Laminate
The laminate with a water-repellent layer having controlled nitrogen, fluorine, and silicon concentrations addresses the issues of insufficient water repellency and abrasion resistance, offering enhanced performance for optical elements and displays.
Patent Information
- Application Number
- PCT/JP2025/004143
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-02-09
- Filing Date
- 2025-02-07
- Publication Date
- 2025-08-14
AI Technical Summary
Existing laminates lack sufficient water repellency, slip properties, and abrasion resistance, particularly in applications requiring better performance.
A laminate structure is developed with a water-repellent layer having specific nitrogen, fluorine, and silicon concentrations, formed from a compound represented by a defined formula, enhancing water repellency and slip properties while providing abrasion resistance.
The laminate achieves improved water repellency, slip properties, and abrasion resistance, making it suitable for various applications including optical elements and displays.
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Abstract
Description
Laminate
[0001] The present disclosure relates to a laminate.
[0002] It is known that certain silane compounds can provide excellent water and oil repellency when used in the surface treatment of a substrate (Patent Document 1).
[0003] Japanese Patent Application Laid-Open No. 2019-44179
[0004] An object of the present disclosure is to provide a laminate including a water-repellent layer that has better water repellency, slip properties, and abrasion resistance.
[0005] The present disclosure includes the following aspects. [1] A laminate including a substrate and a water-repellent layer located on the substrate, wherein the nitrogen concentration at the surface of the water-repellent layer is 0.01 atomic % or more and 10 atomic % or less, and the fluorine concentration at the surface of the water-repellent layer is less than 5 atomic %. [2] The laminate according to item 1, wherein the silicon concentration at the surface of the water-repellent layer is 0.1 atomic % or more and 50 atomic % or less. [3] The laminate according to item 1 or 2, wherein the silicon concentration at the surface of the water-repellent layer is 15 atomic % or more and 25 atomic % or less. [4] The water-repellent layer is formed by the reaction of a compound represented by the following formula (1): [In the formula: R S is a monovalent group containing one or more Si atoms to which no hydroxyl group or hydrolyzable group is directly bonded, and X 1 is a divalent to decavalent group, R Si [5] The laminate according to any one of items 1 to 3, which is a cured product of a compound represented by the formula: [R] is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, and α is an integer of 1 to 9. S is R 1 - (R S1 ) s1 -(SiR 2 2 ) s2 - (R Ar ) s3 -, and R 1 represents a hydrocarbon group, the following group A or group B, and the groups A and B are each a group represented by the following formula: [In the formula: R 51 are each independently R 53 -(SiR53 2 -R 61 ) ma -, and R 61 are each independently a single bond, an oxygen atom, or C 1-6 is an alkylene group, R 53 are each independently a hydrocarbon group or R 51’ and R 51’ is R 51 Each ma is independently an integer of 1 to 5, provided that R 51 Medium, R 51’ The number of is 20 or less, and R 52 are each independently a hydrocarbon group, na is an integer of 1 to 3, and R 54 are each independently a hydrocarbon group, nb is an integer of 1 to 5, and z is 0 or 1. S1 are each independently a single bond or a group represented by the following formula: [In the formula: R 3 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 4 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8-R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 6 are each independently C 1-6 is an alkylene group, R 7 are each independently an optionally substituted arylene group, R 8 are each independently a single bond or C 1-6 is an alkylene group, R 9 are each independently a single bond or an oxygen atom, 5 are each independently a hydrocarbon group, x is an integer of 0 to 500, y is an integer of 0 to 500, z is an integer of 0 to 500, x + y + z is 1 or more, and the order of occurrence of the repeating units enclosed in parentheses with x, y, or z is arbitrary in the formula. 2 are each independently a hydrocarbon group, and s1, s2, and s3 are 0 or 1. [6] The laminate according to item 4, wherein the compound represented by formula (1) is any one of the compounds shown below. CH 3 -[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH2 H. 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 )2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H.3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH2 ) H1 -O-(CH 2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H.3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H.3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H.2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 )2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [CH 3 CH 2 CH 2 CH 2 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2-(CH 2 ) H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH3 )CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 [CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [CH 3 CH 2 CH 2 CH2 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] [CH 3 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] (wherein, n1 is each independently an integer of 0 to 100, and H1 and H2 are each independently an integer of 1 to 50.) [7] The laminate according to Item 6, wherein n1 is each independently 0 or 1, and H1 is each independently an integer of 8 to 40, and H2 is each independently an integer of 1 to 10. [8] The laminate according to Item 6, wherein n1 is each independently an integer of 5 to 100, and H1 is each independently an integer of 8 to 40, and H2 is each independently an integer of 1 to 10. [9] The laminate according to claim 4, wherein the compound represented by formula (1) is any one of the compounds shown below. CH 3 CH 2 CH 2 CH 2 Si(CH3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 40 to 70) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n -(CH 2 ) 3 -OCH 2 -CONH-CH 2 C{CH 2 CH 2 CH 2 Si(OCH 3 ) 3} 3 (n is an integer from 40 to 70) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 10 to 30) (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) n -(CH 2 ) 10 -CON[CH 2 CH 2 CH2 Si(OCH 3 ) 3 2 (n is an integer from 10 to 30) [(CH 3 ) 3 SiO]<000124 \ 3> 2 CH 3 3 SiO(Si(CH 3 3 ) 2 O) n n Si(CH< \ 3 3 ) 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 [[ID=5 \ 0]] 2 CH 2 <00 \ 01263>CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CH 2 2 CONHCH 2 2 CH[CH 2 2 CH 2 2 CH 2 2 Si(OCH 3 3 ) 3 2 2 (n is an integer from 20 to 40) CH 3 3 [Si(CH 3 3 ) 2 O] n n Si(CH 3 3 ) 2 (CH 2 2 ) 22 CONH-CH 2 2 CH[CH 2 2 CH 2 2 CH 2 2 Si(OCH 3 3 ) 3 2 2 (n is an integer from 40 to 70) CH 3 3 CH 2 2 CH 2 2 [[ID=1 \ 19]]CH 2 2 -[Si(CH3 ) 2 O n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 2 (n is an integer from 40 to 80) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 CH 2 O-C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 40 to 80) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 2 (n is an integer from 20 to 40) CH 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 22 CON[CH2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer from 20 to 50) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON [(CH 2 ) 3 Si(OCH 3 ) 3 ] 2 (n is an integer of 40 to 60)
[10] The water-repellent layer contains a compound represented by formula (1) and a compound represented by the following formula (2): [In the formula: R A is a carbon chain containing at least one ethereal oxygen atom, and X A is a single bond or a divalent to decavalent group, R Si is R in the compound represented by formula (1). Si wherein each α1 is independently an integer of 1 to 9, and each β1 is independently an integer of 1 to 9.] The laminate according to any one of items 1 to 9, which is a cured product of a mixture with a compound represented by the formula:
[11] The laminate according to any one of items 1 to 10, wherein the water-repellent layer has a water contact angle of 103° or more.
[12] An article comprising the laminate according to any one of items 1 to 11.
[13] The article according to item 12, which comprises an intermediate layer containing silicon oxide between the substrate and the water-repellent layer.
[14] The article according to item 13, wherein the intermediate layer contains alkali metal atoms.
[15] The article according to item 14, wherein at least a part of the alkali metal atoms are sodium atoms.
[16] The article according to any one of items 12 to 15, which is an optical member.
[17] The article according to any one of items 12 to 16, which is a display.
[18] A compound represented by the formula: (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 )2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 3 (In the formula, H1 is an integer from 11 to 50.)
[0006] According to the present disclosure, it is possible to provide a laminate including a water-repellent layer having better water repellency, slip properties, and abrasion resistance.
[0007] As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end or in the molecular chain of the hydrocarbon group. Note that when simply referring to an "organic group," it refers to a monovalent organic group. Furthermore, the term "divalent organic group" refers to a divalent group containing carbon. Examples of such divalent organic groups include divalent groups in which one more hydrogen atom has been eliminated from an organic group. Similarly, a trivalent or higher organic group refers to a group in which a predetermined number of hydrogen atoms have been eliminated from an organic group.
[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C 1-30 Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.
[0009] As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but examples thereof include a halogen atom, a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl group, C 3-10 Unsaturated cycloalkyl groups, 5- to 10-membered heterocyclyl groups, 5- to 10-membered unsaturated heterocyclyl groups, C 6-10 Examples include one or more groups selected from aryl groups and 5- to 10-membered heteroaryl groups.
[0010] As used herein, the term "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, i.e., a group that can be removed from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR h , -OCOR h , —O—N═CR h 2 , -NR h 2 , -NHR h or —NCO (wherein R h represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms), and preferably —OR h (i.e., an alkoxy group). h Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, with methyl and ethyl groups being more preferred.
[0011] The laminate of the present disclosure includes a substrate and a water-repellent layer located on the substrate, wherein the nitrogen concentration on the surface of the water-repellent layer is 0.01 atomic % or more and 10 atomic % or less, and the fluorine concentration on the surface of the water-repellent layer is less than 5 atomic %.
[0012] [Substrate] The type of substrate included in the laminate of the present disclosure is not particularly limited, and may be composed of any appropriate material, such as glass, resin (which may be a natural or synthetic resin, for example, a general plastic material), metal, ceramics, semiconductors (silicon, germanium, etc.), fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.
[0013] For example, when the article to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. When the article to be manufactured is an optical component, some layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic materials that can be used for the anti-reflection layer include SiO2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , Ta 3 O 5 , Nb 2 O 5 , HfO 2 , Si 3 N 4 , CeO 2 , MgO, Y 2 O 3 , SnO 2 , MgF 2 , W.O. 3 These inorganic materials may be used alone or in combination of two or more (for example, as a mixture). When a multi-layer antireflection layer is formed, the outermost layer may contain SiO 2 and / or SiO is preferably used. When the article to be manufactured is an optical glass component for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a portion of the surface of the substrate (glass). Furthermore, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomization film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, or the like, depending on its specific specifications.
[0014] The shape of the substrate is not particularly limited and may be, for example, a plate, a film, or other form. The surface region of the substrate on which the water-repellent layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined depending on the use and specific specifications of the article to be manufactured.
[0015] In one embodiment, at least the surface portion of such a substrate may be made of a material that originally contains hydroxyl groups. Examples of such materials include glass, metals (especially base metals), ceramics, semiconductors, and the like, on whose surfaces native oxide or thermal oxide films form. Alternatively, in cases where the presence of hydroxyl groups is insufficient, such as in resins, or in cases where hydroxyl groups are not originally present, some kind of pretreatment can be performed on the substrate to introduce or increase the number of hydroxyl groups on the substrate surface. Examples of such pretreatments include plasma treatment (e.g., corona discharge) and ion beam irradiation. Plasma treatment can introduce or increase hydroxyl groups on the substrate surface, and can also be suitably used to clean the substrate surface (remove foreign matter, etc.). Another example of such pretreatment is a method in which an interfacial adsorbent having carbon-carbon unsaturated bond groups is preliminarily formed in the form of a monomolecular film on the substrate surface by the Langmuir-Blodgett method (LB method) or chemical adsorption method, and then the unsaturated bonds are cleaved in an atmosphere containing oxygen, nitrogen, or the like.
[0016] In another embodiment, the substrate may be one whose surface portion is made of a material containing another reactive group, such as a silicone compound having one or more Si—H groups, or an alkoxysilane.
[0017] In a preferred embodiment, the substrate is glass, and examples of such glass include, but are not limited to, sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, crystallized glass, chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass.
[0018] The thickness of the substrate is not particularly limited, but is, for example, 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more, and is, for example, 20 mm or less, preferably 10 mm or less, and more preferably 8 mm or less.
[0019] [Water-repellent layer] The water-repellent layer included in the laminate of the present disclosure is located on the substrate. Note that, in the present disclosure, "on the substrate" does not necessarily refer only to an embodiment in which the water-repellent layer is in direct contact with the substrate, but may also refer to an embodiment in which, for example, an intermediate layer is present between the substrate and the water-repellent layer. In a preferred embodiment, the water-repellent layer is located on the surface of the laminate.
[0020] The water-repellent layer included in the laminate of the present disclosure can be formed by applying a surface treatment agent onto the substrate or intermediate layer.
[0021] The water-repellent layer included in the laminate of the present disclosure has a nitrogen concentration of 0.01 atomic % or more and 10 atomic % or less on the surface thereof, and a fluorine concentration of less than 5 atomic %.
[0022] In one embodiment, the nitrogen concentration on the surface of the water-repellent layer is 0.01 atomic % or more and 10 atomic % or less.
[0023] In one embodiment, the fluorine concentration at the surface of the water-repellent layer is less than 5 atomic %. In a more preferred embodiment, the fluorine concentration at the surface of the water-repellent layer is less than 1 atomic %. In an even more preferred embodiment, the fluorine concentration at the surface of the water-repellent layer is less than 0.1 atomic %.
[0024] In a preferred embodiment, the silicon concentration on the surface of the water-repellent layer is 0.1 atomic % or more and 50 atomic % or less.
[0025] In a more preferred embodiment, the silicon concentration on the surface of the water-repellent layer is 15 atomic % or more and 25 atomic % or less.
[0026] The concentrations of each element on the surface of the water-repellent layer can be determined by surface analysis. Examples of methods that can be used for surface analysis include X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry. Typically, XPS analysis is used.
[0027] The XPS analysis apparatus used to measure the elemental concentrations on the water-repellent layer surface can be a PHI5000 VersaProbe II manufactured by ULVAC-PHI, Inc. The XPS analysis conditions include a monochromated AlKα X-ray source at 25 W, a photoelectron detection area of 1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, and 90 degrees), a pass energy of 23.5 eV, and Ar ions as sputtered ions. Using the above apparatus and measurement conditions, the concentrations of nitrogen, fluorine, and silicon on the water-repellent layer surface can be determined based on the spectra of the N1s, F1s, and Si2p orbitals.
[0028] Specific measurement methods and conditions may be as follows. The surface of the water-repellent layer treated on the substrate can be subjected to XPS measurement using an X-ray photoelectron spectrometer (XPS, PHI5000VersaProbeII manufactured by ULVAC-PHI, Inc.). Measurement conditions for XPS analysis are, for example, as follows: X-ray source: monochromated AlKα radiation (25 W); Photoelectron detection area: 1400 μm × 300 μm; Photoelectron detection angle: 45 degrees; Pass energy: 23.5 eV; Measurement elements: carbon (C1s) 278 to 298 eV, nitrogen (N1s) 390 to 410 eV, oxygen (O1s) 523 to 543 eV, fluorine (F1s) 680 to 698 eV, silicon (Si2p) 94 to 114 eV
[0029] The atomic ratio corresponding to each element can be calculated from the peak shape and intensity obtained in each region.
[0030] The detection depth can be adjusted appropriately by adjusting the photoelectron detection angle in the XPS analysis. For example, a shallow angle close to 20 degrees can achieve a detection depth of about 3 nm, while a deep angle close to 90 degrees can achieve a detection depth of about 10-odd nm.
[0031] In addition, when silicon derived from the substrate is detected in the composition analysis by XPS analysis, the amount of Si detected in the substrate can be calculated from the detected amount of specific atoms in the substrate, for example, if the substrate is glass, metal atoms (e.g., Al, Na, K, B, Ca, Mg, Sn, etc.) contained in trace amounts, and subtracted from the measurement results, thereby making it possible to distinguish between the silicon concentration derived from the water-repellent layer and the silicon concentration derived from the substrate.
[0032] In one embodiment, when measuring the silicon concentration on the surface of the water-repellent layer, silicon originating from an intermediate layer such as a silicon dioxide layer can be detected. In another embodiment, when measuring the silicon concentration on the surface of the water-repellent layer, silicon originating from an intermediate layer such as a silicon dioxide layer is not detected.
[0033] The nitrogen concentration on the surface of the water-repellent layer is defined as the atomic ratio of the total amount of carbon, nitrogen, oxygen, fluorine, and silicon.
[0034] The fluorine concentration on the surface of the water-repellent layer is defined as the atomic ratio of the total amount of carbon, nitrogen, oxygen, fluorine, and silicon.
