Patent ID: 12227667

EXAMPLES

Preparation Examples, Synthesis Examples, Examples and Comparative Examples are given below to more concretely illustrate the present invention, although the present invention is not limited by these Examples.

[Preparation of Curable Component (A)]

[Preparation Example A-1]

A 1 liter flask equipped with a stirrer, a Liebig cooler, a dropping funnel and a thermometer was charged with 96.1 parts by weight of a compound of the average composition formula of CH3(CH3O)2SiOSi(OCH3)2CH3, 18.0 parts by weight of a compound of (CH3)2Si(OCH3)2, and 76.9 parts by weight of toluene, and 3.4 g of methanesulfonic acid was added with stirring, 27.0 parts by weight of water was then further added dropwise over 1 hour, and the mixture was aged at 30° C. for 12 hours.

The obtained liquid was neutralized with sodium bicarbonate, and an alcohol produced as a side product was distilled off, the liquid was washed with water, water was removed, and the liquid was filtered, and then diluted with toluene to a nonvolatile content of 40% by weight as measured after the liquid was left standing at 105° C. for 3 hours, thereby obtaining a silicone resin having a viscosity at 25° C. of 8 mm2/s as measured by Cannon-Fenske and containing a silanol group having a hydroxyl group content of 2.2% by weight as measured by a Grignard method.

250 parts by weight of the obtained silicone resin (100 parts by weight of active ingredients),1 part by weight of (C4H9O)Al(OC(CH3)═CHCOOC2H5)2as a curing catalyst, and150 parts by weight of methyl isobutyl ketone as a solventwere mixed to prepare a curable component A-1 containing a compound containing a silanol group.
[Preparation Example A-2]50 parts by weight of (CH3)(CH3O)2SiOSi(OCH3)2(CH3),40 parts by weight of (CH3)2Si(OCH3)2and10 parts by weight of (C4H9O)Al(OC(CH3)═CHCOOC2H5)2were mixed to obtain a curable component A-2 containing a compound containing an alkoxy group.
[Preparation Example A-3]90 parts by weight of a random copolymer of methyl methacrylate (MMA) and 2-hydroxy-ethyl methacrylate (HEMA) (MMA/HEMA (molar ratio)=88/12, numerical average molecular weight: 8,400, OH group content: 0.0011 mol/g),10 parts by weight of isophorone diisocyanate,0.1 parts by weight of dioctyltin dilaurate,150 parts by weight of tetrahydrofuran; and150 parts by weight of methyl isobutyl ketone 150were mixed to obtain a curable component A-3 containing a compound having 9.7 hydroxyl groups on average per molecule and a compound having 2 isocyanate groups.
[Preparation Example A-4]100 parts by weight of ZX-1059 (NIPPON STEEL Chemical & Material Co., Ltd.) (mixture of bisphenol A type/F-type diglycidyl ether, n=0),1 part by weight of a thermal photoacid generator (TA-100 from San-Apro Ltd.), and149 parts by weight of butyl acetatewere mixed to obtain a curable component A-4 containing a compound containing an epoxy group.
[Synthesis of Component (b1)]
[Synthesis Example 1]

In a 200 mL four-necked flask equipped with a reflux apparatus and a stirrer in a dry air atmosphere, 50.0 g (Si—H group: 0.067 mol) of a mixture containing a compound of the following formula:

(Rf1: —CF2O(CF2CF2O)21.4(CF2O)22.5CF2—, provided that the number of the repeating units is an average value determined by19F-NMR, and the same applies to the following Examples)and 0.79 mol % of a nonfunctional perfluoropolyether compound (b2-1) of the following formula:
F—Rf1—F,
16.3 g (0.070 mol) of CH2═CH(CH2)6Si(OCH3)3, 50.0 g of m-xylene hexafluoride (boiling point: 116° C.), and 0.0884 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 2.2×10−7mol of the complex in terms of Pt alone) were mixed, and the mixture was stirred at 100° C. for 4 hours. Disappearance of a peak derived from a Si—H group was confirmed by1H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, distillation was performed under reduced pressure for 2 hours under the condition of 100° C./267 Pa with an evaporator to remove m-xylene hexafluoride and unreacted CH2═CH(CH2)6Si(OCH3)3, thereby obtaining 56.8 g of a mixture (II-1) containing a compound (b1-1) of the following formula and 0.72 mol % of the nonfunctional perfluoropolyether compound (b2-1). In addition, in the19F-NMR spectrum, a peak of the CF3group of m-xylene hexafluoride was not observed at −64 ppm, and the residual amount of m-xylene hexafluoride was 0% by weight.

[Synthesis Example 2]

A compound (b2-2) of the following formula was added to the mixture (II-1) from Synthesis Example 1 to obtain 10.2 g of a mixture (II-2) containing a total of 3.0 mol % of the component corresponding to (b2).CF3CF2O(CF2CF2O)20.5(CF2O)22.1CF2CF3
[Synthesis Example 3]

A compound (b2-2) of the above formula was added to the mixture (II-1) from

Synthesis Example 1 to obtain 10.4 g of a mixture (II-3) containing a total of 4.8 mol % of the component corresponding to (b2).

