TW202239814A - Composition containing fluoropolyether group-containing silane compound - Google Patents
Composition containing fluoropolyether group-containing silane compound Download PDFInfo
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Abstract
Description
本發明係關於包含具有氟聚醚基之矽烷化合物的組成物。 The present invention relates to a composition comprising a silane compound having a fluoropolyether group.
已知一種含氟矽烷化合物,若用於基材的表面處理,可提供優良的撥水性、撥油性、防污性等。由含有含氟矽烷化合物的組成物(例如表面處理劑)所得之層(以下亦稱為「表面處理層」),作為所謂的機能性薄膜而施用於例如玻璃、塑膠、纖維、建材等各式各樣的基材上。 It is known that a fluorine-containing silane compound can provide excellent water repellency, oil repellency, and antifouling properties if used for surface treatment of substrates. A layer obtained from a composition (such as a surface treatment agent) containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer") is applied as a so-called functional film to various types of glass, plastic, fiber, building materials, etc. on a variety of substrates.
作為這樣的含氟化物,已知一種含全氟聚醚基之矽烷化合物,其係在分子主鏈具有全氟聚醚基、且在分子末端或末端部具有鍵結於Si原子的可水解之基(專利文獻1、2)。 As such a fluorine-containing compound, there is known a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the main chain of the molecule and a hydrolyzable compound bonded to an Si atom at the molecular terminal or terminal portion. base (Patent Documents 1, 2).
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Document]
[專利文獻1]日本特表2008-534696號公報 [Patent Document 1] Japanese National Publication No. 2008-534696
[專利文獻2]國際公開第97/07155號 [Patent Document 2] International Publication No. 97/07155
對於包含具有上述矽烷化合物之組成物的組成物,要求由該組成物所形成之表面處理層具有更良好的摩擦耐久性。 For a composition including a composition having the above-mentioned silane compound, a surface treatment layer formed from the composition is required to have better friction durability.
本揭示提供下述[1]至[24]。 The present disclosure provides the following [1] to [24].
[1] [1]
一種組成物,其包含下述式(A1)或(A2)所表示的具有氟聚醚基之矽烷化合物、及具有下述式(B)所表示之基且分子量為300至500的具有氟烷基之矽烷化合物; A composition comprising a silane compound having a fluoropolyether group represented by the following formula (A1) or (A2), and a fluoroalkane compound having a group represented by the following formula (B) and having a molecular weight of 300 to 500 base silane compounds;
-SiR31 n3R32 3-n3 (B) -SiR 31 n3 R 32 3-n3 (B)
前述具有氟烷基之矽烷化合物之莫耳數相對於前述具有氟聚醚基之矽烷化合物之莫耳數的比率為0.001至1.5;[式中: The ratio of the number of moles of the aforementioned silane compound having a fluoroalkyl group to the number of moles of the aforementioned silane compound having a fluoropolyether group is 0.001 to 1.5; [wherein:
RF1為Rf1-RF-Oq-; R F1 is Rf 1 -R F -O q -;
RF2為-Rf2 p-RF-Oq-; R F2 is -Rf 2 p -R F -O q -;
Rf1為可經1個以上的氟原子取代的C1-16烷基; Rf 1 is a C 1-16 alkyl group that may be substituted by one or more fluorine atoms;
Rf2為可經1個以上的氟原子取代的C1-6伸烷基; Rf 2 is a C 1-6 alkylene group that may be substituted by one or more fluorine atoms;
RF在每次出現時分別獨立地為下式所表示之基, Each occurrence of R F is independently a basis represented by the following formula,
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3RFa 6)d-(OC2F4)e-(OCF2)f-; -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -;
a、b、c、d、e及f分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1,標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意; a, b, c, d, e and f are independently integers from 0 to 200, the sum of a, b, c, d, e and f is at least 1, and a, b, c, d, e or f and the presence order of each repeating unit enclosed in brackets in the formula is arbitrary;
RFa在每次出現時分別獨立地為氫原子、氟原子或氯原子; Each occurrence of R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom;
p為0或1; p is 0 or 1;
q獨立地為0或1; q is independently 0 or 1;
RSi在每次出現時分別獨立地為下述式(S1)至(S2)所表示之基的任一者; Each occurrence of R Si is independently any one of the groups represented by the following formulas (S1) to (S2);
-SiRa1 k1Rb1 l1Rc1 m1 (S1) -SiR a1 k1 R b1 l1 R c1 m1 (S1)
-CRd1 k2Re1 l2Rf1 m2 (S2) -CR d1 k2 R e1 l2 R f1 m2 (S2)
Ra1在每次出現時分別獨立地為-Z1-SiR41 r1R42 r2R43 r3; each occurrence of R a1 is independently -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 ;
Z1在每次出現時分別獨立地為氧原子或2價之有機基; Each occurrence of Z 1 is independently an oxygen atom or a divalent organic group;
R41在每次出現時分別獨立地為-Z1’-SiR41’ r1’R42’ r2’R43’ r3’; Each occurrence of R 41 is independently -Z 1' -SiR 41' r1' R 42' r2' R 43' r3' ;
Z1’在每次出現時分別獨立地為氧原子或2價之有機基; Each occurrence of Z 1' is independently an oxygen atom or a divalent organic group;
R41’在每次出現時分別獨立地為-Z1”-SiR41” r1”R42” r2”; each occurrence of R 41' is independently -Z 1" -SiR 41" r1" R 42" r2" ;
Z1”在每次出現時分別獨立地為氧原子或2價之有機基; Each occurrence of Z 1" is independently an oxygen atom or a divalent organic group;
R41”在每次出現時分別獨立地為羥基或可水解之基; R 41" is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R42”在每次出現時分別獨立地為氫原子或1價之有機基; Each occurrence of R 42" is independently a hydrogen atom or a monovalent organic group;
r1”在每次出現時分別獨立地為0至3的整數; r1" is independently at each occurrence an integer from 0 to 3;
r2”在每次出現時分別獨立地為0至3的整數; r2" is independently at each occurrence an integer from 0 to 3;
R42’在每次出現時分別獨立地為羥基或可水解之基; R 42' is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R43’在每次出現時分別獨立地為氫原子或1價之有機基; Each occurrence of R 43' is independently a hydrogen atom or a monovalent organic group;
r1’在每次出現時分別獨立地為0至3的整數; r1' is independently an integer from 0 to 3 at each occurrence;
r2’在每次出現時分別獨立地為0至3的整數; r2' is independently an integer from 0 to 3 at each occurrence;
r3’在每次出現時分別獨立地為0至3的整數; r3' is independently an integer from 0 to 3 each time it occurs;
R42在每次出現時分別獨立地為羥基或可水解之基; R 42 is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R43在每次出現時分別獨立地為氫原子或1價之有機基; Each occurrence of R43 is independently a hydrogen atom or a monovalent organic group;
r1在每次出現時分別獨立地為0至3的整數; r1 is independently an integer from 0 to 3 at each occurrence;
r2在每次出現時分別獨立地為0至3的整數; r2 is independently an integer from 0 to 3 at each occurrence;
r3在每次出現時分別獨立地為0至3的整數; r3 is independently an integer from 0 to 3 at each occurrence;
Rb1在每次出現時分別獨立地為羥基或可水解之基; each occurrence of R b1 is independently hydroxyl or a hydrolyzable group;
Rc1在每次出現時分別獨立地為氫原子或1價之有機基; Each occurrence of R c1 is independently a hydrogen atom or a monovalent organic group;
k1在每次出現時分別獨立地為0至3的整數; k1 is independently an integer from 0 to 3 at each occurrence;
l1在每次出現時分別獨立地為0至3的整數; l1 is independently an integer from 0 to 3 at each occurrence;
m1在每次出現時分別獨立地為0至3的整數; m1 is independently an integer from 0 to 3 at each occurrence;
惟式(S1)中,至少存在1個與羥基或可水解之基鍵結的Si原子; However, in formula (S1), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group;
Rd1在每次出現時分別獨立地為-Z2-CR51 s1R52 s2R53 s3; R d1 is independently at each occurrence -Z 2 -CR 51 s1 R 52 s2 R 53 s3 ;
Z2在每次出現時分別獨立地為單鍵、氧原子或2價之有機基; Each occurrence of Z2 is independently a single bond, an oxygen atom or a divalent organic group;
R51在每次出現時分別獨立地為-Z2’-CR51’ s1’R52’ s2’; R 51 is independently at each occurrence -Z 2' -CR 51' s1' R 52' s2' ;
Z2’在每次出現時分別獨立地為單鍵、氧原子或2價之有機基; Each occurrence of Z 2' is independently a single bond, an oxygen atom or a divalent organic group;
R51’在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”; R 51' is independently at each occurrence -Z 3 -SiR 51" m1" R 52" 3-m1" ;
Z3在每次出現時分別獨立地為單鍵、氧原子或2價之有機基; Each occurrence of Z3 is independently a single bond, an oxygen atom or a divalent organic group;
R51”在每次出現時分別獨立地為羥基或可水解之基; R 51" is independently at each occurrence a hydroxyl group or a hydrolyzable group;
R52”在每次出現時分別獨立地為氫原子或1價之有機基; R 52" is independently a hydrogen atom or a monovalent organic group at each occurrence;
m1”在每次出現時分別獨立地為0至3的整數; m1" is independently at each occurrence an integer from 0 to 3;
R52’在每次出現時分別獨立地為氫原子、羥基或1價之有機基; Each occurrence of R 52' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;
s1’在每次出現時分別獨立地為0至3的整數; s1' is independently an integer from 0 to 3 each time it occurs;
s2’在每次出現時分別獨立地為0至3的整數; s2' is independently an integer from 0 to 3 each time it occurs;
R52在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”; R 52 is independently at each occurrence -Z 3 -SiR 51" m1" R 52" 3-m1" ;
R53在每次出現時分別獨立地為氫原子、羥基或1價之有機基; Each occurrence of R53 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;
s1在每次出現時分別獨立地為0至3的整數; s1 is independently an integer from 0 to 3 at each occurrence;
s2在每次出現時分別獨立地為0至3的整數; s2 is independently an integer from 0 to 3 at each occurrence;
s3在每次出現時分別獨立地為0至3的整數; s3 is independently an integer from 0 to 3 at each occurrence;
Re1在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”; R e1 is independently at each occurrence -Z 3 -SiR 51" m1" R 52" 3-m1" ;
Rf1在每次出現時分別獨立地為氫原子、羥基或1價之有機基; Each occurrence of R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group;
k2在每次出現時分別獨立地為0至3的整數; k2 is independently an integer from 0 to 3 at each occurrence;
l2在每次出現時分別獨立地為0至3的整數; l2 is independently an integer from 0 to 3 at each occurrence;
m2在每次出現時分別獨立地為0至3的整數; m2 is independently an integer from 0 to 3 at each occurrence;
惟式(S2)中,至少存在1個m1”為1至3的-SiR51” m1”R52” 3-m1”; However, in formula (S2), there is at least one -SiR 51" m1" R 52" 3-m1" in which m1" is 1 to 3;
Rn在每次出現時分別獨立地為-X1-RSi所表示之基、氫原子、苯基或C1-6烷基; Each occurrence of R n is independently a group represented by -X 1 -R Si , a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
X1在每次出現時分別獨立地為單鍵或2價之有機基; Each occurrence of X1 is independently a single bond or a divalent organic group;
R31在每次出現時分別獨立地為羥基或可水解之基; R independently at each occurrence is hydroxyl or a hydrolyzable group;
R32在每次出現時分別獨立地為氫原子或1價之有機基; Each occurrence of R32 is independently a hydrogen atom or a monovalent organic group;
n3在每次出現時分別獨立地為0至3的整數; n3 is independently an integer from 0 to 3 each time it occurs;
惟前述具有氟烷基之矽烷化合物中,至少1個n3為1以上]。 However, in the aforementioned silane compounds having a fluoroalkyl group, at least one n3 is 1 or more].
[2] [2]
如[1]所述之組成物,其中, The composition as described in [1], wherein,
RF在每次出現時分別獨立地為下述式(f1)、(f2)、(f3)、(f4)或(f5)所表示之基: Each occurrence of R F is independently represented by the following formula (f1), (f2), (f3), (f4) or (f5):
-(OC3F6)d-(OC2F4)e- (f1) -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)
[式中,d為1至200的整數,e為0或1]; [wherein, d is an integer from 1 to 200, and e is 0 or 1];
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2) -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f2)
[式中,c及d分別獨立地為0以上30以下的整數,e及f分別獨立地為1以上200以下的整數, [wherein, c and d are each independently an integer of 0 to 30, and e and f are each independently an integer of 1 to 200,
c、d、e及f的和為2以上, The sum of c, d, e and f is 2 or more,
標註c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意]; The order of the repeating units marked with c, d, e or f and enclosed in brackets in the formula is arbitrary];
-(R6-R7)g- (f3) -(R 6 -R 7 ) g - (f3)
[式中,R6為OCF2或OC2F4, [wherein, R 6 is OCF 2 or OC 2 F 4 ,
R7係選自OC2F4、OC3F6、OC4F8、OC5F10及OC6F12之中的基,或是從此等之基獨立選擇的2或3個基的組合, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of 2 or 3 groups independently selected from these groups ,
g為2至100的整數]; g is an integer from 2 to 100];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f4) -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f4)
[式中,e為1以上200以下的整數,a、b、c、d及f分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1,又,標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意]; [wherein, e is an integer ranging from 1 to 200, a, b, c, d, and f are each independently an integer ranging from 0 to 200, and the sum of a, b, c, d, e, and f is at least 1, Also, the order of the repeating units marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary];
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5) -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f5)
[式中,f為1以上200以下的整數,a、b、c、d及e分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1,又,標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意]。 [wherein, f is an integer of 1 to 200, a, b, c, d, and e are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is at least 1, Also, the presence order of each repeating unit in the formula marked with a, b, c, d, e or f and enclosed in brackets is arbitrary].
[3] [3]
如[1]或[2]所述之組成物,其中X1在每次出現時分別獨立地為-(R21)p1-(Xa)q1-所表示之基; The composition as described in [1] or [2], wherein each occurrence of X 1 is independently a group represented by -(R 21 ) p1 -(X a ) q1 -;
[式中: [where:
R21為單鍵、可經1個以上的氟原子取代的-(CH2)p2-或是鄰、間或對伸苯基, R 21 is a single bond, -(CH 2 ) p2 - which may be substituted by one or more fluorine atoms, or an o-, m-, or p-phenylene group,
p2為1至20的整數, p2 is an integer from 1 to 20,
Xa表示-(Xb)q2-、 X a represents -(X b ) q2 -,
Xb在每次出現時分別獨立地為選自由-O-、-S-、鄰、間或對伸苯基、-(OR35)n4-、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CON(R34)-、-O-CON(R34)-、-N(R34)-及-(CH2)n’-所成群組中的基, Each occurrence of X b is independently selected from -O-, -S-, o-, m-, or p-phenylene, -(OR 35 ) n4 -, -C(O)O-, -Si(R 33 ) 2 -, -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CON(R 34 )-, -O-CON(R 34 )-, -N(R 34 ) - and -(CH 2 ) n' - the radical in the group formed,
R33在每次出現時分別獨立地為苯基、C1-6烷基或C1-6烷氧基, R 33 is independently phenyl, C 1-6 alkyl or C 1-6 alkoxy at each occurrence,
R34在每次出現時分別獨立地為氫原子、苯基或C1-6烷基, R 34 is independently a hydrogen atom, a phenyl group or a C 1-6 alkyl group at each occurrence,
R35在每次出現時分別獨立地為C1-6伸烷基, R 35 is independently C 1-6 alkylene at each occurrence,
n4在每次出現時分別獨立地為1至5的整數, n4 is independently an integer from 1 to 5 at each occurrence,
m’在每次出現時分別獨立地為1至100的整數, m' is independently at each occurrence an integer from 1 to 100,
n’在每次出現時分別獨立地為1至20的整數, n' is independently at each occurrence an integer from 1 to 20,
q2為1至10的整數, q2 is an integer from 1 to 10,
p1為0或1, p1 is 0 or 1,
q1為0或1, q1 is 0 or 1,
此處,標註p1或q1並以括弧括起之各重複單元的存在順序為任意]。 Here, the presence order of each repeating unit marked with p1 or q1 and enclosed in brackets is arbitrary].
[4] [4]
如[1]至[3]中任一項所述之組成物,其中Z1及Z3在每次出現時分別獨立地為C1-6伸烷基。 The composition as described in any one of [1] to [3], wherein Z 1 and Z 3 are independently C 1-6 alkylene at each occurrence.
[5] [5]
如[1]至[4]中任一項所述之組成物,其中k1為2或3,且r2為2或3。 The composition according to any one of [1] to [4], wherein k1 is 2 or 3, and r2 is 2 or 3.
[6] [6]
如[1]至[4]中任一項所述之組成物,其中k1為0,l1為2或3。 The composition according to any one of [1] to [4], wherein k1 is 0, and l1 is 2 or 3.
[7] [7]
如[1]至[4]中任一項所述之組成物,其中l2為2或3,且m1”為2或3。 The composition according to any one of [1] to [4], wherein l2 is 2 or 3, and m1" is 2 or 3.
[8] [8]
如[1]至[4]中任一項所述之組成物,其中l2為2,m2為1。 The composition according to any one of [1] to [4], wherein l2 is 2 and m2 is 1.
[9] [9]
如[1]至[8]中任一項所述之組成物,其中Rn為氫原子、苯基或C1-6烷基。 The composition according to any one of [1] to [8], wherein R n is a hydrogen atom, a phenyl group or a C 1-6 alkyl group.
[10] [10]
如[1]至[8]中任一項所述之組成物,其中Rn係以-X1-RSi所表示。 The composition according to any one of [1] to [8], wherein R n is represented by -X 1 -R Si .
[11] [11]
如[10]所述之組成物,其中Rn係以-X1-RSi所表示,式(A1)或(A2)中RSi係以式(S1)所表示,k1為0。 The composition as described in [10], wherein R n is represented by -X 1 -R Si , R Si in formula (A1) or (A2) is represented by formula (S1), and k1 is 0.
[12] [12]
如[1]至[10]中任一項所述之組成物,其中RSi係以式(S1)所表示。 The composition according to any one of [1] to [10], wherein R Si is represented by formula (S1).
[13] [13]
如[1]至[10]中任一項所述之組成物,其中RSi係以式(S2)所表示。 The composition according to any one of [1] to [10], wherein R Si is represented by formula (S2).
[14] [14]
如[1]至[13]中任一項所述之組成物,其中前述具有氟烷基之矽烷化合物係由式(B1)所表示: The composition as described in any one of [1] to [13], wherein the aforementioned silane compound having a fluoroalkyl group is represented by formula (B1):
Rf3-X31-SiR31 n3R32 3-n3 (B1) Rf 3 -X 31 -SiR 31 n3 R 32 3-n3 (B1)
Rf3為可經1個以上的氟原子取代的C1-6烷基; Rf 3 is a C 1-6 alkyl group that may be substituted by one or more fluorine atoms;
X31為單鍵、氧原子或2價之有機基; X31 is a single bond, an oxygen atom or a divalent organic group;
R31分別獨立地為羥基或可水解之基; R 31 are each independently a hydroxyl group or a hydrolyzable group;
R32分別獨立地為氫原子或1價之有機基; R32 are each independently a hydrogen atom or a monovalent organic group;
n3為1至3的整數。 n3 is an integer of 1 to 3.
[15] [15]
如[14]所述之組成物,其中Rf3為C1-6全氟烷基。 The composition as described in [14], wherein Rf 3 is C 1-6 perfluoroalkyl.
[16] [16]
如[14]或[15]所述之組成物,其中, The composition as described in [14] or [15], wherein,
X31係以-(X311)z11-(Z31)z12-所表示, X 31 is represented by -(X 311 ) z11 -(Z 31 ) z12 -,
X311為可經1個以上的氟原子取代的C1-6伸烷基, X 311 is a C 1-6 alkylene group that may be substituted by one or more fluorine atoms,
Z31分別獨立地為氧原子或硫原子, Z 31 are each independently an oxygen atom or a sulfur atom,
z11為1至3的整數, z11 is an integer from 1 to 3,
z12為0至2的整數, z12 is an integer from 0 to 2,
惟以括弧括起之各重複單元的存在順序在X31中為任意。 However, the order of existence of the repeating units enclosed in brackets is arbitrary in X31 .
[17] [17]
如[1]至[16]中任一項所述之組成物,其中n3為3。 The composition according to any one of [1] to [16], wherein n3 is 3.