[0035] The silicon concentration on the surface of the water-repellent layer is defined as the atomic ratio of the total amount of carbon, nitrogen, oxygen, fluorine, and silicon.
[0036] The nitrogen concentration, fluorine concentration, and silicon concentration can be measured at three different points on the surface of the water-repellent layer, and the average values thereof can be used.
[0037] In a preferred embodiment, the water-repellent layer included in the laminate of the present disclosure is represented by the following formula (1): [In the formula: R S is a monovalent group containing one or more Si atoms to which no hydroxyl group or hydrolyzable group is directly bonded, and X 1 is a divalent to decavalent group, R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, and α is an integer of 1 to 9. In other words, the water-repellent layer included in the laminate of the present disclosure may be a cured product of the silane compound.
[0038] R S is a monovalent group containing one or more Si atoms to which no hydroxyl group or hydrolyzable group is directly bonded.
[0039] In one embodiment, R S is a group having at least one branched structure of Si.
[0040] The branched structure is preferably the following structure: In the above formula, the Si atom is tetravalent, but other bonds are not shown.
[0041] In one embodiment, the branched structure has the following structure: [* indicates a bonding site.] That is, it may be branched into two SiOs or three SiOs. In the above formula, the Si atom in SiO is tetravalent, but other bonding sites are not shown. The bonding site indicated by * is R S X that can be included in 1 may be bonded to a group other than R S X that can be included in 1 and X 1 When one * is contained in the branched structure, * may be directly bonded to R S X that can be included in 1 A group or X bonded to 1 When two or more * are contained, each * is preferably directly bonded to R S X that can be included in 1 may be bonded to a group other than R S X that can be included in 1 A group or X bonded to 1 and at least one * may be bonded to X 1 or X 1 It is preferred that the aryl group is bonded to a group that bonds to the aryl group.
[0042] In one embodiment, R S is R 1 - (R S1 ) s1 -(SiR 2 2 ) s2 - (R Ar ) s3 -, and R 1represents a hydrocarbon group, the following group A or group B, and the groups A and B are each a group represented by the following formula: [In the formula: R 51 are each independently R 53 -(SiR 53 2 -R 61 ) ma -, and R 61 are each independently a single bond, an oxygen atom, or C 1-6 is an alkylene group, R 53 are each independently a hydrocarbon group or R 51’ and R 51’ is R 51 Each ma is independently an integer of 1 to 5, provided that R 51 Medium, R 51’ The number of is 20 or less, and R 52 are each independently a hydrocarbon group, na is an integer of 1 to 3, and R 54 are each independently a hydrocarbon group, nb is an integer of 1 to 5, and z is 0 or 1. S1 are each independently a single bond or a group represented by the following formula: [In the formula: R 3 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9- and R 4 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 6 are each independently C 1-6 is an alkylene group, R 7 are each independently an optionally substituted arylene group, R 8 are each independently a single bond or C 1-6 is an alkylene group, R 9 are each independently a single bond or an oxygen atom, 5 are each independently a hydrocarbon group, x is an integer of 0 to 500, y is an integer of 0 to 500, z is an integer of 0 to 500, x + y + z is 1 or more, and the order of occurrence of the repeating units enclosed in parentheses with x, y, or z is arbitrary in the formula. 2 are each independently a hydrocarbon group; s1, s2 and s3 are 0 or 1.
[0043] R 1 is a hydrocarbon group, an A group, or a B group.
[0044] In one embodiment, R 1 is a hydrocarbon group. 1The hydrocarbon group in the formula (I) may preferably be an alkyl group or an aryl group.
[0045] The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group.
[0046] The aryl group may be monocyclic or polycyclic. The aryl is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. The aryl group is particularly preferably a phenyl group.
[0047] R 1 The hydrocarbon group in is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
[0048] In one embodiment, R 1 is C 1-6 Alkyl group, preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.
[0049] In one embodiment, R 1 is C 1-6 Alkyl group, preferably C 1-4 An alkyl group is preferable, and a normal butyl group is more preferable.
[0050] In a preferred embodiment, R 1 is an A group or a B group, more preferably an A group.
[0051] (A group)
[0052] R 51 are each independently R 53 -(SiR 53 2 -R 61 ) ma - is a group represented by the formula:
[0053] R 61 are each independently a single bond, an oxygen atom, or C 1-6It is an alkylene group.
[0054] R 61 C in 1-6 The alkylene group may be a straight chain or a branched chain. 1-6 The alkylene group is preferably C 1-4 Alkylene group, more preferably C 2-4 It may be an alkylene group.
[0055] In one embodiment, R 61 is an oxygen atom or C 1-6 It is an alkylene group.
[0056] In one embodiment, R 61 is an oxygen atom.
[0057] In one embodiment, some R 61 is an oxygen atom, and other R 61 is C 1-6 It is an alkylene group.
[0058] R 53 are each independently a hydrocarbon group or R 51’ is.
[0059] R 53 The hydrocarbon group in the formula (I) may preferably be an alkyl group or an aryl group.
[0060] The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0061] The aryl group may be monocyclic or polycyclic. The aryl is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. The aryl group is particularly preferably a phenyl group.
[0062] R 53 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
[0063] R51’ is R 51 That is, R 51’ is R 53 -(SiR 53 2 O) ma -. However, R 51 Medium, R 51’ The number is 20 or less, preferably 10 or less, more preferably 6 or less, and further preferably 3 or less.
[0064] In one embodiment, R 53 are each independently a hydrocarbon group or R 51’ is.
[0065] In a preferred embodiment, R 53 are each independently a hydrocarbon group.
[0066] In one embodiment, R 53 is R 53’ -(SiR 53’ 2 -R 61’ ) ma’ - [In the formula: R 53’ are each independently a hydrocarbon group or R 53 -(SiR 53 2 -R 61 ) ma - and at least one R 53’ is R 53 -(SiR 53 2 -R 61 ) ma - and R 53 are each independently or a hydrocarbon group, R 61 are each independently a single bond, an oxygen atom, or C 1-6 each m is independently an integer of 1 to 5; 61’ are each independently an oxygen atom or C 1-6 is an alkylene group, and each m a ' is independently an integer of 1 to 5.
[0067] In another embodiment, in one embodiment, R 53 is R53’ -(SiR 53’ 2 -R 61’ ) ma’ - [In the formula: R 53’ are each independently a hydrocarbon group or R 53” -(SiR 53” 2 -R 61” ) ma” - and at least one R 53’ is R 53” -(SiR 53” 2 -R 61” ) ma” - and R 53” are each independently a hydrocarbon group or R 53 -(SiR 53 2 -R 61 ) ma - and at least one R 53” is R 53 -(SiR 52 2 -R 61 ) ma - and R 53 are each independently or a hydrocarbon group, R 61 are each independently an oxygen atom or C 1-6 each m is independently an integer of 1 to 5; 61” are each independently an oxygen atom or C 1-6 each m a ” is independently an integer of 1 to 5; R 61’ are each independently an oxygen atom or C 1-6 is an alkylene group, and each m a ' is independently an integer of 1 to 5.
[0068] Each ma is independently an integer of 1 to 5, preferably 1 or 2.
[0069] R 52 are each independently a hydrocarbon group.
[0070] R 52The hydrocarbon group in the formula (I) may preferably be an alkyl group or an aryl group.
[0071] The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0072] The aryl group may be monocyclic or polycyclic. The aryl is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. The aryl group is particularly preferably a phenyl group.
[0073] R 52 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
[0074] n a is an integer of 1 to 3. In one embodiment, n a is 2. In another embodiment, n a is 3. 51’ When present, na is (SiR 53 2 -R 61 ) ma are selected independently.
[0075] z is 0 or 1. In one embodiment, z is 0. In another embodiment, z is 1.
[0076] In a preferred embodiment, in the A group, R 51 are each independently R 53 -(SiR 53 2 -R 61 ) ma -, and R 61 are each independently a single bond, an oxygen atom, or C 1-6 an alkylene group, preferably an oxygen atom, or C 1-6 is an alkylene group, R 53 are each independently a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms, ma is 1 or 2, and R 52are each independently a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms; and na is 1 or 2.
[0077] Examples of A groups include, but are not limited to, the following groups:
[0078]
[0079]
[0080] In a preferred embodiment, the A group is: is.
[0081] (B group)
[0082] R 54 are each independently a hydrocarbon group.
[0083] R 54 The hydrocarbon group in the formula (I) may preferably be an alkyl group or an aryl group.
[0084] The alkyl group may be linear or branched. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group.
[0085] The aryl group may be monocyclic or polycyclic. The aryl is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. The aryl group is particularly preferably a phenyl group.
[0086] R 54 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
[0087] nb is an integer of 1 to 5, preferably 2 or 3.
[0088] In a preferred embodiment, in the B group, R 54are each independently a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms; and nb is 2 or 3.
[0089] Examples of B groups include, but are not limited to, the following groups:
[0090] R S1 are each independently a single bond or the following formula: (In the formula: R 3 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 4 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R7 -R 9 -R 6 -R 9 - and R 6 are each independently C 1-6 is an alkylene group, R 7 are each independently an optionally substituted arylene group, R 8 are each independently a single bond or C 1-6 is an alkylene group, R 9 are each independently a single bond or an oxygen atom, 5 are each independently a hydrocarbon group, x is an integer of 0 to 500, y is an integer of 0 to 500, z is an integer of 0 to 500, x + y + z is 1 or more, and the order of occurrence of the respective repeating units enclosed in parentheses with x, y, or z is arbitrary in the formula, 2 are each independently a hydrocarbon group, and s is 0 or 1.
[0091] In one embodiment, R S1 is a single bond.
[0092] In another embodiment, R S1 teeth, It is a group represented by the following formula:
[0093] R 3 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9-R 7 -R 9 -R 6 -R 9 -, preferably C 1-12 Alkylene group, or -R 6 -O-R 6 - is.
[0094] R 4 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - is.
[0095] In one embodiment, R 4 are each independently C 1-12 Alkylene group, or -R 6 -O-R 6 - is.
[0096] In another embodiment, R 4 are each independently -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - is.
[0097] In one embodiment, R 3 are each independently C 1-12 Alkylene group, or -R 6 -O-R 6 - and R 4 are each independently C 1-12 Alkylene group, or -R 6 -O-R 6 - is.
[0098] In another embodiment, R 3 are each independently C 1-12 Alkylene group, or -R 6 -O-R 6 - and R 4 are each independently -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - is.
[0099] Above C 1-12 The alkylene group may be a straight chain or a branched chain. 1-12 The alkylene group is preferably straight-chain.
[0100] Above C 1-12 The alkylene group is preferably C 2-8 Alkylene group, more preferably C2-6 It is an alkylene group.
[0101] R 6 are each independently C 1-6 The above C is an alkylene group. 1-6 The alkylene group may be a straight chain or a branched chain. 1-6 The alkylene group is preferably straight-chain.
[0102] Above C 1-6 The alkylene group is preferably C 2-4 Alkylene group, more preferably C 2-3 It is an alkylene group.
[0103] In a preferred embodiment, multiple R 6 In a group containing 6 are the same group.
[0104] R 7 are each independently an optionally substituted arylene group.
[0105] In one embodiment, R 7 are each independently is.
[0106] In one embodiment, R 7 is a phenylene group.
[0107] In another embodiment, R 7 is a naphthylene group.
[0108] The arylene group may have a substituent. The number of the substituents is not particularly limited and is, for example, 1 to 4, preferably 1 or 2.
[0109] In one embodiment, the phenylene group and naphthylene group may have a substituent. The number of substituents is not particularly limited and is, for example, 1 to 4, preferably 1 or 2. The substituted phenylene group is preferably a 2,5-substituted phenylene.
[0110] The substituents on the arylene group are each independently —R 41 -R 42 is.
[0111] R41 is a single bond, an oxygen atom, or a sulfur atom, preferably a single bond or an oxygen atom, more preferably an oxygen atom. 41 is preferably not a nitrogen atom.
[0112] R 42 is C optionally substituted by halogen 1-12 alkyl group, -(O-R 43 ) p , -R 44 -R 45 , -R 44 -OR 46 is.
[0113] The halogen is fluorine, chlorine, bromine or iodine, preferably fluorine.
[0114] R 42 C in 1-12 The alkyl group may be straight or branched.
[0115] R 43 is C 1-6 Alkylene group, preferably C 2-4 It is an alkylene group. Such an alkylene group may be a straight chain or a branched chain.
[0116] R 44 is C 1-12 Alkylene group, preferably C 1-6 It is an alkylene group. Such an alkylene group may be a straight chain or a branched chain.
[0117] R 45 is -CH=CH 2 or -OCOCH=CH 2 is.
[0118] R 46 is a hydrogen atom or C 1-6 The alkyl group may be a straight chain or a branched chain. 1-6 The alkyl group is preferably C 1-3 alkyl group, more preferably C 1-2 It is preferably an alkyl group, more preferably a methyl group.
[0119] R8 are each independently a single bond or C 1-6 It is an alkylene group. 1-6 The alkylene group may be straight-chain or branched.
[0120] In one embodiment, R 8 is a single bond.
[0121] In another embodiment, R 8 is C 1-6 It is an alkylene group.
[0122] R 9 are each independently a single bond or an oxygen atom.
[0123] In one embodiment, R 9 is a single bond.
[0124] In another embodiment, R 9 is an oxygen atom.
[0125] R 5 are each independently a hydrocarbon group. Such hydrocarbon groups may be substituted. When the hydrocarbon groups are substituted, they preferably do not contain a nitrogen atom.
[0126] R 5 are each independently preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted with a halogen atom. Such a halogen atom is preferably a fluorine atom.
[0127] R 5 are each independently preferably C optionally substituted by a halogen atom. 1-18 an alkyl group or an aryl group, more preferably C 1-18 It is an alkyl group or an aryl group.
[0128] Above C 1-18 The alkyl group may be straight-chain or branched, but is preferably straight-chain. 1-18 The alkyl group is preferably C 1-10 alkyl group, more preferably C 1-6 alkyl group, more preferably C 1-4 It is preferably an alkyl group, and even more preferably a methyl group.
[0129] The aryl group is preferably a phenyl group.
[0130] In one embodiment, R 5 are each independently C 1-6 Alkyl group, preferably C 1-4 It is preferably an alkyl group, more preferably a methyl group.
[0131] In another embodiment, R 5 is a phenyl group.
[0132] In another embodiment, R 5 are each independently a methyl group or a phenyl group, preferably a methyl group.
[0133] x is an integer from 0 to 500, preferably an integer from 0 to 300, more preferably an integer from 0 to 100, even more preferably an integer from 1 to 100, even more preferably an integer from 5 to 60, and even more preferably an integer from 10 to 30.
[0134] In one embodiment, x is 0.
[0135] In one embodiment, x is an integer of 1 to 500, preferably an integer of 1 to 300, more preferably an integer of 1 to 100, even more preferably an integer of 5 to 60, still more preferably an integer of 10 to 60, and particularly preferably an integer of 10 to 30, for example, an integer of 2 to 100, 2 to 50, 2 to 30, 5 to 100, 5 to 50, 5 to 30, or 5 to 20. By setting x within this range, the friction durability of the obtained water-repellent layer is improved.
[0136] In another embodiment, x is an integer of 10 to 500, more preferably an integer of 10 to 100, and even more preferably an integer of 10 to 80, for example, an integer of 20 to 500, 20 to 100, 20 to 80, 30 to 80, 40 to 80, or 40 to 70. By setting x within this range, the tactile feel and slipperiness of the resulting water-repellent layer are improved.
[0137] y is an integer of 0 to 500, preferably an integer of 0 to 300, more preferably an integer of 0 to 100, even more preferably an integer of 1 to 100, still more preferably an integer of 5 to 60, and even more preferably an integer of 10 to 30.
[0138] In one embodiment, y is 0.
[0139] In one embodiment, y is an integer of 1 to 500, preferably an integer of 1 to 300, more preferably an integer of 1 to 100, even more preferably an integer of 5 to 60, still more preferably an integer of 10 to 60, and particularly preferably an integer of 10 to 30, for example, an integer of 2 to 100, 2 to 50, 2 to 30, 5 to 100, 5 to 50, 5 to 30, or 5 to 20. By setting y within this range, the friction durability of the obtained water-repellent layer is improved.
