JP2999938B2 - Fluorine-containing organosilicon compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organosilicon compound having a fluorinated group and an acryloyloxy group.

[0002]

2. Description of the Related Art Conventionally, fluorine-containing organosilicon compounds having a silyl group in which a hydrolyzable group is bonded to a silicon atom have been used as surface coating agents and lubricants for metals, glasses, various resins and the like. That is, when this compound is applied to the substrate surface, it forms a cured film on the substrate surface by a hydrolysis / condensation reaction caused by moisture in the air.

[0003]

The above-mentioned fluorine-containing organosilicon compounds have a hydrolyzable group bonded to a silicon atom, and thus exhibit good adhesion to various substrates. It takes 2 to 3 hours or more at room temperature to complete and cure, and it takes 10 to 20 minutes even under heating at about 100 ° C. Further quick curing, especially at room temperature Is desired.

By the way, the hydrolysis rate of the hydrolyzable group bonded to the silicon atom possessed by such a compound increases as the number of hydrolyzable groups becomes two, more than one, and three more than two. Therefore, in order to provide quick curing, the number of hydrolyzable groups may be increased. However, when a compound having a hydrolyzable group bonded to a silicon atom is brought into contact with air during storage, a part of the compound may be hydrolyzed by moisture in the air to form a gel. Accordingly, there is a problem that as the number of hydrolyzable groups increases, a gel-like substance is easily generated, and care must be taken in handling. Therefore, an object of the present invention is to provide a fluorinated organosilicon compound which has good quick-curing properties and is less likely to form a gel.

[0005]

According to the present invention, the following general formula (1):

[0006]

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[0007][Where Rf isGeneral formula: F- (Rf ¹ O) _b -Rf ^Two − (Where Rf ¹ And Rf ^Two Is independently 1 to 3 carbon atoms
Is a linear or branched perfluoroalkylene group
And b is an integer of 1 to 10, and the total number of carbon atoms
Is 2 to 20) Perfluorooxyal
killBaseOrGeneral formula: − (Rf ^Three O) _d -Rf ^Four _e − (Where Rf ^Three And Rf ^Four Is independently 1 to 3 carbon atoms
Is a linear or branched perfluoroalkylene group
And d is an integer of 1 to 40, and e is an integer of 0 to 3.
And the total number of carbon atoms is from 10 to 100. -R
f ^Three O- and -Rf ^Four The sequence with-may be random)
expressed A perfluorooxyalkylene group,
IsC1-C8 alkylene group, C6-C6
10 arylene groups, the alkylene group and the arylene group
And a divalent hydrocarbon group formed by combining _Two −
(CH _Two ) _Three -, -SO _Three − (CH _Two ) _Four -, -CH _Two
O- (CH _Two ) _Three -,-(CH _Two ) _Two -CO- (CH
_Two ) _Two -, -CONH- (CH _Two ) _Three -Or -SO _Two
N (CH _Three )-(CH _Two ) _Three −And R¹ IsCarbon field
An alkyl group, a cycloalkyl group or an alkyl group having 1 to 8
A kenyl group; or at least one hydrogen atom of these groups
A group partially substituted with a halogen atomAnd X is

Embedded image (In the above formula, R ² and R ³ are a hydrogen atom or a carbon atom having 1 to
6, an alkyl group, an alkenyl group, an aryl group or
Selected from the group consisting of halogen-substituted alkyl groups)
A Bareru hydrolyzable group, Y, in the case of the Rf Gapa over fluorooxyalkyl group is 1, the case of the Rf Gapa <br/> over fluorooxyalkylene group is 2, m
Is an integer of 0 to 2; n is an integer of 1 to 3;
m + n is 3 or less ] . According to the present invention, further, the following general formula (2):

[0008]

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Wherein Rf, A, m, R ¹ , X and Y
Is as shown in the general formula (1)) and a hydrolyzable silane compound represented by the following formula (3):

[0010]

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A method for producing the fluorine-containing organosilicon compound represented by the general formula (1) by reacting the silane compound represented by the formula (1) with a condensation catalyst is provided. Hereinafter, the present invention will be described in detail.

