JP5803745B2 - Fluorine-containing organosilicon compound, method for producing the same, antifouling agent and hard coat material - Google Patents

Description

The present invention relates to a novel fluorine-containing organosilicon compound and a method for producing the same, and more specifically, a novel siloxane compound having a fluorine-containing organic group, a hydrocarbon group, and a (meth) acryl group in the same molecule, and It relates to the manufacturing method.
The present invention also relates to an antifouling imparting agent in which fingerprints are not noticeable when this fluorine-containing organosilicon compound is added, and a hard coat material imparted with antifouling property by using the antifouling imparting agent. .

  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 a hard coat material 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. The first is to use a silicone compound or fluorine compound to form a water / oil repellant surface with low surface energy on the hard coat surface, and to apply a process that is difficult to get fingerprints and other dirt. 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 crosslinking 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. Since the fluorine compound has a low refractive index, there is a large difference in refractive index from sebum, sweat, and the like, which are components of fingerprints, and even a slight adhesion trace may be noticeable.
In addition, the attached fingerprint contains 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 it has a high affinity for dirt components, they gradually accumulate or are difficult to wipe off, so that the light transmittance of a display or the like may be reduced.

（式中、Ｒｆはパーフルオロアルキル基またはパーフルオロアルキルエーテル基を示し、Ｍｅはメチル基を示し、ｌは０又は１の整数、ｍは６〜２０の整数、ｎは１〜３の整数を示す。）
しかし、上記含フッ素有機ケイ素化合物は、ハードコート材と結合する官能基が結合していないため、表面に付着している添加剤が拭き取られると指紋を目立ちにくくする効果がなくなってしまうという問題点があった。 In order to improve these, JP-B-7-20975 and JP-A-7-102276 (Patent Documents 5 and 6) propose fluorine-containing organosilicon compounds having the following general formula.

(In the formula, Rf represents a perfluoroalkyl group or a perfluoroalkyl ether group, Me represents a methyl group, l represents an integer of 0 or 1, m represents an integer of 6 to 20, and n represents an integer of 1 to 3. Show.)
However, since the functional group that binds to the hard coat material is not bonded to the fluorine-containing organosilicon compound, there is a problem that the effect of making the fingerprint less noticeable disappears when the additive adhering to the surface is wiped off. There was a point.

JP 2004-250474 A Japanese Patent No. 3963169 JP 2001-353808 A International Publication No. 2009/44912 Pamphlet Japanese Patent Publication No. 7-20975 JP-A-7-102276

The present invention has been made in view of the above circumstances, and has both the characteristics of a fluorine-containing organic group such as water repellency and releasability and the characteristics of a hydrocarbon group such as lipophilicity, and is heat resistant. Another object of the present invention is to provide a novel fluorine-containing organosilicon compound having excellent hydrolysis resistance and a method for producing the same.
Furthermore, it aims at providing the hard-coat material provided with antifouling property by using the antifouling property imparting agent which provides favorable antifouling property, and this antifouling property imparting agent.

［式中、Ｒｆは炭素数２〜１６のフルオロアルキレン基又は炭素数３〜２００の２価フルオロポリエーテル基であり、Ｑは独立に単結合又は炭素数１〜１２の２価の有機基であり、Ｒは独立に酸素原子を含んでもよい炭素数６〜２０のアルキル基又は炭素数７〜２０のアラルキル基であり、Ｒ¹は互いに独立に炭素数１〜６のアルキル基、炭素数６〜１０のアリール基又は炭素数７〜１０のアラルキル基であり、Ｒ²は水素原子又はメチル基であり、Ｘは下記一般式

（式中、Ｒ⁴は炭素数１〜１２の２価炭化水素基である。）
で示される基であり、ｍは２〜８の整数であり、ｎは独立に０、１又は２である。］
で示される新規な含フッ素有機ケイ素化合物を後述する方法で得ることができ、またこの含フッ素有機ケイ素化合物を防汚性付与成分として含有する防汚性付与剤を、例えば耐指紋性付与剤としてハードコート材料に添加することで、指紋などの汚れが目立ちにくく、かつ拭き取り易い表面を有するハードコート皮膜が得られることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have introduced a (meth) acryl group into the molecule and studied the molecular structure, whereby the following general formula (1)