[0140] In another embodiment, y is an integer of 10 to 500, more preferably an integer of 10 to 100, and even more preferably an integer of 10 to 80, for example, an integer of 20 to 500, 20 to 100, 20 to 80, 30 to 80, 40 to 80, or 40 to 70. By setting y within this range, the tactile feel and slipperiness of the resulting water-repellent layer are improved.
[0141] z is an integer of 0 to 500, preferably an integer of 0 to 300, more preferably an integer of 0 to 100, even more preferably an integer of 1 to 100, even more preferably an integer of 5 to 60, and even more preferably an integer of 10 to 30.
[0142] In one embodiment, z is 0.
[0143] In one embodiment, z is an integer of 1 to 500, preferably an integer of 1 to 300, more preferably an integer of 1 to 100, even more preferably an integer of 5 to 60, still more preferably an integer of 10 to 60, and particularly preferably an integer of 10 to 30, for example, an integer of 2 to 100, 2 to 50, 2 to 30, 5 to 100, 5 to 50, 5 to 30, or 5 to 20. By setting z within this range, the friction durability of the obtained water-repellent layer is improved.
[0144] In another embodiment, z is an integer of 10 to 500, more preferably an integer of 10 to 100, and even more preferably an integer of 10 to 80, for example, an integer of 20 to 500, 20 to 100, 20 to 80, 30 to 80, 40 to 80, or 40 to 70. By setting z within this range, the tactile feel and slipperiness of the resulting water-repellent layer are improved.
[0145] In one embodiment, y is 0 and z is 0.
[0146] In another embodiment, x is 0 and y is 0.
[0147] R S1 may be a random polymer or a block polymer.
[0148] s1, s2 and s3 are 0 or 1.
[0149] In a preferred embodiment, R 1 is a methyl group, s1 is 1, R 5 is a methyl group, x is 1, y and z are 0, s2 is 1, and s3 is 0.
[0150] X 1 is a divalent to decavalent group. 1 The group is R on the left S and the right side is R Si Combine with.
[0151] X 1 is a divalent to decavalent group, preferably a divalent to hexavalent group, more preferably a divalent to tetravalent group, and even more preferably a divalent group.
[0152] In one embodiment, X 1 represents a single bond, —CO—, —COO—, or —NR x1 --, --CONR x1 -, -NR x1 CO-, -OCONR x1 -, -NR x1 -CO-NR x1 -, -O-, -S-, and -CON= (wherein R x1 is a hydrogen atom or C 1-6 It is a divalent to decavalent group, for example, a divalent or trivalent group, containing at least one group selected from the group consisting of: 1 may have the same group or different groups.
[0153] In a preferred embodiment, X 1 is -CONRx1 - or -NR x1 CO-(wherein, R x1 is a hydrogen atom or C 1-6 is an alkyl group.
[0154] In one embodiment, R x1 is a hydrogen atom.
[0155] In one embodiment, R x1 is a methyl group.
[0156] In a preferred embodiment, X 1 is represented by the following formula: -X 111 -(-X 112 -X 111 -) m - [In the formula: X 111 are each independently a single bond or a divalent group not containing a nitrogen atom, 112 is -CONR x1 - or -NR x1 CO-, and R x1 is a hydrogen atom or C 1-6 is an alkyl group, and m is an integer of 1 to 30.
[0157] X 111 is a single bond or a divalent group that does not contain a nitrogen atom.
[0158] In one embodiment, X 111 is a single bond.
[0159] In one embodiment, X 111 is a divalent group that does not contain a nitrogen atom.
[0160] X 111 The divalent group not containing a nitrogen atom in the formula (I) is alkylene, phenylene, —CO—, —COO—, —O—, —S—, and —O—(CH 2 ) x1 R may be a group containing at least one group selected from —CO—. x1 is a hydrogen atom or C 1-6It is an alkyl group, and x1 is an integer of 1 to 20. The alkylene preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, for example, 1 to 9, 1 to 6, 2 to 30, 5 to 25, 10 to 30, 10 to 25, 10 to 20, or 12 to 20 carbon atoms.
[0161] X 111 is preferably C 1-9 Alkylene group, C 10-30 Alkylene group, -(CH 2 ) f1 -O-(CH 2 ) f2 - (wherein f1 is an integer of 0 to 6, for example, an integer of 1 to 6, and f2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) f3 -phenylene-(CH 2 ) f4 - (wherein f3 is an integer of 0 to 6, for example, an integer of 1 to 6, and f4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-9 Alkylene group or C 10-30 The alkylene group may be linear or branched. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted with one or more substituents selected from alkynyl groups.
[0162] In another preferred embodiment, X 1 is represented by the following formula: -[(X 121 ) x1 -(X 122 ) x2 ]-: [In the formula: X 121 are each independently a single bond or C 1-30 is an alkylene group, 122 each independently represents a single bond, —CO—, —COO—, —OCO—, or —NR x1 --, --CONR x1 -, -NR x1 CO-, -OCONR x1 -, -NR x1 COO-, -NR x1 -CO-NR x1-, -O-, -S-, -O-(CH 2 ) x3 -CONR x1 -, -O-(CH 2 ) x3 -NR x1 CO- or -O-(CH 2 ) x3 -CO-, and R x1 is a hydrogen atom or C 1-6 is an alkyl group, and x3 is an integer from 1 to 30, 122 At least one of the following is -CONR x1 - or -NR x1 CO—, x1 is an integer of 0 to 6, x2 is an integer of 0 to 6, and the order of the repeating units enclosed in parentheses with x1 or x2 is arbitrary in the formula.
[0163] X 121 are each independently a single bond or C 1-60 It is an alkylene group.
[0164] In one embodiment, X 121 is a single bond.
[0165] In one embodiment, X 121 is C 1-60 It is an alkylene group.
[0166] In one embodiment, X 121 At least one of 7-60 It is an alkylene group.
[0167] In one embodiment, C 1-60 The number of carbon atoms in the alkylene group may be 3 or more, 7 or more, 10 or more, 11 or more, 12 or more, 16 or more, 18 or more, or 22 or more, and may be 60 or less, 40 or less, 36 or less, 32 or less, 30 or less, 28 or less, or 24 or less. 1-60 The number of carbon atoms in the alkylene group may be preferably 3 to 60, more preferably 7 to 40, and even more preferably 10 to 30. 121When a plurality of alkylene groups are present, the alkylene groups may have different numbers of carbon atoms. For example, one may have 1 to 6 carbon atoms and the other may have 10 to 30 carbon atoms.
[0168] In one embodiment, C 1-60 The number of carbon atoms in the alkylene group may be 1 or more, 3 or more, or 4 or more, and may be 60 or less, 30 or less, 10 or less, 6 or less, or 4 or less. 1-60 The number of carbon atoms in the alkylene group may be preferably 1 to 10, more preferably 1 to 6, and even more preferably 3 to 6. 121 When a plurality of alkylene groups are present, the alkylene groups may have different numbers of carbon atoms. For example, one may have 1 to 6 carbon atoms and the other may have 10 to 30 carbon atoms.
[0169] In one embodiment, C 1-60 The alkylene group may preferably have 10 to 60 carbon atoms, more preferably 10 to 40 carbon atoms, and even more preferably 10 to 30 carbon atoms.
[0170] In one embodiment, C 1-60 The alkylene group may preferably have 11 to 60 carbon atoms, more preferably 11 to 40 carbon atoms, and even more preferably 11 to 30 carbon atoms.
[0171] X 122 each independently represents a single bond, —CO—, —COO—, —OCO—, or —NR x1 --, --CONR x1 -, -NR x1 CO-, -OCONR x1 -, -NR x1 COO-, -NR x1 -CO-NR x1 -, -O-, -S-, -O-(CH 2 ) x3 -CONR x1 -, -O-(CH 2 ) x3 -NR x1 CO- or -O-(CH 2 ) x3 -CO-, and R x1 is a hydrogen atom or C 1-6alkyl group, x3 is an integer of 1 to 30, and R x1 is a hydrogen atom or C 1-6 It is an alkyl group.
[0172] R x1 C in 1-6 The alkyl group may be linear or branched. 1-6 The alkyl group is linear. 1-6 The alkyl group is a branched chain. 1-6 The alkyl group is preferably C 1-4 It is preferably an alkyl group, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
[0173] x3 can be an integer from 1 to 30, preferably an integer from 1 to 20, for example, an integer from 1 to 10, 11 to 30, or 11 to 20.
[0174] In one embodiment, X 122 is -CO-, -COO-, -OCO-, -NR x1 --, --CONR x1 -, -NR x1 CO-, -OCONR x1 -, -NR x1 COO-, -NR x1 -CO-NR x1 -, -O-, or -S-.
[0175] In a preferred embodiment, X 122 is -CONR x1 -, -NR x1 It is —CO— or —O—.
[0176] x1 is an integer of 0 to 6, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
[0177] x2 is an integer from 0 to 6, preferably an integer from 0 to 2, for example 0 or 1. In one embodiment, x2 is 0. In another embodiment, x2 is 1.
[0178] In another embodiment, X 1 is represented by the following formula: -(X 221 ) a0 -X 210- [(X 211 ) a1 -(X 212 ) a2 ] - [In the formula: X 221 is R 261 b1 R 262 3-b1 C-, R 263 b2 R 264 3-b2 Si- or R 265 2 N- and R 261 are each independently a single bond or a divalent organic group, 262 are each independently a hydrogen atom or a monovalent organic group, 263 are each independently a single bond or a divalent organic group, 264 are each independently a hydrogen atom or a monovalent organic group, 265 are each independently a single bond or a divalent organic group, b1 is 2 or 3, b2 is 2 or 3, and X 210 is a single bond or an alkylene group having 3 or more carbon atoms, 211 is a single bond or a divalent organic group, 212 is -CO-, -COO-, -OCO-, -NR x1 --, --CONR x1 -, -NR x1 CO-, -OCONR x1 -, -NR x1 COO-, -NR x1 -CO-NR x1 -, -O-, -S-, -O-(CH 2 ) x3 -CONR x1 -, -O-(CH 2 ) x3 -NR x1 CO-, -O-(CH 2 ) x3 -CO- or -CON=, R x1 is a hydrogen atom or C 1-6 is an alkyl group, and x3 is an integer from 1 to 30, 212 At least one of the following is -CONRx1 - or -NR x1 CO-, a0 is 0 or 1, a1 is an integer of 1 to 5, a2 is an integer of 0 to 5, and the order of the repeating units enclosed in parentheses with a1 or a2 is arbitrary in the formula.
[0179] X 221 is R 261 b1 R 262 3-b1 C-, R 263 b2 R 264 3-b2 Si- or R 265 2 It is N-.
[0180] R 261 are each independently a single bond or a divalent organic group.
[0181] R 261 is preferably C 1-6 Alkylene group, -(CH 2 ) f1 -O-(CH 2 ) f2 - (wherein f1 is an integer of 0 to 6, for example, an integer of 1 to 6, and f2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) f3 -phenylene-(CH 2 ) f4 - (wherein f3 is an integer of 0 to 6, for example, an integer of 1 to 6, and f4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups include, for example, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0182] In a preferred embodiment, R 261 is C 1-6 Alkylene group or -(CH 2 )f3 -phenylene-(CH 2 ) f4 -, preferably -phenylene-(CH 2 ) f4 - is.
[0183] In another preferred embodiment, R 261 is C 1-3 In one embodiment, R 261 is -CH 2 CH 2 CH 2 In another embodiment, R 261 is -CH 2 CH 2 -It can be.
[0184] R 262 are each independently a hydrogen atom or a monovalent organic group.
[0185] In one embodiment, R 262 is a hydrogen atom.
[0186] In another embodiment, R 262 is a monovalent organic group.
[0187] R 262 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0188] b1 is 2 or 3. In one embodiment, b1 is 2. In another embodiment, b1 is 3.
[0189] R 263 are each independently a single bond or a divalent organic group.
[0190] R 263 is preferably C 1-6 Alkylene group, -(CH 2 ) g1 -O-(CH 2 ) g2 - (wherein g1 is an integer of 0 to 6, for example, an integer of 1 to 6, and g2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 )g3 -phenylene-(CH 2 ) g4 - (wherein g3 is an integer of 0 to 6, for example, an integer of 1 to 6, and g4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups include, for example, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0191] In a preferred embodiment, R 263 is C 1-6 Alkylene group or -(CH 2 ) g3 -phenylene-(CH 2 ) g4 -, preferably -phenylene-(CH 2 ) g4 - is.
[0192] In another preferred embodiment, R 263 is C 1-3 In one embodiment, R 263 is -CH 2 CH 2 CH 2 In another embodiment, R 263 is -CH 2 CH 2 -It can be.
[0193] R 264 are each independently a hydrogen atom or a monovalent organic group.
[0194] In one embodiment, R 264 is a hydrogen atom.
[0195] In another embodiment, R 264 is a monovalent organic group.
[0196] R 264 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6It is preferably an alkyl group, more preferably a methyl group.
[0197] b2 is 2 or 3. In one embodiment, b2 is 2. In another embodiment, b2 is 3.
[0198] R 265 are each independently a single bond or a divalent organic group.
[0199] R 265 is preferably C 1-6 Alkylene group, -(CH 2 ) h1 -O-(CH 2 ) h2 - (wherein h1 is an integer of 0 to 6, for example, an integer of 1 to 6, and h2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) h3 -phenylene-(CH 2 ) h4 - (wherein h3 is an integer of 0 to 6, for example, an integer of 1 to 6, and h4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups include, for example, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0200] In a preferred embodiment, R 265 is C 1-6 Alkylene group or -(CH 2 ) h3 -phenylene-(CH 2 ) h4 -, preferably -phenylene-(CH 2 ) h4 - is.
[0201] In another preferred embodiment, R 265 is C 1-3 In one embodiment, R 265 is -CH 2 CH 2 CH 2In another embodiment, R 265 is -CH 2 CH 2 -It can be.
[0202] In one embodiment, X 221 is R 261 b1 R 262 3-b1 It's C-.
[0203] In one embodiment, X 221 is R 263 b2 R 264 3-b2 It is Si-.
[0204] In one embodiment, X 221 is R 265 2 It is N-.
[0205] X 210 is a single bond or an alkylene group having 3 or more carbon atoms.
[0206] X 210 The number of carbon atoms in the alkylene group in X may be preferably 3 or more, more preferably 6 or more, even more preferably 10 or more, and still more preferably 12 or more, for example, 16 or more, 18 or more, or 22 or more. 210 The number of carbon atoms in the alkylene group in X may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. 210 The alkylene group in may preferably have 3 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, and even more preferably 10 to 30 carbon atoms.
[0207] X 210 The alkylene group in may be a straight chain or a branched chain. The alkylene group is preferably a straight chain.
[0208] X 211 is a single bond or a divalent organic group.
[0209] The divalent organic group is preferably a divalent hydrocarbon group.
[0210] X 211The hydrocarbon group in the formula (I) is preferably a hydrocarbon group having 1 to 30 carbon atoms.
[0211] The hydrocarbon group may preferably be an alkylene group or an arylene group.
[0212] The alkylene group may be a straight chain or a branched chain, and preferably has 1 to 30 carbon atoms.
[0213] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, C 1-6 Alkylene group, C 2-10 Alkylene group, C 2-8 Alkylene group, or C 2-6 It may be an alkylene group.
[0214] In one embodiment, the alkylene group is, for example, C 11-30 The alkylene group may have preferably 10 or more, 11 or more, more preferably 16 or more, even more preferably 18 or more, and still more preferably 22 or more carbon atoms. 111 The number of carbon atoms in the alkylene group in X may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. 110 and X 111 The alkylene group in may preferably have 11 to 60 carbon atoms, more preferably 12 to 40 carbon atoms, and even more preferably 18 to 30 carbon atoms.
[0215] In one embodiment, the alkylene group is, for example, C 10-30 It may be an alkylene group.
[0216] In one embodiment, the alkylene group is, for example, C 11-30 It may be an alkylene group.
[0217] The arylene group may be monocyclic or polycyclic. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms. The arylene group is particularly preferably a phenylene group.