Fluorinated organosilicon compound The fluorinated organosilicon compound of the present invention has a specific hydrolyzable group (hereinafter simply referred to as a compound represented by the general formula (1)).
(Sometimes referred to as a hydrolyzable group) X is obtained by substituting a part or all of X with a acryloyl group-containing siloxy group, that is, an α-acryloyloxymethyldimethylsiloxy group. That is, since the acryloyl group is introduced, this compound can be easily and instantly cured by irradiating it with ultraviolet rays in the presence of a photopolymerization initiator. For example, it is cured in 1 to 2 minutes by irradiating ultraviolet rays at room temperature. Therefore, instead of increasing the number of hydrolyzable groups, instead of increasing the number of hydrolyzable groups, the acryloyl group-containing siloxy groups are substituted to provide quick curing properties, so that the formation of a gel during storage is effectively prevented.

In the compound of the present invention, the number n of the acryloyl group-containing siloxy groups is not particularly limited and can be set in the range of 1 to 6. For example, when the hydrolyzable group X is left (3-m-
n, or when the value of 3-pq described later is positive),
Curing by moisture in the air is also possible, and has two merits of quick curing by irradiation with ultraviolet rays and adhesion to various substrates due to hydrolyzable groups.

Further, since the fluorine-containing organosilicon compound of the present invention has a monovalent or divalent fluorine-containing group (Rf), it has properties such as chemical resistance, water / oil repellency, low surface tension and non-staining property. And can be applied to resin modifiers, paint additives, various coating agents, mold release agents, stain preventives for sealants, and the like. For example, when all of the hydrolyzable groups X are substituted with a silyl group containing an acryloyl group on the silicon atom (3-pq = 0 and / or 3-
(when mn = 0), it can be applied to uses such as resin modifiers and release agents. The fluorine-containing organosilicon compound of the present invention represented by the general formula (1) has the following general formula (4):

[0015]

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(In the formula, Rf ′ is the same as the general formula F- (R
f ¹ O) _b —Rf ² — is a perfluorooxyalkyl group represented by A, R ¹ , X, m and n are as defined above.
A fluorine-containing organosilicon compound represented by the following general formula (1) , and the following general formula (5):

[0017]

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[In the formula, Rf ″ is a group represented by the general formula-(Rf
³ O) _d -Rf ⁴ _e- is a perfluorooxyalkylene group, p is an integer of 0 to 2, and q
Is an integer of 1 to 3, p + q is 3 or less, and A
Is independently an alkylene group having 1 to 8 carbon atoms,
Arylene group of the number 6 to 10, the alkylene group and aryl
A divalent hydrocarbon group formed by combining with a ren group, -C
O _2- (CH ₂ ) _3- , -SO _3- (CH ₂ ) ₄ -,-
_{CH 2 O- (CH 2) 3} -, - (CH 2) 2 -CO-
_{(CH 2) 2 -, -} CONH- (CH 2) 3 - or -
SO ₂ N (CH ₃ ) — (CH ₂ ) ₃ — , and R ¹ is
Independently an alkyl group having 1 to 8 carbon atoms, cycloalkyl
Or an alkenyl group; or a hydrogen atom of these groups
Is a group in which at least a part of is substituted with a halogen atom , and X is independently

Embedded image (In the above formula, R ² and R ³ are a hydrogen atom or a carbon atom having 1 to
6, an alkyl group, an alkenyl group, an aryl group or
Selected from the group consisting of halogen-substituted alkyl groups)
And m and n are the same as defined in the above general formula.
( Same as (1)) ] .