[Wherein, Rf is a fluoroalkylene group having 2 to 16 carbon atoms or a divalent fluoropolyether group having 3 to 200 carbon atoms, and Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms. And R is an alkyl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may independently contain an oxygen atom, and R ¹ is independently an alkyl group having 1 to 6 carbon atoms and 6 carbon atoms. Is an aryl group having 10 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ² is a hydrogen atom or a methyl group, and X is the following general formula

(In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms.)
, M is an integer of 2 to 8, and n is independently 0, 1 or 2. ]
A novel fluorine-containing organosilicon compound represented by the following can be obtained by a method described later, and an antifouling property-imparting agent containing this fluorine-containing organosilicon compound as an antifouling property-imparting component is used, for example, as a fingerprint resistance imparting agent. By adding to the hard coat material, it has been found that a hard coat film having a surface in which dirt such as fingerprints is hardly noticeable and easy to wipe off can be obtained, and the present invention has been made.

［式中、Ｒｆは−Ｃ _a Ｆ _2a −（ａは２〜１０の整数）で示されるフルオロアルキレン基であり、Ｑは独立に炭素数１〜１２のアルキレン基であり、Ｒは独立に酸素原子を含んでもよい炭素数６〜２０のアルキル基又は炭素数７〜２０のアラルキル基であり、Ｒ¹は互いに独立に炭素数１〜６のアルキル基、炭素数６〜１０のアリール基又は炭素数７〜１０のアラルキル基であり、Ｒ²は水素原子又はメチル基であり、Ｘは下記一般式

（式中、Ｒ⁴は炭素数１〜１２の２価炭化水素基である。）
で示される基であり、ｍは２〜８の整数であり、ｎは０、１又は２である。］
〔２〕
下記一般式（２）

（式中、Ｒｆ、Ｑ、Ｒ¹は式（１）と同じである。）
で示されるヒドロシロキシ基含有含フッ素化合物と、炭素数６〜２０のα−オレフィン系化合物と、アルケノールとを、白金系触媒の存在下、ヒドロシリル化反応させることによって含フッ素有機基変性シロキサンとした後、該シロキサンと、（メタ）アクリル基含有イソシアネート化合物とを反応させることを特徴とする〔１〕に記載の含フッ素有機ケイ素化合物の製造方法。
〔３〕
〔１〕に記載の含フッ素有機ケイ素化合物を防汚性付与成分として含有することを特徴とする防汚性付与剤。
〔４〕
〔３〕に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。
〔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〔４〕に記載の防汚性が付与されたハードコート材料。
Accordingly, the present invention provides the following fluorine-containing organosilicon compound, a process for producing the same, an antifouling agent and a hard coat material.
[1]
A fluorine-containing organosilicon compound represented by the following general formula (1).

Wherein, Rf is -C _a F _2a - _(a is an integer of 2 to 10) is a fluoroalkylene group represented by, Q is an alkylene group having a carbon number of 1 to 12 independently, oxygen R is independently An alkyl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may contain an atom, and R ¹ is independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group of 7 to 10, R ² is a hydrogen atom or a methyl group, and X is the following general formula

(In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms.)
Wherein m is an integer of 2 to 8, and n is 0 , 1 or 2. ]
[2 ]
The following general formula (2)

(In the formula, Rf, Q and R ¹ are the same as those in the formula (1).)
A hydrosiloxy group-containing fluorine-containing compound, an α-olefin compound having 6 to 20 carbon atoms, and an alkenol were hydrosilylated in the presence of a platinum catalyst to obtain a fluorine-containing organic group-modified siloxane. Then, this siloxane and the (meth) acryl group containing isocyanate compound are made to react, The manufacturing method of the fluorine-containing organosilicon compound as described in [1] characterized by the above-mentioned.
[ 3 ]
An antifouling imparting agent comprising the fluorine-containing organosilicon compound according to [1] as an antifouling imparting component.
[ 4 ]
A hard coat material imparted with antifouling property, comprising 0.01 to 10.0% by mass of the antifouling property imparting agent according to [ 3 ].
[ 5 ]
The hard coat material imparted with antifouling properties as described in [ 4 ], wherein the hard coat material comprises an active energy ray-curable resin composition.

