by the formula:

で示されるアリル基含有ポリエーテル化合物７５．０ｇ（シロキサン（１０）中のＳｉＨ基／ポリエーテル化合物（１１）中のアリル基＝０．９５（モル比））を８０〜９０℃で滴下した。滴下終了後、８０℃で１時間加熱した後、減圧下でヘキサフルオロメタキシレンを溜去し、白色ペースト状の生成物を２２４．０ｇ得た。 Next, 150.0 g of the cyclotetrasiloxane (10) obtained above and 112.5 g of hexafluorometaxylene were added to a flask equipped with a reflux condenser and a thermometer. After heating the internal temperature to 80 ° C., 0.18 g of platinum / vinylsiloxane complex toluene solution (containing 0.9 mg of platinum) is added, and the following formula (11):

75.0 g of the allyl group-containing polyether compound (SiH group in siloxane (10) / allyl group in polyether compound (11) = 0.95 (molar ratio)) was added dropwise at 80 to 90 ° C. After the completion of the dropwise addition, the mixture was heated at 80 ° C. for 1 hour, and then hexafluorometaxylene was distilled off under reduced pressure to obtain 224.0 g of a white paste product.

で示される分子中のフッ素原子の質量割合が４２．９％の化合物であった。 As a result of analyzing the product obtained above by measurement of ¹ H-NMR and IR spectrum, the following formula (12):

The mass ratio of the fluorine atom in the molecule | numerator shown by 42.9% was a compound.

で示されるアリル基含有パーフルオロポリエーテル１０３．３ｇ（［シロキサン］／［パーフルオロポリエーテル］＝４．０（モル比））、白金／ビニルシロキサン錯体トルエン溶液０．３２ｇ（白金として１．６ｍｇ含有）、及びヘキサフルオロメタキシレン２０．０ｇを混合した溶液を仕込んだ。内温を８０℃まで加熱したのち、前述の溶液を内温１１０℃以下で滴下した。９０〜１００℃で１時間加熱し、ＩＲスペクトルでパーフルオロポリエーテル（１３）のアリル基由来の吸収が消失していることを確認した後、減圧下でヘキサフルオロメタキシレンと過剰のシクロテトラシロキサンを溜去して、下記式（１４）：

で示されるパーフルオロポリエーテル変性ＳｉＨ基含有シクロテトラシロキサン１２７．３ｇを得た。 [Reference Example 3] Production of perfluoropolyether group-containing polyether-modified polysiloxane used in Example 3 1,3,5,7-tetramethylcyclotetrasiloxane 96 was placed in a flask equipped with a reflux condenser and a thermometer. .2 g and 39.9 g of hexafluorometaxylene are added, and the following formula (13) is added to the dropping funnel:

Allyl group-containing perfluoropolyether 103.3 g ([siloxane] / [perfluoropolyether] = 4.0 (molar ratio)), platinum / vinylsiloxane complex toluene solution 0.32 g (1.6 mg as platinum) Containing) and 20.0 g of hexafluorometaxylene were mixed. After heating the internal temperature to 80 ° C., the above solution was added dropwise at an internal temperature of 110 ° C. or lower. After heating at 90 to 100 ° C. for 1 hour and confirming that allyl group-derived absorption of perfluoropolyether (13) has disappeared by IR spectrum, hexafluorometaxylene and excess cyclotetrasiloxane under reduced pressure The following formula (14):

127.3 g of a perfluoropolyether-modified SiH group-containing cyclotetrasiloxane represented by the formula:

で示されるアリル基含有ポリエーテル化合物１１８．０ｇ（シロキサン（１４）中のＳｉＨ基／ポリエーテル化合物（１５）中のアリル基＝０．９５（モル比））を８０〜９０℃で滴下した。滴下終了後、８０℃で１時間加熱した後、減圧下でヘキサフルオロメタキシレンを溜去し、淡褐色油状の生成物を２１６．９ｇ得た。 Next, 100.0 g of the cyclotetrasiloxane (14) obtained above and 109.0 g of hexafluorometaxylene were charged into a flask equipped with a reflux condenser and a thermometer. After heating the internal temperature to 80 ° C., 0.18 g of a platinum / vinylsiloxane complex toluene solution (containing 0.9 mg of platinum) is added, and the following formula (15):

118.0 g of the allyl group-containing polyether compound (SiH group in siloxane (14) / allyl group in polyether compound (15) = 0.95 (molar ratio)) was added dropwise at 80 to 90 ° C. After completion of the dropwise addition, the mixture was heated at 80 ° C. for 1 hour, and then hexafluorometaxylene was distilled off under reduced pressure to obtain 216.9 g of a light brown oily product.

で示される分子中のフッ素原子の質量割合が２６．７％の化合物であった。 As a result of analyzing the product obtained above by ¹ H-NMR and IR spectrum, the following formula (16):

The mass ratio of the fluorine atom in the molecule | numerator shown by 26.7% was a compound.

Claims (5)

An antifouling agent containing a perfluoropolyether group-containing polyether-modified polysiloxane represented by the following general formula (1) as an antifouling agent.

(Wherein Rf is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms, X is a fluorine atom or a trifluoromethyl group, Q is a group represented by the following formula —CH ₂ —,
—CH ₂ CH ₂ —,
_{- (CH 2) n -O-} CH 2 -,
-OCH ₂ -,
-CO-NH-CH ₂ -,
_{-CO-N (Ph) -CH 2} -,
_{-CO-NH-CH 2 CH 2} -,
_{-CO-N (Ph) -CH 2} CH 2 -,
_{-CO-N (CH 3) -CH} 2 CH 2 CH 2 -,
-CO-O-CH ₂ -,
_{-CO-N (CH 3) -Ph'-} , or -CO-NR ³ -Y'-
(In the formula, Ph is a phenyl group, Ph ′ is a phenylene group, and n is an integer of 1 to 10. Y ′ is —CH ₂ — or the following formula.

R ³ is a hydrogen atom , a methyl group or a phenyl group . )
R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group, R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, a, b, c and d are each independently an integer of 0 to 200, provided that a + b + c + d is 1 or more, e is 0 or 1, and p and q are integers of 0 to 50 independently of each other. However, p + q is 2 or more, and k is an integer of 1 to 3. ) Antifouling imparting component is represented by the following general formula (2):

(In the formula, Q, R, p, q, p + q and k are the same as described above. F is an integer of 2 to 200.)
The antifouling property-imparting agent according to claim 1, which is a perfluoropolyether group-containing polyether-modified polysiloxane represented by the formula: Q in the above formula is
-CH ₂ -O-CH ₂ -,
-CO-NH-CH ₂ -, or _{-CO-N (CH 3) -Ph'} -Si (CH 3) 2 -
(In the formula, Ph ′ is a phenylene group.)
The antifouling property-imparting agent according to claim 1 or 2.   A hard coat material imparted with antifouling property, comprising 0.01 to 10.0% by mass of the antifouling agent according to claim 1, 2, or 3.   The hard coat material imparted with antifouling property according to claim 4, wherein the hard coat material comprises an active energy ray-curable resin composition.