[0218] In one embodiment, X 211 is -X 213 -X 212 -X 214 - [In the formula: X 213 represents an alkylene group, an oxyalkylene group, or -(C j H 2j ) k1 -(O-C j H 2j ) k2 (wherein j is an integer of 1 to 6, k1 is 1 or 0, and k2 is an integer of 1 to 20), and X 212 Ha-CONR x1 -or-NR x1 CO-, and R x1 is a hydrogen atom or C 1-6 an alkyl group, preferably a hydrogen atom; X 214 is a single bond or an alkylene group.
[0219] X 213 represents an alkylene group, an oxyalkylene group, or -(C j H 2j ) k1 -(O-C j H 2j ) k2 (wherein j is an integer of 1 to 6, k1 is 1 or 0, and k2 is an integer of 1 to 20).
[0220] The alkylene group may be a straight chain or a branched chain, and preferably has 1 to 30 carbon atoms.
[0221] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, C 1-6 Alkylene group, C 2-10 Alkylene group, C 2-8 an alkylene group, or C 2-6 It may be an alkylene group.
[0222] In one embodiment, the alkylene group is, for example, C 11-30The alkylene group may have preferably 12 or more carbon atoms, more preferably 16 or more carbon atoms, even more preferably 18 or more carbon atoms, and even more preferably 22 or more carbon atoms. 213 and X 214 The number of carbon atoms in the alkylene group in X may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. 213 and X 214 The alkylene group in may preferably have 11 to 60 carbon atoms, more preferably 12 to 40 carbon atoms, and even more preferably 18 to 30 carbon atoms.
[0223] In one embodiment, the alkylene group is, for example, C 10-30 The alkylene group may be an alkylene group. The number of carbon atoms in the alkylene group may be preferably 10 or more, more preferably 16 or more, even more preferably 18 or more, and still more preferably 22 or more. X 213 and X 214 The number of carbon atoms in the alkylene group in X may be preferably 60 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 24 or less. 213 and X 214 The alkylene group in may preferably have 10 to 60 carbon atoms, more preferably 12 to 40 carbon atoms, and even more preferably 18 to 30 carbon atoms.
[0224] The oxyalkylene group is the alkylene group at the left end (R S The alkylene group is a group having an oxygen atom at the alkyl group side (the alkylene side), that is, an —O-alkylene group.
[0225] j is an integer of 1 to 6, preferably an integer of 2 to 4.
[0226] k1 is 1 or 0, preferably 0.
[0227] k2 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6.
[0228] X 214 is an alkylene group.
[0229] The alkylene group may be a straight chain or a branched chain. The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably a C 1-10 Alkylene group, more preferably C 1-8 Alkylene groups, even more preferably C 1-6 is an alkylene group, for example, C 2-10 Alkylene group, C 2-8 an alkylene group, or C 2-6 It may be an alkylene group.
[0230] In one embodiment, X 211 is -O-R S1 -X 213 -X 212 -X 214 - [In the formula: R S1 has the same meaning as above, and X 212 is -CONR x1 -or-NR x1 CO-, and R x1 is a hydrogen atom or C 1-6 an alkyl group, preferably a hydrogen atom; X 213 represents an alkylene group, an oxyalkylene group, or -(C j H 2j ) k1 -(O-C j H 2j ) k2 (wherein j is an integer of 1 to 6, k1 is 1 or 0, and k2 is an integer of 1 to 20), and X 114 is a single bond or an alkylene group.
[0231] In one embodiment, X 211 is -X 215 -R S1 -X 213 -X 212 -X 214 - [In the formula: R S1 has the same meaning as above, and X 212 is -CONR x1 -or-NR x1 CO-, and R x1 is a hydrogen atom or C 1-6an alkyl group, preferably a hydrogen atom; X 213 represents an alkylene group, an oxyalkylene group, or -(C j H 2j ) k1 -(O-C j H 2j ) k2 (wherein j is an integer of 1 to 6, k1 is 1 or 0, and k2 is an integer of 1 to 20), and X 214 is a single bond or an alkylene group, 215 represents an alkylene group, an oxyalkylene group, or -(C p10 H 2p10 ) q1 -(O-C p10 H 2p10 ) q2 (wherein p10 is an integer of 1 to 6, q1 is 1 or 0, and q2 is an integer of 1 to 20).
[0232] X 215 represents an alkylene group, an oxyalkylene group, or -(C p H 2p ) q1 -(O-C p H 2p ) q2 (wherein p is an integer of 1 to 6, q1 is 1 or 0, and q2 is an integer of 1 to 20).
[0233] The alkylene group may be a straight chain or a branched chain, and preferably has 1 to 30 carbon atoms.
[0234] In one embodiment, the alkylene group is, for example, C 1-10 Alkylene group, C 1-8 Alkylene group, C 1-6 Alkylene group, C 2-10 Alkylene group, C 2-8 Alkylene group, or C 2-6 It may be an alkylene group.
[0235] The oxyalkylene group is the alkylene group at the left end (R A or R BThe alkylene group is a group having an oxygen atom at the alkyl group side (the alkylene side), that is, an —O-alkylene group.
[0236] p10 is an integer of 1 to 6, preferably an integer of 2 to 4.
[0237] q1 is 1 or 0, preferably 0.
[0238] q2 is an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 2 to 6.
[0239] In another preferred embodiment, X 1 is the following formula: [In the formula, X a are each independently a single bond or a divalent organic group.
[0240] X a is a single bond or a divalent organic group directly bonded to the isocyanuric ring. a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.
[0241] X a The following formula: -(CX 121 X 122 ) x1 -(X a1 ) y1 - (CX 123 X 124 ) z1 - (wherein, X 121 ~X 124 are each independently H, OH, or —OSi(OR 121 ) 3 (wherein three R 121 are each independently an alkyl group having 1 to 4 carbon atoms, and a1is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is CX 121 X 122 ), x1 is an integer of 0 to 10, y1 is 0 or 1, and z1 is an integer of 1 to 10.
[0242] Above X a1 is preferably —O— or —C(═O)O—.
[0243] Above X a The following formula: -(CH 2 ) m12 -O-(CH 2 ) m13 - (wherein m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3), a group represented by -(CH 2 ) m15 -O-CH 2 CH(OH)-(CH 2 ) m16 - (wherein m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3), a group represented by -(CH 2 ) m18 - (wherein m18 is an integer of 1 to 3), a group represented by -(CH 2 ) m20 -O-CH 2 CH(OSi(OCH 3 ) 3 )-(CH 2 ) m21 A group represented by the formula: - (wherein m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3) is particularly preferred.
[0244] Above X a is not particularly limited, but specifically includes -CH 2 -, -C 2 H 4 -, -C 3 H 6 -, -C 4 H 8 -, -C 4 H 8 -O-CH 2-, -CO-O-CH 2 -CH(OH)-CH 2 -, -S-, -(CH 2 ) m22 -C(=O)-O-(CH 2 ) m23 -, -(CH 2 ) m22 -OC(=O)-(CH 2 ) m23 -, -(CH 2 ) m22 —C(═O)—NR 121 - (CH 2 ) m23 -, -(CH 2 ) m22 -NR 121 -C(=O)-(CH 2 ) m23 -CH 2 OCH 2 CH(OSi(OCH 3 ) 3 ) CH 2 - (wherein, R 121 is a hydrogen atom or C 1-6 m22 is an integer of 1 to 10, and m23 is an integer of 1 to 10.
[0245] R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded.
[0246] In a preferred embodiment, R Si is represented by the following formula (S1), (S2), (S3), (S4) or (S5): [In the formula: R 11 are each independently a hydroxyl group or a hydrolyzable group, R 12 are each independently a monovalent organic group, and n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of 0 to 3, 11 are each independently a single bond or a divalent organic group, 13 are each independently a hydrogen atom or a monovalent organic group, each t is independently an integer of 2 or more, R14 are each independently a hydrogen atom, a halogen atom or -X 11 -SiR 11 n1 R 12 3-n1 and R 15 are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms; R a1 are each independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 and Z 1 are each independently a divalent organic group, 21 are each independently -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ and R 22 are each independently a hydroxyl group or a hydrolyzable group, R 23 are each independently a monovalent organic group, p1 is each independently an integer of 0 to 3, q1 is each independently an integer of 0 to 3, r1 is each independently an integer of 0 to 3, Z 1’ are each independently a divalent organic group, 21’ are each independently -Z 1” -SiR 22” q1” R 23” r1” and R 22’ are each independently a hydroxyl group or a hydrolyzable group, R 23’ are each independently a monovalent organic group, p1' are each independently an integer of 0 to 3, q1' are each independently an integer of 0 to 3, r1' are each independently an integer of 0 to 3, Z 1” are each independently a divalent organic group, 22”are each independently a hydroxyl group or a hydrolyzable group, R 23” are each independently a monovalent organic group; q1" are each independently an integer of 0 to 3; r1" are each independently an integer of 0 to 3; R b1 are each independently a hydroxyl group or a hydrolyzable group, R c1 are each independently a monovalent organic group, k1 is each independently an integer of 0 to 3, l1 is each independently an integer of 0 to 3, and m1 is each independently an integer of 0 to 3, provided that in formula (S3), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R d1 are each independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 and Z 2 are each independently a single bond, an oxygen atom, or a divalent organic group, and R 31 are each independently -Z 2’ -CR 32’ q2’ R 33’ r2’ and R 32 are each independently -Z 3 -SiR 34 n2 R 35 3-n2 and R 33 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2 is each independently an integer of 0 to 3; q2 is each independently an integer of 0 to 3; r2 is each independently an integer of 0 to 3; Z 2’ are each independently a single bond, an oxygen atom, or a divalent organic group, and R 32’ are each independently -Z 3 -SiR 34 n2 R 35 3-n2 and R 33’are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' are each independently an integer of 0 to 3; r2' are each independently an integer of 0 to 3; Z 3 are each independently a single bond, an oxygen atom, or a divalent organic group; R 34 are each independently a hydroxyl group or a hydrolyzable group, R 35 are each independently a monovalent organic group, n2 is each independently an integer of 0 to 3, R e1 are each independently -Z 3 -SiR 34 n2 R 35 3-n2 and R f1 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group, k2 is each independently an integer of 0 to 3, l2 is each independently an integer of 0 to 3, and m2 is each independently an integer of 0 to 3. However, in formula (S4), there are at least two Si atoms bonded to a hydroxyl group or a hydrolyzable group, and R g1 and R h1 are each independently -Z 4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 and Z 4 are each independently a single bond, an oxygen atom, or a divalent organic group, with the proviso that in formula (S5), there are at least two Si atoms bonded to hydroxyl groups or hydrolyzable groups.
[0247] In the above formula, R 11are each independently a hydroxyl group or a hydrolyzable group.
[0248] R 11 are preferably each independently a hydrolyzable group.
[0249] R 11 are preferably each independently -OR h , -OCOR h or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.
[0250] In the above formula, R 12 are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0251] R 12 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0252] In the above formula, n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of 0 to 3. However, in formula (S1), n1 is 1 to 3 (SiR 11 n1 R 12 3-n1 In other words, in formula (S1), there are at least two Si atoms to which a hydroxyl group or a hydrolyzable group is bonded.
[0253] n1 is (SiR 11 n1 R 12 3-n1 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.
[0254] In the above formula, X 11 are each independently a single bond or a divalent organic group. Such a divalent organic group is preferably -R 28 -O x -R 29 - (wherein, R 28 and R 29 are each independently a single bond or C 1-20 is an alkylene group, and x is 0 or 1. 1-20 The alkylene group may be a straight chain or a branched chain, but is preferably a straight chain. 1-20 The alkylene group is preferably C 1-10 Alkylene group, more preferably C 1-6 Alkylene group, more preferably C 1-3 It is an alkylene group.
[0255] In one embodiment, X 11 are each independently -C 1-6 Alkylene -O-C 1-6 Alkylene- or -O-C 1-6 It is alkylene-.
[0256] In a preferred embodiment, X 11 are each independently a single bond or a linear C 1-6 an alkylene group, preferably a single bond or a straight-chain C 1-3 Alkylene group, more preferably a single bond or a straight chain C 1-2 It is preferably a linear C alkylene group. 1-2 It is an alkylene group.
[0257] In the above formula, R 13 are each independently a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably C 1-20 It is an alkyl group.
[0258] In a preferred embodiment, R 13 are each independently a hydrogen atom or a straight-chain C 1-6 is an alkyl group, preferably a hydrogen atom or a straight-chain C 1-3 It is an alkyl group, preferably a hydrogen atom or a methyl group.
[0259] In the above formula, R 15 are each independently a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
[0260] In one embodiment, R 15 are each independently an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
[0261] In a preferred embodiment, R 15 is a single bond.
[0262] In the above formula, each t is independently an integer of 2 or more.
[0263] In a preferred embodiment, each t is independently an integer of 2 to 10, preferably an integer of 2 to 6.
[0264] In the above formula, R 14 are each independently a hydrogen atom, a halogen atom or -X 11 -SiR 11 n1 R 12 3-n1 Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 is a hydrogen atom.
[0265] In one embodiment, formula (S1) is the following formula (S1-a): [In the formula, R 11 , R 12 , R 13 , X 11and n1 are defined as in formula (S1) above, t1 and t2 are each independently an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 2 to 10, for example, an integer of 1 to 5 or an integer of 2 to 5, and the order of the repeating units enclosed in parentheses with t1 and t2 is arbitrary in the formula.]
[0266] In a preferred embodiment, formula (S1) is the following formula (S1-b): [In the formula, R 11 , R 12 , R 13 , X 11 , n1 and t are defined as in formula (S1) above.
[0267] R a1 are each independently -Z 1 -SiR 21 p1 R 22 q1 R 23 r1 is.
[0268] Z 1 are each independently an oxygen atom or a divalent organic group. 1 The structure written as 21 p1 R 22 q1 R 23 r1 )
[0269] In a preferred embodiment, Z 1 is a divalent organic group.
[0270] In a preferred embodiment, Z 1 Is Z 1 Preferably, in formula (S3), (Si-Z 1 —Si) does not contain a siloxane bond.
[0271] Z 1 is preferably C 1-6 Alkylene group, -(CH 2 ) z1 -O-(CH 2 )z2 - (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0272] In a preferred embodiment, Z 1 is C 1-6 Alkylene group or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 - is.
[0273] In another preferred embodiment, Z 1 is C 1-3 In one embodiment, Z is an alkylene group. 1 is -CH 2 CH 2 CH 2 In another embodiment, Z 1 is -CH 2 CH 2 -It can be.
[0274] R 21 are each independently -Z 1’ -SiR 21’ p1’ R 22’ q1’ R 23’ r1’ is.
[0275] Z 1’are each independently an oxygen atom or a divalent organic group. 1’ The structure written as 21’ p1’ R 22’ q1’ R 23’ r1’ )
[0276] In a preferred embodiment, Z 1’ is a divalent organic group.
[0277] In a preferred embodiment, Z 1’ Is Z 1’ Preferably, in formula (S3), (Si-Z 1’ —Si) does not contain a siloxane bond.
[0278] Z 1’ is preferably C 1-6 Alkylene group, -(CH 2 ) z1’ -O-(CH 2 ) z2’ - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) z3’ -phenylene-(CH 2 ) z4’ - (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0279] In a preferred embodiment, Z 1’ is C 1-6 Alkylene group or -(CH 2 ) z3’ -phenylene-(CH 2) z4’ -, preferably -phenylene-(CH 2 ) z4’ - is.
[0280] In another preferred embodiment, Z 1’ is C 1-3 In one embodiment, Z is an alkylene group. 1’ is -CH 2 CH 2 CH 2 In another embodiment, Z 1’ is -CH 2 CH 2 -It can be.
[0281] The above R 21’ are each independently -Z 1” -SiR 22” q1” R 23” r1” is.
[0282] Above Z 1” are each independently an oxygen atom or a divalent organic group. 1” The structure written as 22” q1” R 23” r1” )
[0283] In a preferred embodiment, Z 1” is a divalent organic group.
[0284] In a preferred embodiment, Z 1” Is Z 1” Preferably, in formula (S3), (Si-Z 1” —Si) does not contain a siloxane bond.