  The fluorine-containing organic silicon compound of the present invention has both the characteristics of a fluorine-containing organic group and the characteristics of a hydrocarbon group, and is excellent in heat resistance and hydrolysis resistance. Further, the antifouling property imparting agent of the present invention using this fluorine-containing organosilicon compound is useful for imparting antifouling property, fingerprint resistance, etc. to the hard coat surface by being blended with the hard coat material. This makes it harder to notice even if human fat such as fingerprints, sebum, sweat, or cosmetics adheres to it, and even if dirt adheres to it, it has excellent wiping properties and has a hard coat surface with excellent durability. give.

2 is an IR spectrum of the compound obtained in Example 1.

Fluorine-containing organosilicon compound The fluorine-containing organosilicon compound which 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 the general formula (1), Rf is a linear or branched fluoroalkylene group having 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, or 3 to 200 carbon atoms, preferably Is a divalent fluoropolyether group having 6 to 100 carbon atoms for imparting properties such as water repellency / oil repellency, antifouling property, and exuding property to the hard coat surface to the compound. When the number of carbon atoms in Rf exceeds the above upper limit, compatibility with the hard coat material is impaired, and there is a possibility that whitening or poor curing may occur.

Examples of such fluorine-containing groups Rf include those shown below.
−C _a F _2a −,
_{- (CF 2) b -CH 2} - (CF 2) c -,
_{- (C g F 2g O)} d - (CF 2 O) e - (CF 2) f -
(Wherein, a is an integer of 2 to 10, preferably 2 to 8, b is an integer of 1 to 8, preferably 2 to 6, c is an integer of 1 to 8, preferably 2 to 6, d and f are 0, 1 or 2, preferably 0 or 1, e is an integer of 1 to 10, preferably 1 to 8, g is an integer of 2 to 6, preferably 2 to 4. Each repeating unit is bonded at random. May be.)

Among these, those shown below can be preferably used.
−C _a F _2a −,
_{- (C g F 2g O)} d - (CF 2 O) e - (CF 2) f -
(Wherein a, d, e, f and g are the same as above)

  In the general formula (1), Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms. Specific examples of the divalent organic group include methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), hexamethylene group, octamethylene group, and the like. It may be an alkylene group, an arylene group such as a phenylene group, or a combination of two or more of these groups (an alkylene / arylene group, etc.), or an ether bond, an amide bond, an ester bond, or a diorganosilylene group. In addition to the above, it may contain one or more structures selected from oxygen atoms, nitrogen atoms, and silicon atoms. The divalent hydrocarbon group which may be sufficient is mentioned.

で表される２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１価炭化水素基である。） Examples of such a divalent organic group of Q include groups represented by the following formulae.
-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 ³ -Y-,
—CO—NR ³ —Y—CH ₂ CH ₂ —
(In the formula, Ph is a phenyl group, Ph ′ is a phenylene group, t is an integer of 1 to 10. Y is —CH ₂ — or the following formula.

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

Here, examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms of R ³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert group -Alkyl group such as butyl group, pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, An aryl group such as a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group, or a part or all of hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, and chlorine, a cyano group (N Substituted with ≡C-), such as chloromethyl, chloropropyl, bromoethyl, trifluoropropyl , Cyanoethyl group and the like.

  In the formula (1), R independently represents an alkyl group having 6 to 20 carbon atoms, preferably 8 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms, which may contain an oxygen atom. The group is introduced in order to make the oil component of dirt and fingerprints compatible and make the dirt and fingerprints less noticeable. For example, as an alkyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tetradecyl group (myristyl group), hexadecyl group (palmityl group), octadecyl group (stearyl group) Group), an eicosyl group, and the like, and examples of the aralkyl group include a benzyl group, a phenylethyl group, and a tolylethyl group. In addition, one or two or more of an ether bond oxygen atom (—O—), a carbonyl bond (—CO—), an ester bond (—COO—), etc. may be interposed in these. Examples include an ethyl acid group, an ethyl octylate group, and an ethoxypentyl group. A plurality of R may be the same group or different groups.

In Formula (1), R ¹ is independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, or 7 to 7 carbon atoms. 10, preferably an aralkyl group having 7 to 8 carbon atoms, which is introduced to impart lipophilicity, compatibility with a hard coat material, and the like to the compound. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group and the like can be mentioned. Among these, a methyl group, an n-butyl group, and a phenyl group are preferable, and a methyl group is particularly preferable. R ¹ may be the same group or different groups.
R ² is a hydrogen atom or a methyl group.