[18] [18]
如[1]至[17]中任一項所述之組成物,其更具有含氟油。 The composition according to any one of [1] to [17], further comprising a fluorine-containing oil.
[19] [19]
如[18]所述之組成物,其中前述含氟油係以下式所表示, The composition as described in [18], wherein the fluorine-containing oil is represented by the following formula,
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6 Rf 5 -(OC 4 F 8 ) a' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c' -(OCF 2 ) d' -Rf 6
Rf5及Rf6分別獨立地為可經1個以上的氟原子取代的碳數1至16烷基, Rf 5 and Rf 6 are each independently an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms,
a’及b’分別獨立地為0以上30以下的整數,c’及d’分別獨立地為1以上200以下的整數,a’、b’、c’及d’的和至少為5以上,標註a’、b’、c’或d’並以括弧括起之各重複單元在式中的存在順序為任意。 a' and b' are each independently an integer of 0 to 30, c' and d' are each independently an integer of 1 to 200, and the sum of a', b', c' and d' is at least 5 or more, The presence order of each repeating unit marked with a', b', c' or d' and enclosed in brackets in the formula is arbitrary.
[20] [20]
如[1]至[19]中任一項所述之組成物,其包含式(A1)所表示的具有氟聚醚基之矽烷化合物及式(A2)所表示的具有氟聚醚基之矽烷化合物以作為具有氟聚醚基之矽烷化合物, The composition according to any one of [1] to [19], comprising a silane compound having a fluoropolyether group represented by formula (A1) and a silane compound having a fluoropolyether group represented by formula (A2) Compounds as silane compounds with fluoropolyether groups,
並且更具有含氟油。 And more with fluorine oil.
[21] [twenty one]
如[1]至[20]中任一項所述之組成物,其不包含選自由前述具有氟烷基之矽烷化合物所成群組中的化合物之寡聚物。 The composition according to any one of [1] to [20], which does not contain an oligomer of a compound selected from the group consisting of the aforementioned fluoroalkyl-containing silane compounds.
[22] [twenty two]
一種表面處理劑,其包含如[1]至[21]中任一項所述之組成物。 A surface treatment agent comprising the composition according to any one of [1] to [21].
[23] [twenty three]
如[22]所述之表面處理劑,其為濕潤被覆用。 The surface treatment agent as described in [22], which is used for wet coating.
[24] [twenty four]
一種物品,其具有:基材、及藉由如[1]至[21]中任一項所述之組成物或如[22]至[23]中任一項所述之表面處理劑形成於該基材表面上的層。 An article, which has: a substrate, and formed on the surface by the composition as described in any one of [1] to [21] or the surface treatment agent as described in any one of [22] to [23] layer on the surface of the substrate.
本揭示提供一種表面處理劑,其有助於形成具有更良好之摩擦耐久性的表面處理層。 The present disclosure provides a surface treatment agent, which helps to form a surface treatment layer with better friction durability.
於本說明書使用時,「烴基」係指含碳及氫之基,其係使1個氫原子從烴脫離而成的基。此烴基並未特別限定,可列舉可經1個以上的取代基取代的碳數1至20的烴基,例如脂肪族烴基、芳香族烴基等。上述「脂肪族烴基」可為直鏈狀、分枝鏈狀或環狀的任一者,亦可為飽和或不飽和的任一者。又,烴基亦可含有1個以上的環構造。此外,該烴基在其末端或分子鏈中亦可具有1個以上的N、O、S、Si、醯胺、磺醯基、矽氧烷、羰基、羰氧基等。 When used in this specification, a "hydrocarbon group" means a group containing carbon and hydrogen, which is a group obtained by detaching one hydrogen atom from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms that may be substituted with one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The aforementioned "aliphatic hydrocarbon group" may be any of linear, branched or cyclic, and may be either saturated or unsaturated. Also, the hydrocarbon group may have one or more ring structures. In addition, the hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.
於本說明書使用時,「烴基」的取代基並未特別限定,可列舉例如:鹵素原子;可經1個以上的鹵素原子取代的選自C1-6烷基、C2-6烯基、C2-6炔基、C3-10環烷基、C3-10不飽和環烷基、5至10員的雜環基、5至10員的不飽和雜環基、C6-10芳基及5至10員的雜芳基之中的1個以上的基。 When used in this specification, the substituent of "hydrocarbyl" is not particularly limited, for example: a halogen atom; one selected from C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-10 cycloalkyl, C 3-10 unsaturated cycloalkyl, 5 to 10 membered heterocyclic group, 5 to 10 membered unsaturated heterocyclic group, C 6-10 aromatic One or more groups among 5- to 10-membered heteroaryl groups.
於本說明書使用時,「有機基」係指含碳之基。有機基並未特別限定,可為烴基。又,「2至10價之有機基」係指含碳的2至10價之基。此2至10價之有機基並未特別限定,可列舉進一步使1至9個氫原子從烴基脫離而成的2至10價之基。例如,2價之有機基並未特別限定,可列舉進一步使1個氫原子從烴基脫離而成的2價之基。 When used in this specification, "organic group" refers to a carbon-containing group. The organic group is not particularly limited, and may be a hydrocarbon group. Also, the "2- to 10-valent organic group" means a carbon-containing 2- to 10-valent group. This 2-10 valent organic group is not specifically limited, The 2-10 valent group which further detached 1-9 hydrogen atoms from a hydrocarbon group is mentioned. For example, the divalent organic group is not particularly limited, and a divalent group in which one hydrogen atom is detached from the hydrocarbon group is further exemplified.
本說明書中,所謂「可水解之基」,於本說明書使用時,係指可接受水解反應之基,亦即係指可藉由水解反應而從化合物的主骨架脫離之基。作為可水解之基的例子,可列舉:-ORh1、-OCORh1、-O-N=CRh1 2、-NRh1 2、-NHRh1、-NCO、鹵素(此等式中,Rh1表示經取代或未經取代的碳數1至4之烷基)等,較佳為-ORh1(亦即烷氧基)。Rh1的例子包含:甲基、乙基、丙基、異丙基、正丁基、異丁基等未經取代之烷基;氯甲基等經取代之烷基。此等之中,較佳為烷基,尤其是未經取代之烷基,更佳為甲基或乙基。一態樣中,可水解之基為甲氧基。另一態樣中,可水解之基為乙氧基。 In this specification, the so-called "hydrolyzable group" when used in this specification refers to a group that can accept a hydrolysis reaction, that is, a group that can be separated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include: -OR h1 , -OCOR h1 , -ON=CR h1 2 , -NR h1 2 , -NHR h1 , -NCO, halogen (in this equation, R h1 means substituted or an unsubstituted alkyl group having 1 to 4 carbon atoms), etc., preferably -OR h1 (that is, an alkoxy group). Examples of R h1 include: unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; substituted alkyl groups such as chloromethyl. Among them, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In one aspect, the hydrolyzable group is methoxy. In another aspect, the hydrolyzable group is ethoxy.
(組成物) (composition)
本揭示的組成物包含具有氟聚醚基之矽烷化合物與具有氟烷基之矽烷化合物。 The disclosed composition includes silane compounds with fluoropolyether groups and silane compounds with fluoroalkyl groups.
具有氟聚醚基之矽烷化合物係以下述式(A1)或(A2)所表示: The silane compound with fluoropolyether group is represented by the following formula (A1) or (A2):
具有氟烷基之矽烷化合物係具有下述式(B)所表示之基且分子量為300至500的化合物: The silane compound having a fluoroalkyl group is a compound having a group represented by the following formula (B) and a molecular weight of 300 to 500:
-SiR31 n3R32 3-n3 (B)。 -SiR 31 n3 R 32 3-n3 (B).
本揭示的組成物中,具有氟烷基之矽烷化合物之莫耳數相對於具有氟聚醚基之矽烷化合物之莫耳數的比率([具有氟烷基之矽烷化合物之莫耳數]/[具有氟聚醚基之矽烷化合物之莫耳數])為0.001至1.5。 In the composition disclosed herein, the ratio of the molar number of the silane compound having a fluoroalkyl group to the molar number of the silane compound having a fluoropolyether group ([the molar number of the silane compound having a fluoroalkyl group]/[ The molar number of the silane compound having a fluoropolyether group]) is 0.001 to 1.5.
用於形成表面處理層的組成物中形成有微膠粒(micelle)的情況,可能導致表面處理層的摩擦耐久性變低。對此,認為本揭示的組成物係藉由以上述的量包含具有氟烷基之矽烷化合物而可抑制具有氟聚醚基之矽烷化合物形成微膠粒,並提升組成物的流平(leveling)性。結果,認為使所形成之表面處理層的表面變得更為平坦,而可抑制摩擦耐久性降低。 When micelles are formed in the composition for forming the surface treatment layer, the friction durability of the surface treatment layer may be reduced. In this regard, it is considered that the composition of the present disclosure can suppress the formation of micelles by the silane compound having a fluoropolyether group and improve the leveling of the composition by including the silane compound having a fluoroalkyl group in the above-mentioned amount. sex. As a result, it is thought that the surface of the formed surface treatment layer becomes flatter, and the fall of friction durability can be suppressed.
另外,所謂的未形成微膠粒,係指在動態光散射法中測量溶質之平均流體力學直徑時,該平均流體力學直徑100nm以上之中不存在散射強度的峰值。具體而言,係指在平均流體力學直徑100nm以上之中不存在散射強度。 In addition, the so-called non-micelle formation means that when the average hydrodynamic diameter of a solute is measured by the dynamic light scattering method, there is no peak of scattering intensity in the average hydrodynamic diameter of 100 nm or more. Specifically, it means that there is no scattering intensity at an average hydrodynamic diameter of 100 nm or more.
另外,係使用下述樣本進行動態光散射法的測量:將包含50質量%之具有氟聚醚基之矽烷化合物的溶液與具有氟烷基之矽烷化合物混合,並將其靜置至測量溫度25℃。溶劑可使用例如HFE7200。 In addition, the following sample was used for the measurement of the dynamic light scattering method: a solution containing 50% by mass of a silane compound having a fluoropolyether group and a silane compound having a fluoroalkyl group were mixed, and left to stand at a measurement temperature of 25 ℃. As a solvent, for example, HFE7200 can be used.
(具有氟聚醚基之矽烷化合物) (silane compound with fluoropolyether group)
具有氟聚醚基之矽烷化合物係以下述式(A1)或(A2)所表示。 The silane compound having a fluoropolyether group is represented by the following formula (A1) or (A2).
上述式(A1)中,RF1為Rf1-RF-Oq-。 In the above formula (A1), R F1 is Rf 1 -R F -O q -.
上述式(A2)中,RF2為-Rf2 p-RF-Oq-。 In the above formula (A2), R F2 is -Rf 2 p -R F -O q -.
上述式中,Rf1在每次出現時分別獨立地為可經1個以上的氟原子取代的C1-16烷基。 In the above formula, each occurrence of Rf 1 is independently a C 1-16 alkyl group which may be substituted with one or more fluorine atoms.
上述可經1個以上的氟原子取代的C1-16烷基中的「C1-16烷基」可為直鏈,亦可為分枝鏈,較佳為直鏈或分枝鏈的C1-6烷基,尤其是C1-3烷基,更佳為直鏈的C1-6烷基,尤其是C1-3烷基。 The "C 1-16 alkyl" in the above-mentioned C 1-16 alkyl that may be substituted by more than one fluorine atom may be a straight chain or a branched chain, preferably a straight or branched C 1-6 alkyl, especially C 1-3 alkyl, more preferably straight chain C 1-6 alkyl, especially C 1-3 alkyl.
上述Rf1較佳為經1個以上的氟原子取代的C1-16烷基,更佳為CF2H-C1-15全氟伸烷基,再佳為C1-16全氟烷基。 The aforementioned Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 HC 1-15 perfluoroalkylene group, and still more preferably a C 1-16 perfluoroalkyl group.
上述C1-16全氟烷基可為直鏈,亦可為分枝鏈,較佳為直鏈或分枝鏈的C1-6全氟烷基,尤其是C1-3全氟烷基,更佳為直鏈的C1-6全氟烷基,尤其是C1-3全氟烷基,具體為-CF3、-CF2CF3或-CF2CF2CF3。 The above-mentioned C 1-16 perfluoroalkyl can be straight chain or branched chain, preferably straight or branched C 1-6 perfluoroalkyl, especially C 1-3 perfluoroalkyl , more preferably straight chain C 1-6 perfluoroalkyl, especially C 1-3 perfluoroalkyl, specifically -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF 3 .
上述式中,Rf2為可經1個以上的氟原子取代的C1-6伸烷基。 In the above formula, Rf 2 is a C 1-6 alkylene group which may be substituted by one or more fluorine atoms.
上述可經1個以上的氟原子取代的C1-6伸烷基中的「C1-6伸烷基」可為直鏈,亦可為分枝鏈,較佳為直鏈或分枝鏈的C1-3伸烷基,更佳為直鏈的C1-3伸烷基。 The "C 1-6 alkylene" in the above-mentioned C 1-6 alkylene that may be substituted by more than one fluorine atom may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1-3 alkylene, more preferably straight chain C 1-3 alkylene.
上述Rf2較佳為經1個以上的氟原子取代的C1-6伸烷基,更佳為C1-6全氟伸烷基,再佳為C1-3全氟伸烷基。 The above-mentioned Rf 2 is preferably a C 1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and still more preferably a C 1-3 perfluoroalkylene group.
上述C1-6全氟伸烷基可為直鏈,亦可為分枝鏈,較佳為直鏈或分枝鏈的C1-3全氟伸烷基,更佳為直鏈的C1-3全氟伸烷基,具體為-CF2-、-CF2CF2-或-CF2CF2CF2-。 The above-mentioned C 1-6 perfluoroalkylene group can be straight chain or branched chain, preferably straight chain or branched C 1-3 perfluoroalkylene group, more preferably straight chain C 1 -3 perfluoroalkylene, specifically -CF 2 -, -CF 2 CF 2 - or -CF 2 CF 2 CF 2 -.
上述式中,p為0或1。一態樣中,p為0。另一態樣中p為1。 In the above formula, p is 0 or 1. In one state, p is 0. In another aspect, p is 1.
上述式中,q在每次出現時分別獨立地為0或1。一態樣中,q為0。另一態樣中q為1。 In the above formula, q is independently 0 or 1 each time it appears. In one form, q is 0. In another aspect, q is 1.
上述式中,RF在每次出現時分別獨立地為2價之氟聚醚基。RF在每次出現時分別獨立地為下式所表示之基: In the above formula, each occurrence of R F is independently a divalent fluoropolyether group. R F is independently represented by the following formula at each occurrence:
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3RFa 6)d-(OC2F4)e-(OCF2)f-。本說明書中,記載為RF的基,左側鍵結於Rf1或Rf2,右側鍵結於O(q為0時為C=O)。 -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -. In this specification, the group described as R F has a left side bonded to Rf 1 or Rf 2 and a right side bonded to O (when q is 0, it is C=O).
上述式中,RFa在每次出現時分別獨立地為氫原子、氟原子或氯原子,較佳為氫原子或氟原子,更佳為氟原子。 In the above formula, each occurrence of R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom, preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.
上述式中,a、b、c、d、e及f分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1。較佳係a、b、c、d、e及f分別獨立地為0以上100以下的整數。a、b、c、d、e及f的和較佳為5以上,更佳為10以上,例如為10以上100以下。標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意。 In the above formula, a, b, c, d, e, and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is at least 1. Preferably, a, b, c, d, e, and f are each independently an integer of 0 to 100. The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less. The presence order of each repeating unit marked a, b, c, d, e or f and enclosed in brackets in the formula is arbitrary.
此等重複單元可為直鏈狀,亦可為分枝鏈狀,但較佳為直鏈狀。例如-(OC6F12)-亦可為-(OCF2CF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2CF2)-、-(OCF2CF2CF(CF3)CF2CF2)-、-(OCF2CF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF2CF(CF3))-等,較佳為-(OCF2CF2CF2CF2CF2CF2)-。-(OC5F10)-可為-(OCF2CF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2CF2)-、-(OCF2CF(CF3)CF2CF2)-、-(OCF2CF2CF(CF3)CF2)-、-(OCF2CF2CF2CF(CF3))-等,較佳為-(OCF2CF2CF2CF2CF2)-。-(OC4F8)-可為-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-及-(OCF2CF(C2F5))-的任一者,較佳為-(OCF2CF2CF2CF2)-。-(OC3F6)-(亦即,上述式中RFa為氟原子)可為-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-及-(OCF2CF(CF3))-的任一者,較佳為-(OCF2CF2CF2)-。又,-(OC2F4)-亦可為-(OCF2CF2)-及-(OCF(CF3))-的任一者,較佳為-(OCF2CF2)-。 These repeating units may be linear or branched, but are preferably linear. For example -(OC 6 F 12 )- can also be -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-,-(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )- , -(OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ))-, etc., preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-. -(OC 5 F 10 )- can be -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-,-(OCF 2 CF(CF 3 ) CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 ))-, etc., preferably -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-. -(OC 4 F 8 )- can be -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )- , -(OCF 2 CF 2 CF(CF 3 ))-, -(OC(CF 3 ) 2 CF 2 )-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF( CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )- (that is, R Fa in the above formula is a fluorine atom) can be -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 Any of CF(CF 3 ))-, preferably -(OCF 2 CF 2 CF 2 )-. Also, -(OC 2 F 4 )- may be any of -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.
一態樣中,RF在每次出現時分別獨立地為下述式(f1)、(f2)、(f3)、(f4)或(f5)所表示之基: In one aspect, each occurrence of R F is independently represented by the following formula (f1), (f2), (f3), (f4) or (f5):
-(OC3F6)d-(OC2F4)e- (f1) -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)
[式中,d為1至200的整數,e為0或1]。 [wherein, d is an integer from 1 to 200, and e is 0 or 1].
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f2) -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f2)
[式中,c及d分別獨立地為0以上30以下的整數,e及f分別獨立地為1以上200以下的整數, [wherein, c and d are each independently an integer of 0 to 30, and e and f are each independently an integer of 1 to 200,
c、d、e及f的和為2以上, The sum of c, d, e and f is 2 or more,
標註c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意] The order of the repeating units marked c, d, e or f and enclosed in brackets in the formula is arbitrary]
-(R6-R7)g- (f3) -(R 6 -R 7 ) g - (f3)
[式中,R6為OCF2或OC2F4, [wherein, R 6 is OCF 2 or OC 2 F 4 ,
R7為選自OC2F4、OC3F6、OC4F8、OC5F10及OC6F12之中的基,或是從此等之基獨立選擇的2或3個基的組合, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of 2 or 3 groups independently selected from these groups ,
g為2至100的整數]。 g is an integer from 2 to 100].
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f4) -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f4)
[式中,e為1以上200以下的整數,a、b、c、d及f分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1,又,標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意]。 [wherein, e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, Also, the presence order of each repeating unit in the formula marked with a, b, c, d, e or f and enclosed in brackets is arbitrary].
-(OC6F12)a-(OC5F10)b-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- (f5) -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f5)
[式中,f為1以上200以下的整數,a、b、c、d及e分別獨立地為0以上200以下的整數,a、b、c、d、e及f的和至少為1,又,標註a、b、c、d、e或f並以括弧括起之各重複單元在式中的存在順序為任意]。 [wherein, f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, Also, the presence order of each repeating unit in the formula marked with a, b, c, d, e or f and enclosed in brackets is arbitrary].
上述式(f1)中,d較佳為5至200,更佳為10至100,再佳為15至50,例如為25至35的整數。上述式(f1)中的(OC3F6)較佳為以(OCF2CF2CF2)或(OCF(CF3)CF2)所表示之基,更佳為以(OCF2CF2CF2)所表示之基。上述式(f1)中的(OC2F4)較佳為以(OCF2CF2)或(OCF(CF3))所表示之基,更佳為以(OCF2CF2)所表示之基。一態樣中,e為0。另一態樣中,e為1。 In the above formula (f1), d is preferably from 5 to 200, more preferably from 10 to 100, even more preferably from 15 to 50, such as an integer of 25 to 35. (OC 3 F 6 ) in the above formula (f1) is preferably represented by (OCF 2 CF 2 CF 2 ) or (OCF(CF 3 )CF 2 ), more preferably (OCF 2 CF 2 CF 2 ) The base represented. (OC 2 F 4 ) in the above formula (f1) is preferably a group represented by (OCF 2 CF 2 ) or (OCF(CF 3 )), more preferably a group represented by (OCF 2 CF 2 ) . In one form, e is 0. In another aspect, e is 1.