[0285] Z 1” is preferably C 1-6 Alkylene group, -(CH 2 ) z1” -O-(CH 2 ) z2” - (wherein z1" is an integer of 0 to 6, for example, an integer of 1 to 6, and z2" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH2 ) z3” -phenylene-(CH 2 ) z4” - (wherein z3" is an integer of 0 to 6, for example, an integer of 1 to 6, and z4" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0286] In a preferred embodiment, Z 1” is C 1-6 Alkylene group or -(CH 2 ) z3” -phenylene-(CH 2 ) z4” -, preferably -phenylene-(CH 2 ) z4” - is. Z 1” is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.
[0287] In another preferred embodiment, Z 1” is C 1-3 In one embodiment, Z is an alkylene group. 1” is -CH 2 CH 2 CH 2 In another embodiment, Z 1” is -CH 2 CH 2 -It can be.
[0288] The above R 22” are each independently a hydroxyl group or a hydrolyzable group.
[0289] The above R 22” are preferably each independently a hydrolyzable group.
[0290] The above R 22” are preferably each independently -OR h , -OCOR h, —O—N═CR h 2 , -NR h 2 , -NHR h or —NCO (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.
[0291] R 23” are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0292] R 23” In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0293] Each q1" is independently an integer of 0 to 3, and each r1" is independently an integer of 0 to 3. The sum of q1" and r1" is (SiR 22” q1” R 23” r1” ) units, it is 3.
[0294] q1″ is (SiR 22” q1” R 23” r1” ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.
[0295] R 22’ are each independently a hydroxyl group or a hydrolyzable group.
[0296] R 22’ are preferably each independently a hydrolyzable group.
[0297] R 22’ are preferably each independently -OR h , or -OCOR h (In these formulas, R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.
[0298] R 23’ are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0299] R 23’ In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0300] Each p1' is independently an integer of 0 to 3, each q1' is independently an integer of 0 to 3, and each r1' is independently an integer of 0 to 3. The sum of p', q1', and r1' is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units, it is 3.
[0301] In one embodiment, p1′ is 0.
[0302] In one embodiment, p1′ is (SiR 21’p1’ R 22’ q1’ R 23’ r1’ ) units may each independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1′ is 3.
[0303] In one embodiment, q1′ is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.
[0304] In one embodiment, p1′ is 0 and q1′ is (SiR 21’ p1’ R 22’ q1’ R 23’ r1’ ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.
[0305] R 22 are each independently a hydroxyl group or a hydrolyzable group.
[0306] R 22 are preferably each independently a hydrolyzable group.
[0307] R 22 are preferably each independently -OR h , or -OCOR h (In these formulas, R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, Rh is an ethyl group.
[0308] The above R 23 are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0309] R 23 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0310] Each of the above p1's is independently an integer of 0 to 3, each of the q1's is independently an integer of 0 to 3, and each of the r1's is independently an integer of 0 to 3. The sum of p1, q1, and r1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units, it is 3.
[0311] In one embodiment, p1 is 0.
[0312] In one embodiment, p1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units may each independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p1 is 3.
[0313] In one embodiment, q1 is (SiR 21 p1 R 22 q1 R 23 r1 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.
[0314] In one embodiment, p1 is 0 and q1 is (SiR 21 p1 R 22 q1 R 23 r1) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.
[0315] In the formula, R b1 are each independently a hydroxyl group or a hydrolyzable group.
[0316] R b1 are preferably each independently a hydrolyzable group.
[0317] R b1 are preferably each independently -OR h , or -OCOR h (In these formulas, R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.
[0318] In the formula, R c1 are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0319] R c1 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0320] Each k1 is independently an integer of 0 to 3, each l1 is independently an integer of 0 to 3, and each m1 is independently an integer of 0 to 3. The sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1m1 ) units, it is 3.
[0321] In one embodiment, k1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units are each independently an integer of 1 to 3, preferably 2 or 3, more preferably 3. In a preferred embodiment, k1 is 3.
[0322] In formula (S3), there are at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded.
[0323] In a preferred embodiment, there are at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded in the terminal portion of formula (S3).
[0324] In a preferred embodiment, the group represented by formula (S3) is -Z 1 -SiR 22 q1 R 23 r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), -Z 1’ -SiR 22’ q1’ R 23’ r1’ (wherein q1' is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1' is an integer of 0 to 2), or -Z 1” -SiR 22” q1” R 23” r1” (wherein q1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2). Z 1 , Z 1’ , Z 1” , R 22 , R 23 , R 22’ , R 23’ , R 22” , and R 23” has the same meaning as above.
[0325] In a preferred embodiment, in formula (S3), R 21’ When present, at least one, preferably all, R 21’ In the formula, q1″ is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0326] In a preferred embodiment, in formula (S3), R 21 When present, at least one, preferably all, R 21 In the formula (I), p1' is 0, and q1' is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0327] In a preferred embodiment, in formula (S3), R a1 When present, at least one, preferably all, R a1 In the formula (I), p1 is 0, and q1 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0328] In a preferred embodiment, in formula (S3), k1 is 2 or 3, preferably 3; p1 is 0; and q1 is 2 or 3, preferably 3.
[0329] R d1 are each independently -Z 2 -CR 31 p2 R 32 q2 R 33 r2 is.
[0330] Z 2 are each independently a single bond, an oxygen atom, or a divalent organic group. 2 The structure written as follows is (CR 31 p2 R 32 q2 R 33 r2 )
[0331] In a preferred embodiment, Z 2 is a divalent organic group.
[0332] In a preferred embodiment, Z 2 does not contain siloxane bonds.
[0333] Z 2 is preferably C 1-6 Alkylene group, -(CH 2 ) z5 -O-(CH 2 ) z6 - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z7 -phenylene-(CH 2 ) z8 - (wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0334] In a preferred embodiment, Z 2 is C 1-6 Alkylene group or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene-(CH 2 ) z8 - is. Z 2 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.
[0335] In another preferred embodiment, the Z 2 is C 1-3 In one embodiment, Z is an alkylene group. 2 is -CH 2 CH 2 CH 2 In another embodiment, Z 2 is -CH 2 CH 2 -It can be.
[0336] R 31are each independently -Z 2’ -CR 32’ q2’ R 33’ r2’ is.
[0337] Z 2’ are each independently a single bond, an oxygen atom, or a divalent organic group. 2’ The structure written as follows is (CR 32’ q2’ R 33’ r2’ )
[0338] In a preferred embodiment, Z 2’ does not contain siloxane bonds.
[0339] Z 2’ is preferably C 1-6 Alkylene group, -(CH 2 ) z5’ -O-(CH 2 ) z6’ - (wherein z5' is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z7’ -phenylene-(CH 2 ) z8’ - (wherein z7' is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0340] In a preferred embodiment, Z 2’ is C 1-6 Alkylene group or -(CH 2 ) z7’ -phenylene-(CH 2 ) z8’ -, preferably -phenylene-(CH 2 )z8’ - is. Z 2’ is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.
[0341] In another preferred embodiment, the Z 2’ is C 1-3 In one embodiment, Z is an alkylene group. 2’ is -CH 2 CH 2 CH 2 In another embodiment, Z 2’ is -CH 2 CH 2 -It can be.
[0342] R 32’ are each independently -Z 3 -SiR 34 n2 R 35 3-n2 is.
[0343] Z 3 are each independently a single bond, an oxygen atom, or a divalent organic group. 3 The structure written as 34 n2 R 35 3-n2 )
[0344] In one embodiment, Z 3 is an oxygen atom.
[0345] In one embodiment, Z 3 is a divalent organic group.
[0346] In a preferred embodiment, Z 3 does not contain siloxane bonds.
[0347] Z 3 is preferably C 1-6 Alkylene group, -(CH 2 ) z5” -O-(CH 2 ) z6” -(wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), -(CH 2 ) z7”-phenylene-(CH 2 ) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z9” -OCONR z1 - (CH 2 ) z10” - (wherein, R z1 is a hydrogen atom or C 1-6 z9" is an integer of 0 to 6, for example, an integer of 1 to 6, and z10" is an integer of 0 to 6, for example, an integer of 1 to 6. 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0348] In a preferred embodiment, Z 3 is C 1-6 Alkylene group, -(CH 2 ) z7” -phenylene-(CH 2 ) z8” - or - (CH 2 ) z9” -OCONR z1 - (CH 2 ) z10” -, preferably -phenylene-(CH 2 ) z8” - or - (CH 2 ) z9” -OCONR z1 - (CH 2 ) z10” - is. Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.
[0349] In another preferred embodiment, the Z 3 is C 1-3 In one embodiment, Z is an alkylene group. 3 is -CH 2CH 2 CH 2 In another embodiment, Z 3 is -CH 2 CH 2 -It can be.
[0350] R 34 are each independently a hydroxyl group or a hydrolyzable group.
[0351] R 34 are preferably each independently a hydrolyzable group.
[0352] R 34 are preferably each independently -OR h , -OCOR h , —O—N═CR h 2 , -NR h 2 , -NHR h , —NCO, or halogen (wherein R h is a substituted or unsubstituted C 1-4 alkyl group), and more preferably -OR h (i.e., an alkoxy group). h Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl; and substituted alkyl groups such as chloromethyl. Among these, alkyl groups, particularly unsubstituted alkyl groups, are preferred, and methyl or ethyl groups are more preferred. In one embodiment, R h is a methyl group, and in another embodiment, R h is an ethyl group.
[0353] R 35 are each independently a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0354] R 35 In the formula (I), the monovalent organic group is preferably C 1-20 alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.
[0355] n2 is (SiR 34n2 R 35 3-n2 ) units are each independently an integer of 0 to 3. However, in the terminal portion of formula (S4), n2 is 1 to 3 (SiR 34 n2 R 35 3-n2 In other words, there are at least two Si atoms to which hydroxyl groups or hydrolyzable groups are bonded in the terminal portion of formula (S4).
[0356] n2 is (SiR 34 n2 R 35 3-n2 ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.
[0357] R 33’ are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0358] R 33’ In the formula (I), the monovalent organic group is preferably C 1-20 Alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 -H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1-20 alkyl group, more preferably C 1-6 An alkyl group, particularly preferably a methyl group.
[0359] In one embodiment, R 33’ is a hydroxyl group.
[0360] In another embodiment, R 33’ is a monovalent organic group, preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.
[0361] Each of the q2's is independently an integer of 0 to 3, and each of the r2's is independently an integer of 0 to 3. The sum of q2' and r2' is (CR 32’ q2’ R 33’ r2’ ) units, it is 3.
[0362] q2' is (CR 32’ q2’ R 33’ r2’ ) units are each independently an integer of preferably 1 to 3, more preferably 2 to 3, and even more preferably 3.
[0363] R 32 are each independently -Z 3 -SiR 34 n2 R 35 3-n2 This is -Z 3 -SiR 34 n2 R 35 3-n2 is the above R 32’ This has the same meaning as the description in
[0364] R 33 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0365] R 33 In the formula (I), the monovalent organic group is preferably C 1-20 Alkyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 -H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1-20 alkyl group, more preferably C 1-6 An alkyl group, particularly preferably a methyl group.
[0366] In one embodiment, R 33 is a hydroxyl group.
[0367] In another embodiment, R 33 is a monovalent organic group, preferably C 1-20 alkyl group, more preferably C 1-6 It is an alkyl group.
[0368] Each p2 is independently an integer of 0 to 3, each q2 is independently an integer of 0 to 3, and each r2 is independently an integer of 0 to 3. The sum of p2, q2, and r2 is (CR 31 p2 R 32 q2 R 33 r2 ) units, it is 3.
[0369] In one embodiment, p2 is 0.
[0370] In one embodiment, p2 is (CR 31 p2 R 32 q2 R 33 r2 ) units may each independently be an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p2 is 3.
[0371] In one embodiment, q2 is (CR 31 p2 R 32 q2 R 33 r2 ) units are each independently an integer of 1 to 3, preferably an integer of 2 or 3, and more preferably 3.
[0372] In one embodiment, p2 is 0 and q2 is (CR 31 p2 R 32 q2 R 33 r2 ) units are each independently an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3.
[0373] R e1 are each independently -Z3 -SiR 34 n2 R 35 3-n2 This is -Z 3 -SiR 34 n2 R 35 3-n2 is the above R 32’ This has the same meaning as the description in
[0374] R f1 are each independently a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups excluding the above-mentioned hydrolyzable groups.
[0375] R f1 In the formula (I), the monovalent organic group is preferably C 1-20 Alkyl group, C 2-20 alkenyl group or -(C s H 2s ) t1 -(O-C s H 2s ) t2 -H (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably C 1-20 Alkyl group or C 2-20 Alkenyl groups, more preferably C 1-6 Alkyl group or C 2-6 An alkenyl group is particularly preferred, and a methyl group, an ethyl group, or a 2-propenyl group is particularly preferred.
[0376] In one embodiment, R f1 is a hydrogen atom.
[0377] In one embodiment, R f1 is a hydroxyl group.
[0378] In another embodiment, R f1 is a monovalent organic group, preferably C 1-20 Alkyl group or C 2-20 alkenyl group, more preferably C 1-6 Alkyl group or C 2-6 It is an alkenyl group.
[0379] Each k2 is independently an integer of 0 to 3, each l2 is independently an integer of 0 to 3, and each m2 is independently an integer of 0 to 3. The sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) units, it is 3.
[0380] In one embodiment, n2 is 1 to 3, preferably 2 or 3, more preferably 3 (SiR 34 n2 R 35 3-n2 ) units are present at each terminal portion of formula (S4) in an amount of 2 or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, even more preferably 2 to 3, and particularly preferably 3.
[0381] In a preferred embodiment, in formula (S4), R 32’ When present, at least one, preferably all, R 32’ In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0382] In a preferred embodiment, in formula (S4), R 32 When present, at least one, preferably all, R 32 In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0383] In a preferred embodiment, in formula (S4), R e1 When present, at least one, preferably all, R a1 In the formula, n2 is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.
[0384] In a preferred embodiment, in formula (S4), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
[0385] R g1 and R h1 are each independently -Z4 -SiR 11 n1 R 12 3-n1 , -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , -Z 4 -CR d1 k2 R e1 l2 R f1 m2 Here, R 11 , R 12 , R a1 , R b2 , R c1 , R d1 , R e1 , R f1 , n1, k1, l1, m1, k2, l2, and m2 have the same meanings as above.
[0386] In a preferred embodiment, R g1 and R h1 are each independently -Z 4 -SiR 11 n1 R 12 3-n1 is.
[0387] Above Z 4 are each independently a single bond, an oxygen atom, or a divalent organic group. 4 The structure written as 11 n1 R 12 3-n1 )
[0388] In one embodiment, Z 4 is an oxygen atom.
[0389] In one embodiment, Z 4 is a divalent organic group.
[0390] In a preferred embodiment, Z 4 does not contain siloxane bonds.
[0391] Z 4 is preferably C1-6 Alkylene group, -(CH 2 ) z5” -O-(CH 2 ) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z7” -phenylene-(CH 2 ) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene group may be linear or branched, but is preferably linear. These groups may contain, for example, a fluorine atom, a C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.
[0392] In a preferred embodiment, Z 4 is C 1-6 Alkylene group or -(CH 2 ) z7” -phenylene-(CH 2 ) z8” -, preferably -phenylene-(CH 2 ) z8” - is. Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be improved.
[0393] In another preferred embodiment, the Z 4 is C 1-3 In one embodiment, Z is an alkylene group. 4 is -CH 2 CH 2 CH 2 In another embodiment, Z 4 is -CH 2 CH 2 -It can be.
[0394] In one embodiment, formulas (S1), (S2), (S3), and (S4) do not contain siloxane bonds.
[0395] In one embodiment, R Si is a group represented by formula (S2), (S3), (S4), or (S5).
[0396] In one embodiment, R Si is a group represented by formula (S2), (S3), or (S4).
[0397] In one embodiment, R Si is a group represented by formula (S3), (S4) or (S5).
[0398] In one embodiment, R Si is a group represented by formula (S3) or (S4).
[0399] In one embodiment, R Si is a group represented by formula (S4) or (S5).