When Y is 1 in the general formula (1) or in the general formula (4), Rf and Rf ′ are carbon atoms.
It is a perfluorooxyalkyl group having 2 to 20 children .
This perfluorooxyalkyl group has the following general formula: F— (Rf ¹ O) _b —Rf ² — (wherein Rf ¹ and Rf ^{2 each} independently have 1 to 3 carbon atoms.
A linear or branched perfluoroalkylene group, b is 1 to 10, Ri preferably an integer of 1 to 6 der, or
And the total number of carbon atoms is 2 to 20 ), and specifically, for example, the following formula:

[0020]

Embedded image , , ,

[0021] In as possible out there may be mentioned those represented. When Y is 2 in the general formula (1) or in the general formula (5), Rf and Rf ″ are each a group having 10 to 10 carbon atoms.
100 perfluorooxyalkylene groups .

This perfluorooxyalkylene group is
The following general _{^{formula: - (Rf 3 O) d}} -Rf 4 e - ( wherein, Rf ³ and Rf ⁴ are independently 1 to 3 carbon atoms
Is a linear or branched perfluoroalkylene group, d is an integer of 1 to 40, and e is an integer of 0 to 3
And the total number of carbon atoms is from 10 to 100 . However, -Rf ³ O-and -Rf ⁴ - the sequence of is random you express by also may) group, specifically, for example, the following formula:

[0023]

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[0024] Ki represented by like De be exemplified by at
You . Of course, in the above, the number of perfluorooxyalkylene blocks can be changed as appropriate.

[0025] A is main styrene group, an ethylene group, an alkylene group having carbon atoms such as a propylene group is 1-8; phenylene group, tolylene group, xylylene group, naphthylene group, number of carbon atoms, such as biphenylene group 6 10 arylene group; and _{formula: -Ph-CH 2 CH 2 -} , -CH 2 -Ph-CH 2
A divalent hydrocarbon group selected from the group consisting of a combination of the above-mentioned alkylene group and arylene group, such as CH ₂ —, (Ph represents a p-phenylene group in the above) , preferably
Properly is the divalent hydrocarbon group having 2 to 10 carbon atoms. Or A is but it may also be a group containing a hetero atom.

The group containing such a hetero atom includes —CO ₂ — (CH ₂ ) ₃ —, —SO ₃ — (CH ₂ ) _{4
-, -CH 2 O- (CH 2} ) 3 -, - (CH 2) 2 -CO- (CH 2) 2 -, -CONH- (CH 2) 3 -, and the following formula: -SO ₂ N ( _{CH 3) - (CH 2)} 3 - with a group represented, preferable _{one, -CO 2 - (CH 2)} 3 -, - CH 2 O- (CH 2) 3 -, -CONH- ( _{CH 2) 3 -, - SO} 2 N (CH 3) -
(CH ₂ ) ₃ −.

[0027] or R ¹ Is an alkyl having 1 to 8 carbon atoms
(For example, methyl, ethyl, propyl, etc. )
Chloroalkyl group (for example, cyclohexyl group, etc. )
A kenyl group (eg, a vinyl group, an allyl group, an isopropenoxy group, etc. ); or at least one hydrogen atom of these groups.
A group partially substituted with a halogen atom (eg, 3,3,3
-Trifluoropropyl group, 3,3,4,4,5,5
6,6,6-nonafluorohexyl group, chloromethyl group, 3-chloropropyl group, etc. ). A preferred R ¹ is
It is of 1 to 6 carbon atoms.

The hydrolyzable group X is, those represented by the following formula
It is .

[0029]

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[0030] However, in the above formulas, R ^2, R ³ is a hydrogen atom or 1 to 6 carbon atoms, an alkyl group (e.g., methylcarbamoyl <br/> group, an ethyl group, a propyl group, an isopropyl group, a butyl Group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, etc. ), alkenyl group (for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group) , A cyclohexenyl group, etc. ), an aryl group (eg, a phenyl group ) or a halogen atom-substituted alkyl group (eg , a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc.) . is there. Particularly preferred as such a hydrolyzable group X are a chlorine atom, a methoxy group,
Ethoxy, acetoxy, propenoxy, isopropenoxy, diethylamino,

[0031]

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Is as follows. The above-mentioned fluorine-containing organosilicon compound is a photopolymerization initiator known per se, for example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone,
3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-acetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro -4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-
8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxyketal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- [4- (methylthio) phenyl] -2
-Combined with morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, etc., and is immediately cured by ultraviolet irradiation. The amount of the photopolymerization initiator used is usually
For 100 parts by weight of the above fluorine-containing organosilicon compound, 0.
It may be about 01 to 10 parts by weight. In this case, a sensitizer can be used in combination as needed. In addition, as described above, when the hydrolyzable group X is present, it can be cured by moisture in the air.