（式中、Ｒ⁴はメチレン基、エチレン基、プロピレン基等のアルキレン基、フェニレン基、ナフチレン基等のアリーレン基などの炭素数１〜１２の２価炭化水素基である。） In the formula (1), X is represented by the following general formula.

(In the formula, R ⁴ is a C 1-12 divalent hydrocarbon group such as an alkylene group such as a methylene group, an ethylene group or a propylene group, or an arylene group such as a phenylene group or a naphthylene group.)

  In the formula (1), n is independently 0, 1 or 2, preferably 2. m is an integer of 2-8, preferably an integer of 2-6.

  The fluoroalkylene group and / or the divalent fluoropolyether group Rf in the compound of the formula (1) is a fluorine atom in the molecule, particularly when the fluorine-containing organic silicon compound is used for an antifouling property imparting agent or a hard coat material. It is preferable that it exists in the ratio used as the mass ratio of an atom becoming 3-30 mass%, More preferably, it is a ratio used as 5-20 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.

（但し、ｘ＋ｙ（平均）＝５） Specific examples of the fluorine-containing organosilicon compound represented by the general formula (1) include those shown below.

(However, x + y (average) = 5)

（式中、Ｒｆ、Ｑ、Ｒ¹は上記と同じである。）
で示されるヒドロシロキシ基含有含フッ素化合物と、式（１）のＲ基から水素原子１個を除いた残基に対応する炭素数６〜２０のα−オレフィン系化合物と、アルケノールとを、好ましくは白金系触媒の存在下、従来公知の方法によりヒドロシリル化付加反応させることによって含フッ素有機基変性シロキサンとした後、該シロキサンと、（メタ）アクリル基含有イソシアネート化合物とを反応させることで製造することができる。 Production method of fluorine-containing organic silicon compound The fluorine-containing organic silicon compound represented by the general formula (1) of the present invention can be easily produced by a known method. For example, the following general formula (2)

(In the formula, Rf, Q, and R ¹ are the same as above.)
Preferably a hydrosiloxy group-containing fluorine-containing compound represented by formula (1), an α-olefin compound having 6 to 20 carbon atoms corresponding to a residue obtained by removing one hydrogen atom from the R group of formula (1), and an alkenol. Is produced by reacting the siloxane with a (meth) acrylic group-containing isocyanate compound after hydrosilylation addition reaction by a conventionally known method in the presence of a platinum-based catalyst to form a fluorinated organic group-modified siloxane. be able to.

  Here, the α-olefin compound is an olefin obtained by removing one hydrogen atom from R in the formula (1), preferably an olefin having a vinyl group at one end. When both end vinyl group-containing olefins are used, a cross-linking reaction may occur between molecules during the hydrosilylation addition reaction. When the product is polymerized to gel or used as an antifouling agent, There is a risk that the solubility in the hard coat material may decrease. Specific examples of the α-olefin compound having 6 to 20 carbon atoms include 1-hexadecene, 1-dodecene, 10-undecenoic acid ethyl, ethoxy-1-pentene and the like.

Moreover, as an alkenol, what is shown by a following formula can be illustrated.
HO—R ⁵ —CH═CH ₂
(In the formula, R ⁵ is a single bond or an alkylene group such as a methylene group having 1 to 6 carbon atoms, an ethylene group, a propylene group, or a butylene group.)

  The hydrosiloxy group-containing fluorine-containing compound and the α-olefin compound having 6 to 20 carbon atoms are reacted so that at least one SiH group of the hydrosiloxy group-containing fluorine-containing compound remains. The molar ratio (Vi / SiH ratio) between the SiH group of the siloxy group-containing fluorine-containing compound and the terminal vinyl group of the α-olefin compound is 0.167 to 0.833, more preferably 0.333 to 0.667. Thus, it is preferable to obtain a fluorine-containing organic group-modified siloxane having at least one, preferably 1 to 3, SiH groups. If the α-olefin compound is excessive, the turbidity may occur when added to the hard coat material.