上述式(f2)中,e及f分別獨立,較佳為5以上200以下,更佳為10至200的整數。又,c、d、e及f的和較佳為5以上,更佳為10以上,可為例如15以上或20以上。一態樣中,上述式(f2)較佳為以-(OCF2CF2CF2CF2)c-(OCF2CF2CF2)d-(OCF2CF2)e-(OCF2)f-所表示之基。另一態樣中,式(f2)可為以-(OC2F4)e-(OCF2)f-所表示之基。 In the above formula (f2), e and f are each independently, preferably 5 to 200, more preferably an integer of 10 to 200. Also, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably represented by -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 ) f - the basis of the representation. In another aspect, formula (f2) may be a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
上述式(f3)中,R6較佳為OC2F4。上述(f3)中,R7較佳為選自OC2F4、OC3F6及OC4F8之中的基,或是從此等之基獨立選擇的2或3個基的組合,更佳為選自OC3F6及OC4F8之中的基。從OC2F4、OC3F6及OC4F8獨立選擇的2或3個基的組合並未特別限定,可列舉例如:-OC2F4OC3F6-、-OC2F4OC4F8-、-OC3F6OC2F4-、-OC3F6OC3F6-、-OC3F6OC4F8-、-OC4F8OC4F8-、-OC4F8OC3F6-、-OC4F8OC2F4-、-OC2F4OC2F4OC3F6-、-OC2F4OC2F4OC4F8-、-OC2F4OC3F6OC2F4-、-OC2F4OC3F6OC3F6-、-OC2F4OC4F8OC2F4-、-OC3F6OC2F4OC2F4-、-OC3F6OC2F4OC3F6-、-OC3F6OC3F6OC2F4-及-OC4F8OC2F4OC2F4-等。上述式(f3)中,g較佳為3以上,更佳為5以上的整數。上述g較佳為50以下的整數。上述式(f3)中,OC2F4、OC3F6、OC4F8、OC5F10及OC6F12可為直鏈或分枝鏈的任一者,較佳為直鏈。此態樣中,上述式(f3)較佳為-(OC2F4-OC3F6)g-或-(OC2F4-OC4F8)g-。 In the above formula (f3), R 6 is preferably OC 2 F 4 . In (f3) above, R 7 is preferably a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups, more Preferably, it is a group selected from OC 3 F 6 and OC 4 F 8 . The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited, for example: -OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 -, -OC 3 F 6 OC 2 F 4 -, -OC 3 F 6 OC 3 F 6 -, -OC 3 F 6 OC 4 F 8 -, -OC 4 F 8 OC 4 F 8 -, -OC 4 F 8 OC 3 F 6 -, -OC 4 F 8 OC 2 F 4 -, -OC 2 F 4 OC 2 F 4 OC 3 F 6 -, -OC 2 F 4 OC 2 F 4 OC 4 F 8 -, -OC 2 F 4 OC 3 F 6 OC 2 F 4 -, -OC 2 F 4 OC 3 F 6 OC 3 F 6 -, -OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 3 F 6 -, -OC 3 F 6 OC 3 F 6 OC 2 F 4 - and -OC 4 F 8 OC 2 F 4 OC 2 F 4 -etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The aforementioned g is preferably an integer of 50 or less. In the above formula (f3), OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be any of straight chain or branched chain, preferably straight chain. In this aspect, the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g - or -(OC 2 F 4 -OC 4 F 8 ) g -.
上述式(f4)中,e較佳為1以上100以下,更佳為5以上100以下的整數。a、b、c、d、e及f的和較佳為5以上,更佳為10以上,例如10以上100以下。 In the above formula (f4), e is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
上述式(f5)中,f較佳為1以上100以下,更佳為5以上100以下的整數。a、b、c、d、e及f的和較佳為5以上,更佳為10以上,例如10以上100以下。 In the above formula (f5), f is preferably an integer of 1 to 100, more preferably 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.
一態樣中,上述RF係以上述式(f1)所表示之基。 In one aspect, the aforementioned R F is a group represented by the aforementioned formula (f1).
一態樣中,上述RF係以上述式(f2)所表示之基。 In one aspect, the aforementioned R F is a group represented by the aforementioned formula (f2).
一態樣中,上述RF係以上述式(f3)所表示之基。 In one aspect, the aforementioned R F is a group represented by the aforementioned formula (f3).
一態樣中,上述RF係以上述式(f4)所表示之基。 In one aspect, the aforementioned R F is a group represented by the aforementioned formula (f4).
一態樣中,上述RF係以上述式(f5)所表示之基。 In one aspect, the aforementioned R F is a group represented by the aforementioned formula (f5).
較佳的態樣中,RF係下式(f2)所表示之基: In a preferred aspect, R F is a base represented by the following formula (f2):
-(OC4F8)c-(OC3F6)d-(OC2F4)e-(OCF2)f- -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -
式中,c及d分別獨立地為0以上30以下的整數,e及f分別獨立地為1以上200以下,較佳為5以上200以下,更佳為10以上200以下的整數,標註e或f並以括弧括起之各重複單元在式中的存在順序為任意。RF更具體為以-(OC2F4)e-(OCF2)f-所表示之基。 In the formula, c and d are independently integers ranging from 0 to 30, e and f are independently integers ranging from 1 to 200, preferably ranging from 5 to 200, more preferably integers ranging from 10 to 200, and e or The order in which f and the repeating units enclosed in brackets in the formula is arbitrary. More specifically, R F is a group represented by -(OC 2 F 4 ) e -(OCF 2 ) f -.
RF中,e相對於f的比(以下稱為「e/f比」)為0.1至10,較佳為0.2至5,更佳為0.2至2,再佳為0.2至1.5,再更佳為0.2至0.85。藉由使e/f比在10以下,由含此化合物之組成物所得之硬化層(例如表面處理層)的平滑性、摩擦耐久性及耐化學性(例如對於人工汗的耐久性)更加提升。e/f比越小,則硬化層的平滑性及摩擦耐久性越提升。另一方面,藉由使e/f比為0.1以上,可更加 提高化合物的穩定性。e/f比越大,則具有氟聚醚基之矽烷化合物的穩定性更加提升。此情況中,f的值為1以上。 In R F , the ratio of e to f (hereinafter referred to as "e/f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, further preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e/f ratio 10 or less, the smoothness, friction durability and chemical resistance (such as durability against artificial sweat) of the hardened layer (such as surface treatment layer) obtained from the composition containing this compound are further improved . The smaller the e/f ratio, the more improved the smoothness and friction durability of the hardened layer. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. The larger the e/f ratio is, the more stable the silane compound with fluoropolyether group is. In this case, the value of f is 1 or more.
一態樣中,上述e/f比較佳為0.2至0.95,更佳為0.2至0.9。 In one aspect, the above e/f ratio is preferably from 0.2 to 0.95, more preferably from 0.2 to 0.9.
一態樣中,e/f比小於0.9,較佳為0.8以下、0.7以下,可為0.65以下。e/f比例如為0.2以上、0.3以上、0.4以上、0.5以上、0.55以上。e/f比可列舉例如0.2以上且小於0.9,具體為0.4以上0.8以下,更具體為0.5以上0.8以下。藉由具有上述e/f比,本揭示的組成物(例如表面處理劑)可形成具有更良好之平滑性的表面處理層。 In one aspect, the e/f ratio is less than 0.9, preferably less than 0.8, less than 0.7, and may be less than 0.65. The e/f ratio is, for example, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, and 0.55 or more. The e/f ratio is, for example, 0.2 or more and less than 0.9, specifically 0.4 or more and 0.8 or less, more specifically 0.5 or more and 0.8 or less. By having the above-mentioned e/f ratio, the composition (such as a surface treatment agent) of the present disclosure can form a surface treatment layer with better smoothness.
一態樣中,e/f比可為0.4以上0.7以下,可為0.5以上0.7以下,可為0.55以上0.7以下,亦可為0.55以上0.65以下。 In one aspect, the e/f ratio may be 0.4 to 0.7, 0.5 to 0.7, 0.55 to 0.7, or 0.55 to 0.65.
一態樣中,從耐熱性的觀點來看,上述e/f比較佳為1.0以上,更佳為1.0以上2.0以下。 In one aspect, from the viewpoint of heat resistance, the above-mentioned e/f ratio is preferably 1.0 or more, and more preferably 1.0 or more and 2.0 or less.
-RF-部分的數量平均分子量並未特別限定,例如為500至30,000,較佳為1,500至30,000,更佳為2,000至10,000。上述數量平均分子量係藉由19F-NMR所測量的值。 The number average molecular weight of the -R F - moiety is not particularly limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. The above number average molecular weight is a value measured by 19 F-NMR.
另一態樣中,-RF-部分的數量平均分子量為500至30,000,較佳為1,000至20,000,更佳為2,000至15,000,再更佳為2,000至10,000,例如可為3,000至6,000。 In another aspect, the number average molecular weight of the moiety -RF- is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000, for example, 3,000 to 6,000.
另一態樣中,-RF-部分的數量平均分子量可為4,000至30,000,較佳為5,000至10,000,更佳為6,000至10,000。 In another aspect, the number average molecular weight of the moiety -RF- may be from 4,000 to 30,000, preferably from 5,000 to 10,000, more preferably from 6,000 to 10,000.
上述X1可理解為將「主要提供撥水性及表面平滑性等的氟聚醚部分(RF1及RF2)」和「提供與基材之結合能力的部分(RSi)」予以連結的連結子 (linker)。因此,只要式(A1)及(A2)所表示的化合物可穩定存在,則該X1可為單鍵,亦可為任意之基。 The above X 1 can be understood as a connection between "the fluoropolyether part (R F1 and R F2 ) that mainly provides water repellency and surface smoothness" and "the part that provides the ability to bond with the substrate (R Si )" child (linker). Therefore, as long as the compounds represented by the formulas (A1) and (A2) can exist stably, the X 1 may be a single bond or any group.
較佳係X1在每次出現時分別獨立地為單鍵或2價之有機基。此外,上述X1中,F各式的左側鍵結於N,右側鍵結於RSi。 Preferably, each occurrence of X 1 is independently a single bond or a divalent organic group. In addition, in the above-mentioned X 1 , the left side of each formula of F is bonded to N, and the right side is bonded to R Si .
一態樣中,X1為單鍵。 In one aspect, X 1 is a single bond.
一態樣中,X1為2價之有機基。 In one aspect, X 1 is a divalent organic group.
一態樣中,X1可列舉例如單鍵或下述式所表示的2價之有機基: In one aspect, X can include, for example, a single bond or a divalent organic group represented by the following formula:
-(R21)p1-(Xa)q1- -(R 21 ) p1 -(X a ) q1 -
R21為單鍵、-(CH2)p2-或是鄰、間或對伸苯基,較佳為-(CH2)p2-, R 21 is a single bond, -(CH 2 ) p2 - or o-, m-, or p-phenylene, preferably -(CH 2 ) p2 -,
p2為1至20的整數,較佳為1至6的整數,更佳為1至3的整數,再更佳為1或2, p2 is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, more preferably 1 or 2,
Xa表示(Xb)q2-, X a represents (X b ) q2 -,
Xb在每次出現時分別獨立地表示選自由-O-、-S-、鄰、間或對伸苯基、-(OR35)n4-、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-及-(CH2)n’-所成群組中的基, Each occurrence of X b is independently selected from the group consisting of -O-, -S-, o-, m-, or p-phenylene, -(OR 35 ) n4 -, -C(O)O-, -Si(R 33 ) 2 -, -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CONR 34 -, -O-CONR 34 -, -NR 34 -and-(CH 2 ) n' - the basis in the group formed by,
R33在每次出現時分別獨立地表示苯基、C1-6烷基或C1-6烷氧基,較佳為苯基或C1-6烷基,更佳為甲基, Each occurrence of R independently represents phenyl, C 1-6 alkyl or C 1-6 alkoxy, preferably phenyl or C 1-6 alkyl, more preferably methyl,
R34在每次出現時分別獨立地表示氫原子、苯基或C1-6烷基(較佳為甲基), R 34 independently represent a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence,
R35在每次出現時分別獨立地為C1-6伸烷基, R 35 is independently C 1-6 alkylene at each occurrence,
n4在每次出現時分別獨立地為1至5的整數, n4 is independently an integer from 1 to 5 at each occurrence,
m’在每次出現時分別獨立地為1至100的整數,較佳為1至20的整數, m' is independently an integer from 1 to 100, preferably an integer from 1 to 20, each occurrence,
n’在每次出現時分別獨立地為1至20的整數,較佳為1至6的整數,更佳為1至3的整數, n' is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,
q2為1至10的整數,較佳為1至5的整數,更佳為1至3的整數, q2 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p1為0或1, p1 is 0 or 1,
q1為0或1, q1 is 0 or 1,
標註p1或q1並以括弧括起之各重複單元的存在順序為任意。 The order of presence of each repeating unit marked p1 or q1 and enclosed in parentheses is arbitrary.
此處,p1及q1的至少一者為1。 Here, at least one of p1 and q1 is 1.
此處,X1(典型而言係X1的氫原子)可經選自氟原子、C1-3烷基及C1-3氟烷基之中的1個以上的取代基所取代。較佳的態樣中,X1未經此等基所取代。 Here, X 1 (typically, a hydrogen atom of X 1 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred aspect, X1 is not substituted by these groups.
較佳的態樣中,上述X1分別獨立地為-(R21)p1-(Xa)q1-R22-。 In a preferred aspect, the aforementioned X 1 are each independently -(R 21 ) p1 -(X a ) q1 -R 22 -.
R22表示單鍵、-(CH2)p3-或鄰、間或對伸苯基,較佳為-(CH2)p3-。p3為1至20的整數,較佳為2至6的整數,更佳為2至3的整數。此處,R22(典型而言係R22的氫原子)可經選自氟原子、C1-3烷基及C1-3氟烷基之中的1個以上的取代基所取代。較佳的態樣中,R22未經此等基所取代。R21、p1、Xa、q1與上述同義。 R 22 represents a single bond, -(CH 2 ) p3 -, or o-, m-, or p-phenylene, preferably -(CH 2 ) p3 -. p3 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 22 (typically, a hydrogen atom of R 22 ) may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group. In a preferred aspect, R 22 is not substituted by these groups. R 21 , p1, X a , and q1 have the same definitions as above.
較佳係上述X1可分別獨立地為單鍵、C1-20伸烷基、-R21-Xa-R22-或-Xa1-R22- Preferably, the aforementioned X 1 can be independently a single bond, a C 1-20 alkylene group, -R 21 -X a -R 22 - or -X a1 -R 22 -
[式中,R21及R22與上述同義, [wherein, R 21 and R 22 have the same meaning as above,
Xa表示:-O-、 -S-、-C(O)O-、-CONR34-、-O-CONR34-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-O-(CH2)u5-(Si(R33)2O)m’-Si(R33)2-、-O-(CH2)u5-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、-O-(CH2)u5-Si(OCH3)2OSi(OCH3)2-、-CONR34-(CH2)u5-(Si(R33)2O)m’-Si(R33)2-、-CONR34-(CH2)u5-N(R34)-或-CONR34-(鄰、間或對伸苯基)-Si(R33)2- X a represents: -O-, -S-, -C(O)O-, -CONR 34 -, -O-CONR 34 -, -Si(R 33 ) 2 -, -(Si(R 33 ) 2 O ) m' -Si(R 33 ) 2 -, -O-(CH 2 ) u5 -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -O-(CH 2 ) u5 - Si(R 33 ) 2 -O-Si(R 33 ) 2 -CH 2 CH 2 -Si(R 33 ) 2 -O-Si(R 33 ) 2 -, -O-(CH 2 ) u5 -Si(OCH 3 ) 2 OSi(OCH 3 ) 2 -, -CONR 34 -(CH 2 ) u5 -(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 -, -CONR 34 -(CH 2 ) u5 -N(R 34 )-or-CONR 34 -(o-, m-, or p-phenylene)-Si(R 33 ) 2 -
(式中,R33、R34及m’與上述同義, (wherein, R 33 , R 34 and m' have the same meaning as above,
u5為1至20的整數,較佳為2至6的整數,更佳為2至3的整數), u5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3),
Xa1表示:-S-、-C(O)O-或-O-CONR34- X a1 means: -S-, -C(O)O- or -O-CONR 34 -
(式中,各記號與上述同義)]。 (In the formula, each symbol has the same meaning as above)].
一態樣中,X1分別獨立地為單鍵或C1-6伸烷基,較佳為C1-6伸烷基,更佳為C1-3伸烷基,例如亞甲基。 In one aspect, X 1 are each independently a single bond or a C 1-6 alkylene group, preferably a C 1-6 alkylene group, more preferably a C 1-3 alkylene group, such as methylene.
上述X1分別獨立地可經選自氟原子、C1-3烷基及C1-3氟烷基(較佳為C1-3全氟烷基)之中的1個以上的取代基所取代。一態樣中,X1為未經取代者。 The above-mentioned X 1 can be independently replaced by one or more substituents selected from fluorine atoms, C 1-3 alkyl groups and C 1-3 fluoroalkyl groups (preferably C 1-3 perfluoroalkyl groups). replace. In one aspect, X 1 is unsubstituted.
X1的具體例可列舉例如:單鍵、-CH2OCH2-、-CH2O(CH2)2-、-CH2O(CH2)3-、-CH2O(CH2)4-、-CH2O(CH2)5-、-CH2O(CH2)6-、-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、-CH2OCF2CHFOCF2-、-CH2OCF2CHFOCF2CF2-、-CH2OCF2CHFOCF2CF2CF2-、-CH2OCH2CF2CF2OCF2-、-CH2OCH2CF2CF2OCF2CF2-、-CH2OCH2CF2CF2OCF2CF2CF2-、 -CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、-CH2OCH2CHFCF2OCF2-、-CH2OCH2CHFCF2OCF2CF2-、-CH2OCH2DHFCF2OCF2CF2CF2-、-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、-CH2OCF2CHFOCF2CF2CF2-C(O)NH-CH2-、-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、-(CH2)2-Si(CH3)2-(CH2)2-、-CH2-、-(CH2)2-、-(CH2)3-、-(CH2)4-、-(CH2)5-、-(CH2)6-、 -CO-、-S-(CH2)3-、-(CH2)2S(CH2)3-、-C(O)O-(CH2)3-、-C(O)O-(CH2)6-、-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、-OCH2-、-O(CH2)3-、-OCFHCF2-、 Specific examples of X 1 include, for example, a single bond, -CH 2 OCH 2 -, -CH 2 O(CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 -, -CH 2 O(CH 2 ) 4 -, -CH 2 O(CH 2 ) 5 -, -CH 2 O(CH 2 ) 6 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 OSi(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 2 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 3 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 10 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 O(CH 2 ) 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) 20 Si(CH 3 ) 2 (CH 2 ) 2 -, -CH 2 OCF 2 CHFOCF 2 - , -CH 2 OCF 2 CHFOCF 2 CF 2 -, -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 )CF 2 OCF 2 CF 2 -, -CH 2 OCH 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 CF 2 -, -CH 2 OCH 2 CHFCF 2 OCF 2 -, -CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 -, -CH 2 OCH 2 DHFCF 2 OCF 2 CF 2 CF 2 -, -CH 2 OCH 2 CHFCF 2 OCF(C F 3 )CF 2 OCF 2 -, -CH 2 OCH 2 CHFCF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 -, -CH 2 OCH 2 CHFCF 2 OCF(CF 3 )CF 2 OCF 2 CF 2 CF 2 - , -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 -C(O)NH-CH 2 -, -CH 2 OCH 2 (CH 2 ) 7 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 -, -CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 3 -, - CH 2 OCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 2 OSi(OCH 2 CH 3 ) 2 (CH 2 ) 3 -, -CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 2 OSi(OCH 3 ) 2 (CH 2 ) 2 -, -CH 2 OCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 2 OSi(OCH 2 CH 3 ) 2 (CH 2 ) 2 -, -(CH 2 ) 2 -Si( CH 3 ) 2 -(CH 2 ) 2 -, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -(CH 2 ) 5 -, - (CH 2 ) 6 -, -CO-, -S-(CH 2 ) 3 -, -(CH 2 ) 2 S(CH 2 ) 3 -, -C(O)O-(CH 2 ) 3 -, - C(O)O-(CH 2 ) 6 -, -CH 2 -O-(CH 2 ) 3 -Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -(CH 2 ) 2 -, -CH 2 -O-(CH 2 ) 3 -Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -CH(CH 3 )-, -CH 2 -O-(CH 2 ) 3 -Si(CH 3 ) 2 -(CH 2 ) 2 -Si(CH 3 ) 2 -(CH 2 ) 3 -, -CH 2 -O-(CH 2 ) 3 -Si(CH 3 ) 2 -( CH 2 ) 2 -Si(CH 3 ) 2 -CH(CH 3 )-CH 2 -, -OCH 2 -, -O(CH 2 ) 3 -, -OCFHCF 2 -,
上述式中,RSi在每次出現時分別獨立地為以下述(S1)至(S2)所表示之基的任一者。 In the above formula, each occurrence of R Si is independently any one of the groups represented by the following (S1) to (S2).