Method for Producing Fluorinated Organosilicon Compound The fluorinated organosilicon compound of the present invention comprises a hydrolyzable silane compound represented by the above formula (2) and a silane compound represented by the above formula (3): That is, it is produced by reacting with α-acryloyloxymethyldimethylsilanol. This reaction proceeds, for example, according to the following reaction formula.

[0034]

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(Rf, A, X, R ¹ , m, n and Y are as described above, Me is a methyl group, and Ac is an acryloyloxymethyl group.) (1) The target compound of the formula and by-products of the formula: HX are obtained. The temperature of this condensation reaction is sufficient from room temperature to about 80 ° C. Since the by-product represented by the formula: HX may react with the silanol of the starting silane compound of the formula (3), the by-product generated by the reaction is preferably immediately removed from the reaction system. Since this by-product has a relatively low boiling point, it is desirable to carry out the reaction under normal pressure or reduced pressure. For example, by performing the reaction under reduced pressure of 20 mmHg to 200 mmHg, the by-product can be easily removed from the system. .

As understood from the above reaction formula,
By adjusting the amount of the silane compound of the general formula (3) with respect to the hydrolyzable group X in the silane compound of the general formula (2), an acryloyl group-containing siloxy group, that is, α-acryloyloxymethyldimethylsiloxy The degree of substitution by the group can be adjusted. For example, by using the silane compound of the general formula (3) in stoichiometric excess with respect to the hydrolyzable group X, the remaining hydrolyzable group X can be reduced to zero. The silane compound of the general formula (2) has the following formula:

[0037]

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Wherein Rf ′, A, X, R ¹ and m are as defined above, and the following formula:

[0039]

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Wherein Rf ″, A, X, R ¹ and m are as defined above. The above-mentioned reaction optionally uses a condensation catalyst. Such condensation catalysts include, for example, lead-2-ethyl octoate, dibutyltin diacetate, dibutyltin dilaurate, butyltin tri-2-ethylhexoate, and iron-2. -Ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, tin butylate ,
Metal salts of organic carboxylic acids such as titanium naphthenate, zinc naphthenate, cobalt naphthenate and zinc stearate;
Organic titanates such as tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate and tetra (isopropenyloxy) titanate; organic titanium compounds such as organosiloxytitanium and β-carbonyltitanium; potassium acetate, sodium acetate; Lower fatty acid salts of alkali metals such as lithium oxalate; dialkylhydroxylamines such as dimethylhydroxyamine and diethylhydroxylamine; tetramethylguanidine; and the following formulas (6) and (7):

[0041]

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A guanidyl compound such as a guanidyl group-containing silane or siloxane;
These can be used alone or in combination of two or more. Suitable as such a condensation catalyst are tin salts of organic carboxylic acids, organic titanates,
It is a guanidyl compound. The addition amount of these condensation catalysts,
It is used in an amount of about 0.001 to 5.0 parts by weight based on 100 parts by weight of the hydrolyzable silane compound of the general formula (2).