  The remaining SiH groups are then reacted with alkenol. The fluorine-containing organic group-modified siloxane having at least one SiH group obtained by reacting the hydrosiloxy group-containing fluorine-containing compound and the α-olefin compound, and alkenol are the SiH group and alkenol of the fluorine-containing organic group-modified siloxane. The fluorine-containing organic group modification having no SiH group is carried out by carrying out the reaction so that the molar ratio (Vi / SiH ratio) to vinyl group is 0.2 to 1.5, particularly 0.333 to 1.2. It is preferred to obtain siloxane.

In the above reaction, a conventionally known platinum group metal catalyst used for hydrosilylation can be used as the platinum-based catalyst. 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 amount of the platinum-based catalyst used may be a catalytic amount. The amount of the platinum-based catalyst is 0.1 to 500 ppm (platinum conversion) with respect to 100 parts by mass of the total amount of the hydrosiloxy group-containing fluorine-containing compound and the α-olefin compound or alkenol. preferable.

  The reaction temperature is appropriately determined depending on the amount and type of the solvent, and is usually from room temperature to 200 ° C, preferably from 40 to 100 ° C. The reaction time is not particularly limited, and it is sufficient that the reaction proceeds sufficiently according to individual reaction conditions.

  When performing the hydrosilylation reaction of each said step, you may use a solvent as needed. It is desirable that the solvent dissolves all of the hydrosiloxy group-containing fluorine-containing compound, the α-olefin compound and the alkenol, but even if only one of them dissolves, the hydrosilylation reaction is inhibited. If it does not do, it will not be restricted in particular. The amount of the solvent used is appropriately selected depending on the viscosity and amount of the hydrosiloxy group-containing fluorine-containing compound, α-olefin compound and alkenol and the resulting fluorine-containing organic group-modified siloxane, but the hydrosiloxy group-containing fluorine-containing compound, 10-200 mass parts is preferable with respect to 100 mass parts of total amounts of an α-olefin compound and alkenol, and 20-20 mass parts is particularly preferable.

  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 difloyl (Daikin Industries), hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 2- (trimethyl) Siloxy) -1,1 Chain siloxanes such as 1,2,3,3,3-heptamethyltrisiloxane, cyclic siloxanes such as octamethylcyclopentasiloxane and decamethylcyclopentasiloxane, fomblin, Galden (manufactured by Solvay Solexis), demnum (Daikin) And perfluoropolyether compounds such as Krytox (manufactured by DuPont). Of these, toluene, xylene, and hexafluorometaxylene are preferable because they are excellent in the solubility of hydrosiloxy group-containing fluorine-containing compounds, α-olefin compounds, alkenols, and generated fluorine-containing organic group-modified siloxanes.

  The resulting fluorine-containing organic group-modified siloxane is reacted with a (meth) acryl group-containing isocyanate compound. At this time, the amount of alcohol in the fluorinated organic group-modified siloxane is quantified, and the amount of the (meth) acrylic group-containing isocyanate compound is reacted with 1.2 to 3 times the molar amount, preferably 1.5 to 2 times the molar amount. It is desirable to make it.

（式中、Ｒ²、Ｒ⁴は上記と同じである。） Here, examples of the (meth) acrylic group-containing isocyanate compound include those represented by the following formula.

(Wherein R ² and R ⁴ are the same as above)

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

  A suitable catalyst may also be added to increase the rate of reaction. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, alkyltin ester compounds such as stannous dioctanoate, tetraisopropoxytitanium, tetra- n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and other titanates or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxy Monoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate) G), but zirconium tetraacetyl acetonate, zirconium chelate compound and the like, these are not limited to one type thereof may be used as a mixture of two or more kinds. The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.

  Moreover, you may dilute with a suitable solvent as needed and may react. As such a solvent, any solvent that does not react with isocyanate and hydroxyl group can be used without particular limitation. Specifically, ethers such as tetrahydrofuran, diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones, esters such as ethyl acetate and butyl acetate, and aromatic hydrocarbon solvents such as toluene and xylene.

  The novel fluorine-containing organosilicon compound of the present invention is excellent in water and oil repellency, chemical resistance, hydrolysis resistance, lubricity, releasability, etc., and compared with conventional fluorine-containing organic group-containing compounds. Excellent compatibility with substances such as organic solvents or paints, cosmetics, various coating materials, etc., so that cosmetic additives, mold release agents that improve mold release during molding, Additives for imparting oil repellency, additives for improving the wear resistance of lubricating oils, aids for improving the colorability and dispersibility of pigments in the dye and pigment industry, flowability for correcting paint defects In addition, it is useful as an agent for imparting dent prevention properties.