-SiRa1 k1Rb1 l1Rc1 m1 (S1) -SiR a1 k1 R b1 l1 R c1 m1 (S1)
-CRd1 k2Re1 l2Rf1 m2 (S2) -CR d1 k2 R e1 l2 R f1 m2 (S2)
一態樣中,RSi係以式(S1)所表示。 In one aspect, R Si is represented by formula (S1).
一態樣中,RSi係以式(S2)所表示。 In one aspect, R Si is represented by formula (S2).
式(S1)中, In formula (S1),
上述Ra1在每次出現時分別獨立地為-Z1-SiR41 r1R42 r2R43 r3。 Each occurrence of the above R a1 is independently -Z 1 -SiR 41 r1 R 42 r2 R 43 r3 .
上述Z1在每次出現時分別獨立地為氧原子或2價之有機基。另外,以下記載為Z1的構造,右側鍵結於(SiR41 r1R42 r2R43 r3)。 The above-mentioned Z 1 is independently an oxygen atom or a divalent organic group at each occurrence. In addition, in the structure described below as Z 1 , the right side is bonded to (SiR 41 r1 R 42 r2 R 43 r3 ).
較佳的態樣中,Z1為2價之有機基。 In a preferred aspect, Z 1 is a divalent organic group.
較佳的態樣中,Z1不包含與Z1所鍵結之Si原子形成矽氧烷鍵者。亦即,式(S1)中,(Si-Z1-Si)不含矽氧烷鍵。 In a preferred aspect, Z 1 does not include one that forms a siloxane bond with the Si atom to which Z 1 is bonded. That is, in formula (S1), (Si-Z 1 -Si) does not contain a siloxane bond.
上述Z1較佳為C1-6伸烷基、-(CH2)z1-O-(CH2)z2-(式中,z1為0至6的整數,例如1至6的整數,z2為0至6的整數,例如1至6的整數)或-(CH2)z3-伸苯基-(CH2)z4-(式中,z3為0至6的整數,例如1至6的整數,z4為0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但較佳為直鏈。此等之基,例如,可經選自氟原子、C1-6烷基、C2-6烯基、及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 The above-mentioned Z 1 is preferably a C 1-6 alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2 - (wherein, z1 is an integer from 0 to 6, such as an integer from 1 to 6, and z2 is an integer of 0 to 6, such as an integer of 1 to 6) or -(CH 2 ) z3 -phenylene group-(CH 2 ) z4 -(wherein, z3 is an integer of 0 to 6, such as an integer of 1 to 6, z4 is an integer from 0 to 6, such as an integer from 1 to 6). The C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups, for example, may be substituted by one or more substituents selected from fluorine atom, C 1-6 alkyl, C 2-6 alkenyl, and C 2-6 alkynyl, but preferably is not replaced.
較佳的態樣中,Z1為C1-6伸烷基或-(CH2)z3-伸苯基-(CH2)z4-,較佳為-伸苯基-(CH2)z4-。Z1為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 1 is C 1-6 alkylene or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 - . When Z1 is the basis, light resistance, especially ultraviolet resistance becomes higher.
另一較佳態樣中,Z1為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z1可為-CH2CH2CH2-。另一態樣中,Z1可為-CH2CH2-。 In another preferred aspect, Z 1 is C 1-6 alkylene, preferably C 1-3 alkylene. In one aspect, Z 1 may be -CH 2 CH 2 CH 2 -. In another aspect, Z 1 can be -CH 2 CH 2 -.
上述R41在每次出現時分別獨立地為-Z1’-SiR41’ r1’R42’ r2’R43’ r3’。 Each occurrence of the above R 41 is independently -Z 1' -SiR 41' r1' R 42' r2' R 43' r3' .
上述Z1’在每次出現時分別獨立地為氧原子或2價之有機基。此外,以下記載為Z1’的構造,右側鍵結於(SiR41’ r1’R42’ r2’R43’ r3’)。 Each occurrence of the aforementioned Z 1' is independently an oxygen atom or a divalent organic group. In addition, in the structure described below as Z 1' , the right side is bonded to (SiR 41' r1' R 42' r2' R 43' r3' ).
較佳的態樣中,Z1’為2價之有機基。 In a preferred aspect, Z 1' is a divalent organic group.
較佳的態樣中,Z1’不包含與Z1’所鍵結之Si原子形成矽氧烷鍵者。亦即,式(S1)中,(Si-Z1’-Si)不含矽氧烷鍵。 In a preferred aspect, Z 1' does not include those that form siloxane bonds with Si atoms to which Z 1' is bonded. That is, in formula (S1), (Si-Z 1' -Si) does not contain a siloxane bond.
上述Z1’較佳為C1-6伸烷基、-(CH2)z1’-O-(CH2)z2’-(式中,z1’為0至6的整數,例如1至6的整數,z2’為0至6的整數,例如1至6的整數)或-(CH2)z3’-伸苯基-(CH2)z4’-(式中,z3’為0至6的整數,例如1至6的整數,z4’為0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但較佳為直鏈。此等之基,例如可經選自氟原子、C1-6烷基、C2-6烯基、及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 The above-mentioned Z 1' is preferably a C 1-6 alkylene group, -(CH 2 ) z1' -O-(CH 2 ) z2' - (wherein, z1' is an integer from 0 to 6, for example, from 1 to 6 Integer, z2' is an integer from 0 to 6, such as an integer from 1 to 6) or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' -(wherein, z3' is an integer from 0 to 6 , such as an integer from 1 to 6, z4' is an integer from 0 to 6, such as an integer from 1 to 6). The C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups, for example, may be substituted with one or more substituents selected from fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups, and C 2-6 alkynyl groups, but are preferably Not replaced.
較佳的態樣中,Z1’為C1-6伸烷基或-(CH2)z3’-伸苯基-(CH2)z4’-,較佳為-伸苯基-(CH2)z4’-。Z1’為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 1' is C 1-6 alkylene or -(CH 2 ) z3' -phenylene-(CH 2 ) z4'- , preferably -phenylene-(CH 2 ) z4'- . When Z 1' is the basis, light resistance, especially ultraviolet resistance becomes higher.
另一較佳態樣中,上述Z1’為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z1’可為-CH2CH2CH2-。另一態樣中,Z1’可為-CH2CH2-。 In another preferred aspect, the aforementioned Z 1' is a C 1-6 alkylene group, preferably a C 1-3 alkylene group. In one aspect, Z 1' may be -CH 2 CH 2 CH 2 -. In another aspect, Z 1' may be -CH 2 CH 2 -.
上述R41’在每次出現時分別獨立地為-Z1”-SiR41” r1”R42” r2”。 The above-mentioned R 41' is independently -Z 1" -SiR 41" r1" R 42" r2" at each occurrence.
上述Z1”在每次出現時分別獨立地為氧原子或2價之有機基。 The above-mentioned Z 1" is independently an oxygen atom or a divalent organic group each time it appears.
Z1”在每次出現時分別獨立地為氧原子或2價之有機基。此外,以下記載為Z1”的構造,右側鍵結於(SiR41” r1”R42” r2”)。 Each occurrence of Z 1" is independently an oxygen atom or a divalent organic group. In addition, in the structure described below as Z 1" , the right side is bonded to (SiR 41" r1" R 42" r2" ).
較佳的態樣中,Z1”為2價之有機基。 In a preferred aspect, Z 1" is a divalent organic group.
較佳的態樣中,Z1”不包含與Z1”鍵結之Si原子形成矽氧烷鍵者。亦即,式(S1)中,(Si-Z1”-Si)不含矽氧烷鍵。 In a preferred aspect, Z 1" does not include Si atoms bonded to Z 1" to form siloxane bonds. That is, in the formula (S1), (Si-Z 1" -Si) does not contain a siloxane bond.
上述Z1”較佳為C1-6伸烷基、-(CH2)z1”-O-(CH2)z2”-(式中,z1”為0至6的整數,例如1至6的整數,z2”為0至6的整數,例如1至6的整數)、或-(CH2)z3”-伸苯基-(CH2)z4”-(式中,z3”為0至6的整數,例如1至6的整數,z4”為 0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但較佳為直鏈。此等之基,例如,可經選自氟原子、C1-6烷基、C2-6烯基及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 The above Z 1" is preferably a C 1-6 alkylene group, -(CH 2 ) z1" -O-(CH 2 ) z2" - (wherein, z1" is an integer from 0 to 6, for example, from 1 to 6 Integer, z2" is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH 2 ) z3" -phenylene-(CH 2 ) z4" -(wherein, z3" is an integer from 0 to 6 Integer, such as an integer from 1 to 6, z4 "is an integer from 0 to 6, such as an integer from 1 to 6). This C 1-6 alkylene group can be a straight chain or a branched chain, but is preferably Straight chain. These groups, for example, may be substituted by one or more substituents selected from fluorine atom, C 1-6 alkyl, C 2-6 alkenyl and C 2-6 alkynyl, but Preferably it is unsubstituted.
較佳的態樣中,Z1”為C1-6伸烷基或-(CH2)z3”-伸苯基-(CH2)z4”-,較佳為-伸苯基-(CH2)z4”-。Z1”為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 1" is C 1-6 alkylene or -(CH 2 ) z3" -phenylene-(CH 2 ) z4" -, preferably -phenylene-(CH 2 ) z4” -. When Z 1" is the basis, the light resistance, especially the ultraviolet resistance becomes higher.
另一較佳態樣中,上述Z1”為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z1”可為-CH2CH2CH2-。另一態樣中,Z1”可為-CH2CH2-。 In another preferred aspect, the above-mentioned Z 1" is a C 1-6 alkylene group, preferably a C 1-3 alkylene group. In one aspect, Z 1" can be -CH 2 CH 2 CH 2 - . In another aspect, Z 1" can be -CH 2 CH 2 -.
上述R41”在每次出現時分別獨立地為羥基或可水解之基。 The above-mentioned R 41 ″ is independently a hydroxyl group or a hydrolyzable group at each occurrence.
R41”較佳係在每次出現時分別獨立地為可水解之基。可水解之基與上述同義。 R 41 ″ is preferably independently a hydrolyzable group at each occurrence. The hydrolyzable group has the same meaning as above.
上述R42”在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 The above-mentioned R 42 ″ is independently a hydrogen atom or a monovalent organic group at each occurrence. The monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable group.
上述R42”中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R 42" , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述r1”在每次出現時分別獨立地為0至3的整數;上述r2”在每次出現時分別獨立地為0至3的整數。此外,在(SiR41” r1”R42” r2”)單元中,r1”與r2”合計為3。 The above-mentioned r1" is independently an integer of 0 to 3 at each occurrence; the above-mentioned r2" is an integer of 0 to 3 independently at each occurrence. In addition, in the (SiR 41” r1” R 42” r2” ) unit, the sum of r1” and r2” is 3.
r1”在每個(SiR41” r1”R42” r2”)單元中分別獨立地較佳為1至3的整數,更佳為2至3,再佳為3。 r1" in each (SiR 41" r1" R 42" r2" ) unit is independently preferably an integer of 1 to 3, more preferably 2 to 3, and still more preferably 3.
上述R42’在每次出現時分別獨立地為羥基或可水解之基。 The above-mentioned R 42' is independently a hydroxyl group or a hydrolyzable group at each occurrence.
R42’較佳係在每次出現時分別獨立地為可水解之基。可水解之基與上述同義。 R 42' is preferably independently at each occurrence a hydrolyzable group. The hydrolyzable group has the same meaning as above.
上述R43’在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 Each occurrence of the above R 43' is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
上述R43’中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R 43' , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述r1’在每次出現時分別獨立地為0至3的整數;上述r2’在每次出現時分別獨立地為0至3的整數;上述r3’在每次出現時分別獨立地為0至3的整數。此外,在(SiR41’ r1’R42’ r2’R43’ r3’)單元中,r1’、r2’及r3’合計為3。 The above-mentioned r1' is independently an integer from 0 to 3 at each occurrence; the above-mentioned r2' is an integer from 0 to 3 independently at each occurrence; the above-mentioned r3' is independently an integer from 0 to 3 at each occurrence; Integer of 3. In addition, in the (SiR 41' r1' R 42' r2' R 43' r3' ) unit, the total of r1', r2' and r3' is 3.
一態樣中,r1’為0。 In one aspect, r1' is 0.
一態樣中,r1’在每個(SiR41’ r1’R42’ r2’R43’ r3’)單元中分別獨立地為1至3的整數,可為2至3的整數,或可為3。較佳的態樣中,r1’為3。 In one aspect, r1' in each (SiR 41' r1' R 42' r2' R 43' r3' ) unit is independently an integer of 1 to 3, may be an integer of 2 to 3, or may be 3. In a preferred aspect, r1' is 3.
一態樣中,r2’在每個(SiR41’ r1’R42’ r2’R43’ r3’)單元中分別獨立地為1至3的整數,較佳為2至3的整數,更佳為3。 In one aspect, r2' in each (SiR 41' r1' R 42' r2' R 43' r3' ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, more preferably for 3.
一態樣中,在每個(SiR41’ r1’R42’ r2’R43’ r3’)單元中分別獨立,r1’為0,r2’為1至3的整數,r3’為0至2的整數,較佳係r1’為0,r2’為2至3的整數,r3’為0至1的整數,更佳係r2’為3。 In one aspect, in each (SiR 41' r1' R 42' r2' R 43' r3' ) unit, r1' is 0, r2' is an integer from 1 to 3, and r3' is 0 to 2 Integers, preferably r1' is 0, r2' is an integer from 2 to 3, r3' is an integer from 0 to 1, more preferably r2' is 3.
一態樣中,r2’為0,r3’在每個(SiR41’ r1’R42’ r2’R43’ r3’)單元中分別獨立地為1至3的整數,較佳為2至3的整數,再佳為3。 In one aspect, r2' is 0, and r3' is independently an integer from 1 to 3 in each (SiR 41' r1' R 42' r2' R 43' r3' ) unit, preferably 2 to 3 An integer of , preferably 3.
上述R42在每次出現時分別獨立地為羥基或可水解之基。 The above-mentioned R 42 is independently a hydroxyl group or a hydrolyzable group at each occurrence.
R42較佳係在每次出現時分別獨立地為可水解之基。可水解之基與上述同義。 R 42 is preferably independently at each occurrence a hydrolyzable group. The hydrolyzable group has the same meaning as above.
上述R43在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 Each occurrence of the above R 43 is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
上述R43中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R 43 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述r1在每次出現時分別獨立地為0至3的整數;上述r2在每次出現時分別獨立地為0至3的整數;上述r3在每次出現時分別獨立地為0至3的整數。此外,在(SiR41 r1R42 r2R43 r3)單元中,r1、r2及r3合計為3。 The above r1 is independently an integer from 0 to 3 each time it occurs; the above r2 is an integer from 0 to 3 each time it appears independently; the above r3 is an integer from 0 to 3 each time it appears independently . In addition, in the (SiR 41 r1 R 42 r2 R 43 r3 ) unit, the total of r1, r2 and r3 is 3.
一態樣中,r1為0。 In one form, r1 is 0.
一態樣中,r1為0,r2為0至3的整數,r3為0至3的整數。 In one aspect, r1 is 0, r2 is an integer from 0 to 3, and r3 is an integer from 0 to 3.
一態樣中,r1在每個(SiR41 r1R42 r2R43 r3)單元中分別獨立地為1至3的整數,可為2至3的整數,或可為3。較佳的態樣中,r1為3。 In one aspect, r1 in each (SiR 41 r1 R 42 r2 R 43 r3 ) unit is independently an integer of 1 to 3, may be an integer of 2 to 3, or may be 3. In a preferred aspect, r1 is 3.
一態樣中,在每個(SiR41 r1R42 r2R43 r3)單元中分別獨立,r1為1至3的整數,r2為0至2的整數,r3為0至2的整數;另一態樣中,r1為2或3,r2為0或1,r3為0或1。 In one aspect, each (SiR 41 r1 R 42 r2 R 43 r3 ) unit is independent, r1 is an integer from 1 to 3, r2 is an integer from 0 to 2, and r3 is an integer from 0 to 2; the other In the aspect, r1 is 2 or 3, r2 is 0 or 1, and r3 is 0 or 1.
一態樣中,r2在每個(SiR41 r1R42 r2R43 r3)單元中分別獨立地為1至3的整數,較佳為2至3的整數,更佳為3。 In one aspect, r2 in each (SiR 41 r1 R 42 r2 R 43 r3 ) unit is independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
一態樣中,在每個(SiR41 r1R42 r2R43 r3)單元中分別獨立,r1為0至2的整數,r2為1至3的整數,r3為0至2的整數;另一態樣中,r1為0或1,r2為2或3,r3為0或1;另一態樣中,r2為3。 In one aspect, each (SiR 41 r1 R 42 r2 R 43 r3 ) unit is independent, r1 is an integer from 0 to 2, r2 is an integer from 1 to 3, and r3 is an integer from 0 to 2; the other In one aspect, r1 is 0 or 1, r2 is 2 or 3, and r3 is 0 or 1; in another aspect, r2 is 3.
一態樣中,r1為0,r2在每個(SiR41 r1R42 r2R43 r3)單元中分別獨立地為1至3的整數,較佳為2至3的整數,再佳為3。 In one aspect, r1 is 0, and r2 is independently an integer of 1 to 3 in each (SiR 41 r1 R 42 r2 R 43 r3 ) unit, preferably an integer of 2 to 3, and more preferably 3.
一態樣中,r1為0,r2為1至3的整數,r3為0至2的整數,較佳係r1為0,r2為2或3,r3為0或1,更佳係r1及r3為0,r2為3。 In one aspect, r1 is 0, r2 is an integer from 1 to 3, r3 is an integer from 0 to 2, preferably r1 is 0, r2 is 2 or 3, r3 is 0 or 1, more preferably r1 and r3 is 0 and r2 is 3.
上述式中,Rb1在每次出現時分別獨立地為羥基或可水解之基。 In the above formula, each occurrence of R b1 is independently a hydroxyl group or a hydrolyzable group.
上述Rb1較佳係在每次出現時分別獨立地為可水解之基。可水解之基與上述同義。 The above-mentioned R b1 is preferably a hydrolyzable group independently at each occurrence. The hydrolyzable group has the same meaning as above.
上述式中,Rc1在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 In the above formula, each occurrence of R c1 is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
上述Rc1中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R c1 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述k1在每次出現時分別獨立地為0至3的整數;上述l1在每次出現時分別獨立地為0至3的整數;上述m1在每次出現時分別獨立地為0至3的整數。此外,在(SiRa1 k1Rb1 l1Rc1 m1)單元中,k1、l1及m1合計為3。 The above k1 is independently an integer of 0 to 3 at each occurrence; the above l1 is an integer of 0 to 3 independently at each occurrence; the above m1 is independently an integer of 0 to 3 at each occurrence . In addition, in the (SiR a1 k1 R b1 l1 R c1 m1 ) unit, the total of k1, l1, and m1 is three.
一態樣中,k1在每個(SiRa1 k1Rb1 l1Rc1 m1)單元中分別獨立地為1至3的整數,較佳為2或3,更佳為3。較佳的態樣中,k1為3。 In one aspect, k1 in each (SiR a1 k1 R b1 l1 R c1 m1 ) unit is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3. In a preferred aspect, k1 is 3.
一態樣中,在每個(SiRa1 k1Rb1 l1Rc1 m1)單元中分別獨立,k1為1至3的整數,l1為0至2的整數,m1為0至2的整數;另一態樣中,k1為2或3,l1為0或1,m1為0或1;另一態樣中,k1為3。 In one aspect, each (SiR a1 k1 R b1 l1 R c1 m1 ) unit is independent, k1 is an integer from 1 to 3, l1 is an integer from 0 to 2, and m1 is an integer from 0 to 2; the other In one aspect, k1 is 2 or 3, l1 is 0 or 1, and m1 is 0 or 1; in another aspect, k1 is 3.
