CURABLE COMPOSITION

Abstract

A curable composition includes a perfluoro(poly)ether group-containing silane compound represented by the general formula (I) (wherein, definitions of each group are as described in the specification); (b) an organic silicon compound having at least two OR.sup.2 groups bonded to Si atom (here, R.sup.2s are each independently a hydrogen atom or a monovalent organic group at each appearance) or a partially hydrolyzed condensate thereof; and (c) a condensation catalyst.

Claims

1. A curable composition which comprises (a) a perfluoro(poly)ether group-containing silane compound represented by the following general formula (I): ##STR00032## wherein, R.sup.3s each independently represent a hydrogen atom or a monovalent organic group at each appearance, R.sup.4s each independently represent a hydroxyl group or a hydrolyzable group(s) at each appearance, R.sup.5s each independently represent a j+a valent organic group at each appearance, R.sup.6s each independently represent a divalent organic group at each appearance, R.sup.7s each independently represent a hydrogen atom or a lower alkyl group at each appearance, provided that, at least one of R's is a hydrogen atom, PFPE's each independently represent a divalent perfluoro(poly)ether group represented by the formula:
—(C.sub.fF.sub.2f)—(OCF.sub.2).sub.a1—(OC.sub.2F.sub.4).sub.a2—(OC.sub.3X.sup.10.sub.6).sub.a3—(OC.sub.4F.sub.8).sub.a4—(OC.sub.5F.sub.10).sub.a5—(OC.sub.6F.sub.12).sub.a6—(OC.sub.7F.sub.14).sub.a7—(OC.sub.8F.sub.16).sub.a8— wherein, f is an integer of 1 or more and 10 or less, a1, a2, a3, a4, a5, a6, a7 and a8 are each independently an integer of 0 or more and 200 or less, a sum of a1, a2, a3, a4, a5, a6, a7 and a8 is an integer of 5 or more and 200 or less, and the unit represented by (C.sub.fF.sub.2f) is located at the left end of the group, the order of existence of each repeating unit enclosed in parentheses with the subscript a1, a2, a3, a4, a5, a6, a7 or a8 is arbitrary in the formula, X.sup.10s are each independently a hydrogen atom, a fluorine atom or a chlorine atom at each appearance, provided that when all X.sup.10s are hydrogen atoms or chlorine atoms, at least one of a1, a2, a4, a5, a6, a7 and a8 is an integer of 1 or more at each appearance, js are each independently an integer of 1 to 9 at each appearance, p and q are each 0 or 1, and r is an integer of 1 or more; (b) an organic silicon compound having at least two OR.sup.2 groups, where, Res are each independently a hydrogen atom or a monovalent organic group at each appearance, bonded to an Si atom, provided that, the (a) PFPE-containing silane compound is excluded, or a partially hydrolyzed condensate thereof; and (c) a condensation catalyst.

2. The curable composition according to claim 1, wherein R's in the perfluoro(poly)ether group-containing silane compound are all hydrogen atoms.

3. The curable composition according to claim 1, wherein r in the perfluoro(poly)-ether group-containing silane compound is an integer of 1 or more and 5 or less.

4. The curable composition according to claim 3, wherein R.sup.5 and R.sup.6 in the perfluoro(poly)ether group-containing silane compound are both divalent alkylene groups.

5. The curable composition according to claim 3, wherein j in the perfluoro(poly)-iether group-containing silane compound is 1.

6. The curable composition according to any claim 1, wherein the PFPE.sup.1 in the perfluoro(poly)ether group-containing silane compound is a divalent perfluoro(poly)ether group represented by the formula:
(C.sub.fF.sub.2f)—(OCF.sub.2).sub.a1—(OCF.sub.2CF.sub.2).sub.a2l—(OCF(CF.sub.3)).sub.a2′—(OCF.sub.2CF.sub.2CF.sub.2).sub.a3l—(OCF.sub.2CF(CF.sub.3)).sub.a3′—(OCF(CF.sub.3)CF.sub.2).sub.a3″—(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.a4— where, f is an integer of 1 or more and 4 or less, a1, a2, a3 and a4 are as defined in claim 1, a2l, a2′, a3l, a3′ and a3″ are each independently an integer of 0 or more and 200 or less, a sum of a2l and a2′ equals to a2, a sum of a3l, a3′ and a3″ equals to a3, a sum of a1, a2l, a2′, a3l, a3′, a3″ and a4 is 5 or more, and the order of existence of each repeating unit is arbitrary in the formula.