[Synthesis Example 4]

In a 200 mL four-necked flask equipped with a reflux apparatus and a stirrer in a dry air atmosphere, 50.0 g (Si—H group: 0.067 mol) of a compound (III) of the following formula for which it was confirmed a CF3- group (terminal) derived from a nonfunctional perfluoropolyether compound (b2) was not detectable by19F-NMR:

(Rf2: —CF2O(CF2CF2O)20.9(CF2O)21.2CF2—, 16.3 g (0.070 mol) of CH2═CH(CH2)6Si(OCH3)3, 50.0 g of m-xylene hexafluoride, and 0.0884 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 2.2×10−7mol of the complex in terms of Pt alone) were mixed, and the mixture was stirred at 100° C. for 4 hours. Disappearance of a peak derived from a Si-H group was confirmed by1H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, m-xylene hexafluoride and unreacted CH2═CH(CH2)6Si(OCH3)3were removed to obtain 56.9 g of a compound (IV-I) of the following formula which is free of the component (b2). In addition, the residual amount of m-xylene hexafluoride was 0.002% by weight as determined from a peak integral value of CF3groups of m-xylene hexafluoride in a19F-NMR spectrum with hexafluorobenzene as a standard substance.

[Preparation of surface modification component (B)]

Undiluted or 80 parts by weight of MEK were blended to 20 parts by weight of each of the mixtures (II-1), (II-2) and (II-3) of Synthesis Examples, a compound (IV-1), and a compound (V) of the following formula which had been synthesized in accordance with the method described in JP-A 2012-233157. In this way, surface modification components (B1 to 7) of Table 1 below were prepared.

[Chem. 56]
(H3CO)3Si—CH2—CH2—CH2—O—CH2—Rf2—CH2—O—CH2—CH2—CH2—Si(OCH3)3
(Rf2: —CF2O(CF2CF2O)20.9(CF2O)21.2CF2—)

In addition, Synthesis Examples II-1 and II-2 and solvents were blended as in Table 2 to prepare a surface modification components (B8 to 12).

TABLE 1B-1B-2B-3B-4B-5B-6B-7Synthesis Example1234455Mixture or compound(II-1)(II-2)(II-3)(IV-1)(IV-1)(V)(V)Mixture or compound20202020202020Compounding amount(pbw)(b2) mol %0.723.04.80000Compounding amount808080800800of MEK (pbw)AppearanceTransparentTransparentSlightTransparentSlightCloudySlightcloudycloudycloudy(b2) mol % indicates a value relative against the total amount of component (b1) and component (b2), which is defined as 100 mol %

TABLE 2B-8B-9B-10B-11B-12Synthesis Example11122Compound(II-1)(II-1)(II-1)(II-2)(II-2)Compound1020402020Compounding amount(pbw)(b2) mol %0.720.720.723.03.0Type of solventHeptaneN-butanolHexaneIsododecaneMPEGCompounding amount9080608080of solvent (pbw)AppearanceTransparentTransparentTransparentTransparentTransparent(b2) mol % indicates a value relative against the total amount of component (b1) and component (b2), which is defined as 100 mol %
[Examples 1 to 20 and Comparative Examples 1 to 9]
[Preparation of Fluorine-Containing Curable Composition and Results of Evaluation]

Fluorine-containing curable compositions of the present invention and Comparative Examples which do not correspond to the present invention were prepared with the formulation shown in Table 3 to 8, and application, curing and evaluation of cured products were performed by the following methods. Samples which became cloudy at the time of preparing the fluorine-containing curable composition was not cured and evaluated any more.

[Application and Curing of Fluorine-Containing Curable Composition]

Method for Application and Curing (1):

The fluorine-containing curable composition was applied onto a glass plate with a wire bar having a gap of 24 μm, left standing at 150° C. for 1 hour, and then naturally cooled to room temperature to obtain a cured film.

Method for Application and Curing (2):

The fluorine-containing curable composition was applied onto a polycarbonate plate with a wire bar having a gap of 12 μm, left standing in an environment at 25° C. for 48 hours to obtain a cured film.

Method for Application and Curing (3):

The fluorine-containing curable composition was applied onto a glass plate with a wire bar having a gap of 18 μm, left standing in an environment at 120° C. for 2 hours, and then naturally cooled to room temperature to obtain a cured film.

Method for Application and Curing (4):

The fluorine-containing curable composition was applied onto a glass plate by spin coating at 3,000 rpm for 30 seconds, left standing in an environment at 100° C. for 1 hour, and then naturally cooled to room temperature to obtain a cured film.

Evaluation Method

[Appearance]

The transparency of the coating film and existence or non-existence of defects were examined.

[Water Contact Angle]

The water contact angle was measured at a liquid volume of 2 μL using a contact angle meter (A3 Type manufactured by Kyowa Interface Science Co., Ltd.).