一態樣中,在每個(SiRa1 k1Rb1 l1Rc1 m1)單元中分別獨立,k1為1或2,l1為2或1,m1為0。 In one aspect, k1 is 1 or 2, l1 is 2 or 1, and m1 is 0 in each (SiR a1 k1 R b1 l1 R c1 m1 ) unit.
一態樣中,在每個(SiRa1 k1Rb1 l1Rc1 m1)單元中分別獨立,k1為1或2,l1為0,m1為2或1。 In one aspect, in each (SiR a1 k1 R b1 l1 R c1 m1 ) unit, k1 is 1 or 2, l1 is 0, and m1 is 2 or 1, respectively.
一態樣中,k1為0。換言之,以-SiRa1 k1Rb1 l1Rc1 m1所表示之基為-SiRb1 l1Rc1 m1,l1與m1合計為3。惟,本態樣中,式(A1)及式(A2)的末端部分中,至少存在1個與羥基或可水解之基鍵結的Si原子。 In one aspect, k1 is 0. In other words, the group represented by -SiR a1 k1 R b1 l1 R c1 m1 is -SiR b1 l1 R c1 m1 , and the total of l1 and m1 is 3. However, in this aspect, at least one Si atom bonded to a hydroxyl group or a hydrolyzable group exists in the terminal part of formula (A1) and formula (A2).
上述l1在每次出現時分別獨立地較佳為1至3的整數,更佳為2或3,再佳為3。 The above l1 is preferably an integer from 1 to 3, more preferably 2 or 3, and even more preferably 3, independently at each occurrence.
一態樣中,k1為0,l1較佳為2或3,更佳係k1為0,l1為3。 In one aspect, k1 is 0, l1 is preferably 2 or 3, more preferably k1 is 0, l1 is 3.
式(S1)中,至少存在1個與羥基或可水解之基鍵結的Si原子。亦即,以式(S1)所表示之基具有下述任一者:-SiRb1 l1Rc1 m1(式中,l1為1至3的整數,較佳為2或3,更佳為3,l1與m1合計為3)、-SiR42 r2R43 r3(式中,r2為1至3的整數,較佳為2或3,更佳為3,r2與r3合計為3)、-SiR42’ r2’R43’ r3’(式中,r2’為1至3的整數,較佳為2或3,更佳為3,r2’與r3’合計為3)、或-SiR41” r1”R42” r2”(式中,r1”為1至3的整數,較佳為2或3,更佳為3、r1”與r2”合計為3)。 In formula (S1), at least one Si atom bonded to a hydroxyl group or a hydrolyzable group exists. That is, the base represented by formula (S1) has any of the following: -SiR b1 l1 R c1 m1 (wherein, l1 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, The total of l1 and m1 is 3), -SiR 42 r2 R 43 r3 (wherein, r2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3, the total of r2 and r3 is 3), -SiR 42 ' r2' R 43' r3' (wherein, r2' is an integer from 1 to 3, preferably 2 or 3, more preferably 3, the total of r2' and r3' is 3), or -SiR 41” r1” R 42" r2" (wherein, r1" is an integer from 1 to 3, preferably 2 or 3, more preferably 3, the total of r1" and r2" is 3).
較佳的態樣中,式(A1)及式(A2)的末端部分中,RSi係以(S1)所表示時,至少存在2個與羥基或可水解之基鍵結的Si原子。 In a preferred aspect, when R Si is represented by (S1) in the terminal portion of formula (A1) and formula (A2), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group.
較佳的態樣中,式(S1)中存在Ra1時,在至少1個、較佳為所有的Ra1中,r2為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when there is R a1 in formula (S1), in at least one, preferably all of R a1 , r2 is an integer from 1 to 3, preferably 2 or 3, more preferably 3 .
較佳的態樣中,式(S1)中存在Ra1時,在至少1個、較佳為所有的Ra1中,r1為0至2的整數,r2為1至3的整數,r3為0至2的整數,較佳係r1為0或1,r2為2或3,r3為0或1,更佳係r2為3。 In a preferred aspect, when there is R a1 in formula (S1), in at least one, preferably all of R a1 , r1 is an integer from 0 to 2, r2 is an integer from 1 to 3, and r3 is 0 An integer of up to 2, preferably r1 is 0 or 1, r2 is 2 or 3, r3 is 0 or 1, more preferably r2 is 3.
較佳的態樣中,式(S1)中存在R41時,在至少1個、較佳為所有的R41中,r2’為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when there is R 41 in formula (S1), in at least one, preferably all R 41 , r2' is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
較佳的態樣中,式(S1)中存在R41時,在至少1個、較佳為所有的R41中,r1’為0至2的整數,r2’為1至3的整數,r3’為0至2的整數,較佳係r1’為0或1,r2’為2或3、r3’為0或1,更佳係r2’為3。 In a preferred aspect, when there is R 41 in formula (S1), in at least one, preferably all R 41 , r1' is an integer from 0 to 2, r2' is an integer from 1 to 3, r3 ' is an integer from 0 to 2, preferably r1' is 0 or 1, r2' is 2 or 3, r3' is 0 or 1, more preferably r2' is 3.
較佳的態樣中,式(S1)中存在R41’時,在至少1個、較佳為所有的R41’中,r1”為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when there is R 41' in formula (S1), in at least one, preferably all R 41' , r1" is an integer from 1 to 3, preferably 2 or 3, more preferably The best is 3.
較佳的態樣中,式(S1)中,k1為2或3,較佳為3,r1為0,r2為2或3,較佳為3。 In a preferred aspect, in formula (S1), k1 is 2 or 3, preferably 3, r1 is 0, r2 is 2 or 3, preferably 3.
較佳的態樣中,在式(S1)中,k1為2或3,l1為0或1,m1為0或1,r1為0,r2為2或3,r3為0或1;較佳係k1為3,r1為0,r2為2或3,r3為0或1;更佳係k1為3,r2為3。 In a preferred aspect, in formula (S1), k1 is 2 or 3, l1 is 0 or 1, m1 is 0 or 1, r1 is 0, r2 is 2 or 3, r3 is 0 or 1; preferably System k1 is 3, r1 is 0, r2 is 2 or 3, r3 is 0 or 1; more preferably system k1 is 3, r2 is 3.
式(S2)中, In formula (S2),
上述Rd1在每次出現時分別獨立地為-Z2-CR51 s1R52 s2R53 s3。 Each occurrence of the above-mentioned R d1 is independently -Z 2 -CR 51 s1 R 52 s2 R 53 s3 .
上述Z2在每次出現時分別獨立地為單鍵、氧原子或2價之有機基。另外,以下記載為Z2的構造,右側鍵結於(CR51 s1R52 s2R53 s3)。 Each occurrence of the above Z 2 is independently a single bond, an oxygen atom or a divalent organic group. In addition, in the structure described below as Z 2 , the right side is bonded to (CR 51 s1 R 52 s2 R 53 s3 ).
較佳的態樣中,Z2為2價之有機基。 In a preferred aspect, Z 2 is a divalent organic group.
上述Z2較佳為C1-6伸烷基、-(CH2)z5-O-(CH2)z6-(式中,z5為0至6的整數,例如1至6的整數,z6為0至6的整數,例如1至6的整數)、或-(CH2)z7-伸苯基-(CH2)z8-(式中,z7為0至6的整數,例如1至6的整數,z8為0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但較佳為直鏈。此等之基,例如,可經選自氟原子、C1-6烷基、C2-6烯基及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 The above-mentioned Z 2 is preferably a C 1-6 alkylene group, -(CH 2 ) z5 -O-(CH 2 ) z6 - (wherein, z5 is an integer from 0 to 6, such as an integer from 1 to 6, and z6 is an integer of 0 to 6, such as an integer of 1 to 6), or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -(wherein, z7 is an integer of 0 to 6, such as an integer of 1 to 6 , z8 is an integer from 0 to 6, such as an integer from 1 to 6). The C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups, for example, may be substituted by one or more substituents selected from fluorine atoms, C 1-6 alkyl groups, C 2-6 alkenyl groups and C 2-6 alkynyl groups, but are preferably Not replaced.
較佳的態樣中,Z2為C1-6伸烷基或-(CH2)z7-伸苯基-(CH2)z8-,較佳為-伸苯基-(CH2)z8-。Z2為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 2 is C 1-6 alkylene or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene-(CH 2 ) z8 - . When Z 2 is the basis, light resistance, especially ultraviolet resistance becomes higher.
另一較佳態樣中,Z2為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z2可為-CH2CH2CH2-。另一態樣中,Z2可為-CH2CH2-。 In another preferred aspect, Z 2 is C 1-6 alkylene, preferably C 1-3 alkylene. In one aspect, Z 2 may be -CH 2 CH 2 CH 2 -. In another aspect, Z 2 can be -CH 2 CH 2 -.
上述R51在每次出現時分別獨立地為-Z2’-CR51’ s1’R52’ s2’。 Each occurrence of the above R 51 is independently -Z 2' -CR 51' s1' R 52' s2' .
上述Z2’在每次出現時分別獨立地為單鍵、氧原子或2價之有機基。另外,以下記載為Z2’的構造,右側鍵結於(CR51’ s1’R52’ s2’)。 The above-mentioned Z 2' is independently a single bond, an oxygen atom, or a divalent organic group each time it appears. In addition, in the structure described below as Z 2' , the right side is bonded to (CR 51' s1' R 52' s2' ).
Z2’較佳為C1-6伸烷基、-(CH2)z5’-O-(CH2)z6’-(式中,z5’為0至6的整數,例如1至6的整數,z6’為0至6的整數,例如1至6的整數)、或-(CH2)z7’-伸苯基-(CH2)z8’-(式中,z7’為0至6的整數,例如1至6的整數,z8’為0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但較佳為直鏈。此等之基,例如,可經選自氟原子、C1-6烷基、C2-6烯基、及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 Z 2' is preferably a C 1-6 alkylene group, -(CH 2 ) z5' -O-(CH 2 ) z6' -(wherein, z5' is an integer from 0 to 6, such as an integer from 1 to 6 , z6' is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' -(wherein, z7' is an integer from 0 to 6 , such as an integer from 1 to 6, z8' is an integer from 0 to 6, such as an integer from 1 to 6). The C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups, for example, may be substituted by one or more substituents selected from fluorine atom, C 1-6 alkyl, C 2-6 alkenyl, and C 2-6 alkynyl, but preferably is not replaced.
較佳的態樣中,Z2’為C1-6伸烷基或-(CH2)z7’-伸苯基-(CH2)z8’-,較佳為-伸苯基-(CH2)z8’-。Z2’為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 2' is C 1-6 alkylene or -(CH 2 ) z7' -phenylene-(CH 2 ) z8'- , preferably -phenylene-(CH 2 ) z8'- . When Z 2' is the basis, light resistance, especially ultraviolet resistance becomes higher.
另一較佳態樣中,上述Z2’為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z2’可為-CH2CH2CH2-。另一態樣中,Z2’可為-CH2CH2-。 In another preferred aspect, the above-mentioned Z 2' is a C 1-6 alkylene group, preferably a C 1-3 alkylene group. In one aspect, Z 2' may be -CH 2 CH 2 CH 2 -. In another aspect, Z 2' can be -CH 2 CH 2 -.
上述R51’在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”。 The above-mentioned R 51' is independently -Z 3 -SiR 51" m1" R 52" 3-m1" at each occurrence.
上述Z3在每次出現時分別獨立地為單鍵、氧原子或2價之有機基。此外,以下記載為Z3的構造,右側鍵結於(SiR51” m1”R52” 3-m1”)。 The above-mentioned Z 3 is each independently a single bond, an oxygen atom or a divalent organic group at each occurrence. In addition, in the structure described below as Z 3 , the right side is bonded to (SiR 51" m1" R 52" 3-m1" ).
一態樣中,Z3為氧原子。 In one aspect, Z 3 is an oxygen atom.
一態樣中,Z3為2價之有機基。 In one aspect, Z 3 is a divalent organic group.
上述Z3較佳為C1-6伸烷基、-(CH2)z5”-O-(CH2)z6”-(式中,z5”為0至6的整數,例如1至6的整數,z6”為0至6的整數,例如1至6的整數)、或-(CH2)z7”-伸苯基-(CH2)z8”-(式中,z7”為0至6的整數,例如1至6的整數,z8”為0至6的整數,例如1至6的整數)。此C1-6伸烷基可為直鏈,亦可為分枝鏈,但 較佳為直鏈。此等之基,例如,可經選自氟原子、C1-6烷基、C2-6烯基、及C2-6炔基之中的1個以上的取代基所取代,但較佳為未經取代。 The above Z 3 is preferably a C 1-6 alkylene group, -(CH 2 ) z5" -O-(CH 2 ) z6" - (wherein, z5" is an integer from 0 to 6, such as an integer from 1 to 6 , z6" is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" -(wherein, z7" is an integer from 0 to 6 , such as an integer from 1 to 6, z8" is an integer from 0 to 6, such as an integer from 1 to 6). The C 1-6 alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. These groups, for example, may be substituted by one or more substituents selected from fluorine atom, C 1-6 alkyl, C 2-6 alkenyl, and C 2-6 alkynyl, but preferably is not replaced.
較佳的態樣中,Z3為C1-6伸烷基或-(CH2)z7”-伸苯基-(CH2)z8”-,較佳為-伸苯基-(CH2)z8”-。Z3為此基時,耐光性、尤其是紫外線耐性變得更高。 In a preferred aspect, Z 3 is C 1-6 alkylene or -(CH 2 ) z7" -phenylene-(CH 2 ) z8" -, preferably -phenylene-(CH 2 ) z8" - . When Z3 is the basis, the light resistance, especially the ultraviolet resistance becomes higher.
另一較佳態樣中,上述Z3為C1-6伸烷基,較佳為C1-3伸烷基。一態樣中,Z3可為-CH2CH2CH2-。另一態樣中,Z3可為-CH2CH2-。 In another preferred aspect, the above Z 3 is a C 1-6 alkylene group, preferably a C 1-3 alkylene group. In one aspect, Z 3 may be -CH 2 CH 2 CH 2 -. In another aspect, Z 3 may be -CH 2 CH 2 -.
上述R51”在每次出現時分別獨立地為羥基或可水解之基。 The above-mentioned R 51 ″ is independently a hydroxyl group or a hydrolyzable group at each occurrence.
R51”較佳係在每次出現時分別獨立地為可水解之基。可水解之基與上述同義。 R 51 ″ is preferably independently a hydrolyzable group at each occurrence. The hydrolyzable group has the same meaning as above.
上述R52”在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 The above-mentioned R 52 ″ is independently a hydrogen atom or a monovalent organic group at each occurrence. The monovalent organic group is a monovalent organic group excluding the above-mentioned hydrolyzable group.
上述R52”中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R 52" , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述m1”,在每個(SiR51” m1”R52” 3-m1”)單元中分別獨立地為0至3的整數。式(S2)中,至少存在1個m1”為1至3的-SiR51” m1”R52” 3-m1”。亦即,此末端部分中,所有的m1”皆不為0。換言之,式(A1)及(A2)的末端部分中,至少存在1個鍵結於羥基或可水解之基的Si原子。 The above m1" is independently an integer from 0 to 3 in each (SiR 51" m1" R 52" 3-m1" ) unit. In formula (S2), at least one m1" is 1 to 3 -SiR 51” m1” R 52” 3-m1” . That is, in this terminal part, all m1" are not 0. In other words, in the terminal parts of formulas (A1) and (A2), there is at least one Si atom bonded to a hydroxyl group or a hydrolyzable group.
m1”在每個(SiR51” m1”R52” 3-m1”)單元中分別獨立地較佳為1至3的整數,更佳為2至3,再佳為3。 m1" in each (SiR 51" m1" R 52" 3-m1" ) unit is independently preferably an integer of 1 to 3, more preferably 2 to 3, and even more preferably 3.
上述R52’在每次出現時分別獨立地為氫原子、羥基或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 The above-mentioned R 52' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
R52’中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In R 52' , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
一態樣中,R52’為羥基。 In one aspect, R 52' is hydroxyl.
另一態樣中,R52’為1價之有機基,較佳為C1-20烷基,更佳為C1-6烷基。 In another aspect, R 52' is a monovalent organic group, preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
上述s1’在每次出現時分別獨立地為0至3的整數;上述s2’在每次出現時分別獨立地為0至3的整數。另外,在(CR51’ s1’R52’ s2’)單元中,s1’與s2’合計為3。 The above s1' is independently an integer from 0 to 3 each time it appears; the above s2' is an integer from 0 to 3 each time it appears independently. In addition, in the (CR 51' s1' R 52' s2' ) unit, the total of s1' and s2' is 3.
s1’在每個(CR51’ s1’R52’ s2’)單元中分別獨立地較佳為1至3的整數,更佳為2至3的整數,再佳為3。 s1' in each (CR 51' s1' R 52' s2' ) unit is independently preferably an integer of 1 to 3, more preferably an integer of 2 to 3, and still more preferably 3.
上述R52在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”。此-Z3-SiR51” m1”R52” 3 m1”與上述R51’中的-Z3-SiR51” m1”R52” 3-m1”同義。 The above-mentioned R 52 is independently -Z 3 -SiR 51" m1" R 52" 3-m1" at each occurrence. This -Z 3 -SiR 51” m1” R 52” 3 m1” is synonymous with -Z 3 -SiR 51” m1” R 52” 3-m1” in the above R 51′ .
上述R53在每次出現時分別獨立地為氫原子、羥基或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 The above-mentioned R 53 is each independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
上述R53中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the above R 53 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
一態樣中,R53為羥基。 In one aspect, R 53 is hydroxyl.
另一態樣中,R53中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基。 In another aspect, in R 53 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.
上述s1在每次出現時分別獨立地為0至3的整數;上述s2在每次出現時分別獨立地為0至3的整數;上述s3在每次出現時分別獨立地為0至3的整數。另外,在(CR51 s1R52 s2R53 s3)單元中,s1、s2及s3合計為3。 The above-mentioned s1 is independently an integer from 0 to 3 each time it occurs; the above-mentioned s2 is an integer from 0 to 3 each time it appears independently; the above-mentioned s3 is an integer from 0 to 3 each time it appears independently . In addition, in the (CR 51 s1 R 52 s2 R 53 s3 ) unit, the total of s1, s2 and s3 is 3.
一態樣中,s1為0。 In one aspect, s1 is 0.
一態樣中,s1為0,s2為0至3的整數,s3為0至3的整數。一態樣中,s1為0,s2為2至3的整數,s3為0至1的整數,另一態樣中,s1為0,s2為3的整數,s3為0。 In one aspect, s1 is 0, s2 is an integer from 0 to 3, and s3 is an integer from 0 to 3. In one aspect, s1 is 0, s2 is an integer from 2 to 3, and s3 is an integer from 0 to 1. In another aspect, s1 is 0, s2 is an integer from 3, and s3 is 0.
一態樣中,s1在每個(CR51 s1R52 s2R53 s3)單元中分別獨立地為1至3的整數,可為2至3的整數,或可為3。較佳的態樣中,s1為3。 In one aspect, s1 in each (CR 51 s1 R 52 s2 R 53 s3 ) unit is independently an integer of 1 to 3, may be an integer of 2 to 3, or may be 3. In a preferred aspect, s1 is 3.
一態樣中,s2在每個(CR51 s1R52 s2R53 s3)單元中分別獨立地為1至3的整數,較佳為2至3的整數,更佳為3。 In one aspect, s2 in each (CR 51 s1 R 52 s2 R 53 s3 ) unit is independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3.
一態樣中,s1為0,s2在每個(CR51 s1R52 s2R53 s3)單元中分別獨立地為1至3的整數,較佳為2至3的整數,再佳為3。 In one aspect, s1 is 0, and s2 in each (CR 51 s1 R 52 s2 R 53 s3 ) unit is independently an integer from 1 to 3, preferably an integer from 2 to 3, and more preferably 3.
上述Re1在每次出現時分別獨立地為-Z3-SiR51” m1”R52” 3-m1”。此-Z3-SiR51” m1”R52” 3-m1”與上述R51’中的-Z3-SiR51” m1”R52” 3-m1”同義。 Each occurrence of the above R e1 is independently -Z 3 -SiR 51" m1" R 52" 3-m1" . This -Z 3 -SiR 51” m1 ” R 52” 3-m1” is synonymous with -Z 3 -SiR 51” m1” R 52” 3-m1” in the above R 51′ .
上述Rf1在每次出現時分別獨立地為氫原子、羥基或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 Each occurrence of the above-mentioned R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
上述Rf1中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In the aforementioned R f1 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
一態樣中,Rf1為羥基。 In one aspect, R f1 is hydroxyl.