[0043]

EXAMPLES In the following examples, Me represents a methyl group and Et represents an ethyl group. Example 1 In a 100 ml three-necked flask connected to a vacuum line through a stirrer, a thermometer, a dropping funnel, and a Liebig condenser, the following formula (2-1):

[0044]

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Fluorine-containing organosilicon compound represented by the formula 1
3.1 g and 0.005 g of the guanidine derivative (condensation catalyst) represented by the above formula (6) were charged. The inside of the flask is promptly replaced with dry nitrogen gas, and gradually heated while stirring to bring the internal temperature to 50 ° C. Next, the following formula is added to the dropping funnel.
(3-1):

[0046]

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19.2 g of a solution obtained by diluting the organosilicon compound represented by the above to 50% with toluene is added and set in the above-mentioned 100 ml three-necked flask. Then, inside the three-necked flask
While reducing the pressure to 120 mmHg, the organosilicon compound of the formula (3-1) was added dropwise over about 10 minutes. After completion of the dropwise addition, the mixture was aged for about 20 minutes, and the pressure in the system was reduced to 3 mmHg, and the solvent and low-boiling components were completely distilled off. As a result, 31.5 g of a pale yellow transparent liquid was obtained. When this was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, the results were as follows. ¹ H-NMR: (TMS standard)

[0048]

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A: 0.15 ppm (s, 17.10H) b: 0.51 ppm (m, 2H) c: 1.60 ppm (m, 2H) d: 3.33 ppm (m, 2H) e: 3.45 ppm (s, 0.45H) f: 3.72 ppm (s, 5.70H) g: 5.5 to 6.5 ppm (m, 8.55H) h: 7.48 ppm (bs, 1H) ¹⁹ F-NMR: (CF ₃ COOH standard)

[0050]

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A: −3.65 ppm b: −5.11 ppm c: −6.04 ppm d: −52.63 ppm e: −55.76 ppm f: −67.97 ppm IR: The chart is shown in FIG. The characteristic absorption is as follows.

Ν _NH : 3350 cm ⁻¹ ν _{C = O} (acryloyl): 1725 cm ⁻¹ ν _{C = O} (amide): 1710 cm ⁻¹ ν _{C = C} : 1635 cm ⁻¹ Was confirmed to be a compound represented by the following formula.

[0053]

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[0054] In Example 1, in place of the fluorine-containing organic silicon compound represented by the formula (2-1), the following equation (2-2):

[0055]

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15.3 The fluorine-containing organosilicon compound represented by the formula
g, 0.04 g of dibutyltin dilaurate (condensation catalyst) was charged into a 100 ml three-necked flask in place of the guanidine derivative (condensation catalyst) represented by the above formula (6), and used in Example 1 in a dropping funnel. (3-1) 20.8 g of a pale yellow transparent liquid was obtained in exactly the same manner as in Example 1, except that 13.0 g of a 50% solution of the organosilicon compound of the formula in toluene was added.
was gotten. When this was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, the results were as follows. ¹ H-NMR: (TMS standard)

[0057]

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A: 0.17 ppm (s, 11.34H) b: 0.90 ppm (m, 2H) c: 1.02 ppm (t, 3.33H) d: 1.82 ppm (s, 3.33H) e: 2.25 ppm (q, 0.74 ppm) H) f: 2.31 ppm (m, 2H) g: 3.73 ppm (s, 3.78H) h: 5.5 to 6.5 ppm (m, 5.67H) ¹⁹ F-NMR: CF ₃ COOH standard

[0059]

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A: -3.35 ppm b: -4.82 ppm c: -6.63 ppm d: -10.78 ppm e: -43.11 ppm f: -52.54 ppm g: -68.07 ppm

[0061] IR: chart is shown in Figure 2. In addition, characteristic absorption is as follows. ^{_{ν C = O: 1725cm -1 ν}} C = C: 1635cm -1 ν CF: from 1100～1300Cm ^-1 above results, the compound obtained was confirmed to be those represented by the following formula.

[0062]

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Example 3 In Example 1, the following formula ( 2-3 ) was used in place of the fluorine-containing organosilicon compound represented by the formula (2-1).