7. The curable composition according to claim 6, wherein, in the PFPE.sup.1 of the perfluoro(poly)ether group-containing silane compound, a1 is an integer of 0 or more and 50 or less, a2 is an integer of 0 or more and 50 or less, a3 is an integer of 0 or more and 30 or less, a4 is an integer of 0 or more and 30 or less, and a sum of a1, a2, a3 and a4 is 5 or more and 200 or less.

8. The curable composition according to claim 1, wherein Component (b) contains a compound represented by the following formula:
R.sup.1.sub.nSi(OR.sup.2).sub.4-n wherein, R.sup.1s each independently represent a substituted or unsubstituted monovalent hydrocarbon group at each appearance, R.sup.2s each independently represent a hydrogen atom or a monovalent organic group at each appearance, and n is 0, 1 or 2, or a partially hydrolyzed condensate thereof.

9. The curable composition according to claim 8, wherein Component (b) further contains a compound represented by the following formula (B2): ##STR00033## wherein, R.sup.g3s are each independently a hydrogen atom or a monovalent organic group at each appearance, R.sup.g4 is a substituted or unsubstituted monovalent hydrocarbon group, R.sup.g6s are each independently R.sup.g8—R.sup.g7— at each appearance, R.sup.g7s are each independently an alkylene group having 1 to 10 carbon atoms or a group having 1 to 10 carbon atoms and containing a nitrogen atom(s) or an oxygen atom(s) in a main chain at each appearance, R.sup.g8s are each independently a primary amino group, an epoxy group, a (meth)acryloyl group, a (meth)acryloxy group, a mercapto group or an isocyanate group at each appearance, ε4 is 2 or 3, ε5 is 0 or 1, and ε6 is 1 or 2, provided that a sum of ε4, ε5 and ε6 is 4, or a partially hydrolyzed condensate thereof.

Description

EXAMPLES

[1322] The present invention will be explained more specifically by referring to the following Examples, but is not limited to these Examples. Incidentally, in the present Examples, the order of existence of recurring units constituting the perfluoro(poly)ether is arbitrary.

Production Example 1

[1323] Preparation of PFPE-Containing Silane Compound (a)

[1324] In 2,000 mL of a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer were charged 1,000 g of a PFPE-modified ester material represented by an average composition of CH.sub.3OCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17—OCF.sub.2—COOCH.sub.3 and 500 g of 1,3-bis(trifluoromethyl)benzene, and after adding 10 mL of ethylenediamine using a dropping funnel under nitrogen stream, the mixture was stirred at 25° C. for one hour. Subsequently, after adding 51 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for one hour. Thereafter, by distilling off the volatile component under reduced pressure, a PFPE-containing silane compound (a) represented by the following formula was obtained. Regarding the obtained PFPE-containing silane compound (a), integrated values of the peaks of —CF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 and -CF.sub.2—COOCH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 97 mol %.

[1325] PFPE-Containing Silane Compound (a)

(CH.sub.3O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17OCF.sub.2—CONHCH.sub.2CH.sub.2NHCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17—OCF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3

Production Example 2

[1326] Preparation of PFPE-Containing Silane Compound (a′)

[1327] In 1,000 mL of a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged 1,000 g of a PFPE-modified ester material represented by an average composition of CH.sub.3OCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17—OCF.sub.2—COOCH.sub.3, and after adding 102 mL of 3-aminopropyltrimethoxysilane under nitrogen stream, the mixture was stirred at 25° C. for one hour. Thereafter, by distilling off the volatile component under reduced pressure, a PFPE-containing silane compound (a′) represented by the following formula was obtained. Regarding the obtained PFPE-containing silane compound (a′), integrated values of the peaks of —CF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 and -CF.sub.2—COOCH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 95 mol %.

[1328] PFPE-Containing Silane Compound (a′)

(CH.sub.3O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17—OCF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3

[1329] PFPE-Modified Ester Material

CH.sub.3OCO—CF.sub.2—(OCF.sub.2).sub.29—(OCF.sub.2CF.sub.2).sub.17—OCF.sub.2—COOCH.sub.3

Production Example 3

[1330] Preparation of PFPE-Containing Silane Compound (b)