另一態樣中,Rf1為-O(Rf11O)n1Rf12所表示之基。Rf11為C1-6伸烷基,較佳為C1-3伸烷基,n1為1至10的整數,較佳為1至6的整數,Rf12為C1-10烷基,較佳為C1-3烷基,例如甲基。 In another aspect, R f1 is a group represented by -O(R f11 O) n1 Rf 12 . R f11 is C 1-6 alkylene, preferably C 1-3 alkylene, n1 is an integer from 1 to 10, preferably an integer from 1 to 6, R f12 is C 1-10 alkyl, relatively Preferably it is C 1-3 alkyl, such as methyl.
上述k2在每次出現時分別獨立地為0至3的整數,l2在每次出現時分別獨立地為0至3的整數,m2在每次出現時分別獨立地為0至3的整數。此外,在(CRd1 k2Re1 l2Rf1 m2)單元中,k2、l2及m2合計為3。 The above k2 is independently an integer of 0 to 3 each time, l2 is an integer of 0 to 3 each time, and m2 is an integer of 0 to 3 each time. In addition, in the (CR d1 k2 R e1 l2 R f1 m2 ) unit, the total of k2, l2, and m2 is three.
一態樣中,RSi為式(S2)所表示之基時,在式(A1)及式(A2)的各末端部分中,較佳係存在2個以上、例如2至27個、較佳為2至9個、更佳為2至6個、再佳為2至3個、特佳為3個「m1”為1至3、較佳為2或3、更佳為3的(SiR51” m1”R52” 3-m1”)單元」。 In one aspect, when R Si is a group represented by formula (S2), in each terminal part of formula (A1) and formula (A2), there are preferably 2 or more, such as 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, particularly preferably 3 "m1" is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 51 " m1" R 52" 3-m1" ) unit".
較佳的態樣中,式(S2)中存在R51’時,在至少1個、較佳為所有的R51’中,m1”為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when there is R 51' in formula (S2), in at least one, preferably all R 51' , m1" is an integer from 1 to 3, preferably 2 or 3, more preferably The best is 3.
較佳的態樣中,式(S2)中存在R52時,在至少1個、較佳為所有的R52中,m1”為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when there is R 52 in formula (S2), in at least one, preferably all of R 52 , m1" is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
較佳的態樣中,式(S2)中存在Re1時,在至少1個、較佳為所有的Re1中,m1”為1至3的整數,較佳為2或3,更佳為3。 In a preferred aspect, when R e1 exists in formula (S2), in at least one, preferably all of R e1 , m1" is an integer from 1 to 3, preferably 2 or 3, more preferably 3.
較佳的態樣中,式(S2)中,k2為0,l2為2或3,較佳為3,m1”為2或3,較佳為3。 In a preferred aspect, in formula (S2), k2 is 0, l2 is 2 or 3, preferably 3, and m1" is 2 or 3, preferably 3.
較佳的態樣中,式(S2)中,k2為0,l2為2或3,m2為0或1,較佳係l2為3。本態樣中,m1”為2或3,較佳為3。 In a preferred aspect, in formula (S2), k2 is 0, l2 is 2 or 3, m2 is 0 or 1, preferably l2 is 3. In this aspect, m1" is 2 or 3, preferably 3.
一態樣中,式(S2)中,k2為0,m2為1,l2為2,m1”為2或3,較佳為3。例如,Rf係以-O(Rf11O)n1Rf12所表示之基。Rf11、n1、Rf12與上述同義。 In one aspect, in the formula (S2), k2 is 0, m2 is 1, l2 is 2, m1" is 2 or 3, preferably 3. For example, R f is represented by -O(R f11 O) n1 Rf The group represented by 12. R f11 , n1 and R f12 have the same definitions as above.
上述Rn在每次出現時分別獨立地為-X1-RSi所表示之基、氫原子、苯基或C1-6烷基。 Each occurrence of the above R n is independently a group represented by -X 1 -R Si , a hydrogen atom, a phenyl group or a C 1-6 alkyl group.
一態樣中,Rn為氫原子、苯基或C1-6烷基,較佳為氫原子或甲基,更佳為氫原子。 In one aspect, R n is a hydrogen atom, a phenyl group or a C 1-6 alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
一態樣中,Rn為氫原子。一態樣中,Rn為苯基。一態樣中,Rn為C1-6烷基。 In one aspect, Rn is a hydrogen atom. In one aspect, Rn is phenyl. In one aspect, R n is C 1-6 alkyl.
一態樣中,Rn為-X1-RSi所表示之基。Rn中的-X1-RSi與式(A1)或(A2)中的-X1-RSi同義。 In one aspect, R n is a group represented by -X 1 -R Si . -X 1 -R Si in R n is synonymous with -X 1 -R Si in formula (A1) or (A2).
一態樣中,Rn為氫原子或甲基,較佳為氫原子;RSi係以式(S1)所表示之基。 In one aspect, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si is a group represented by formula (S1).
式(S1)中,較佳係k1為2或3,l1為0或1,m1為0或1(惟k1、l1及m1合計為3),更佳係k1為3。此處,r2為2或3,較佳為3。另外,r1、r2及r3合計為3。 In the formula (S1), preferably k1 is 2 or 3, l1 is 0 or 1, and m1 is 0 or 1 (but the total of k1, l1 and m1 is 3), more preferably k1 is 3. Here, r2 is 2 or 3, preferably 3. In addition, the total of r1, r2, and r3 is three.
一態樣中,Rn為氫原子或甲基,較佳為氫原子;RSi係以式(S2)所表示之基。 In one aspect, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si is a group represented by formula (S2).
式(S2)中,較佳係l2為2或3,m2為0或1(惟l2及m2合計為3),更佳係l2為3。此處,m1”為2或3,較佳為3。 In the formula (S2), preferably l2 is 2 or 3, m2 is 0 or 1 (but the total of l2 and m2 is 3), more preferably l2 is 3. Here, m1" is 2 or 3, preferably 3.
一態樣中,Rn為氫原子或甲基,較佳為氫原子;RSi係以式(S2)所表示之基。 In one aspect, R n is a hydrogen atom or a methyl group, preferably a hydrogen atom; R Si is a group represented by formula (S2).
式(S2)中,較佳係l2為2,m2為1。此處,m1”為2或3,較佳為3。 In formula (S2), preferably l2 is 2 and m2 is 1. Here, m1" is 2 or 3, preferably 3.
一態樣中,Rn為-X1-RSi所表示之基,式(A1)或(A2)中RSi係以式(S1)所表示之基。 In one aspect, R n is a group represented by -X 1 -R Si , and R Si in formula (A1) or (A2) is a group represented by formula (S1).
式(S1)中,較佳係k1為2或3,l1為0或1,m1為0或1(惟k1、l1及m1合計為3),更佳係k1為3。此處,r2為2或3,較佳為3。另外,r1、r2及r3合計為3。 In the formula (S1), preferably k1 is 2 or 3, l1 is 0 or 1, and m1 is 0 or 1 (but the total of k1, l1 and m1 is 3), more preferably k1 is 3. Here, r2 is 2 or 3, preferably 3. In addition, the total of r1, r2, and r3 is three.
一態樣中,Rn為-X1-RSi所表示之基,式(A1)或(A2)中RSi係以式(S2)所表示之基。 In one aspect, R n is a group represented by -X 1 -R Si , and R Si in formula (A1) or (A2) is a group represented by formula (S2).
式(S2)中,較佳係l2為2或3,m2為0或1(惟l2及m2合計為3),更佳係l2為3。此處,m1”為2或3,較佳為3。 In the formula (S2), preferably l2 is 2 or 3, m2 is 0 or 1 (but the total of l2 and m2 is 3), more preferably l2 is 3. Here, m1" is 2 or 3, preferably 3.
一態樣中,Rn為-X1-RSi所表示之基,式(A1)或(A2)中RSi係以式(S1)所表示之基,k1為0。較佳係l1為2或3,更佳係l1為3。 In one aspect, R n is a group represented by -X 1 -R Si , R Si in formula (A1) or (A2) is a group represented by formula (S1), and k1 is 0. The preferred series l1 is 2 or 3, and the more preferred series l1 is 3.
一態樣中,本揭示的組成物中,具有氟聚醚基之矽烷化合物係式(A1)所表示的化合物。 In one aspect, in the composition disclosed herein, the silane compound having a fluoropolyether group is a compound represented by formula (A1).
另一態樣中,本揭示的組成物中,具有氟聚醚基之矽烷化合物係式(A2)所表示的化合物。 In another aspect, in the composition disclosed herein, the silane compound having a fluoropolyether group is a compound represented by formula (A2).
上述式(A1)或式(A2)所表示的具有氟聚醚基之矽烷化合物並未特別限定,可具有5×102至1×105的平均分子量。在此範圍中,從摩擦耐久性的觀點來看,較佳係具有2,000至32,000、更佳為2,500至12,000的平均分子量。另外,此「平均分子量」係指數量平均分子量,「平均分子量」係以19F-NMR所測量的值。 The silane compound having a fluoropolyether group represented by the above formula (A1) or formula (A2) is not particularly limited, and may have an average molecular weight of 5×10 2 to 1×10 5 . Within this range, it is preferable to have an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000 from the viewpoint of friction durability. In addition, the "average molecular weight" refers to a number average molecular weight, and the "average molecular weight" refers to a value measured by 19 F-NMR.
具有氟聚醚基之矽烷化合物的含量,相對於組成物,例如可為含有10質量%以下,亦可為含有3質量%以下。上述含量可為例如0.5質量%以上,亦可為0.01質量%以上。 The content of the silane compound having a fluoropolyether group may be, for example, 10% by mass or less, or 3% by mass or less with respect to the composition. The said content may be 0.5 mass % or more, for example, and may be 0.01 mass % or more.
(具有氟烷基之矽烷化合物) (silane compound with fluoroalkyl group)
具有氟烷基之矽烷化合物具有式: Silane compounds with fluoroalkyl groups have the formula:
-SiR31 n3R32 3-n3所表示之基。具有氟烷基之矽烷化合物的分子量為300至500。 A group represented by -SiR 31 n3 R 32 3-n3 . The molecular weight of the silane compound having a fluoroalkyl group is 300 to 500.
較佳為具有氟烷基之矽烷化合物係以式(B1)所表示。 Preferably, the silane compound having a fluoroalkyl group is represented by formula (B1).
Rf3-X31-SiR31 n3R32 3-n3 (B1) Rf 3 -X 31 -SiR 31 n3 R 32 3-n3 (B1)
上述R31在每次出現時分別獨立地為羥基或可水解之基。可水解之基與上述同義。 The above-mentioned R 31 is independently a hydroxyl group or a hydrolyzable group at each occurrence. The hydrolyzable group has the same meaning as above.
上述R32在每次出現時分別獨立地為氫原子或1價之有機基。此1價之有機基係排除上述可水解之基的1價之有機基。 Each occurrence of the above R 32 is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is a monovalent organic group excluding the aforementioned hydrolyzable groups.
R32中,1價之有機基較佳為C1-20烷基,更佳為C1-6烷基,再佳為甲基。 In R 32 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.
上述n3在每次出現時分別獨立地為0至3的整數。惟具有氟烷基之矽烷化合物中,至少1個n3為1以上。 The above-mentioned n3 is an integer of 0 to 3 independently each time it appears. However, in the silane compound having a fluoroalkyl group, at least one n3 is 1 or more.
n3較佳為1至3的整數,更佳為2或3,再佳為3。 n3 is preferably an integer of 1 to 3, more preferably 2 or 3, and still more preferably 3.
上述Rf3為可經1個以上的氟原子取代的C1-6烷基,較佳為C1-6全氟烷基,更佳為C2-6全氟烷基。 The aforementioned Rf 3 is a C 1-6 alkyl group which may be substituted by one or more fluorine atoms, preferably a C 1-6 perfluoroalkyl group, more preferably a C 2-6 perfluoroalkyl group.
一態樣中Rf3為C2-5全氟烷基。一態樣中Rf3為C3-5全氟烷基。 In one aspect, Rf 3 is C 2-5 perfluoroalkyl. In one aspect, Rf 3 is C 3-5 perfluoroalkyl.
上述X31為單鍵、氧原子或2價之有機基。 The above-mentioned X31 is a single bond, an oxygen atom or a divalent organic group.
一態樣中,X31為單鍵。 In one aspect, X 31 is a single bond.
一態樣中,X31為氧原子。 In one aspect, X 31 is an oxygen atom.
一態樣中,X31為2價之有機基。 In one aspect, X 31 is a divalent organic group.
X31較佳為-(X311)z11-(Z31)z12-。以括弧括起之各重複單元的存在順序在X31中為任意。另外,X31中,左側鍵結於Rf3。 X 31 is preferably -(X 311 ) z11 -(Z 31 ) z12 -. The order of presence of each repeating unit enclosed in parentheses is arbitrary in X31 . In addition, in X 31 , the left side is bonded to Rf 3 .
上述X311為可經1個以上的氟原子取代的C1-6伸烷基,較佳係未經氟原子取代的C1-3伸烷基。 The aforementioned X311 is a C 1-6 alkylene group which may be substituted by one or more fluorine atoms, preferably a C 1-3 alkylene group which is not substituted by a fluorine atom.
上述Z31分別獨立地為氧原子或硫原子,較佳為氧原子。 The aforementioned Z 31 are each independently an oxygen atom or a sulfur atom, preferably an oxygen atom.
上述z11為1至3的整數。一態樣中,z11為1。一態樣中,z11為2。一態樣中,z11為3。 Said z11 is an integer of 1-3. In one aspect, z11 is 1. In one aspect, z11 is 2. In one aspect, z11 is 3.
上述z12為0至2的整數。一態樣中,z12為0。一態樣中,z12為1。 The above z12 is an integer of 0 to 2. In one aspect, z12 is 0. In one aspect, z12 is 1.
一態樣中,上述z11為1至5的整數。 In one aspect, the above z11 is an integer from 1 to 5.
X31較佳係以-X311-Z31-X311-或-X311-表示。可列舉例如:C1-5伸烷基-O-C1-5伸烷基、C1-5伸烷基。 X 31 is preferably represented by -X 311 -Z 31 -X 311 - or -X 311 -. Examples thereof include C 1-5 alkylene-OC 1-5 alkylene, and C 1-5 alkylene.
X31具體可列舉以下的構造。-CH2-、-(CH2)2-、-(CH2)3-、-(CH2)4-、-CH2-O-(CH2)2-、-CH2-O-(CH2)3-、-CH2-O-(CH2)4- Specific examples of X 31 include the following structures. -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -CH 2 -O-(CH 2 ) 2 -, -CH 2 -O-(CH 2 ) 3 -, -CH 2 -O-(CH 2 ) 4 -
具有氟烷基之矽烷化合物可列舉例如以下的構造:C4F9(CH2)2Si(OCH3)3、C4F9CH2O(CH2)2Si(OCH3)3、 C4F9CH2O(CH2)3Si(OCH3)3、C5F11(CH2)2Si(OCH3)3、C5F11CH2O(CH2)2Si(OCH3)3、C5F11CH2O(CH2)3Si(OCH3)3、C6F13(CH2)2Si(OCH3)3、C6F13CH2O(CH2)2Si(OCH3)3、C6F13CH2O(CH2)3Si(OCH3)3。 Examples of silane compounds having a fluoroalkyl group include the following structures: C 4 F 9 (CH 2 ) 2 Si(OCH 3 ) 3 , C 4 F 9 CH 2 O(CH 2 ) 2 Si(OCH 3 ) 3 , C 4 F 9 CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 , C 5 F 11 (CH 2 ) 2 Si(OCH 3 ) 3 , C 5 F 11 CH 2 O(CH 2 ) 2 Si(OCH 3 ) 3 , C 5 F 11 CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 , C 6 F 13 (CH 2 ) 2 Si(OCH 3 ) 3 , C 6 F 13 CH 2 O(CH 2 ) 2 Si(OCH 3 ) 3 , C 6 F 13 CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 .
具有氟烷基之矽烷化合物的含有率,相對於具有氟聚醚基之矽烷化合物,以莫耳比([具有氟烷基之矽烷化合物之莫耳數]/[具有氟聚醚基之矽烷化合物之莫耳數])計為0.001至1.5,較佳為0.001至0.5,更佳為0.001至0.1,再佳為0.001至0.02。 The content rate of the silane compound with fluoroalkyl group, relative to the silane compound with fluoropolyether group, is expressed in molar ratio ([the number of moles of silane compound with fluoroalkyl group]/[silane compound with fluoropolyether group] The number of moles]) is 0.001 to 1.5, preferably 0.001 to 0.5, more preferably 0.001 to 0.1, even more preferably 0.001 to 0.02.
具有氟烷基之矽烷化合物的含量,相對於組成物,例如可含有0.02質量%以下,亦可為0.0002質量%以下。上述含量,例如可為0.00002質量%以上,亦可為0.000002質量%以上。 The content of the silane compound having a fluoroalkyl group may be, for example, 0.02 mass % or less, or 0.0002 mass % or less with respect to the composition. The said content may be 0.00002 mass % or more, for example, and may be 0.000002 mass % or more.
一態樣中,本揭示的組成物不包含具有氟烷基之矽烷化合物的寡聚物。 In one aspect, the composition of the present disclosure does not include oligomers of silane compounds having fluoroalkyl groups.
(其他化合物) (other compounds)
本揭示的組成物可更包含溶劑、可理解為含氟油的(非反應性)氟聚醚化合物、較佳為全氟(聚)醚化合物(以下統稱「含氟油」)、可理解為矽酮油(silicone oil,亦稱為聚矽氧油)的(非反應性)矽酮化合物(以下稱為「矽酮油」)、觸媒、界面活性劑、聚合抑制劑、敏化劑等。 The composition of the present disclosure may further include a solvent, a (non-reactive) fluoropolyether compound that can be understood as a fluorine-containing oil, preferably a perfluoro(poly)ether compound (hereinafter collectively referred to as "fluorine-containing oil"), which can be understood as Silicone oil (also known as polysiloxane oil) (non-reactive) silicone compound (hereinafter referred to as "silicone oil"), catalyst, surfactant, polymerization inhibitor, sensitizer, etc. .
上述溶劑,相對於本揭示的組成物,可含有50至99.8質量%,亦可含有90至99.8質量%。 The above-mentioned solvent may be contained in an amount of 50 to 99.8% by mass, or may be contained in an amount of 90 to 99.8% by mass relative to the composition of the present disclosure.
溶劑可列舉例如:己烷、環己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、礦油精等脂肪族烴類;苯、甲苯、二甲苯、萘、溶劑油(solvent naphtha)等芳香族烴類;乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸正丁酯、乙酸異丙酯、乙酸異丁酯、乙酸賽路蘇、丙二醇甲醚乙酸酯、乙酸卡必醇酯、草酸二乙酯、丙酮酸乙酯、丁酸乙基-2-羥酯、乙醯乙酸乙酯、乙酸戊酯、乳酸甲酯、乳酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、2-羥基異丁酸甲酯、2-羥基異丁酸乙酯等酯類;丙酮、甲乙酮、甲基異丁基酮、2-己酮、環己酮、甲胺基酮、2-庚酮等酮類;乙基賽路蘇、甲基賽路蘇、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丁醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丁醚乙酸酯、二丙二醇二甲醚、乙二醇單烷醚等二醇醚類;甲醇、乙醇、異丙醇、正丁醇、異丁醇、第三丁醇、第二丁醇、3-戊醇、辛醇、3-甲基-3-甲氧基丁醇、第三戊醇等醇類;乙二醇、丙二醇等二醇類;四氫呋喃、四氫吡喃、二烷等環狀醚類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類;甲基賽路蘇、賽路蘇、異丙基賽路蘇、丁基賽路蘇、二乙二醇單甲醚等醚醇類;二乙二醇單乙醚乙酸酯;1,1,2-三氯-1,2,2-三氟乙烷、1,2-二氯-1,1,2,2-四氟乙烷、二甲基亞碸、1,1-二氯-1,2,2,3,3-五氟丙烷(HCFC225)、1,1,2,2,3,3,4-七氟環戊烷(例如,日本ZEON股份有限公司製的ZEORORA(註冊商標)H)、全氟丁基甲醚(C4F9OCH3)(例如Sumitomo 3M股份有限公司製的Novec(商標)7100)、全氟丁基乙醚(C4F9OC2H5)(例如Sumitomo 3M股份有限公司製的Novec(商標)7200)、全氟 己基甲醚(C2F5CF(OCH3)C3F7)(例如Sumitomo 3M股份有限公司製的Novec(商標)7300)等含氟溶劑等。或此等的2種以上之混合溶劑等。 Examples of solvents include aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits; benzene, toluene, xylene, naphthalene, Solvent naphtha and other aromatic hydrocarbons; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, celuxo acetate, propylene glycol methyl ether acetate , Carbitol Acetate, Diethyl Oxalate, Ethyl Pyruvate, Ethyl-2-Hydroxy Butyrate, Ethyl Acetate, Amyl Acetate, Methyl Lactate, Ethyl Lactate, 3-Methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate and other esters; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexyl Ketones, cyclohexanone, methylamino ketone, 2-heptanone and other ketones; Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, ethylene glycol monoalkyl ether, etc. Alcohol ethers; methanol, ethanol, isopropanol, n-butanol, isobutanol, tertiary butanol, second butanol, 3-pentanol, octanol, 3-methyl-3-methoxybutanol , third pentanol and other alcohols; ethylene glycol, propylene glycol and other glycols; tetrahydrofuran, tetrahydropyran, two Alkanes and other cyclic ethers; N,N-dimethylformamide, N,N-dimethylacetamide and other amides; methyl celuso, celuso, isopropyl celuso, Butyl celuso, diethylene glycol monomethyl ether and other ether alcohols; diethylene glycol monoethyl ether acetate; 1,1,2-trichloro-1,2,2-trifluoroethane, 1, 2-dichloro-1,1,2,2-tetrafluoroethane, dimethylsulfene, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), 1, 1,2,2,3,3,4-Heptafluorocyclopentane (for example, ZEOORA (registered trademark) H manufactured by Japan ZEON Co., Ltd.), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (for example, Sumitomo Novec (trademark) 7100 manufactured by 3M Co., Ltd.), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) (for example, Novec (trademark) 7200 manufactured by Sumitomo 3M Co., Ltd.), perfluorohexyl methyl ether ( Fluorinated solvents such as C 2 F 5 CF(OCH 3 )C 3 F 7 ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.) and the like. Or a mixed solvent of two or more of these, etc.