[0064]

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Fluorinated organosilicon compound 2 represented by
Using 1.4 g, 0.01 g of the guanidine derivative (condensation catalyst) represented by the formula (7) is charged into a 100 ml three-necked flask and dropped, instead of the guanidine derivative (condensation catalyst) represented by the formula (6). The funnel used in Example 1 (3-
1) 26.9 g of a pale yellow transparent liquid was obtained by the same procedure as in Example 1 except that 13.0 g of a 50% solution of the organosilicon compound of the formula in toluene was added. This was analyzed by ¹ H-NMR,
^When analyzed by ¹⁹ F-NMR and IR, the results were as follows. ¹ H-NMR: (TMS standard)

[0066]

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A: 0.17 ppm (s, 12H) b: 0.22 ppm (s, 3H) c: 0.59 ppm (m, 2H) d: 1.66 ppm (m, 2H) e: 3.57 ppm (t, 2H) f: 3.74 ppm (s, 4H) g: 4.04 ppm (d, 2H) h: 5.5 to 6.5 ppm (m, 6H) ¹⁹ F-NMR: CF ₃ COOH standard

[0068]

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[0069] a: - 3.40 ppm b: - 4.72 ppm c: - 5.84 ppm d: -52.44 ppm e: -55.66 ppm f: -67.58 ppm IR: shows the chart in Figure 3. In addition, characteristic absorption is as follows. ν _{C = O} : 1725 cm ^-1 ν _{C = C} : 1635 cm ^-1 ν _CF : From 1100 to 1300 cm ^-1 or more, it was confirmed that the obtained compound was represented by the following formula.

[0070]

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[0071] Example 4 In Example 1, in place of the fluorine-containing organic silicon compound represented by the formula (2-1), the following equation (2 4):

[0072]

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The fluorinated organosilicon compound 31.4
g, a guanidine derivative (condensation catalyst) 0.01 g represented by the formula (6) was charged into a three-necked flask, and the dropping funnel was charged with the organosilicon compound of the formula (3-1) used in Example 1 By exactly the same procedure as in Example 1 except that 27.2 g of a 50% solution of toluene was added, 43.5 g of a colorless transparent liquid was obtained. When this was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, the results were as follows. ¹ H-NMR; TMS standard

[0074]

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A: 0.17 ppm (s, 24H) b: 0.21 ppm (s, 6H) c: 0.59 ppm (m, 4H) d: 1.64 ppm (m, 4H) e: 3.55 ppm (t, 4H) f: 3.70 ppm (s, 8H) g: 4.00 ppm (d, 4H) h: 5.5 to 6.5 ppm (m, 12H) ¹⁹ F-NMR; CF ₃ COOH standard

[0076]

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A: -3.60 ppm b: -6.19 ppm c: -9.36 ppm d: -52.05 ppm e: -67.87 ppm IR; FIG. 4 shows a chart. In addition, characteristic absorption is as follows. ν _{c = O} : 1725 cm ^-1 ν _{C = C} : 1635 cm ^-1 ν _CF : 1100 to 1300 cm ^{-1 From the} above results, it was confirmed that the obtained compound was represented by the following formula.

[0078]

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[0079] In Example 5 Example 1, in place of the fluorine-containing organic silicon compound represented by the formula (2-1), the following equation (2 5):

[0080]

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Fluorine-containing organosilicon compound 29.2
g, 0.06 g of dibutyltin dilaurate (condensation catalyst) was charged into a 100 ml three-necked flask in place of the guanidine derivative (condensation catalyst) represented by the above formula (6), and used in Example 1 in a dropping funnel. Except that 13.3 g of a 50% solution of the organosilicon compound of the formula (3-1) in toluene was added, 41.3 g of a pale yellow transparent liquid was obtained in exactly the same procedure as in Example 1.
I got This was analyzed by ¹ H-NMR, ¹⁹ F-NMR and I
When analyzed by R, the results were as follows. ¹ H-NMR; TMS standard

[0082]

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A: 0.17 ppm (s, 23.28H) b: 0.91 ppm (m, 4H) c: 1.07 ppm (t, 6.36H) d: 1.84 ppm (s, 6.36H) e: 2.28 ppm (q, 4.24 H) f: 2.35 ppm (m, 4H) g: 3.77 ppm (s, 7.76H) h: 5.5 to 6.5 ppm (m, 11.64H) ¹⁹ F-NMR; CF ₃ COOH standard

[0084]

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A: −3.59 ppm b: −6.62 ppm c: −9.37 ppm d: −10.78 ppm e: −43.11 ppm f: −68.07 ppm IR; FIG. 5 shows a chart. In addition, characteristic absorption is as follows. ν _{C = O} : 1725 cm ^-1 ν _{C = C} : 1635 cm ^-1 ν _CF : From 1100 to 1300 cm ^-1 or more, it was confirmed that the obtained compound was represented by the following formula.