[0400] In one embodiment, R Si is a group represented by formula (S1): In a preferred embodiment, n1 is 1 to 3, preferably 2 to 3, and more preferably 3.
[0401] In one embodiment, R Si is a group represented by formula (S2): In a preferred embodiment, n1 is 1 to 3, preferably 2 to 3, and more preferably 3.
[0402] In one embodiment, R Si is a group represented by formula (S3). In a preferred embodiment, formula (S3) is -SiR a1 2 R c1 , or -SiR a1 3 and R a1 Is, -Z 1 -SiR 22 q1 R 23 r1 and Z 1 is C 1-6 Alkylene group, -(CH 2 ) z1 -O-(CH 2 ) z2- (wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 - (wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6), preferably C 1-6 It is an alkylene group, and q1 is 1 to 3, preferably 2 to 3, and more preferably 3.
[0403] In one embodiment, R Si is a group represented by formula (S4). In a preferred embodiment, formula (S4) is -CR e1 2 R f1 , or -CR e1 3 and R e1 Is, -Z 3 -SiR 34 n2 R 35 3-n2 and Z 3 is C 1-6 Alkylene group, -(CH 2 ) z5” -O-(CH 2 ) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z7” -phenylene-(CH 2 ) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6), preferably C 1-6 It is an alkylene group, and n2 is 1 to 3, preferably 2 to 3, and more preferably 3.
[0404] In one embodiment, R Si is a group represented by formula (S5). g1 and R h1 Is, -Z 4 -SiR 11 n1 R12 3-n1 and Z 4 is C 1-6 Alkylene group, -(CH 2 ) z5” -O-(CH 2 ) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or - (CH 2 ) z7” -phenylene-(CH 2 ) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6), preferably C 1-6 It is an alkylene group, and n1 is 1 to 3, preferably 2 to 3, and more preferably 3.
[0405] In a preferred embodiment, formula (S5) is the following formula: In the following formula, * represents X 1 Represents the point of attachment to
[0406] In a preferred embodiment, X 1 At least one nitrogen atom of R Si is bonded to at least one Si atom of the group via a group having a chain length of 1 or more and less than 7, which is composed of other atoms. For example, X 1 and at least one nitrogen atom of R Si Between at least one Si atom of 1-6 Preferably, an alkylene group is present.
[0407] Preferably, the compound represented by the formula (1) contains at least one bond selected from the group consisting of an amide bond, a urethane bond, and a urea bond.
[0408] The compound represented by the above formula (1) may contain only one type of bond selected from the group consisting of an amide bond, a urethane bond, and a urea bond, or may contain multiple types of bonds.
[0409] Preferably, the compound represented by formula (1) does not contain an amino group. More preferably, the compound represented by formula (1) does not contain nitrogen atoms other than those in amide bonds, urethane bonds, and urea bonds.
[0410] When the compound represented by the formula (1) contains an amide bond, R Si A N atom derived from an amide bond is preferably present within 15 atoms, more preferably within 10 atoms, and even more preferably within 7 atoms from any silicon atom in the aryl group.
[0411] When the compound represented by the formula (1) contains a urethane bond, R Si A N atom derived from a urethane bond is preferably present within 15 atoms, more preferably within 10 atoms, and even more preferably within 7 atoms from any silicon atom in the aryl group.
[0412] When the compound represented by the formula (1) contains a urea bond, R Si A N atom derived from a urea bond is preferably present within 15 atoms, more preferably within 10 atoms, and even more preferably within 7 atoms from any silicon atom in the group.
[0413] The number of nitrogen atoms contained in the compound represented by the above formula (1) is n N , the number of silicon atoms is n Si Then, preferably, n Si ≧n N and more preferably n Si ≧n N It's +3.
[0414] In one embodiment, the number of nitrogen atoms contained in the compound represented by the formula (1) is n N , the number of silicon atoms is n Si Then, preferably, n Si = n N is.
[0415] In one embodiment, the number of nitrogen atoms contained in the compound represented by the formula (1) is n N , the number of silicon atoms is n Si Then, preferably, n Si = 2n N is.
[0416] Preferred examples of the compound represented by the above formula (1) include the compounds shown below: CH 3 -[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 )2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 )3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 )2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H.3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3)Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ]3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 )3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 )H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 --(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [CH 3 CH 2 CH 2 CH 2 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 )H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H.3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 [CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [CH 3 -[Si(CH 3 ) 2 O]n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [CH 3 CH 2 CH 2 CH 2 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] [CH 3 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (wherein, each n1 independently represents an integer of 0 to 100, and each H1 and H2 independently represents an integer of 1 to 50.)
[0417] Each n1 is independently an integer of 0 to 100.
[0418] In one embodiment, each n1 is independently 0 or 1.
[0419] In another embodiment, each n1 is independently an integer from 5 to 100, preferably from 10 to 80.
[0420] Each H1 is independently an integer of 1 to 50, preferably 8 to 40, and more preferably 11 to 30.
[0421] Each H2 is independently an integer of 1 to 50, preferably 1 to 10, and more preferably 1 to 5.
[0422] Preferred specific examples of the compound represented by the above formula (1) include the following compounds: CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer of 40 to 70, for example, 59) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n - (CH 2 ) 3 -OCH 2 -CONH-CH 2 C{CH 2 CH 2 CH 2 Si(OCH3 ) 3} 3 (n is an integer between 40 and 70, for example, 55) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 10 to 30, for example, 16)
[0423] Other preferred examples of the compound represented by the above formula (1) include the following compounds: (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) n - (CH 2 ) 10 -CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer of 10 to 30, for example, 19) [(CH 3 ) 3 SiO] 2 CH 3 SiO(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CONHCH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer of 20 to 40, for example, 26) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CONH-CH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer of 40 to 70, for example, 57) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 -C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer of 40 to 80, for example, 63) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] nSi(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer of 40 to 80, for example, 60) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer of 20 to 40, for example, 26) CH 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 22 CON [CH 2 CH 2 CH 2 ) 3 Si(OCH 3 ) 3 ] 2 (n is an integer of 20 to 50, for example, 34) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON [(CH 2 ) 3 Si(OCH 3 ) 3 ] 2 (n is an integer between 40 and 60, for example, 48)
[0424] The compound represented by the above formula (1) is not particularly limited, but may be 5×10 2 ~1 x 10 5 The compound represented by the formula (1) preferably has a number average molecular weight of 1,000 to 30,000, more preferably 1,500 to 10,000, from the viewpoint of wear durability. 1 The value is measured by H-NMR.
[0425] The compound represented by formula (1) is, for example, a compound represented by the following formula: 161 -COOH [wherein, R 161 is R 1ab -R S is a containing group, R 1ab is a hydrocarbon group, an A group, or a B group; R S has the same meaning as above.] is reacted with a compound represented by the following formula: 2 -R 162 [In the formula, R 162 is an allyl group-containing group.] to obtain a compound represented by the following formula: 161 -CONH-R 163 -R 164 [In the formula, R 161 is R 1ab -R S is a containing group, R 163 is an (n+1)-valent linker group, R 164 is an allyl group.] is obtained. Then, the obtained allyl compound is reacted with HSiR 165 m R 166 3-m [In the formula, R 165 is independently in each occurrence a hydroxyl group or a hydrolyzable group; R 166 is independently in each occurrence a monovalent organic group, and m is 1 to 3.
[0426] Alternatively, the compound represented by formula (1) can be obtained, for example, as follows.
[0427] First, an unsaturated carboxylic acid or an unsaturated carboxylic acid ester, such as a compound represented by the formula: 2 =CH-R 171 -COOR 172 [In the formula, R 171 is an alkylene group, R 172 is a hydrogen atom or C 1-3 and a silane compound, for example, a compound represented by the formula: R 1ab -R S -SiR 2a 2 -H [in the formula: R 1ab is a hydrocarbon group, an A group, or a B group; R 2a are each independently a hydrocarbon group.] to react with a compound represented by the formula: R 1ab -R S -SiR 2a 2 -CH 2 CH 2 -R 171 -COOR 172 Then, the resulting compound is reacted with an amine derivative having a terminal carbon-carbon double bond, for example, a compound represented by the formula: NH 2 -R 173 [In the formula, R 173 is -R 174 -CH=CH 2 , or -R 175 (-R 174 -CH=CH 2 ) 3 and R 174 is a single bond or C 1-6 is an alkylene group, R 175 is -R 176 -C and R 174 is a single bond or C 1-6 is an alkylene group.] to react with a compound represented by 1ab -R S -SiR 2a 2 -CH 2 CH 2 -R 171 -CONH 2 -R 174 -CH=CH2 , or R 1ab -R S -SiR 2a 2 -CH 2 CH 2 -R 171 -CONH 2 -R 175 (-R 174 -CH=CH 2 ) 3 Finally, the compound obtained above is reacted with, for example, a compound represented by the formula: HSi(R 176 ) 3 [In the formula, R 176 is a hydrolyzable group.], the compound represented by formula (1) can be obtained by reacting the compound represented by formula (1) with the compound represented by formula (1).
[0428] In one embodiment, the water-repellent layer included in the laminate of the present disclosure has the following formula (2): [In the formula: R A is a carbon chain containing at least one ethereal oxygen atom, and X A is a divalent to decavalent group, R Si is R in the compound represented by formula (1). Si wherein each α1 is independently an integer of 1 to 9, and each β1 is independently an integer of 1 to 9.
[0429] R A is a carbon chain containing at least one ethereal oxygen atom.
[0430] R A is preferably R A1 -O-(R A3 O) n -R A2 - [In the formula: R A1 is C 1-36 is an alkyl group, R A2 is C 1-36 is an alkylene group, R A3 are each independently C 1-6 is an alkylene group, and n is an integer of 0 to 200.
[0431] R A1 is C 1-36 is an alkyl group, preferably C 1-30 alkyl group, more preferably C 1-26 alkyl group, more preferably C 1-16 alkyl group, even more preferably C 1-6 It may be an alkyl group. Such alkyl groups may be straight-chain or branched-chain. In one embodiment, the alkyl group is straight-chain. In another embodiment, the alkyl group is branched-chain.
[0432] R A2 is C 1-36 is an alkylene group, preferably C 1-30 Alkylene group, more preferably C 1-26 Alkylene group, more preferably C 1-16 Alkylene groups, even more preferably C 1-6 The alkyl group may be an alkylene. Such alkyl groups may be straight-chain or branched-chain. In one embodiment, the alkylene group is straight-chain. In another embodiment, the alkylene group is branched-chain.
[0433] R A3 are each independently C 1-6 is an alkylene group, preferably C 1-4 Alkylene group, more preferably C 2-3 Alkylene groups, more preferably —CH 2 CH 2 -. Such alkyl groups may be straight-chain or branched-chain. In one embodiment, the alkylene group is straight-chain. In another embodiment, the alkylene group is branched-chain.
[0434] n is an integer of 0 to 200, and may be an integer of preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 10, and still more preferably 1 to 6. The lower limit of n may be, for example, 0, 1, 3, 5, 7, 10, 15, 20, 30, or 50. The upper limit of n may be 200, 150, 100, 50, 30, 20, 15, 10, or 6. From the viewpoint of fingerprint wiping ability, n is preferably 1 to 30, and more preferably 1 to 10. From the viewpoint of friction durability, n is preferably 50 to 100.
[0435] X A is an ether moiety (R A ) and the silane moiety (R Si ) and the linker. A is not particularly limited as long as the compound represented by formula (1A) can exist stably.
[0436] X A are each independently a single bond or a divalent to decavalent organic group.
[0437] X A The divalent to decavalent organic group in the formula (I) is preferably a divalent to octavalent organic group. In one embodiment, the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another embodiment, the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group. Each α1 is independently an integer of 1 to 9, and in one embodiment, preferably 1, and in another embodiment, preferably an integer of 1 to 6, more preferably 1 to 4. Each β1 is independently an integer of 1 to 9, and in one embodiment, preferably 1, and in another embodiment, more preferably an integer of 2 to 7, more preferably 2 to 5.
[0438] In one embodiment, X A represents a single bond or a divalent organic group, and α1 and β1 are 1.
[0439] In one embodiment, X A is a trivalent to hexavalent organic group, α1 is 1, and β1 is an integer of 2 to 5.
[0440] In one embodiment, X A is a trivalent organic group, α1 is 1, and β1 is 2.
[0441] X A When is a single bond or a divalent organic group, formula (2) is represented by the following formula (2').
[0442] In one embodiment, X A is a divalent organic group. A is a divalent organic group, α1 and β1 in the formula are 1.
[0443] In one embodiment, X A Examples of the formula include: 81 ) p5 -(X 81 ) q5 - [In the formula: R 81 is a single bond, -(CH 2 ) s5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) s5 -, s5 is an integer of 1 to 30, preferably an integer of 1 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 6, for example an integer of 1 to 3, or an integer of 1 to 20, preferably an integer of 4 to 15, more preferably an integer of 7 to 13, X 81 is -(X 82 ) l5 - and X 82 each independently represents an —O—, —S—, o-, m-, or p-phenylene group, —CO—, —C(O)O—, or —CONR 84 --, --O-CONR 84 -, -NR 84 -, -(CH 2 ) n5 -, -Si(R 89 ) 2 -, and -SiO(R 89 ) 2 - is a group selected from the group consisting of R 84 are each independently a hydrogen atom or a monovalent organic group, and are preferably a hydrogen atom, a phenyl group, or C1-6 an alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms, R 89 is an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or a phenyl group, each n5 is independently an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10, even more preferably an integer of 1 to 6, for example, an integer of 1 to 3, l5 is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, p5 is 0 or 1, q5 is 0 or 1, wherein at least one of p5 and q5 is 1, and the order of the repeating units enclosed in parentheses with p5 or q5 is arbitrary. A (Typically X A hydrogen atom) is a fluorine atom, C 1-3 Alkyl group and C 1-3 In a preferred embodiment, X A is not substituted with these groups.
[0444] The oxyalkylene-containing group having 1 to 10 carbon atoms is —O—C 1-10 alkylene-containing groups, such as -R 85 -(-O-C 1-10 alkylene) n -R 86 (In the formula, R 85 is a single bond or a divalent organic group, preferably C 1-6 is an alkylene group, n is an integer, preferably an integer of 2 to 10, and R 86 is a hydrogen atom or a monovalent organic group, preferably C 1-6 The alkylene group may be a straight chain or a branched chain.
[0445] In a preferred embodiment, X A are each independently -(R 81 ) p5 -(X 81 ) q5 -R 82 - is. R 82is a single bond, -(CH 2 ) t5 - or an o-, m- or p-phenylene group, preferably -(CH 2 ) t5 t5 is an integer of 1 to 30, preferably an integer of 4 to 15, more preferably an integer of 7 to 13. 82 (Typically R 82 hydrogen atom) is a fluorine atom, C 1-3 Alkyl group and C 1-3 In a preferred embodiment, R 86 is not substituted with these groups.
[0446] Preferably, X A are each independently 1-30 Alkylene group (preferably a straight-chain C 1-20 alkylene group), -R 81 -X 83 -R 82 -, or [wherein R 81 and R 82 has the same meaning as above, and X 83 -O-, -S-, -CO-, -C(O)O-, -CONR 84 -, -O-CONR 84 -, -O-(CH 2 ) u5 -CONR 84 -, -O-(CH 2 ) u5 -CO-, or -CONR 84 - (CH 2 ) u5 -N(R 84 )-, (wherein, R 84 has the same meaning as above, and u5 is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
[0447] More preferably, X A are each independently 1-30 Alkylene group (preferably a straight-chain C 1-20 alkylene group), -(CH 2 )s5 -X 83 -, -X 83 - (CH 2 ) t5 - or -(CH 2 ) s5 -X 83 - (CH 2 ) t5 - [wherein, X 83 , s5 and t5 have the same meanings as above.]
[0448] In a preferred embodiment, X A are each independently 1-30 Alkylene group (preferably a straight-chain C 1-30 alkylene group), -(CH 2 ) s5 -X 83 -, -X 83 - (CH 2 ) t5 - or - (CH 2 ) s5 -X 83 - (CH 2 ) t5 - [wherein, X 83 is -O-, -CO-, -CONR 84 --, --O-CONR 84 -, -O-(CH 2 ) u5 -CONR 84 -, or -O-(CH 2 ) u5 -CO-, and R 84 are each independently a hydrogen atom, a phenyl group, or C 1-6 an alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms, and s5, t5, and u5 are as defined above.