[1331] In 2,000 mL of a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer were charged 1,000 g of a PFPE-modified ester material represented by an average composition of CH.sub.3CH.sub.2OCO—CF.sub.2—(OCF.sub.2).sub.12—(OCF.sub.2CF.sub.2).sub.12—OCF.sub.2—COOCH.sub.2CH.sub.3 and 500 g of 1,3-bis(trifluoromethyl)benzene, and after adding 13 mL of ethylenediamine using a dropping funnel under nitrogen stream, the mixture was stirred at 25° C. for one hour. Subsequently, after adding 69 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 25° C. for one hour. Thereafter, by distilling off the volatile component under reduced pressure, a PFPE-containing silane compound (b) represented by the following formula was obtained. Regarding the obtained PFPE-containing silane compound (b), integrated values of the peaks of —CF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OR′).sub.3 and -CF.sub.2—COOCH.sub.2CH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 98 mol %. Incidentally, as R′ in the following formula, CH.sub.3 was 89 mol % and CH.sub.2CH.sub.3 was 11 mol % by .sup.1H-NMR analysis.

[1332] PFPE-Containing Silane Compound (b)

(R′O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF.sub.2—(OCF.sub.2).sub.12—(OCF.sub.2CF.sub.2).sub.12—OCF.sub.2—CONHCH.sub.2CH.sub.2NHCO—CF.sub.2—(OCF.sub.2).sub.12—(OCF.sub.2CF.sub.2).sub.12—OCF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OR′).sub.3

Production Example 4

[1333] Preparation of PFPE-Containing Silane Compound (b′)

[1334] In 1,000 mL of a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged 1,000 g of a PFPE-modified ester material represented by an average composition of CH.sub.3CH.sub.2OCO—CF.sub.2—(OCF.sub.2).sub.12—(OCF.sub.2CF.sub.2).sub.12—OCF.sub.2—COOCH.sub.2CH.sub.3, and after adding 141 mL of 3-aminopropyltrimethoxysilane under nitrogen stream, the mixture was stirred at 25° C. for one hour. Thereafter, by distilling off the volatile component under reduced pressure, a PFPE-containing silane compound (b′) represented by the following formula was obtained. Regarding the obtained PFPE-containing silane compound (b′), integrated values of the peaks of —CF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OR′).sub.3 and -CF.sub.2—COOCH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 99 mol %. Incidentally, as R′ in the following formula, CH.sub.3 was 91 mol % and CH.sub.2CH.sub.3 was 9 mol % by .sup.1H-NMR analysis.

[1335] PFPE-Containing Silane Compound (b′)

(RO′).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF.sub.2—(OCF.sub.2).sub.12—(OCF.sub.2CF.sub.2).sub.12—OCF.sub.2—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OR′).sub.3

Production Example 5

[1336] Preparation of PFPE-Containing Silane Compounds (c1) and (c2)

[1337] A PFPE mixture 1 containing the following Components (C1) and (C2) was prepared.

CH.sub.3OCO—CF(CF.sub.3)—{OCF.sub.2CF(CF.sub.3)}.sub.m—OCF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.n—CF(CF.sub.3)—COOCH.sub.3(m+n=12)  (C1)

CF.sub.3CF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.12—CF(CF.sub.3)—COOCH.sub.3

(1):(C.sub.2)=75:15 (molar ratio)  (C2)

[1338] In 2,000 mL of a four-necked flask equipped with a reflex condenser, a thermometer and a stirrer were charged 1,000 g of the PFPE mixture 1 and 500 g of 1,3-bis(trifluoromethyl)benzene, using a dropping funnel under nitrogen stream, and after adding 13 mL of ethylenediamine using a dropping funnel, the mixture was stirred at 70° C. for 10 hours. Subsequently, after adding 57 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 70° C. for 12 hours. Thereafter, by distilling off the volatile component under reduced pressure, PFPE-containing silane compounds (el) and (c2) represented by the following formulae were obtained. Regarding the obtained PFPE-containing silane compounds (el) and (c2), integrated values of the peaks of —CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 and —CF(CF.sub.3)—COOCH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 99 mol %.