溶劑較佳為含氟溶劑,更佳為氫氟醚,再佳為選自由全氟丁基甲醚、全氟丁基乙醚及全氟己基甲醚所成群組中的至少一者,特佳為全氟丁基甲醚(C4F9OCH3)及/或全氟丁基乙醚(C4F9OC2H5)。 The solvent is preferably a fluorinated solvent, more preferably a hydrofluoroether, and more preferably at least one selected from the group consisting of perfluorobutyl methyl ether, perfluorobutyl ethyl ether and perfluorohexyl methyl ether, especially preferably all Fluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ).
上述含氟油並未特別限定,可列舉例如:以下述通式(3)所表示的化合物(全氟(聚)醚化合物)。 The said fluorine-containing oil is not specifically limited, For example, the compound (perfluoro(poly)ether compound) represented by following general formula (3) is mentioned.
Rf5-(OC4F8)a’-(OC3F6)b’-(OC2F4)c’-(OCF2)d’-Rf6...(3) Rf 5 -(OC 4 F 8 ) a' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c' -(OCF 2 ) d' -Rf 6 . . . (3)
式中,Rf5表示可經1個以上的氟原子取代的碳數1至16烷基(較佳為C1-16的全氟烷基)、Rf6表示可經1個以上的氟原子取代的碳數1至16烷基(較佳為C1-16全氟烷基)、氟原子或氫原子,Rf5及Rf6更佳係分別獨立地為C1-3全氟烷基。 In the formula, Rf 5 represents an alkyl group having 1 to 16 carbons that may be substituted by one or more fluorine atoms (preferably a C 1-16 perfluoroalkyl group), and Rf 6 represents that it may be substituted by one or more fluorine atoms C 1 to 16 alkyl (preferably C 1-16 perfluoroalkyl), fluorine atom or hydrogen atom, Rf 5 and Rf 6 are more preferably C 1-3 perfluoroalkyl independently.
a’、b’、c’及d’分別表示構成聚合物之主骨架的全氟(聚)醚之4種重複單元數,其互相獨立地為0以上300以下的整數,a’、b’、c’及d’的和至少為1,較佳為1至300,更佳為20至300。標註a’、b’、c’或d’並以括弧括起之各重複單元在式中的存在順序為任意。此等重複單元之中,-(OC4F8)-可為-(OCF2CF2CF2CF2)-、-(OCF(CF3)CF2CF2)-、-(OCF2CF(CF3)CF2)-、-(OCF2CF2CF(CF3))-、-(OC(CF3)2CF2)-、-(OCF2C(CF3)2)-、-(OCF(CF3)CF(CF3))-、-(OCF(C2F5)CF2)-及(OCF2CF(C2F5))-的任一者,較佳為-(OCF2CF2CF2CF2)-。-(OC3F6)-可為-(OCF2CF2CF2)-、-(OCF(CF3)CF2)-及(OCF2CF(CF3))-的任一者,較佳為-(OCF2CF2CF2)-。-(OC2F4)-可為-(OCF2CF2)-及(OCF(CF3))-的任一者,較佳為-(OCF2CF2)-。 a', b', c' and d' respectively represent the number of four repeating units of perfluoro(poly)ether constituting the main skeleton of the polymer, which are independently integers ranging from 0 to 300, and a' and b' The sum of , c' and d' is at least 1, preferably 1-300, more preferably 20-300. The presence order of each repeating unit marked with a', b', c' or d' and enclosed in brackets in the formula is arbitrary. Among these repeating units, -(OC 4 F 8 )- may be -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF( CF 3 )CF 2 )-,-(OCF 2 CF 2 CF(CF 3 ))-,-(OC(CF 3 ) 2 CF 2 )-,-(OCF 2 C(CF 3 ) 2 )-,-( Any one of OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and (OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )- can be any of -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and (OCF 2 CF(CF 3 ))-, preferably is -(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )- may be any of -(OCF 2 CF 2 )- and (OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.
上述通式(3)所表示的全氟(聚)醚化合物的例子可列舉以下述通式(3a)及(3b)的任一者所示之化合物(可為1種或2種以上的混合物)。 Examples of the perfluoro(poly)ether compound represented by the above-mentioned general formula (3) include compounds represented by either of the following general formulas (3a) and (3b) (which may be one or a mixture of two or more ).
Rf5-(OCF2CF2CF2)b”-Rf6...(3a) Rf 5 -(OCF 2 CF 2 CF 2 ) b” -Rf 6 …(3a)
Rf5-(OCF2CF2CF2CF2)a”-(OCF2CF2CF2)b”-(OCF2CF2)c”-(OCF2)d”-Rf6...(3b) Rf 5 -(OCF 2 CF 2 CF 2 CF 2 ) a" -(OCF 2 CF 2 CF 2 ) b" -(OCF 2 CF 2 ) c" -(OCF 2 ) d" -Rf 6 . . . (3b)
此等式中,Rf5及Rf6如上所述;式(3a)中,b”為1以上100以下的整數;式(3b)中,a”及b”分別獨立地為0以上30以下的整數,c”及d”分別獨立地為1以上300以下的整數。標註a”、b”、c”、d”並以括弧括起之各重複單元在式中的存在順序為任意。 In this equation, Rf 5 and Rf 6 are as above; in formula (3a), b" is an integer ranging from 1 to 100; in formula (3b), a" and b" are independently from 0 to 30 Integers, c" and d" are each independently an integer of 1 to 300. The presence order of each repeating unit marked a", b", c", and d" and enclosed in parentheses in the formula is arbitrary.
又,從另一觀點來看,含氟油可為通式Rf4-F(式中,Rf4為C5-16全氟烷基)所表示的化合物。又,亦可為氯三氟乙烯寡聚物。 Also, from another point of view, the fluorine-containing oil may be a compound represented by the general formula Rf 4 -F (wherein, Rf 4 is a C 5-16 perfluoroalkyl group). Moreover, it may be a chlorotrifluoroethylene oligomer.
上述含氟油可具有500至10000的平均分子量。含氟油的分子量可使用GPC測量。 The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of fluorine-containing oils can be measured using GPC.
相對於本揭示的組成物,例如可含有0至50質量%的含氟油,較佳為0至30質量%,更佳為0至5質量%。一態樣中,本揭示的組成物中實質上不具有含氟油。實質上不具有含氟油,係指完全不具有含氟油,或是可具有極微量的含氟油。 Relative to the composition of the present disclosure, for example, fluorine-containing oil may be contained in an amount of 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 5% by mass. In one aspect, the composition of the present disclosure contains substantially no fluorine-containing oil. Substantial absence of fluorine-containing oil means that there is no fluorine-containing oil at all, or there may be a very small amount of fluorine-containing oil.
一態樣中,可使含氟油的平均分子量大於具有氟聚醚基之矽烷化合物的平均分子量。藉由成為這樣的平均分子量,尤其是在藉由真空蒸鍍法形成表面處理層時,可得到更優良的摩擦耐久性與表面平滑性。 In one aspect, the average molecular weight of the fluorine-containing oil can be made larger than the average molecular weight of the silane compound having a fluoropolyether group. By having such an average molecular weight, more excellent friction durability and surface smoothness can be obtained especially when the surface treatment layer is formed by a vacuum evaporation method.
一態樣中,亦可使含氟油的平均分子量小於具有氟聚醚基之矽烷化合物的平均分子量。藉由成為這樣的平均分子量,可抑制由此化合物所得之表 面處理層的透明性降低,並且可形成具有高摩擦耐久性及高表面平滑性的硬化物。 In one aspect, the average molecular weight of the fluorine-containing oil can also be made smaller than the average molecular weight of the silane compound having a fluoropolyether group. By becoming such an average molecular weight, the surface obtained by this compound can be suppressed The transparency of the surface treatment layer decreases, and a hardened product having high friction durability and high surface smoothness can be formed.
含氟油有助於提升由本揭示之組成物所形成之層的表面平滑性。 Fluorine-containing oils help to improve the surface smoothness of layers formed from compositions of the present disclosure.
一態樣中,相對於具有氟聚醚基之矽烷化合物及具有氟烷基之矽烷化合物的合計,含有0.001至50莫耳%的含氟油,例如可含有0.01至40莫耳%的含氟油。 In one aspect, 0.001 to 50 mole % of fluorine-containing oil is contained relative to the total of the silane compound having a fluoropolyether group and the silane compound having a fluoroalkyl group, for example, it may contain 0.01 to 40 mole % of fluorine-containing oil Oil.
一態樣中,本揭示的組成物含有式(A1)所表示的化合物及式(A2)所表示的化合物以作為具有氟聚醚基之矽烷化合物,並且更含有含氟油。 In one aspect, the composition of the present disclosure contains a compound represented by formula (A1) and a compound represented by formula (A2) as a silane compound having a fluoropolyether group, and further contains a fluorine-containing oil.
一態樣中,相對於式(A1)所表示的化合物、式(A2)所表示的化合物、具有氟烷基之矽烷化合物及含氟油的合計,較佳係含有0.001至70莫耳%的式(A2)所表示的化合物以及0.001至50莫耳%的含氟油,更佳係含有0.01至60莫耳%的式(A2)所表示的化合物以及0.01至40莫耳%的含氟油,再佳係含有0.1至50莫耳%的式(A2)所表示的化合物以及0.1至30莫耳%的含氟油。另外,具有氟烷基之矽烷化合物之莫耳數相對於具有氟聚醚基之矽烷化合物之莫耳數的比率為0.001至1.5。 In one aspect, it is preferable to contain 0.001 to 70 mol% of the compound represented by formula (A1), the compound represented by formula (A2), the silane compound having a fluoroalkyl group, and the fluorine-containing oil. Compound represented by formula (A2) and 0.001 to 50 mol% of fluorine-containing oil, more preferably containing 0.01 to 60 mol% of compound represented by formula (A2) and 0.01 to 40 mol% of fluorine-containing oil , and more preferably contain 0.1 to 50 mol% of the compound represented by the formula (A2) and 0.1 to 30 mol% of the fluorine-containing oil. In addition, the ratio of the number of moles of the silane compound having a fluoroalkyl group to the number of moles of the silane compound having a fluoropolyether group is 0.001 to 1.5.
一態樣中,相對於式(A1)所表示的化合物、式(A2)所表示的化合物、具有氟烷基之矽烷化合物及含氟油的合計,較佳係含有0.001至70莫耳%的式(A1)所表示的化合物以及0.001至50莫耳%的含氟油,更佳係含有0.01至60莫耳%的式(A1)所表示的化合物以及0.01至40莫耳%的含氟油,再佳係含有0.1至50莫耳%的式(A1)所表示的化合物以及0.1至30莫耳%的含氟油。另外,具有氟烷基之矽烷化合物之莫耳數相對於具有氟聚醚基之矽烷化合物之莫耳數的比率為0.001至1.5。 In one aspect, it is preferable to contain 0.001 to 70 mol% of the compound represented by formula (A1), the compound represented by formula (A2), the silane compound having a fluoroalkyl group, and the fluorine-containing oil. The compound represented by formula (A1) and 0.001 to 50 mol% of fluorine-containing oil, more preferably containing 0.01 to 60 mol% of the compound represented by formula (A1) and 0.01 to 40 mol% of fluorine-containing oil , preferably containing 0.1 to 50 mol % of the compound represented by formula (A1) and 0.1 to 30 mol % of fluorine-containing oil. In addition, the ratio of the number of moles of the silane compound having a fluoroalkyl group to the number of moles of the silane compound having a fluoropolyether group is 0.001 to 1.5.
作為上述矽酮油,可使用例如矽氧烷鍵在2,000以下的直鏈狀或環狀的矽酮油。直鏈狀的矽酮油,可為所謂的直鏈矽酮油(straight silicone oil)及改質矽酮油。直鏈矽酮油可列舉:二甲基矽酮油、甲基苯基矽酮油、甲基氫矽酮油。改質矽酮油可列舉:以烷基、芳烷基、聚醚、高級脂肪酸酯、氟烷基、胺基、環氧基、羧基、醇等將直鏈矽酮油改質而成者。環狀的矽酮油可列舉例如:環狀二甲基矽氧烷油等。 As the above-mentioned silicone oil, for example, linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of linear silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Modified silicone oils can be listed: modified linear silicone oils with alkyl groups, aralkyl groups, polyethers, higher fatty acid esters, fluoroalkyl groups, amino groups, epoxy groups, carboxyl groups, alcohols, etc. . Cyclic silicone oils include, for example, cyclic dimethylsiloxane oils and the like.
本揭示的組成物(例如表面處理劑)中,相對於上述本揭示的具有氟聚醚基之矽烷化合物的合計100質量份(2種以上時為此等的合計,以下亦同),可含有例如0至300質量份、較佳為50至200質量份的該矽酮油。 The composition (such as a surface treatment agent) of the present disclosure may contain 100 parts by mass of the silane compounds having a fluoropolyether group in the above-mentioned present disclosure in total (when there are two or more kinds, it is the total of these, and the same applies hereinafter). For example, 0 to 300 parts by mass, preferably 50 to 200 parts by mass of the silicone oil.
矽酮油有助於提升表面處理層的表面平滑性。 Silicone oil helps to improve the surface smoothness of the surface treatment layer.
上述觸媒可列舉:酸(例如乙酸、三氟乙酸等)、鹼(例如氨、三乙胺、二乙胺等)、過渡金屬(例如Ti、Ni、Sn等)等。 Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
觸媒係促進本揭示的具有氟聚醚基之矽烷化合物的水解及脫水縮合,並促進由本揭示的組成物(例如表面處理劑)所形成之層的形成。 The catalyst is to promote the hydrolysis and dehydration condensation of the silane compound with fluoropolyether group disclosed herein, and to promote the formation of the layer formed by the composition (such as surface treatment agent) disclosed herein.
作為其他成分,除了上述以外,亦可列舉例如:四乙氧基矽烷、甲基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、甲基三乙醯氧基矽烷等。 Other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane in addition to the above. , Methyltriacetyloxysilane, etc.
(表面處理劑) (surface treatment agent)
本揭示的組成物可使用作為對基材進行表面處理的表面處理劑。 The composition of the present disclosure can be used as a surface treatment agent for surface treatment of a substrate.
一態樣中,本揭示的表面處理劑可含浸於作為多孔質物質之例如多孔質的陶瓷材料、作為金屬纖維之例如鋼絲絨經硬化成綿狀者,然後形成顆粒。該顆粒可用於例如真空蒸鍍。 In one aspect, the surface treatment agent of the present disclosure can be impregnated into a porous material such as a porous ceramic material, or a metal fiber such as steel wool that is hardened into a sponge, and then formed into particles. The particles can be used, for example, for vacuum evaporation.
一態樣中,本揭示的表面處理劑可用於濕潤被覆。 In one aspect, the surface treatments of the present disclosure can be used for wet coating.
(物品) (thing)
以下說明本揭示的物品。 The articles of the present disclosure are described below.
本揭示的物品包含基材、以及由包含本揭示的具有氟聚醚基之矽烷化合物的表面處理劑形成於該基材表面上的層(表面處理層)。 The article of the present disclosure includes a substrate, and a layer (surface treatment layer) formed on the surface of the substrate with a surface treatment agent containing the silane compound having a fluoropolyether group of the present disclosure.
一態樣中,本揭示的物品亦可包含基材與由本揭示的具有氟聚醚基之矽烷化合物形成於該基材表面上的層。 In one aspect, the disclosed article may also include a substrate and a layer formed of the disclosed silane compound having a fluoropolyether group on the surface of the substrate.
本揭示中可使用的基材可以例如玻璃、樹脂(天然或合成樹脂,例如可為一般的塑膠材料,亦可為板狀、膜、其他型態)、金屬,陶瓷、半導體(矽、鍺等)、纖維(織物、不織布等)、毛皮、皮革、木材、陶磁器、石材等、建築構件等任意適當材料所構成。 The substrates that can be used in this disclosure can be, for example, glass, resin (natural or synthetic resin, such as general plastic material, plate, film, or other forms), metal, ceramic, semiconductor (silicon, germanium, etc. ), fibers (fabric, non-woven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., and building components, etc., of any suitable material.
例如,欲製造之物品為光學構件時,構成基材表面的材料可為光學構件用材料,例如玻璃或透明塑膠等。又,欲製造之物品為光學構件時,可在基材表面(最外層)上形成任意層(或膜)、例如硬塗層及抗反射層等。抗反射層可使用單層抗反射層及多層抗反射層的任一者。可用於抗反射層的無機物的例子可列舉:SiO2、SiO、ZrO2、TiO2、TiO、Ti2O3、Ti2O5、Al2O3、Ta2O5、CeO2、MgO、Y2O3、SnO2、MgF2、WO3等。此等無機物可單獨使用,或是將此等2種以上組合(例如作為混合物)使用。多層抗反射層的情況,其最外層較佳係使用SiO2及/或SiO。欲製造的物品為觸控面板用的光學玻璃零件時,基材(玻璃)表面的一部分可具有透明電極,例如使用有氧化銦錫(ITO)或氧化銦鋅等的薄膜。又,基材亦可因應其具體規格等而具有絕緣層、黏著層、保護層、裝飾框層(I-CON)、霧化膜層、硬塗層、偏光膜、相位差膜及液晶表示模組等。 For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate can be a material for optical components, such as glass or transparent plastic. Also, when the article to be manufactured is an optical member, an arbitrary layer (or film) such as a hard coat layer and an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, any of a single-layer antireflection layer and a multilayer antireflection layer can be used. Examples of inorganic substances that can be used in the antireflection layer include: SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO, Y 2 O 3 , SnO 2 , MgF 2 , WO 3 , etc. These inorganic substances may be used alone or in combination (for example, as a mixture) of two or more of these. In the case of a multilayer antireflection layer, it is preferable to use SiO 2 and/or SiO as the outermost layer. When the article to be manufactured is an optical glass part for a touch panel, a part of the surface of the substrate (glass) may have a transparent electrode, for example, a thin film of indium tin oxide (ITO) or indium zinc oxide is used. In addition, the substrate can also have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coat layer, a polarizing film, a retardation film, and a liquid crystal display module in response to its specific specifications. group etc.
基材的形狀並未特別限定。又,欲形成表面處理層之基材的表面區域,只要為基材表面的至少一部分即可,可因應欲製造之物品的用途及具體規格等適當決定。 The shape of the substrate is not particularly limited. In addition, the surface area of the base material on which the surface treatment layer is to be formed should be at least a part of the surface of the base material, and can be appropriately determined according to the application and specific specifications of the article to be manufactured.