[0449] In a preferred embodiment, X A are each independently 1-30 Alkylene group (preferably a straight-chain C 1-30 alkylene group), -(CH 2 ) s5 -O-(CH 2 ) t5 -, -(CH 2 )s5 -CONR 84 - (CH 2 ) t5 -, -(CH 2 ) s5 -O-(CH 2 ) u5 -CO-, or -(CH 2 ) s5 -O-(CH 2 ) u5 -CONR 54 - (CH 2 ) t5 - [wherein, R 84 are each independently a hydrogen atom, a phenyl group, or C 1-6 an alkyl group (preferably a methyl group) or an oxyalkylene-containing group having 1 to 10 carbon atoms, and s5, t5, and u5 are as defined above.
[0450] In a preferred embodiment, X A is C 1-30 an alkylene group, or -(CH 2 ) s5 -CONH-(CH 2 ) t5 - is.
[0451] In one embodiment, X A is C 1-30 In this embodiment, the number of carbon atoms in the alkylene group is preferably 7 or more, 10 or more, 11 or more, 18 or more, or 22 or more from the viewpoint of friction durability. Furthermore, the number of carbon atoms in the alkylene group is preferably 25 or less, or 20 or less from the viewpoint of ease of synthesis. X A For example, C 7-30 Alkylene group, C 11-30 Alkylene group, or C 21-30 It may be an alkylene group.
[0452] In another embodiment, X A is -(CH 2 ) s5 -CONH-(CH 2 ) t5 - is.
[0453] X A are each independently a fluorine atom, C1-3 Alkyl group and C 1-3 Fluoroalkyl groups (preferably C 1-3 In one embodiment, X may be substituted with one or more substituents selected from the group consisting of alkyl, aryl, aryls ... A is non-substituted.
[0454] In addition, the above X A The left side of each equation is R A and the right side is R Si Combine with.
[0455] In one preferred embodiment, X A is a trivalent organic group. A is a trivalent organic group, α1 is 2 and β1 is 1, or α1 is 1 and β1 is 2.
[0456] The trivalent organic group is preferably represented by the following formula: [In the formula, X a represents X in the compound represented by formula (1). a and the like.
[0457] In a preferred embodiment, X A At least one nitrogen atom of R Si is bonded to at least one Si atom of the group via a group having a chain length of 1 or more and less than 7, which is composed of other atoms. For example, X A and at least one nitrogen atom of R Si Between at least one Si atom of 1-6 Preferably, an alkylene group is present.
[0458] Preferably, the compound represented by the above formula (2) contains at least one amide bond.
[0459] Preferably, the compound represented by the above formula (2) does not contain an amino group, and more preferably does not contain a nitrogen atom other than an amide bond.
[0460] When the compound represented by the formula (2) contains an amide bond, R SiA N atom derived from an amide bond is preferably present within 15 atoms, more preferably within 10 atoms, and even more preferably within 7 atoms from any silicon atom in the aryl group.
[0461] The number of nitrogen atoms contained in the compound represented by the above formula (2) is n N , the number of silicon atoms is n Si Then, preferably, n Si ≧n N and more preferably n Si ≧n N It's +3.
[0462] The water-repellent layer included in the laminate of the present disclosure may be a cured product of a compound represented by formula (1) above or a mixture of a compound represented by formula (1) above and a compound represented by formula (2).
[0463] A cured product of the compound represented by formula (1) above or a mixture of the compound represented by formula (1) above and the compound represented by formula (2) above can be formed by applying the compound represented by formula (1) above, a mixture of the compound represented by formula (1) above and the compound represented by formula (2) above, or a composition containing the compound or mixture to a substrate of the laminate of the present disclosure, and causing a dehydration condensation reaction between the compounds by heat treatment of the surface, or the like.
[0464] The compound represented by the formula (1), a mixture of the compound represented by the formula (1) and the compound represented by the formula (2), or a composition containing the compound or the mixture can be a surface treatment agent.
[0465] In one embodiment, the surface treatment agent contains at least one compound represented by the formula (1).
[0466] In one embodiment, the content of the compound represented by formula (1) above may be preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, even more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass%, based on the total mass of the surface treatment agent.
[0467] In another embodiment, the content of the compound represented by formula (1) above may be preferably 0.001 to 30 mass%, more preferably 0.01 to 10 mass%, even more preferably 0.05 to 5 mass%, and particularly preferably 0.05 to 2 mass%, based on the total mass of the surface treatment agent.
[0468] In one embodiment, the surface treatment agent contains a mixture of at least one compound represented by the formula (1) and at least one compound represented by the formula (2).
[0469] In one embodiment, the content of the mixture may be preferably 0.1 to 50.0 mass%, more preferably 1.0 to 30.0 mass%, even more preferably 5.0 to 25.0 mass%, and particularly preferably 10.0 to 20.0 mass%, based on the total mass of the surface treatment agent.
[0470] In another embodiment, the content of the mixture may be preferably 0.001 to 30 mass%, more preferably 0.01 to 10 mass%, even more preferably 0.05 to 5 mass%, and particularly preferably 0.05 to 2 mass%, based on the total mass of the surface treatment agent.
[0471] In one embodiment, the surface treatment agent contains at least one of a compound represented by formula (1) or formula (2) and a condensate in which at least a portion of the compound is condensed.
[0472] In the above aspect, the content of the condensate may be preferably 40% by mass or less, more preferably 30% by mass or less, based on the total of the compound represented by formula (1) or (2) and the condensate. Here, the content of the condensate can be determined, for example, from the abundance ratio of peak position and area in GPC (gel permeation chromatography).
[0473] The surface treatment agent may include a solvent, a (non-reactive) silicone compound that can be understood as silicone oil (hereinafter referred to as "silicone oil"), alcohols, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer, and the like.
[0474] In one embodiment, the surface treatment agent is R 71 OR 72 , R 73n8 C 6 H 6-n8 , R 74 R 75 R 76 Si—(O—SiR 77 R 78 ) m8 -R 79 , and (OSiR 77 R 78 ) m9 [In the formula R 71 ~R 79 are each independently a monovalent organic group having 1 to 10 carbon atoms, m8 is an integer of 1 to 6, m9 is an integer of 3 to 8, and n8 is an integer of 0 to 6.
[0475] The monovalent organic group having 1 to 10 carbon atoms may be a straight chain or a branched chain, and may further contain a cyclic structure.
[0476] In one embodiment, the monovalent organic group having 1 to 10 carbon atoms may contain an oxygen atom, a nitrogen atom, or a halogen atom.
[0477] In another embodiment, the monovalent organic group having 1 to 10 carbon atoms does not contain a halogen atom.
[0478] In a preferred embodiment, the monovalent organic group having 1 to 10 carbon atoms is a hydrocarbon group which may be substituted with a halogen, preferably a hydrocarbon group which is not substituted with a halogen.
[0479] In one embodiment, the hydrocarbon group is linear.
[0480] In another embodiment, the hydrocarbon group is branched.
[0481] In another embodiment, the hydrocarbon group comprises a cyclic structure.
[0482] In one embodiment, the solvent is R 71 OR 72 is.
[0483] R 71 and R 72are each independently preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably C 1-6 or an alkyl group of C 5-8 It can be a cycloalkyl group of the formula:
[0484] In one embodiment, the solvent is R 73 n8 C 6 H 6-n8 is.
[0485] C 6 H 6-n8 is an n-octavalent benzene ring. That is, R 73 n8 C 6 H 6-n8 is n8 R 73 is benzene substituted with
[0486] R 73 are each independently a halogen or a C optionally substituted by a halogen. 1-6 The alkyl group may be:
[0487] n8 is preferably an integer of 1 to 3.
[0488] In one embodiment, the solvent is R 74 R 75 R 76 Si—(O—SiR 77 R 78 ) m8 -R 79 is.
[0489] In one embodiment, the solvent is (OSiR 77 R 78 ) m9 (OSiR 77 R 78 ) m9 is a set of multiple OSiRs 77 R 78 It is a cyclic siloxane formed by bonding units in a ring.
[0490] R 74 ~R 79 are each independently a hydrogen atom or C 1-6 alkyl group, preferably C 1-6 alkyl groups of the formula C1-3 The alkyl group is preferably a methyl group.
[0491] m8 is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, and even more preferably 1 or 2.
[0492] m9 is preferably an integer of 3 to 6, more preferably an integer of 3 to 5.
[0493] In one embodiment, the solvent may be, for example, an aliphatic hydrocarbon such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, or mineral spirit; an aromatic hydrocarbon such as benzene, toluene, xylene, naphthalene, or solvent naphtha; or an alkyl ester such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, or ethyl-2-hydroxybutyl acetate. esters such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, 2-heptanone; ethyl cellosolve, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether ... glycol ethers such as 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, and ethylene glycol monoalkyl ether; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate;Polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C; 6 F 13 CH 2 CH 3 (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C 6 F 13 H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, (CF 3 ) 2 fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 O.C. 2 H 5 ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF 3 CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF 2Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) AS-300 manufactured by Asahi Glass Co., Ltd.) and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxide. Alternatively, examples include mixed solvents of two or more of these. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, benzene, toluene, xylene, naphthalene, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Preferred are ethyl hydroxyisobutyrate propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane.
[0494] The silicone oil is not particularly limited, but examples thereof include silicone oils represented by the following general formula (3a): 1a -(SiR 3a 2-O) a1 -SiR 3a 2 -R 1a ...(3a) [wherein: R 1a are each independently a hydrogen atom or a hydrocarbon group, 3a are each independently a hydrogen atom or a hydrocarbon group, and a1 is 2 to 3,000.
[0495] R 3a are each independently a hydrogen atom or a hydrocarbon group. Such hydrocarbon groups may be substituted.
[0496] R 3a are each independently preferably an unsubstituted hydrocarbon group or a hydrocarbon group substituted with a halogen atom. Such a halogen atom is preferably a fluorine atom.
[0497] R 3a are each independently preferably C optionally substituted by a halogen atom. 1-6 an alkyl group or an aryl group, more preferably C 1-6 It is an alkyl group or an aryl group.
[0498] Above C 1-6 The alkyl group may be straight-chain or branched, but is preferably straight-chain. 1-6 The alkyl group is preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.
[0499] The aryl group is preferably a phenyl group.
[0500] In one embodiment, R 3a are each independently C 1-6 Alkyl group, preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.
[0501] In another embodiment, R 3a is a phenyl group.
[0502] In another embodiment, R 3a is a methyl group or a phenyl group, preferably a methyl group.
[0503] R 1a are each independently a hydrogen atom or a hydrocarbon group, and R 3a It has the same meaning as:
[0504] R 1a are each independently preferably C optionally substituted by a halogen atom. 1-6 an alkyl group or an aryl group, more preferably C 1-6 It is an alkyl group or an aryl group.
[0505] In one embodiment, R 1a are each independently C 1-6 Alkyl group, preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group.
[0506] In another embodiment, R 1a is a phenyl group.
[0507] In another embodiment, R 1a is a methyl group or a phenyl group, preferably a methyl group.
[0508] The above a1 is 2 to 1500. a1 is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, for example, 30 or more, or 50 or more. a1 is preferably 1000 or less, more preferably 500 or less, even more preferably 200 or less, even more preferably 150 or less, for example, 100 or less, or 80 or less.
[0509] a1 may be preferably 5 to 1000, more preferably 10 to 500, even more preferably 15 to 200, and even more preferably 15 to 150.
[0510] Another silicone oil is the following (3b): 1a -R S2 -R 3a ...(3b) [wherein: R 1a are each independently a hydrocarbon group; R 3a are each independently a hydrocarbon group; R S2 has the same meaning as in formula (2).
[0511] The silicone oil may have an average molecular weight of 500 to 1,000,000, preferably 1,000 to 100,000. The molecular weight of the silicone oil can be measured using GPC.
[0512] Examples of the silicone oil include -(SiR 3a 2 -O) a1 Linear or cyclic silicone oils in which a1 is 30 or less can be used. The linear silicone oils may be so-called straight silicone oils or modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, epoxy, carboxyl, alcohol, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil.
[0513] The silicone oil may be contained in an amount of, for example, 0 to 50% by mass, preferably 0.001 to 30% by mass, and more preferably 0.1 to 5% by mass, relative to the surface treatment agent.
[0514] In the surface treatment agent, the silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and even more preferably 0 to 10 parts by mass, relative to 100 parts by mass of the total of the compounds represented by formula (1) above (when there are two or more types, the total of these, the same applies hereinafter), or relative to 100 parts by mass of the mixture of the compounds represented by formula (1) above and the compounds represented by formula (2).
[0515] The silicone oil contributes to improving the surface slipperiness of the water-repellent layer.
[0516] Examples of the alcohols include methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol. Addition of these alcohols to the surface treatment agent improves the stability of the surface treatment agent.
[0517] Examples of the catalyst include acids (e.g., acetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc.), bases (e.g., sodium hydroxide, potassium hydroxide, ammonia, triethylamine, diethylamine, etc.), transition metals (e.g., Ti, Ni, Sn, Zr, Al, B, Si, Ta, Nb, Mo, W, Cr, Hf, V, etc.), sulfur-containing compounds having an unshared electron pair in the molecular structure, or nitrogen-containing compounds (e.g., sulfoxide compounds, aliphatic amine compounds, aromatic amine compounds, phosphoric acid amide compounds, amide compounds, urea compounds), etc.
[0518] Examples of the aliphatic amine compounds include diethylamine, triethylamine, etc. Examples of the aromatic amine compounds include aniline, pyridine, etc.
[0519] In a preferred embodiment, the transition metal is contained as a transition metal compound represented by M-R (wherein M is a transition metal atom and R is a hydrolyzable group). By using a transition metal compound in which a transition metal is bonded to a hydrolyzable group, the transition metal atom can be contained more efficiently in the water-repellent layer, and the friction durability and chemical resistance of the water-repellent layer can be further improved.
[0520] The hydrolyzable group means a group that can undergo a hydrolysis reaction, similar to the hydrolyzable group in the compound represented by formula (1) or formula (2), that is, a group that can be eliminated from a transition metal atom by a hydrolysis reaction. Examples of the hydrolyzable group include -OR m , -OCOR m , —O—N═CR m 2 , -NR m2 , -NHR m , —NCO, or halogen (wherein R m is a substituted or unsubstituted C 1-4 (representing an alkyl group) and the like.
[0521] In a preferred embodiment, the hydrolyzable group is —OR m The use of an alkoxy group as the hydrolyzable group allows the transition metal atom to be more efficiently incorporated into the water-repellent layer, thereby further improving the friction durability and chemical resistance of the water-repellent layer.
[0522] In one embodiment, the hydrolyzable group may be the same as the hydrolyzable group contained in the compound represented by formula (1) or (2). By using the same hydrolyzable group in the silane compound and the transition metal compound, even if the hydrolyzable groups are exchanged with each other, the effect can be reduced.
[0523] In another embodiment, the hydrolyzable group may be different from the hydrolyzable group contained in the compound represented by formula (1) or (2). By making the hydrolyzable groups in the silane compound and the transition metal compound different, the hydrolysis reactivity can be controlled.
[0524] In one embodiment, the hydrolyzable group and the hydrolyzable group contained in the compound represented by formula (1) or (2) may be interchanged in the surface treatment agent.
[0525] In a preferred embodiment, the transition metal compound is Ta(OR m ) 5 (In the formula, R m is a substituted or unsubstituted C 1-4 is an alkyl group.), and preferably Ta(OCH 2 CH 3 ) 5 , or Si(OR m ) 1-m1 R m’ m1 (In the formula, R m is a substituted or unsubstituted C 1-4is an alkyl group, and R m’ is C 1-4 is an alkyl group, and m1 is 0 or 1.), and preferably tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxysilane, dimethyldiethoxysilane, or dimethyldimethoxysilane.