[1339] PFPE-Containing Silane Compound (c1)

(CH.sub.3O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF(CF.sub.3)—{OCF.sub.2CF(CF.sub.3)}m-OCF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.n—CF(CF.sub.3)—CONHCH.sub.2CH.sub.2NHCO—CF(CF.sub.3)—{OCF.sub.2CF(CF.sub.3)}.sub.m—OCF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.n′—CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 (wherein, m+n=12, m′+n′=12)

[1340] PFPE-Containing Silane Compound (c2)

CF.sub.3CF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.12—CF(CF.sub.3)—CONHCH.sub.2CH.sub.2NHCO—CF(CF.sub.3)—{OCF.sub.2CF(CF.sub.3)}.sub.m—OCF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.n—CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 (wherein, m+n=12)

Production Example 6

[1341] Preparation of PFPE-Containing Silane Compounds (c1′) and (c2′)

[1342] In 1,000 mL of a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer were charged 1,000 g of the PFPE mixture 1 and 500 g of 1,3-bis(trifluoromethyl)benzene, under nitrogen stream, and after adding 123 mL of 3-aminopropyltrimethoxysilane, the mixture was stirred at 70° C. for 12 hours. Thereafter, by distilling off the volatile component under reduced pressure, PFPE-containing silane compounds (c1′) and (c2′) represented by the following formulae were obtained. Regarding the obtained PFPE-containing silane compounds (c1′) and (c2′), integrated values of the peaks of —CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 and —CF(CF.sub.3)—COOCH.sub.3 which is the raw material were compared by .sup.19F-NMR analysis, and the silane terminalization rate was calculated to be 98 mol %.

[1343] PFPE-Containing Silane Compound (c1′)

(CH.sub.3O).sub.3Si—CH.sub.2CH.sub.2CH.sub.2—NHCO—CF(CF.sub.3)—{OCF.sub.2CF(CF.sub.3)}.sub.m—OCF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.n—CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3 (wherein, m+n=12)

[1344] PFPE-Containing Silane Compound (c2′)

CF.sub.3CF.sub.2CF.sub.2O—{CF(CF.sub.3)CF.sub.2O}.sub.12—CF(CF.sub.3)—CONH—CH.sub.2CH.sub.2CH.sub.2—Si(OCH.sub.3).sub.3

Example 1

[1345] Preparation of Curable Composition

[1346] In a glass apparatus for mixing were weighed 100 parts by mass of the PFPE-containing silane compound (a), 2 parts by mass of methyltrimethoxysilane as a crosslinking agent and 0.1 part by mass of dibutylbis(triethoxysiloxy)tin as a catalyst, and stirring was carried out using a magnetic stirrer to produce a curable composition.

Example 2

[1347] In the same manner as in Example 1 except for using 2 parts by mass of diisopropoxytitanium bis(ethylacetacetate) as a catalyst in place of dibutylbis(triethoxy-siloxy)tin, a curable composition was produced.

Example 3

[1348] In the same manner as in Example 2 except for changing the PFPE-containing silane compound (a) to the PFPE-containing silane compound (b) of Production Example 3, a curable composition was produced.

Comparative Example 1

[1349] In the same manner as in Example 1 except for changing the PFPE-containing silane compound (a) to the following compound (a′), a curable composition was produced.

Comparative Example 2

[1350] In the same manner as in Example 2 except for changing the PFPE-containing silane compound (a) to the above-mentioned compound (a′), a curable composition was produced.

[1351] (Deep Part Curability Test)

[1352] The curable composition produced in each Example and Comparative Example were poured into a mold made of polytetrafluoroethylene (PTFE) having a height and width of 5 cm and a depth of 2 mm so as to have a height of 20 mm, and placed in an atmosphere of 23° C., and a relative humidity of 50%. Whether it is cured or not was judged by observing the interface between the solid and the liquid, the distance from the surface to the cured portion was measured, and the time required for curing to a thickness of 500 μm was measured. The results are shown in the following Table 1.

TABLE-US-00001 TABLE 1 500 μm curing time (hr) Example 1 18 Example 2 27 Example 3 24 Comparative Example 1 44 Comparative Example 2 48

[1353] As shown in Table 1, in Examples, that is, the curable compositions using the PFPE-containing silane compound (a) or (b) wherein r=1 or more in the general formula (I), the time of curing to a thickness of 500 μm was short, and it could be understood that they were excellent in deep part curability. On the other hand, in Comparative Examples, that is, the compound wherein r=0 in the general formula (I), the time of curing to a deep part was long, and thus, the curable compositions of Examples were superior in the points of reliability that the adhesion of an adhesive substrate could be carried out more certainly and stably, and operability that stable adhesion of the substrate could be completed in a short time.

UTILIZABILITY IN INDUSTRY

[1354] The present invention provides a curable composition which can be cured by moisture at room temperature and cures to a deep part. Since it is good in deep part curability, the curable composition of the present invention has high reliability in adhesion, and can be suitably used in peripherals of electrical and electronic parts and peripheral uses of automobile parts.