[0086]

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[0087] In Example 6 Example 1, in place of the fluorine-containing organic silicon compound represented by the formula (2-1), the following equation (2-6):

[0088]

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A fluorine-containing organosilicon compound represented by the following formula:
g, 0.05 g of the guanidine derivative (condensation catalyst) represented by the above formula (6) is charged into a 100 ml three-necked flask,
And except that 26.6 g of a 50% toluene solution of the organosilicon compound of the formula (3-1) used in Example 1 was added to the dropping funnel.
By the same procedure as in Example 1, a light yellow transparent liquid 63.5
g was obtained. When this was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, the results were as follows. ¹ H-NMR; TMS standard

[0090]

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A: 0.17 ppm (s, 23.70H) b: 0.52 ppm (m, 2H) c: 1.63 ppm (m, 2H) d: 3.34 ppm (m, 2H) e: 3.46 ppm (s, 6.15H) f: 3.75 ppm (s, 7.90H) g: 5.5 to 6.5 ppm (m, 11.85H) h: 7.52 ppm (bs, 1H) ¹⁹ F-NMR; CF ₃ COOH standard

[0092]

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A: -3.50 ppm b: -5.97 ppm c: -9.37 ppm d: -55.63 ppm e: -67.81 ppm IR; FIG. 6 shows a chart. In addition, characteristic absorption is as follows. ν _NH : 3350 cm ⁻¹ ν _{C = O} (acryloyl): 1725 cm ⁻¹ ν _{C = O} (amide): 1710 cm ⁻¹ ν _{C = C} : 1635 cm ⁻¹ δ _NH : 1535 cm ⁻¹ ν _CF : 1100 to 1300 cm ⁻¹ From the above results, it was confirmed that the obtained compound was represented by the following formula.

[0094]

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[0095]

Since the compound of the present invention has an acryloyl group, it can be easily cured in a short time, for example, about 1 to 2 minutes, by irradiation with ultraviolet light in the presence of a photopolymerization initiator. Further, when this compound has a hydrolyzable group X, the adhesiveness to various substrates can be improved as well as the rapid curability by irradiation with ultraviolet rays.

[Brief description of the drawings]

FIG. 1 is an IR chart of the compound of the present invention obtained in Example 1.

FIG. 2 is an IR chart of the compound of the present invention obtained in Example 2.

FIG. 3 is an IR chart of the compound of the present invention obtained in Example 3.

FIG. 4 is an IR chart of the compound of the present invention obtained in Example 4.

FIG. 5 is an IR chart of the compound of the present invention obtained in Example 5.

FIG. 6 is an IR chart of the compound of the present invention obtained in Example 6 .