此基材可為至少其表面部分由原本就具有羥基的材料所構成者。此材料可列舉玻璃,又可列舉表面形成有自然氧化膜或熱氧化膜的金屬(尤其是卑金屬)、陶瓷、半導體等。或是如樹脂等,雖具有羥基卻不充分的情況或是原本就不具有羥基的情況,藉由對基材實施某種前處理,可將羥基導入基材的表面,或使羥基增加。此前處理的例子可列舉電漿處理(例如電暈放電)或離子束照射。電漿處理係可將羥基導入基材表面或使羥基增加,並且亦可理想地用於潔淨基材表面(去除異物等)。又,該前處理的其他例子可列舉:藉由LB法(朗謬-布洛傑(Langmuir-Blodgett)法)或化學吸附法等,使具有碳-碳不飽和鍵的界面吸附劑預先以單分子膜的型態形成於基材表面,之後在包含氧或氮等的環境下使不飽和鍵開裂的方法。 The substrate may be formed of at least a surface portion of a material originally having hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, etc., on which a natural oxide film or thermal oxide film is formed on the surface. Or if resins have hydroxyl groups but not enough or do not have hydroxyl groups originally, by performing some pretreatment on the substrate, the hydroxyl groups can be introduced into the surface of the substrate, or the hydroxyl groups can be increased. Examples of the pretreatment include plasma treatment (such as corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the surface of the substrate, and is also ideal for cleaning the surface of the substrate (removing foreign matter, etc.). In addition, other examples of the pretreatment include: by LB method (Langmuir-Blodgett (Langmuir-Blodgett) method) or chemical adsorption method, etc., the interfacial adsorbent having carbon-carbon unsaturated bonds is pre-mixed with a single A method in which a molecular film is formed on the surface of a substrate, and then unsaturated bonds are cleaved in an environment containing oxygen or nitrogen.
又或是作為此基材,亦可為至少其表面部分由包含其他反應性基、例如具有1個以上的Si-H基的矽酮化合物或烷氧基矽烷的材料所構成者。 Alternatively, as the base material, at least the surface portion thereof may be made of a material containing other reactive groups, for example, a silicone compound or an alkoxysilane having one or more Si—H groups.
接著,在此基材表面形成上述本揭示之表面處理劑的層,因應需求對該層進行後處理,藉此可由本揭示之表面處理劑形成層。 Next, a layer of the above-mentioned surface treatment agent of the present disclosure is formed on the surface of the substrate, and the layer is post-treated as required, whereby a layer can be formed from the surface treatment agent of the present disclosure.
本揭示的表面處理劑的層形成,可藉由對基材表面以被覆該表面的方式施用上述組成物來實施。被覆方法並未特別限定。例如,可使用濕潤被覆法及乾燥被覆法。 The layer formation of the surface treatment agent of this disclosure can be implemented by applying the above-mentioned composition to the surface of a base material so that the said surface may be covered. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.
濕潤被覆法的例子可列舉:浸漬塗布法、旋塗法、流動塗布法、噴塗法、輥塗法、凹版塗布及類似的方法。 Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and the like.
乾燥被覆法的例子可列舉:蒸鍍(通常為真空蒸鍍)、濺鍍、CVD及類似的方法。蒸鍍法(通常為真空蒸鍍法)的具體例可列舉:使用有電阻加熱、電子束、微波等的高頻加熱、離子束及類似的方法。CVD法的具體例可列舉:電漿-CVD、光學CVD、熱CVD及類似的方法。 Examples of the dry coating method include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and the like. Specific examples of the vapor deposition method (usually a vacuum vapor deposition method) include methods using resistance heating, high-frequency heating such as electron beams and microwaves, ion beams, and the like. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and the like.
再者,亦可由常壓電漿法來進行被覆。 Furthermore, the coating can also be performed by an atmospheric pressure plasma method.
使用濕潤被覆法時,可用溶劑將本揭示之表面處理劑稀釋後再施用於基材表面。從本揭示的組成物的穩定性及溶劑的揮發性的觀點來看,較佳係使用下述溶劑:碳數5至12的全氟脂肪族烴(例如,全氟己烷、全氟甲基環己烷及全氟-1,3-二甲基環己烷);聚氟芳香族烴(例如雙(三氟甲基)苯);聚氟脂肪族烴(例如,C6F13CH2CH3(例如旭硝子股份有限公司製的ASAHIKLIN(註冊商標)AC-6000)、1,1,2,2,3,3,4-七氟環戊烷(例如日本ZEON股份有限公司製的ZEORORA(註冊商標)H);氫氟醚(HFE)(例如全氟丙基甲醚(C3F7OCH3)(例如Sumitomo 3M股份有限公司製的Novec(商標)7000)、全氟丁基甲醚(C4F9OCH3)(例如Sumitomo 3M股份有限公司製的Novec(商標)7100)、全氟丁基乙醚(C4F9OC2H5)(例如Sumitomo 3M股份有限公司製的Novec(商標)7200)、全氟己基甲醚(C2F5CF(OCH3)C3F7)(例如Sumitomo 3M股份有限公司製的Novec(商標)7300)等烷基全氟烷醚(全氟烷基及烷基可為直鏈或分枝狀)、或CF3CH2OCF2CHF2(例如旭硝子股份有限公司製的ASAHIKLIN(註冊商標)AE-3000))等。此等的溶劑可單獨使用或作為2種以上的混合物使用。其中,較佳為氫氟醚,特佳為全氟丁基甲醚(C4F9OCH3)及/或全氟丁基乙醚(C4F9OC2H5)。 When using the wet coating method, the surface treatment agent disclosed in the present invention can be diluted with a solvent and then applied to the surface of the substrate. From the viewpoint of the stability of the composition disclosed in the present disclosure and the volatility of the solvent, it is preferable to use the following solvents: perfluoroaliphatic hydrocarbons with 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethyl cyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (such as bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (such as C 6 F 13 CH 2 CH 3 (such as ASAHIKLIN (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (such as ZEOORA ( registered trademark) H); hydrofluoroether (HFE) (such as perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (such as Novec (trademark) 7000 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (such as Novec (trademark) 7100 manufactured by Sumitomo 3M Co., Ltd.), perfluorobutyl ether (C 4 F 9 OC 2 H 5 ) (such as Novec (trademark) manufactured by Sumitomo 3M Co., Ltd. 7200), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) (for example, Novec (trademark) 7300 manufactured by Sumitomo 3M Co., Ltd.) and other alkyl perfluoroalkyl ethers (perfluoroalkyl and the alkyl group may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (for example, ASAHIKLIN (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) etc. These solvents may be used alone or Use as a mixture of two or more types. Among them, hydrofluoroethers are preferred, and perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) and/or perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) are particularly preferred. .
較佳係使用與本揭示之組成物的溶劑相同的溶劑來作為濕潤被覆法中所使用的溶劑。 It is preferable to use the same solvent as that of the composition of the present disclosure as the solvent used in the wet coating method.
使用乾燥被覆法時,本揭示的表面處理劑可直接使用於乾燥被覆法,或是以上述溶劑稀釋後再用於乾燥被覆法。 When using the dry coating method, the surface treatment agent disclosed in the present disclosure can be directly used in the dry coating method, or diluted with the above-mentioned solvent and then used in the dry coating method.
本揭示的表面處理劑,從可得到良好分散性的觀點來看,可有效地用於濕潤被覆法,尤其是噴塗法。 The surface treatment agent disclosed in the present disclosure can be effectively used in a wet coating method, especially a spray coating method, from the viewpoint of obtaining good dispersibility.
表面處理劑的層形成,較佳係以在層中使本揭示的表面處理劑與用以水解及脫水縮合的觸媒共存的方式實施。簡而言之,以濕潤被覆法進行時,可在以溶劑稀釋本揭示的表面處理劑後,在即將施用於基材表面之前,在本揭示之表面處理劑的稀釋液中添加觸媒。以乾燥被覆法進行時,直接將添加有觸媒的本揭示之表面處理劑進行蒸鍍(通常為真空蒸鍍),或是可使用使添加有觸媒的本揭示之表面處理劑含浸於鐵或銅等金屬多孔體而成的顆粒狀物質來進行蒸鍍(通常為真空蒸鍍)處理。 The layer formation of the surface treatment agent is preferably carried out in such a manner that the surface treatment agent of the present disclosure and a catalyst for hydrolysis and dehydration condensation coexist in the layer. In short, when performing the wet coating method, after diluting the surface treatment agent of the present disclosure with a solvent, a catalyst can be added to the diluted solution of the surface treatment agent of the present disclosure immediately before applying it to the surface of the substrate. When the dry coating method is carried out, the surface treatment agent of the disclosure added with the catalyst is directly evaporated (usually vacuum evaporation), or the surface treatment agent of the disclosure added with the catalyst can be impregnated into the iron or copper or other metal porous body for vapor deposition (usually vacuum vapor deposition) treatment.
觸媒可使用任何適當的酸或鹼。酸觸媒可使用例如乙酸、甲酸、三氟乙酸等。又,鹼觸媒可使用例如氨、有機胺類等。 Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as an alkali catalyst, ammonia, organic amines, etc. can be used, for example.
如上所述,在基材表面形成源自本揭示之表面處理劑的層,製造本揭示的物品。藉此所得之上述層兼具高的表面平滑性與高的摩擦耐久性。又,上述層,除了高的摩擦耐久性以外,雖亦與所使用之表面處理劑的組成有關,但可具有撥水性、撥油性、防污性(例如防止指紋等污漬附著)、防水性(防止水浸入電子零件等)、表面平滑性(或潤滑性,例如指紋等污漬的擦除性、以及對手指的優良觸感)等,而可理想地用作機能性薄膜。 The article of the present disclosure is produced by forming a layer derived from the surface treatment agent of the present disclosure on the surface of the substrate as described above. The above-mentioned layer thus obtained has both high surface smoothness and high friction durability. In addition, the above-mentioned layer, in addition to high friction durability, is also related to the composition of the surface treatment agent used, but it may have water-repellent properties, oil-repellent properties, anti-fouling properties (such as preventing adhesion of stains such as fingerprints), water-repellent properties ( Prevent water from entering electronic parts, etc.), surface smoothness (or lubricity, such as the ability to wipe off stains such as fingerprints, and excellent touch to fingers), etc., and can be ideally used as a functional film.
亦即本揭示亦進一步關於一種在最外層具有上述表面處理層的光學材料。 That is, the present disclosure further relates to an optical material having the above-mentioned surface treatment layer on the outermost layer.
作為光學材料,除了與後述例示之顯示器等相關的光學材料以外,可較佳地列舉各式各樣的光學材料,例如:陰極射線管(CRT;例如,個人電腦顯示器)、液晶顯示器、電漿顯示器、有機EL顯示器、無機薄膜EL點陣顯示器、背面投影型顯示器、螢光顯示管(VFD)、場發射顯示器(FED;Field Emission Display)等顯示器或該等的顯示器之保護板,或是在該等的表面實施有抗反射膜處理者。 As the optical material, in addition to the optical materials related to the display etc. which will be exemplified later, various optical materials such as cathode ray tube (CRT; for example, personal computer monitor), liquid crystal display, plasma display, organic EL display, inorganic thin film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED; Field Emission Display) and other displays or protective plates for such displays, or in These surfaces are treated with anti-reflective coating.
具有由本揭示所得之層的物品並未特別限定,可為光學構件。作為光學構件的例子,可列舉如下:眼鏡等鏡片;PDP、LCD等顯示器之前保護板、抗反射板、偏光板、抗眩光板;行動電話、行動資訊終端等設備的觸控面板薄片;藍光(Blu-ray(註冊商標))碟、DVD碟、CD-R、MO等光碟的碟面;光纖;時鐘的顯示面等。 An article having a layer obtained from the present disclosure is not particularly limited, and may be an optical member. Examples of optical components include the following: lenses such as glasses; protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for mobile phones and mobile information terminals; blue light ( Disc surfaces of Blu-ray (registered trademark) discs, DVD discs, CD-R, MO and other optical discs; optical fibers; display surfaces of clocks, etc.
又,具有由本揭示所得之層的物品可為醫療設備或醫療材料。 Also, an article having a layer resulting from the present disclosure can be a medical device or a medical material.
又,具有由本揭示所得之層的物品可為汽車內外裝構件。外裝材的例子可列舉如下:窗戶、燈罩、車外攝影機罩。作為內裝材的例子,可列舉如下:儀錶板蓋、導航系統觸控面板、裝飾內裝材料。 Also, an article having a layer obtained from the present disclosure may be an automotive interior and exterior member. Examples of exterior materials include the following: windows, lamp covers, and exterior camera covers. Examples of interior materials include instrument panel covers, navigation system touch panels, and decorative interior materials.
上述層的厚度並未特別限定。光學構件的情況,從光學性能、表面平滑性、摩擦耐久性及防污性的觀點來看,上述層的厚度較佳為1至50nm、1至30nm,較佳為1至15nm的範圍。 The thickness of the above layer is not particularly limited. In the case of an optical member, the thickness of the above layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, preferably 1 to 15 nm from the viewpoint of optical performance, surface smoothness, friction durability and antifouling property.
以上詳述使用本揭示之組成物(例如表面處理劑)所得之物品。另外,包含本揭示之具有氟聚醚基之矽烷化合物或具有氟聚醚基之矽烷化合物的組成物之用途、使用方法以及物品的製造方法等,不限於上述例示者。 The articles obtained by using the composition (such as the surface treatment agent) of the present disclosure are described in detail above. In addition, the use, method of use, and method of manufacturing the composition including the silane compound having a fluoropolyether group or the composition containing a silane compound having a fluoropolyether group of the present disclosure are not limited to those exemplified above.
以上雖說明實施型態,但應理解只要不脫離申請專利範圍的主旨及範圍,及可進行型態及細節的各種變更。 Although the embodiment has been described above, it should be understood that various changes in the form and details are possible unless departing from the gist and scope of the claims.
[實施例] [Example]
通過以下的實施例更具體說明本發明的表面處理劑,但本發明不限於此等實施例。另外,本實施例中,以下所示的化學式皆表示平均組成。本實施例中,構成全氟聚醚的重複單元之存在順序為任意。 The surface treatment agent of the present invention will be described more specifically by the following examples, but the present invention is not limited to these examples. In addition, in this Example, all the chemical formulas shown below represent an average composition. In this example, the order of existence of the repeating units constituting the perfluoropolyether is arbitrary.
(實施例1至7) (Examples 1 to 7)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A1)溶解於氫氟醚(3M公司製,Novec HFE-7200)。再者,以表1所述之比率在該溶液中添加具有氟烷基之矽烷化合物(化合物B1至B3),製備表面處理劑。另外,表中記載為「莫耳比」的數值,係指具有氟烷基之矽烷化合物之莫耳數相對於化合物A1之莫耳數的比率(莫耳比)。 A silane compound (compound A1) having a fluoropolyether group was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass. Furthermore, silane compounds (compounds B1 to B3) having a fluoroalkyl group were added to this solution at the ratios described in Table 1 to prepare a surface treatment agent. In addition, the value described as "molar ratio" in the table|surface means the ratio (molar ratio) of the number of moles of the silane compound which has a fluoroalkyl group with respect to the number of moles of compound A1.
(m≒21,n≒35) (m≒21, n≒35)
化合物B1: C2F5CH2OCH2CH2CH2Si(OCH3)3 Compound B1: C 2 F 5 CH 2 OCH 2 CH 2 CH 2 Si(OCH 3 ) 3
化合物B2: C4F9CH2CH2Si(OCH3)3 Compound B2: C 4 F 9 CH 2 CH 2 Si(OCH 3 ) 3
化合物B3: C6F13CH2CH2Si(OCH3)3 Compound B3: C 6 F 13 CH 2 CH 2 Si(OCH 3 ) 3
(實施例8至14) (Examples 8 to 14)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A2)溶解於氫氟醚(3M公司製,Novec HFE-7200)。再者,以表2所述之比率在該溶液中添加具有氟烷基之矽烷化合物(化合物B1至B3),製備表面處理劑。另外,表中記載為「莫耳比」的數值,係指具有氟烷基之矽烷化合物之莫耳數相對於化合物A2之莫耳數的比率(莫耳比)。 A silane compound (compound A2) having a fluoropolyether group was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass. Furthermore, silane compounds (compounds B1 to B3) having a fluoroalkyl group were added to this solution at the ratios described in Table 2 to prepare a surface treatment agent. In addition, the numerical value described as "molar ratio" in a table|surface means the ratio (molar ratio) of the number of moles of the silane compound which has a fluoroalkyl group with respect to the number of moles of compound A2.
(m≒21,n≒35) (m≒21, n≒35)
(比較例1) (comparative example 1)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A1)溶解於氫氟醚(3M公司製,Novec HFE-7200),製備表面處理劑。 A surface treatment agent was prepared by dissolving a silane compound (compound A1) having a fluoropolyether group in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass.
(比較例2) (comparative example 2)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A1)溶解於氫氟醚(3M公司製,Novec HFE-7200)。再者,以表1所述之量在該溶液中添加具有氟烷基之矽烷化合物(化合物B2),製備表面處理劑。 A silane compound (compound A1) having a fluoropolyether group was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass. Furthermore, a silane compound (compound B2) having a fluoroalkyl group was added to this solution in the amount described in Table 1 to prepare a surface treatment agent.
(比較例3) (comparative example 3)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A2)溶解於氫氟醚(3M公司製,Novec HFE-7200),製備表面處理劑。 A surface treatment agent was prepared by dissolving a silane compound (compound A2) having a fluoropolyether group in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass.
(比較例4) (comparative example 4)
以成為固形分濃度0.06質量%的方式使具有氟聚醚基之矽烷化合物(化合物A2)溶解於氫氟醚(3M公司製,Novec HFE-7200)。再者,以表2所述之量在該溶液中添加具有氟烷基之矽烷化合物(化合物B2),製備表面處理劑。 A silane compound (compound A2) having a fluoropolyether group was dissolved in hydrofluoroether (manufactured by 3M, Novec HFE-7200) so that the solid content concentration was 0.06% by mass. Furthermore, a silane compound (compound B2) having a fluoroalkyl group was added to this solution in the amount described in Table 2 to prepare a surface treatment agent.
(表面處理層的形成) (Formation of surface treatment layer)
使用搭載有雙流體噴嘴的噴塗裝置(東邦化成公司製),將上述製備的表面處理劑均勻地噴塗在基材(化學強化玻璃(Corning公司製,「Gorilla」玻璃,厚度0.7mm)的表面。表面處理劑的塗布量為48g/m2。於150℃將塗布後的基材加熱30分鐘,形成硬化膜。 Using a spraying device equipped with a two-fluid nozzle (manufactured by Toho Chemical Co., Ltd.), the surface treatment agent prepared above was uniformly sprayed on the surface of a substrate (chemically strengthened glass (manufactured by Corning, "Gorilla" glass, thickness 0.7 mm). The coating amount of the surface treatment agent was 48 g/m 2 . The coated substrate was heated at 150° C. for 30 minutes to form a cured film.
(評價) (Evaluation)
測量上述實施例1至14及比較例1至4中所得之硬化膜的磨耗耐久性。 The abrasion durability of the cured films obtained in Examples 1 to 14 and Comparative Examples 1 to 4 above was measured.
(耐橡皮擦摩擦耐久性試驗) (Eraser friction durability test)
使用摩擦試驗機(新東科學公司製),以下述條件每摩擦2500次即測量對水的接觸角,持續試驗至小於100°為止。試驗環境條件為25℃,濕度40%RH。將小於100°時的摩擦次數視為橡皮擦摩擦耐久性試驗的結果並呈示於表1及2。 Using a friction tester (manufactured by Shinto Scientific Co., Ltd.), the contact angle to water was measured every 2500 times of friction under the following conditions, and the test was continued until it was less than 100°. The environmental conditions of the test are 25°C and 40%RH. The number of times of rubbing at less than 100° is regarded as the result of the eraser rubbing durability test and is shown in Tables 1 and 2.
橡皮擦:Raber Eraser(Minoan公司製) Eraser: Raber Eraser (manufactured by Minoan Corporation)
接地面積:6mm Ground area: 6mm
移動距離(單向):30mm Moving distance (unidirectional): 30mm
移動速度:40來回/分鐘 Movement speed: 40 back and forth / minute
載重:1kg/6mm Load: 1kg/6mm
[表1]
[表2]
[產業上的可利用性] [industrial availability]
本揭示的表面處理劑可理想地用於在各式各樣的基材、尤其是要求穿透性的光學構件表面形成表面處理層。 The surface treatment agent disclosed herein can be ideally used to form a surface treatment layer on a variety of substrates, especially optical members requiring penetrability.
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