Antifouling imparting agent The antifouling imparting agent of the present invention is prepared, for example, as a solution in which the fluorine-containing organosilicon compound represented by the general formula (1) described above is uniformly dissolved in an organic solvent as an antifouling imparting component. be able to. 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 is obtained, but usually 1 to 50% by mass, preferably 5 to 30% by mass, More preferably, it may be about 5 to 20% by mass.

  The organic solvent that dissolves the fluorine-containing organosilicon compound is selected from those that do not react with the hard coat material to which the antifouling property-imparting agent is added, for example, aliphatic hydrocarbon solvents such as hexane, heptane, isooctane, isododecane, 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, ethylene glycol mono-t- Examples include glycol ether solvents such as butyl ether and propylene glycol monomethyl ether, and ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. 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 with the above fluorine-containing organosilicon compound used in the present invention and cured.

  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 Organic metal salts known as catalysts for urethanization reactions, for example, organic lead compounds such as lead naphthenate, lead octylate, lead stearate or the like, or tin naphthenate, tin octylate A single or mixture of organic tin compounds such as tin laurate, tetra-n-butyltin, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, etc., and appropriately mixed with a solvent such as a ketone 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, and 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, these (meth) acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, A hydroxyl group selected from urethane-modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resin, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate (Meth) acrylate having polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate Polyfunctional (meth) acrylate mixtures such as urethane acrylates that have been reacted with acid salts and copolymers in which a (meth) acryloyl group is introduced into the side chain of the acrylate copolymer can be used. A photopolymerization initiator such as benzoin, benzoin methyl ether, benzophenone, or 1-hydroxycyclohexyl phenyl ketone is blended and used. Moreover, it can also dilute suitably with the solvent etc. which were illustrated as a solvent which can be mix | blended with an antifouling property imparting agent. 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 hard coat surface by being blended with the hard coat material. As a result, even when human fats such as fingerprints, sebum, sweat, cosmetics, etc. are attached, it becomes inconspicuous, and even when 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.

で示される含フッ素ヒドロシロキサン４３．１ｇ（０．０５０モル）、トルエン２１．１ｇ、白金／ビニルシロキサン錯体トルエン溶液０．０４ｇ（白金として０．２ｍｇ含有）を仕込んだ。内温を６０℃まで加熱した後、滴下漏斗より１−ヘキサデセン４４．９ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。６０〜７０℃で１時間加熱した後、４−ペンテノール１７．２ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。ＩＲスペクトルで含フッ素ヒドロシロキサン（３）のＳｉＨ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（４）

で示される含フッ素シロキサン９３．８ｇを得た。 [Example 1]
In a flask equipped with a reflux condenser and a thermometer, the following formula (3)

Were charged with 43.1 g (0.050 mol) of a fluorine-containing hydrosiloxane, 21.1 g of toluene, and 0.04 g of a platinum / vinylsiloxane complex toluene solution (containing 0.2 mg of platinum). After heating the internal temperature to 60 ° C., 44.9 g (0.20 mol) of 1-hexadecene was dropped from the dropping funnel while adjusting the dropping speed so that the internal temperature did not become 70 ° C. or higher. After heating at 60 to 70 ° C. for 1 hour, 17.2 g (0.20 mol) of 4-pentenol was added dropwise while adjusting the dropping speed so that the internal temperature did not become 70 ° C. or higher. After confirming the disappearance of the SiH group-derived absorption of the fluorine-containing hydrosiloxane (3) by IR spectrum, the hexafluorometaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure to obtain the following formula (4 )

93.8 g of the fluorine-containing siloxane represented by

  Next, in a flask equipped with a reflux condenser and a thermometer, 44.8 g (0.030 mol) of the fluorinated siloxane (4) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and Methyl isobutyl ketone 53.7 g was charged. After heating the internal temperature to 50 ° C., 0.02 g of dibutyltin dilaurate was added and reacted at 50-60 ° C. for 2 hours. After the reaction, 0.90 g of ethanol was added, and after confirming that NCO absorption disappeared by IR, the solvent was distilled off at 25 ° C. to obtain 49.9 g of a transparent pasty product.

で示されるアクリル基含有含フッ素シロキサン化合物であった。 The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum.