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takafumi Sakamoto 1-10 Hitomi, Matsuida-machi, Usui-gun, Gunma Prefecture Inside Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Masatoshi Arai Matsui, Usui-gun, Gunma Prefecture Hitomi Tamachi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (56) References JP-A-63-185989 (JP, A) JP-A-61-87102 (JP, A) JP-A-4 JP-A-168116 (JP, A) JP-A-62-61988 (JP, A) JP-A-62-283313 (JP, A) JP-A-2-304093 (JP, A) JP-A-5-25278 (JP, A) U.S. Pat. No. 4,743,106 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 7/18 C08G 77/20 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] (1) The following general formula (1): [Where Rf isGeneral formula: F- (Rf ¹ O) _b -Rf ^Two − (Where Rf ¹ And Rf ^Two Is independently 1 to 3 carbon atoms
Is a linear or branched perfluoroalkylene group
And b is an integer of 1 to 10, and the total number of carbon atoms
Is 2 to 20) Perfluorooxyal
killBaseOrGeneral formula: − (Rf ^Three O) _d -Rf ^Four _e − (Where Rf ^Three And Rf ^Four Is independently 1 to 3 carbon atoms
Is a linear or branched perfluoroalkylene group
And d is an integer of 1 to 40, and e is an integer of 0 to 3.
And the total number of carbon atoms is from 10 to 100. -R
f ^Three O- and -Rf ^Four The sequence with-may be random)
expressed A perfluorooxyalkylene group,
IsC1-C8 alkylene group, C6-C6
10 arylene groups, the alkylene group and the arylene group
And a divalent hydrocarbon group formed by combining _Two −
(CH _Two ) _Three -, -SO _Three − (CH _Two ) _Four −, -CH _Two O- (CH _Two ) _Three -,-(CH _Two ) _Two -CO-
(CH _Two ) _Two −, -CONH- (CH _Two ) _Three -Or -SO _Two N (CH
_Three )-(CH _Two ) _Three − And R¹ Is1 carbon atom
8, alkyl, cycloalkyl or alkenyl
Groups; or at least some of the hydrogen atoms in these groups
Replace with halogen atom Substituted groupAnd X is (In the above formula, R ² And R ³ Is a hydrogen atom or a carbon number of 1 to
6, an alkyl group, an alkenyl group, an aryl group or
Selected from the group consisting of halogen-substituted alkyl groups)
FallY is a hydrolyzable group,But-Full
In the case of an oxyalkyl group, it is 1, and the RfBut
Is 2 in the case of -fluorooxyalkylene group;
Is an integer of 0 to 2; n is an integer of 1 to 3;
m + n is 3 or less]Fluorine-containing organosilicon represented by
Elemental compounds. 2. A compound represented by the following general formula (4): (Where Rf ′ isThe general formula F- (Rf ¹ O) _b −
Rf ^Two Expressed by −With a perfluorooxyalkyl group
Yes, A, R¹ , X, m, and n areGeneral formula (1)
2. The fluorine-containing composition according to claim 1, wherein
Organosilicon compounds. 3. The following general formula (5): [Where Rf ″ isThe general formula-(Rf ^Three O) _d -R
f ^Four _e Expressed by −Perfluorooxyalkylene group
And p is an integer of 0 to 2, and q is an integer of 1 to 3.
Is a number, p + q is 3 or less, and A is independentlycarbon
An alkylene group having 1 to 8 atoms, an alkylene group having 6 to 10 carbon atoms
A arylene group, the alkylene group and an arylene group
Combined divalent hydrocarbon groups, -CO _Two − (CH
_Two ) _Three -, -SO _Three − (CH _Two ) _Four −, -CH _Two O- (CH _Two ) _Three -,-(CH _Two ) _Two -CO-
(CH _Two ) _Two −, -CONH- (CH _Two ) _Three -Or -SO _Two N (CH
_Three )-(CH _Two ) _Three − And R¹ IndependentlyCarbon atom
An alkyl group, a cycloalkyl group or an alk
Nyl group; or at least one hydrogen atom of these groups
Group in which the moiety is substituted with a halogen atomAnd X is independently: (In the above formula, R ² And R ³ Is a hydrogen atom or a carbon number of 1 to
6, an alkyl group, an alkenyl group, an aryl group or
A halogen atom-substituted alkyl group) Choose from
FallA hydrolyzable group, and m and n are as defined above.General formula
(1)Is synonymous with]2. The method according to claim 1, wherein
Fluorinated organosilicon compounds. 4. The following general formula (2): (Wherein, Rf, A, m, R ¹ , X and Y are as shown in the general formula (1)), and a hydrolyzable silane compound represented by the following formula (3): 7] A method for producing a fluorinated organosilicon compound represented by the general formula (1) by reacting a silane compound represented by the following formula with a condensation catalyst.