FLUORINE-CONTAINING CURABLE COMPOSITION AND ARTICLE

Abstract

This fluorine-containing curable composition comprises a curable component (A) that provides a cured product under the effect of heat or moisture, and a surface-modifying component (B) that contains a perfluoropolyether compound (b1) having a prescribed structure. The perfluoropolyether compound (b1) in the surface-modifying component (B) is present at 0.005-50 mass parts per 100 mass parts of the curable component (A) excluding volatile components. The fluorine-containing curable composition can be cured by heat or moisture, can be coated on the surface of an article even not containing a fluorine-containing solvent, and can provide the cured product surface with excellent surface characteristics.

Claims

1. A fluorine-containing curable composition comprising a curable component (A) which is formed into a cured product by heat or moisture; and a surface modification component (B) containing a perfluoropolyether compound (b1) of the following general formula (1), the surface modification component (B) containing 0.005 to 50 parts by weight of the perfluoropolyether compound (b1) per 100 parts by weight of the curable component (A) excluding volatile components:
[M.sub.cR.sub.bSi—Z.sup.2].sub.a—Q.sup.1—Z.sup.1—Rf—Z.sup.1—Q.sup.1—[Z.sup.2—SiR.sub.bM.sub.c].sub.a   (1) wherein Rf is a divalent perfluoropolyether group having a numerical average molecular weight of 1,500 to 20,000; each Z.sup.1 is independently a divalent linking group, optionally contains an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, and may be a group having a cyclic structure and/or an unsaturated bond; each Z.sup.2 is independently a divalent hydrocarbon group having 2 to 20 carbon atoms, may have a cyclic structure, and optionally contains an intermediate ether bond (-0-); each Q.sup.1 is independently a linking group with a valence of (a+1), has a structure with two or more of a hydrogen atom, a carbon atom, an oxygen atom, a silicon atom and a nitrogen atom, and may have a ring shape; each a is independently an integer of 1 to 10, each b is independently an integer of 0 to 2, each c is independently an integer of 1 to 3, and b and c on one silicon atom satisfy b+c=3; all “a” number of Z.sup.2 in the square bracket in formula (1) are bonded to the silicon atom in the Q.sup.1 structure; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and each M is independently a group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxy alkyl group having 2 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen group.

2. The fluorine-containing curable composition according to claim 1, wherein the surface modification component (B) further contains a non-functional perfluoropolyether compound (b2) of the following general formula (2) at less than 5 mol % per a total of 100 mol % of the perfluoropolyether compound (b1) of general formula (1) and the component (b2), the total amount of the component (b1) and the component (b2) in the surface modification component (B) is 0.005 to 50 parts by weight per 100 parts by weight of the curable component (A) excluding volatile components, and the content of a fluorine-containing solvent having a boiling point of 260° C. or lower at normal pressure is less than 1% by weight with respect to the entire component (B):
F—Rf′–F   (2) wherein Rf' is a divalent perfluoropolyether group having a numerical average molecular weight of 1,500 to 20,000.

3. The fluorine-containing curable composition according to claim 1, wherein in formulae (1) and (2), Rf and Rf each include a repeating unit having at least one structure selected from the group of the following divalent perfluoroether groups: —CF.sub.2O—; —CF.sub.2CF.sub.2O—; —CF.sub.2CF.sub.2CF.sub.2O—; —CF(CF.sub.3)CF.sub.2O—; —CF.sub.2CF.sub.2CF.sub.2CF.sub.2O—; —CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2O—; and —CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2O—, and a perfluoroalkylene group having 1 to 6 carbon atoms.

4. The fluorine-containing curable composition according to claim 1, wherein in formulae (1) and (2), Rf and Rf each has one of: —CF.sub.2O(CF.sub.2O).sub.p(CF.sub.2CF.sub.2O).sub.qCF.sub.2— —CF.sub.2CF.sub.2O(CF.sub.2O).sub.p(CF.sub.2CF.sub.2O).sub.qCF.sub.2CF.sub.2— wherein p is an integer of 10 to 290, q is an integer of 5 to 170, and p +q is an integer of 15 to 295; the sequence of the repeating units of —CF.sub.2O— and —CF.sub.2CF.sub.2O— is random; and —CF(CF.sub.3)[OCF.sub.2CF(CF.sub.3)].sub.sO(C.sub.uF.sub.2uO).sub.v[CF(CF)CF.sub.2O].sub.tCF(CF.sub.3)— —CF.sub.2CF.sub.2CF.sub.2O[CF(CF.sub.3)CF.sub.2O].sub.tCF.sub.2CF.sub.2— wherein each of s and t is independently an integer of 1 to 120, s+t is an integer of 4 to 121, u is an integer of 1 to 6, and v is an integer of 0 to 10.