It was an acryl-group containing fluorine-containing siloxane compound shown by these.

The results of analysis by ¹ H-NMR (manufactured by BRUKER, AVANCE III400) are shown below.
¹ H-NMR (CHCl ₃ basis, ppm): 0.0-0.1 (≡Si—C H ₃ , 36H), 1.1-1.4 (—C H ₂ —, 132H), 5.7 -6.3 (acrylic group, 6H)
FIG. 1 shows an IR spectrum (KBr method, manufactured by Horiba, Ltd., FT-730) of the compound.

で示される含フッ素ヒドロシロキサン４３．１ｇ（０．０５０モル）、トルエン１８．８ｇ、白金／ビニルシロキサン錯体トルエン溶液０．０４ｇ（白金として０．２ｍｇ含有）を仕込んだ。内温を６０℃まで加熱した後、滴下漏斗より１−ドデセン３３．６ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。６０〜７０℃で１時間加熱した後、４−ペンテノール１７．２ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。ＩＲスペクトルで含フッ素ヒドロシロキサン（３）のＳｉＨ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（５）

で示される含フッ素シロキサン８０．４ｇを得た。 [Example 2]
In a flask equipped with a reflux condenser and a thermometer, the following formula (3)

Were charged with 43.1 g (0.050 mol) of a fluorine-containing hydrosiloxane, 18.8 g of toluene, and 0.04 g of a platinum / vinylsiloxane complex toluene solution (containing 0.2 mg of platinum). After heating the internal temperature to 60 ° C., 33.6 g (0.20 mol) of 1-dodecene was dropped from the dropping funnel while adjusting the dropping speed so that the internal temperature did not become 70 ° C. or higher. After heating at 60 to 70 ° C. for 1 hour, 17.2 g (0.20 mol) of 4-pentenol was added dropwise while adjusting the dropping speed so that the internal temperature did not become 70 ° C. or higher. After confirming the disappearance of the SiH group-derived absorption of the fluorine-containing hydrosiloxane (3) by IR spectrum, hexafluorometaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure to obtain the following formula (5 )

Thus, 80.4 g of a fluorine-containing siloxane represented by the formula (1) was obtained.

  Next, in a flask equipped with a reflux condenser and a thermometer, 31.4 g (0.030 mol) of the fluorinated siloxane (5) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and 40.3 g of methyl isobutyl ketone was charged. After heating the internal temperature to 50 ° C., 0.02 g of dibutyltin dilaurate was added and reacted at 50-60 ° C. for 2 hours. After the reaction, 1.55 g of ethanol was added, and after confirming that NCO absorption disappeared by IR, the solvent was distilled off at 25 ° C. to obtain 36.4 g of a transparent pasty product.

で示されるアクリル基含有含フッ素シロキサン化合物であった。 The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum.

It was an acryl-group containing fluorine-containing siloxane compound shown by these.

で示される含フッ素ヒドロシロキサン４３．１ｇ（０．０５０モル）、トルエン２０．６ｇ、白金／ビニルシロキサン錯体トルエン溶液０．０４ｇ（白金として０．２ｍｇ含有）を仕込んだ。内温を６０℃まで加熱した後、滴下漏斗より１０−ウンデセン酸エチル４２．５ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。６０〜７０℃で１時間加熱した後、４−ペンテノール１７．２ｇ（０．２０モル）を内温が７０℃以上にならないように滴下スピードを調整して、滴下した。ＩＲスペクトルで含フッ素ヒドロシロキサン（３）のＳｉＨ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）

で示される含フッ素シロキサン９３．４ｇを得た。 [Example 3]
In a flask equipped with a reflux condenser and a thermometer, the following formula (3)

Was charged with 43.1 g (0.050 mol) of a fluorine-containing hydrosiloxane, 20.6 g of toluene, and 0.04 g of a platinum / vinylsiloxane complex toluene solution (containing 0.2 mg of platinum). After heating the internal temperature to 60 ° C., 42.5 g (0.20 mol) of ethyl 10-undecenoate was added dropwise from a dropping funnel while adjusting the dropping speed so that the internal temperature did not become 70 ° C. or higher. After heating at 60 to 70 ° C. for 1 hour, 17.2 g (0.20 mol) of 4-pentenol was added dropwise while adjusting the dropping speed 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 (3) disappeared by IR spectrum, hexafluorometaxylene and excess cyclotetrasiloxane were distilled off under reduced pressure, and the following formula (6 )