[Felt Marker Ink-Repellent Property]

For the felt marker ink-repellent property, the degree of repellency was visually examined when a line was drawn on a surface of the cured film using Hi-Mckee Black Bold manufactured by ZEBRA Co., Ltd.

[Fingerprint Wipe-Off Property]

A fingerprint was put on the surface, and then wiped off with tissue paper, and the appearance was then visually evaluated.

TABLE 3Example 1Example 2Example 3Example 4Example 5Component (A)A-1A-1A-1A-1A-2Number of100100100100100parts by weight of (A)Component (B)B-1B-2B-4B-5B-1Number of1.251.251.250.255parts by weight of (B)Appearance in mixingTransparentTransparentTransparentTransparentTransparentMethod for application(1)(1)(1)(1)(2)and curingFilm thickness15 μm15 μm15 μm15 μm12 μmafter curingAppearance of filmTransparentTransparentTransparentTransparentTransparentafter curingand smoothand smoothand smoothand smoothand smoothWater contact angle (°)111113112111110Felt markerWell repellentWell repellentWell repellentWell repellentWell repellentink-repellent propertyFingerprintEasilyEasilyEasilyEasilyEasilywiping propertywiped offwiped offwiped offwiped offwiped off

TABLE 4Example 6Example 7Example 8Example 9Example 10Component (A)A-2A-2A-3A-3A-3Number of100100100100100parts by weight of (A)Component (B)B-2B-5B-1B-2B-5Number of5151.250.25parts by weight of (B)Appearance in mixingTransparentTransparentTransparentTransparentTransparentMethod for application(2)(1)(1)(3)(3)and curingFilm thickness15 μm24 μm6 μm4.5 μm4.5 μmafter curingAppearance of filmTransparentTransparentTransparentTransparentTransparentafter curingand smoothand smoothand smoothand smoothand smoothWater contact angle (°)111112112113113Felt markerWell repellentWell repellentWell repellentWell repellentWell repellentink-repellent propertyFingerprintEasilyEasilyEasilyEasilyEasilywiping propertywiped offwiped offwiped offwiped offwiped off

TABLE 5Example 11Example 12Example 13Example 14Example 15Component (A)A-4A-4A-1A-1A-1Number of100100100100100parts by weight of (A)Component (B)B-2B-5B-8B-9B-10Number of0.50.251.251.251.25parts by weight of (B)Appearance in mixingTransparentTransparentTransparentTransparentTransparentMethod for application(4)(4)(1)(1)(1)and curingFilm thickness4 μm4 μm15 μm15 μm15 μmafter curingAppearance of filmTransparentTransparentTransparentTransparentTransparentafter curingand smooth*and smooth*and smoothand smoothand smoothWater contact angle (°)113112112111113Felt markerWell repellentWell repellentWell repellentWell repellentWell repellentink-repellent propertyFingerprintEasilyEasilyEasilyEasilyEasilywiping propertywiped offwiped offwiped offwiped offwiped off*Slightly red color was observed immediately after heating, but disappeared with the lapse of time

TABLE 6Example 16Example 17Example 18Example 19Example 20Component (A)A-2A-2A-3A-1A-3Number of100100100100100parts by weight of (A)Component (B)B-11B-12B-5B-3B-3Number of0.150.50.250.10.1parts by weight of (B)Appearance in mixingTransparentTransparentTransparentSlight cloudySlight cloudyMethod for application(1)(2)(3)(4)(4)and curingFilm thickness24 μm12 μm4.5 μm5 μm2 μmafter curingAppearance of filmTransparentTransparentTransparentSlightly cloudyTransparentafter curingand smoothand smoothand smoothand smoothand smoothWater contact angle (°)111113113112113Felt markerWell repellentWell repellentWell repellentWell repellentWell repellentink-repellent propertyFingerprintEasilyEasilyEasilyEasilyEasilywiping propertywiped offwiped offwiped offwiped offwiped off

TABLE 7ComparativeComparativeComparativeComparativeComparativeExample 1Example 2Example 3Example 4Example 5Component (A)A-1A-1A-2A-3A-4Number of parts by weight of (A)100100100100100Component (B)B-6B-7B-7B-7B-7Number of parts by weight of (B)1.250.2510.250.1Appearance in mixingCloudyCloudyCloudyCloudyCloudy

TABLE 8ComparativeComparativeComparativeComparativeExample 6Example 7Example 8Example 9Component (A)A-1A-2A-3A-4Number of parts by weight of (A)100100100100Component (B)————Number of parts by weight of (B)0000AppearanceTransparentTransparentTransparentTransparentMethod for application and curing(1)(2)(3)(4)Appearance of film after curingTransparentTransparentTransparentTransparentand smoothand smoothand smoothand smoothWater contact angle (°)95927984Felt marker ink-repellent propertyNot repellentNot repellentNot repellentNot repellentFingerprint wiping propertyHardly wiped offHardly wiped offHardly wiped offHardly wiped off