5. The fluorine-containing curable composition according to claim 1, wherein in formula (1), Z.sup.2 has the following formula: —(CH.sub.2).sub.w— wherein w is an integer of 2 to 20.

6. The fluorine-containing curable composition according to claim 1, wherein in formula (1), each Q.sup.1 is independently a linking group with a valence of (a+1) which has a siloxane structure with at least (a+1) number of silicon atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof.

7. The fluorine-containing curable composition according to claim 1, wherein in formula (1), Q.sup.1 is a cyclic siloxane structure.

8. The fluorine-containing curable composition according to claim 1, wherein in formula (1), Z.sup.1 is one selected from ##STR00027##

9. The fluorine-containing curable composition according to claim 1, wherein the surface modification component (B) further contains 10 to 2,000 parts by weight of a volatile organic solvent (b3) free of a fluorine atoms per 100 parts by weight of the component (1)1).

10. The fluorine-containing curable composition according to claim 1, wherein the curable component (A) contains at least one compound selected from compounds having a hydroxyl group, a carboxyl group, an amino group, an epoxy group, a mercapto group, an isocyanate group, a hydrolyzable silyl group, a silanol group and a carboxylic anhydride group, and is reacted and cured by heat or moisture.

11. The fluorine-containing curable composition according to claim 1, wherein the curable component (A) contains a hydrolyzable silane compound, a hydrolyzable siloxane compound or a silanol group-containing silicone resin which is free of a fluorine atom.

12. The fluorine-containing curable composition according to claim 1, wherein the curable component (A) contains at least one of tetraalkoxysilane, trialkoxysilane and dialkoxysilane, or a partial hydrolytic condensate thereof, or a hydrolyzed/partially condensed product of the partial hydrolytic condensate.

13. The fluorine-containing curable composition according to claim 1, wherein the curable component (A) contains a compound free of a fluorine atom which has two or more isocyanate groups per molecule and a compound free of a fluorine atom which has two or more hydroxyl groups per molecule.

14. The fluorine-containing curable composition according to claim 1, wherein the curable component (A) contains an epoxy compound free of a fluorine atom.

15. The fluorine-containing curable composition according to claim 1, wherein the water contact angle of a surface of the cured product is 100° or more.

16. An article having a cured film of the fluorine-containing curable composition according to claim 1 on a surface thereof.

Description

EXAMPLES

[0230] 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]

[0231] 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 CH.sub.3(CH.sub.3O).sub.2SiOSi(OCH.sub.3).sub.2CH.sub.3, 18.0 parts by weight of a compound of (CH.sub.3).sub.2Si(OCH.sub.3).sub.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.

[0232] 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 mm.sup.2/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.

[0233] 250 parts by weight of the obtained silicone resin (100 parts by weight of active ingredients), [0234] 1 part by weight of (C.sub.4H.sub.9O)Al(OC(CH.sub.3)═CHCOOC.sub.2H.sub.5).sub.2 as a curing catalyst, and [0235] 150 parts by weight of methyl isobutyl ketone as a solvent [0236] were mixed to prepare a curable component A-1 containing a compound containing a silanol group.

[Preparation Example A-2]

[0237] 50 parts by weight of (CH.sub.3)(CH.sub.3O).sub.2SiOSi(OCH.sub.3).sub.2(CH.sub.3), [0238] 40 parts by weight of (CH.sub.3).sub.2Si(OCH.sub.3).sub.2 and [0239] 10 parts by weight of (C.sub.4H.sub.9O)Al(OC(CH.sub.3)═CHCOOC.sub.2H.sub.5).sub.2 [0240] were mixed to obtain a curable component A-2 containing a compound containing an alkoxy group.

[Preparation Example A-3]

[0241] 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), [0242] 10 parts by weight of isophorone diisocyanate, [0243] 0.1 parts by weight of dioctyltin dilaurate, [0244] 150 parts by weight of tetrahydrofuran; and [0245] 150 parts by weight of methyl isobutyl ketone 150 [0246] were 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]

[0247] 100 parts by weight of ZX-1059 (NIPPON STEEL Chemical & Material Co., Ltd.) (mixture of bisphenol A type/F-type diglycidyl ether, n=0), [0248] 1 part by weight of a thermal photoacid generator (TA-100 from San-Apro Ltd.), and [0249] 149 parts by weight of butyl acetate [0250] were mixed to obtain a curable component A-4 containing a compound containing an epoxy group.
[Synthesis of Component (b1)]

[Synthesis Example 1]

[0251] 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:

##STR00023##

(Rf.sup.1: —CF.sub.2O(CF.sub.2CF.sub.2O).sub.21.4(CF.sub.2O).sub.22.5CF.sub.2—, provided that the number of the repeating units is an average value determined by .sup.19F-NMR, and the same applies to the following Examples) [0252] and 0.79 mol % of a nonfunctional perfluoropolyether compound (b2-1) of the following formula:

F—Rf.sup.1—F,

16.3 g (0.070 mol) of CH.sub.2═CH(CH.sub.2).sub.6Si(OCH.sub.3).sub.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.sup.−7 mol 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 by .sup.1H-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 CH.sub.2═CH(CH.sub.2).sub.6Si(OCH.sub.3).sub.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 the .sup.19F-NMR spectrum, a peak of the CF.sub.3 group of m-xylene hexafluoride was not observed at −64 ppm, and the residual amount of m-xylene hexafluoride was 0% by weight.