93.4 g of a fluorine-containing siloxane represented by

  Next, in a flask equipped with a reflux condenser and a thermometer, 30.9 g (0.030 mol) of the fluorinated siloxane (6) obtained above, 8.9 g (0.063 mol) of acryloxyethyl isocyanate, and 39.8 g of methyl isobutyl ketone was charged. After heating the internal temperature to 50 ° C., 0.02 g of dibutyltin dilaurate was added and reacted at 50-60 ° C. for 2 hours. After the reaction, 1.58 g of ethanol was added, and after confirming that NCO absorption disappeared by IR, the solvent was distilled off at 25 ° C. to obtain 34.2 g of a transparent pasty product.

で示されるアクリル基含有含フッ素シロキサン化合物であった。 The product obtained above was analyzed by measurement of ¹ H-NMR and IR spectrum.

It was an acryl-group containing fluorine-containing siloxane compound shown by these.

[Examples 4 to 6, Comparative Examples 1 and 2]
Preparation of antifouling property imparting agent 2.0 g of an acrylic group-containing fluorinated siloxane compound shown in Table 1 and 8.0 g of methyl isobutyl ketone were weighed into a 10 ml glass sample bottle, sealed, and shaken for 30 minutes. After confirming that the acrylic group-containing fluorine-containing siloxane compound was completely dissolved, it was filtered through a PTFE (polytetrafluoroethylene) membrane filter having a pore size of 0.45 μm to impart antifouling properties to the acrylic group-containing fluorine-containing siloxane compound. Antifouling property-imparting agents containing 20% by mass as ingredients were prepared.
In addition, the acryl-group containing fluorine-containing siloxane compound of Examples 4-6 was synthesize | combined according to the method of the said Examples 1-3, respectively.

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 20% by mass): 5.0 parts by mass

Preparation of hard coat coating material Each solution (hard coat composition) containing an antifouling property imparting agent is spin-coated on a black polymethyl methacrylate plate (5 × 5 × 0.2 cm) and irradiated with a conveyor type ultraviolet ray. With a device (manufactured by Panasonic Electric Works Co., Ltd.), an ultraviolet ray of 1.6 J / cm ² was irradiated in a nitrogen atmosphere to form a cured film. The film thickness of the hard coat film after curing was 7 μm. The material coated with the hard coat film 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 (fingerprint visibility, fingerprint wiping property) 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 used as the evaluation result. When two or more evaluation values were the same number, the evaluation value was determined by discussion of five persons. The results are shown in Table 2.

-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 off the fingerprint. The state after wiping was visually observed from 45 ° obliquely 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 off in less than 3 round trips.
○: The fingerprint could be wiped off at 3 to 5 round trips.
×: Fingerprints could not be wiped off even when wiped 5 times or more.

Claims (5)

A fluorine-containing organosilicon compound represented by the following general formula (1).

Wherein, Rf is -C _a F _2a - _(a is an integer of 2 to 10) is a fluoroalkylene group represented by, Q is an alkylene group having a carbon number of 1 to 12 independently, oxygen R is independently An alkyl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms which may contain an atom, and R ¹ is independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. An aralkyl group of 7 to 10, R ² is a hydrogen atom or a methyl group, and X is the following general formula

(In the formula, R ⁴ is a divalent hydrocarbon group having 1 to 12 carbon atoms.)
Wherein m is an integer of 2 to 8, and n is 0 , 1 or 2. ] The following general formula (2)

(In the formula, Rf, Q and R ¹ are the same as those in the formula (1).)
A hydrosiloxy group-containing fluorine-containing compound, an α-olefin compound having 6 to 20 carbon atoms, and an alkenol were hydrosilylated in the presence of a platinum catalyst to obtain a fluorine-containing organic group-modified siloxane. after, and said siloxane, (meth) process for producing a fluorinated organosilicon compound of claim 1 which comprises reacting an acrylic group-containing isocyanate compound. An antifouling imparting agent comprising the fluorine-containing organosilicon compound according to claim 1 as an antifouling imparting component. A hard coat material imparted with antifouling property, comprising 0.01 to 10.0% by mass of the antifouling agent according to claim 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.

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