##STR00024##

[Synthesis Example 2]

[0253] 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). [0254] CF.sub.3CF.sub.2O(CF.sub.2CF.sub.2O).sub.20.5(CF.sub.2O).sub.22.1CF.sub.2CF.sub.3

[Synthesis Example 3]

[0255] A compound (b2-2) of the above formula was added to the mixture (II-1) from

[0256] 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]

[0257] 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 CF.sub.3- group (terminal) derived from a nonfunctional perfluoropolyether compound (b2) was not detectable by .sup.19F-NMR:

##STR00025##

(Rf.sup.2: —CF.sub.2O(CF.sub.2CF.sub.2O).sub.20.9(CF.sub.2O).sub.21.2CF.sub.2—, 16.3 g (0.070 mol) of CH.sub.2═CH(CH.sub.2).sub.6Si(OCH.sub.3).sub.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.sup.−7 mol 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 by .sup.1H-NMR and IR, the reaction solution was cooled to room temperature. Subsequently, m-xylene hexafluoride and unreacted CH.sub.2═CH(CH.sub.2).sub.6Si(OCH.sub.3).sub.3 were 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 CF.sub.3 groups of m-xylene hexafluoride in a .sup.19F-NMR spectrum with hexafluorobenzene as a standard substance.

##STR00026##

[Preparation of surface modification component (B)]

[0258] 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.

[0259] [Chem. 56]

(H.sub.3CO).sub.3Si—CH.sub.2—CH.sub.2—CH.sub.2—O—CH.sub.2—Rf.sup.2—CH.sub.2—O—CH.sub.2—CH.sub.2—CH.sub.2—Si(OCH.sub.3).sub.3

(Rf.sup.2: —CF.sub.2O(CF.sub.2CF.sub.2O).sub.20.9(CF.sub.2O).sub.21.2CF.sub.2—)

[0260] 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-US-00001 TABLE 1 B-1 B-2 B-3 B-4 B-5 B-6 B-7 Synthesis Example 1 2 3 4 4 5 5 Mixture or compound (II-1) (II-2) (II-3) (IV-1) (IV-1) (V) (V) Mixture or compound 20 20 20 20 20 20 20 Compounding amount (pbw) (b2) mol % 0.72 3.0 4.8 0 0 0 0 Compounding amount 80 80 80 80 0 80 0 of MEK (pbw) Appearance Transparent Transparent Slight Transparent Slight Cloudy Slight cloudy cloudy cloudy (b2) mol % indicates a value relative against the total amount of component (b1) and component (b2), which is defined as 100 mol %

TABLE-US-00002 TABLE 2 B-8 B-9 B-10 B-11 B-12 Synthesis Example 1 1 1 2 2 Compound (II-1) (II-1) (II-1) (II-2) (II-2) Compound 10 20 40 20 20 Compounding amount (pbw) (b2) mol % 0.72 0.72 0.72 3.0 3.0 Type of solvent Heptane N-butanol Hexane Isododecane MPEG Compounding amount 90 80 60 80 80 of solvent (pbw) Appearance Transparent Transparent Transparent Transparent Transparent (b2) mol % indicates a value relative against the total amount of component (b1) and component (b2), which is defined as 100 mol %

[0261] [Examples 1 to 20 and Comparative Examples 1 to 9]

[Preparation of Fluorine-Containing Curable Composition and Results of Evaluation]

[0262] 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):

[0263] 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):

[0264] 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):

[0265] 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):

[0266] 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]

[0267] The transparency of the coating film and existence or non-existence of defects were examined.

[Water Contact Angle]

[0268] 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]

[0269] 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]

[0270] A fingerprint was put on the surface, and then wiped off with tissue paper, and the appearance was then visually evaluated.

TABLE-US-00003 TABLE 3 Example 1 Example 2 Example 3 Example 4 Example 5 Component (A) A-1 A-1 A-1 A-1 A-2 Number of 100 100 100 100 100 parts by weight of (A) Component (B) B-1 B-2 B-4 B-5 B-1 Number of  1.25  1.25  1.25  0.25  5 parts by weight of (B) Appearance in mixing Transparent Transparent Transparent Transparent Transparent Method for application (1) (1) (1) (1) (2) and curing Film thickness  15 μm  15 μm  15 μm  15 μm  12 μm after curing Appearance of film Transparent Transparent Transparent Transparent Transparent after curing and smooth and smooth and smooth and smooth and smooth Water contact angle (°) 111 113 112 111 110 Felt marker Well repellent Well repellent Well repellent Well repellent Well repellent ink-repellent property Fingerprint Easily Easily Easily Easily Easily wiping property wiped off wiped off wiped off wiped off wiped off

TABLE-US-00004 TABLE 4 Example 6 Example 7 Example 8 Example 9 Example 10 Component (A) A-2 A-2 A-3 A-3 A-3 Number of 100 100 100 100 100 parts by weight of (A) Component (B) B-2 B-5 B-1 B-2 B-5 Number of  5  1  5  1.25  0.25 parts by weight of (B) Appearance in mixing Transparent Transparent Transparent Transparent Transparent Method for application (2) (1) (1) (3) (3) and curing Film thickness  15 μm  24 μm  6 μm  4.5 μm  4.5 μm after curing Appearance of film Transparent Transparent Transparent Transparent Transparent after curing and smooth and smooth and smooth and smooth and smooth Water contact angle (°) 111 112 112 113 113 Felt marker Well repellent Well repellent Well repellent Well repellent Well repellent ink-repellent property Fingerprint Easily Easily Easily Easily Easily wiping property wiped off wiped off wiped off wiped off wiped off

TABLE-US-00005 TABLE 5 Example 11 Example 12 Example 13 Example 14 Example 15 Component (A) A-4 A-4 A-1 A-1 A-1 Number of 100 100 100 100 100 parts by weight of (A) Component (B) B-2 B-5 B-8 B-9 B-10 Number of  0.5  0.25  1.25  1.25  1.25 parts by weight of (B) Appearance in mixing Transparent Transparent Transparent Transparent Transparent Method for application (4) (4) (1) (1) (1) and curing Film thickness  4 μm  4 μm  15 μm  15 μm  15 μm after curing Appearance of film Transparent Transparent Transparent Transparent Transparent after curing and smooth* and smooth* and smooth and smooth and smooth Water contact angle (°) 113 112 112 111 113 Felt marker Well repellent Well repellent Well repellent Well repellent Well repellent ink-repellent property Fingerprint Easily Easily Easily Easily Easily wiping property wiped off wiped off wiped off wiped off wiped off *Slightly red color was observed immediately after heating, but disappeared with the lapse of time

TABLE-US-00006 TABLE 6 Example 16 Example 17 Example 18 Example 19 Example 20 Component (A) A-2 A-2 A-3 A-1 A-3 Number of 100 100 100 100 100 parts by weight of (A) Component (B) B-11 B-12 B-5 B-3 B-3 Number of  0.15  0.5  0.25  0.1  0.1 parts by weight of (B) Appearance in mixing Transparent Transparent Transparent Slight cloudy Slight cloudy Method for application (1) (2) (3) (4) (4) and curing Film thickness  24 μm  12 μm  4.5 μm  5 μm  2 μm after curing Appearance of film Transparent Transparent Transparent Slightly cloudy Transparent after curing and smooth and smooth and smooth and smooth and smooth Water contact angle (°) 111 113 113 112 113 Felt marker Well repellent Well repellent Well repellent Well repellent Well repellent ink-repellent property Fingerprint Easily Easily Easily Easily Easily wiping property wiped off wiped off wiped off wiped off wiped off

TABLE-US-00007 TABLE 7 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Component (A) A-1 A-1 A-2 A-3 A-4 Number of parts by weight of (A) 100 100 100 100 100 Component (B) B-6 B-7 B-7 B-7 B-7 Number of parts by weight of (B)  1.25  0.25  1  0.25  0.1 Appearance in mixing Cloudy Cloudy Cloudy Cloudy Cloudy

TABLE-US-00008 TABLE 8 Comparative Comparative Comparative Comparative Example 6 Example 7 Example 8 Example 9 Component (A) A-1 A-2 A-3 A-4 Number of parts by weight of (A) 100 100 100 100 Component (B) — — — — Number of parts by weight of (B)  0  0  0  0 Appearance Transparent Transparent Transparent Transparent Method for application and curing (1) (2) (3) (4) Appearance of film after curing Transparent Transparent Transparent Transparent and smooth and smooth and smooth and smooth Water contact angle (°)  95  92  79  84 Felt marker ink-repellent property Not repellent Not repellent Not repellent Not repellent Fingerprint wiping property Hardly wiped off Hardly wiped off Hardly wiped off Hardly wiped off