[0526] The catalyst may be contained in an amount of, for example, 0.0002% by mass or more relative to the entire surface treatment agent. The catalyst is preferably contained in an amount of 0.02% by mass or more, and more preferably 0.04% by mass or more, relative to the entire surface treatment agent. The catalyst may be contained in an amount of, for example, 10% by mass or less, and particularly 1% by mass or less, relative to the entire surface treatment agent. By containing the catalyst at the above-mentioned concentration, the surface treatment agent can contribute to the formation of a water-repellent layer with better durability.
[0527] The content of the catalyst is preferably 0 to 10 mass %, more preferably 0 to 5 mass %, and particularly preferably 0 to 1 mass %, based on the compound represented by formula (1) or the mixture of the compound represented by formula (1) and the compound represented by formula (2).
[0528] The catalyst promotes the hydrolysis and dehydration condensation of the compound represented by formula (1) or (2) above, and promotes the formation of the layer formed by the surface treatment agent.
[0529] In addition to the above, other components include, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane, and the like.
[0530] In addition to the above components, the surface treatment agent may contain trace amounts of impurities such as Pt, Rh, Ru, 1,3-divinyltetramethyldisiloxane, triphenylphosphine, NaCl, KCl, and silane condensates.
[0531] In one embodiment, the surface treatment agent is for dry coating, preferably vacuum deposition.
[0532] In one embodiment, the surface treatment agent is for a wet coating method, preferably for dip coating.
[0533] The surface treatment agent can be impregnated into a porous material, such as a porous ceramic material or a metal fiber, such as a flocculated steel wool, to form pellets, which can be used for vacuum deposition, for example.
[0534] The water-repellent layer may further have water repellency, oil repellency, stain resistance, waterproofing (preventing water from penetrating into electronic components, etc.), surface slipperiness (or lubricity, e.g., excellent tactile feel against fingers), chemical resistance, etc., depending on the composition of the composition contained therein. Furthermore, the water-repellent layer contained in the laminate of the present disclosure may have both high abrasion resistance and fingerprint wiping properties. For example, the water-repellent properties, such as water repellency, oil repellency, and surface slipperiness, possessed by the water-repellent layer may be retained to a high degree from the pre-abrasion properties even after the layer has been abraded a predetermined number of times.
[0535] The water contact angle of the water-repellent layer may be, for example, 95° or more, or even 100° or more, preferably 103° or more, more preferably 106° or more, or even more preferably 110° or more, and may be, for example, 140° or less, or even 125° or less.
[0536] The above contact angle with water and contact angles with other liquids can be measured by the method described in the examples of this specification.
[0537] The thickness of the water-repellent layer is not particularly limited, but is preferably 15 nm or less, for example, 1 to 15 nm, 1 to 13 nm, or 1 to 10 nm.
[0538] The laminate of the present disclosure can be produced by applying a surface treatment agent containing a compound represented by formula (1) or a mixture of a compound represented by formula (1) and a compound represented by formula (2) to the surface of a substrate (e.g., glass), and then post-treating the resulting mixture as needed to form a layer of a cured product of the compound or mixture (i.e., a water-repellent layer).
[0539] The water-repellent layer can be formed by applying the surface treatment agent to the surface of the substrate so as to coat the surface. The coating method is not particularly limited. For example, a wet coating method or a dry coating method can be used.
[0540] Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, wipe coating, squeegee coating, die coating, ink jet, casting, Langmuir-Blodgett coating, and similar methods.
[0541] Examples of dry coating methods include vapor deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of vapor deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating using microwaves, etc., ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.
[0542] Furthermore, coating by atmospheric pressure plasma method is also possible.
[0543] When using the wet coating method, the surface treatment agent of the present disclosure can be diluted with a solvent and then applied to the surface of a substrate. From the viewpoint of the stability of the composition of the present disclosure and the volatility of the solvent, the following solvents are preferably used: aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha, etc.; methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbohydrate acetate, etc. Esters such as ethanol, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methyl amino ketone, and 2-heptanone; ethyl cellosolve, methyl cellosol glycol ethers such as propylene glycol 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, and ethylene glycol monoalkyl ethers; alcohols such as methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, 3-pentanol, octyl alcohol, 3-methyl-3-methoxybutanol, and tert-amyl alcohol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone;Ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, and diethylene glycol monomethyl ether; diethylene glycol monoethyl ether acetate; polyfluoroaromatic hydrocarbons (e.g., 1,3-bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (e.g., C; 6 F 13 CH 2 CH 3 (For example, Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), C 6 F 13 H (for example, Asahiklin (registered trademark) AC-2000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Zeon Corporation); fluorine-containing hydrocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (HCFC225), and 1,3-bis(trifluoromethyl)benzene; CF 3 CH 2 OH, CF 3 CF 2 CH 2 OH, (CF 3 ) 2 fluorine-containing alcohols such as CHOH; hydrofluoroethers (HFEs) (for example, perfluoropropyl methyl ether (C 3 F 7 OCH 3 ) (e.g., Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (e.g., Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 O.C. 2 H 5 ) (e.g., Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C 2 F 5 CF (OCH3 ) C 3 F 7 ) (e.g., Novec™ 7300 manufactured by Sumitomo 3M Limited) (the perfluoroalkyl group and the alkyl group may be linear or branched), or CF 3 CH 2 OCF 2 CHF 2 (e.g., Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.), hydrofluoroolefins; CF 3 CH═CHCl (e.g., CELEFIN® 1233Z manufactured by Central Glass Co., Ltd.), CHF 2Examples of suitable solvents include ethers such as CF═CHCl (for example, AMOLEA (registered trademark) AS-300 manufactured by Asahi Glass Co., Ltd.) and cyclopentyl methyl ether; siloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and tetradecamethylhexasiloxane; and dimethyl sulfoxide. Alternatively, mixed solvents of two or more of these solvents may be used. Among these, aliphatic hydrocarbons, aromatic hydrocarbons, esters, glycol ethers, alcohols, ether alcohols, and siloxanes are preferred. For example, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, benzene, toluene, xylene, naphthalene, methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, amyl acetate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, 2- Preferred are ethyl hydroxyisobutyrate propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, methanol, ethanol, iso-propanol, n-butanol, isobutanol, tert-butanol, sec-butanol, diethylene glycol monomethyl ether, hexamethyldisiloxane, hexaethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, octamethylcyclotetrasiloxane, and octamethylcyclopentasiloxane.
[0544] When the dry coating method is used, the surface treatment agent may be subjected to the dry coating method as it is, or may be diluted with the above-mentioned solvent before being subjected to the dry coating method.
[0545] The water-repellent layer is preferably formed so that the surface treatment agent is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of a wet coating method, the surface treatment agent may be diluted with a solvent, and then a catalyst may be added to the diluted solution of the surface treatment agent immediately before application to the substrate surface. In the case of a dry coating method, the surface treatment agent to which the catalyst has been added may be directly vapor-deposited (usually vacuum vapor-deposited), or a pellet-shaped material impregnated with the surface treatment agent to which the catalyst has been added may be vapor-deposited (usually vacuum vapor-deposited) onto a porous metal such as iron or copper.
[0546] The catalyst may be any appropriate acid or base, transition metal (e.g., Ti, Ni, Sn, Zr, Al, B, etc.), sulfur-containing compound having an unshared electron pair in its molecular structure, or nitrogen-containing compound (e.g., sulfoxide compound, aliphatic amine compound, aromatic amine compound, phosphoric acid amide compound, amide compound, urea compound), etc. Examples of acid catalysts that can be used include acetic acid, formic acid, trifluoroacetic acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Examples of base catalysts that can be used include ammonia, sodium hydroxide, potassium hydroxide, and organic amines such as triethylamine and diethylamine. Examples of transition metals, aliphatic amine compounds, and aromatic amine compounds are the same as those described above.
[0547] The articles of the present disclosure are described below.
[0548] The article of the present disclosure includes the laminate.
[0549] In one embodiment, the article of the present disclosure may include an intermediate layer containing silicon oxide between the glass and the water-repellent layer. By providing such an intermediate layer, adhesion between the glass and the water-repellent layer is improved, and durability is improved.
[0550] In a preferred embodiment, the intermediate layer may contain alkali metal atoms in addition to silicon oxide.
[0551] Examples of the alkali metal atom include lithium, sodium, potassium, etc. The alkali metal atom is preferably sodium.
[0552] The thickness of the intermediate layer is not particularly limited, but is preferably 1 to 200 nm, and particularly preferably 1 to 20 nm. By making the thickness of the intermediate layer equal to or greater than the lower limit of the above range, the effect of the intermediate layer in improving adhesiveness becomes greater.
[0553] The alkali metal atom concentration in the intermediate layer can be measured by various surface analysis devices, such as TOF-SIMS, XPS, and XRF.
[0554] The proportion of alkali metal atoms in the total atoms of the entire intermediate layer can be obtained by XPS depth profile analysis using ion sputtering, which is performed by alternately repeating XPS measurement and surface etching by ion sputtering using an ion gun built into the XPS apparatus.
[0555] The average alkali metal concentration in the region of the intermediate layer that is 1 nm or less deep from the surface in contact with the water-repellent layer is determined by obtaining a depth profile of the alkali metal atom concentration by TOF-SIMS (time-of-flight secondary ion mass spectrometry) depth profile analysis using ion sputtering, and then calculating the average alkali metal atom concentration in the profile. TOF-SIMS depth profile analysis using ion sputtering is performed by alternately repeating TOF-SIMS measurement and surface etching by ion sputtering using an ion gun built into the TOF-SIMS device.
[0556] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.
[0557] The article of the present disclosure may also be a medical device or medical material. The article having a water-repellent layer obtained by the present disclosure may also be an automobile interior or exterior component. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.
[0558] The intermediate layer containing silicon oxide can be formed by applying a silicon oxide precursor to the surface of a substrate. When the intermediate layer contains alkali metal atoms, the intermediate layer can be formed by applying a composition containing a silicon oxide precursor and an alkali metal source to the surface of a substrate.
[0559] Examples of the silicon oxide precursor include silicic acid, partial condensates of silicic acid, alkali metal silicates, silane compounds having a hydrolyzable group bonded to a silicon atom, and partial hydrolysis condensates of the silane compounds. Silicic acid and its partial condensates can be converted into silicon oxide by dehydration condensation. Alkali metal silicates can be converted into silicic acid or its partial condensates by the addition of an acid or a cation exchange resin, and the resulting silicic acid or its partial condensates can then be dehydration condensed into silicon oxide. Examples of the hydrolyzable group in a silane compound having a hydrolyzable group bonded to a silicon atom include an alkoxy group and a chlorine atom. The hydrolyzable group in the silane compound can be hydrolyzed to a hydroxyl group, and the resulting silanol compound can be dehydration condensed to form silicon oxide. Examples of silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxysilanes such as tetraalkoxysilanes and alkyltrialkoxysilanes, and tetrachlorosilane.
[0560] Examples of the alkali metal source include alkali metal hydroxides, water-soluble alkali metal salts, etc. Examples of the water-soluble alkali metal salts include alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydrochlorides, alkali metal nitrates, etc. As the alkali metal source, alkali metal hydroxides and alkali metal carbonates are preferred.
[0561] Alkali metal silicates can be used as silicon oxide precursors and alkali metal sources. Alkali metal silicates can be converted to silicon oxide via silicic acid, but a small amount of alkali metal may remain in the resulting silicon oxide. Therefore, by adjusting the amount of remaining alkali metal atoms, silicon oxide containing a predetermined amount of alkali metal atoms can be obtained.
[0562] The water-repellent layer included in the article of the present disclosure can have high abrasion resistance as described above. In addition to high abrasion resistance, the water-repellent layer can have water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (for example, preventing water penetration into electronic components), surface slipperiness (or lubricity, for example, ease of wiping off stains such as fingerprints and excellent tactile feel), chemical resistance, etc., depending on the composition of the surface treatment agent used, and can be suitably used as a functional thin film.
[0563] Therefore, the present disclosure also relates to an optical material having the above-described water-repellent layer as the outermost layer.
[0564] Preferred examples of the optical material include optical materials relating to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin-film EL dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), and field emission displays (FEDs), or protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.
[0565] The article of the present disclosure may be, but is not particularly limited to, an optical member. Examples of optical members include lenses for eyeglasses and the like; front protective plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs; touch panel sheets for devices such as mobile phones and personal digital assistants; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs; optical fibers; and the display surfaces of watches and clocks.
[0566] The article of the present disclosure may also be a medical device or medical material. The article having a layer obtained by the present disclosure may also be an automobile interior or exterior component. Examples of exterior components include windows, light covers, and exterior camera covers. Examples of interior components include instrument panel covers, navigation system touch panels, and decorative interior components.
[0567] The thickness of the layer is not particularly limited. In the case of an optical member, the thickness of the layer may be, for example, in the range of 1 to 50 nm, preferably 1 to 30 nm, and more preferably 1 to 15 nm, from the viewpoints of optical performance, abrasion resistance, and antifouling properties.
[0568] An X-ray photoelectron spectroscopy (XPS) device, such as a PHI5000 VersaProbe II manufactured by ULVAC-PHI, can be used to measure the atomic composition and atomic ratio of the water-repellent layer. The measurement conditions for XPS analysis include a monochromated AlKα X-ray source at 25 W, a photoelectron detection area of 1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, or 90 degrees), and a pass energy of 23.5 eV. Gas cluster ion beams or Ar ions can be used for sputtering. Using the above-described device and measurement conditions, the peak areas of F1s, C1s, O1s, and Si2p can be observed, and the atomic ratios of fluorine, carbon, oxygen, and silicon can be calculated to determine the composition of the water-repellent layer and intermediate layer.
[0569] Depth analysis can also be performed. Measurement conditions for XPS analysis include using a monochromated AlKα ray at 25 W as the X-ray source, a photoelectron detection area of 1400 μm × 300 μm, a photoelectron detection angle in the range of 20 to 90 degrees (e.g., 20, 45, or 90 degrees), and a pass energy of 23.5 eV. Ar ions, gas cluster ions, or C ions can be used as sputtering ions. Sputtering can be performed to etch 1 to 100 nm, and the composition of the coating film at each post-etching depth can be determined.
[0570] The detection depth can be adjusted appropriately by adjusting the photoelectron detection angle in the XPS analysis. For example, a shallow angle close to 20 degrees can achieve a detection depth of about 3 nm, while a deep angle close to 90 degrees can achieve a detection depth of about 10-odd nm.
[0571] The intermediate layer containing silicon oxide can be formed by applying a silicon oxide precursor to the surface of the substrate. When the intermediate layer contains an alkali metal, the intermediate layer can be formed by applying a composition containing a silicon oxide precursor and an alkali metal source to the surface of the substrate.
[0572] Examples of the silicon oxide precursor include silicic acid, partial condensates of silicic acid, alkali metal silicates, silane compounds having a hydrolyzable group bonded to a silicon atom, and partial hydrolysis condensates of the silane compounds. Silicic acid and its partial condensates can be converted into silicon oxide by dehydration condensation. Alkali metal silicates can be converted into silicic acid or its partial condensates by the addition of an acid or a cation exchange resin, and the resulting silicic acid or its partial condensates can then be dehydration condensed into silicon oxide. Examples of the hydrolyzable group in a silane compound having a hydrolyzable group bonded to a silicon atom include an alkoxy group and a chlorine atom. The hydrolyzable group in the silane compound can be hydrolyzed to a hydroxyl group, and the resulting silanol compound can be dehydration condensed to form silicon oxide. Examples of silane compounds having a hydrolyzable group bonded to a silicon atom include alkoxysilanes such as tetraalkoxysilanes and alkyltrialkoxysilanes, and tetrachlorosilane.
[0573] Examples of the alkali metal source include alkali metal hydroxides, water-soluble alkali metal salts, etc. Examples of the water-soluble alkali metal salts include alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydrochlorides, alkali metal nitrates, etc. As the alkali metal source, alkali metal hydroxides and alkali metal carbonates are preferred.
[0574] Alkali metal silicates can be used as silicon oxide precursors and alkali metal sources. Alkali metal silicates can be converted to silicon oxide via silicic acid, but a small amount of alkali metal may remain in the resulting silicon oxide. Therefore, by adjusting the amount of the remaining alkali metal, silicon oxide containing a desired amount of alkali metal atoms can be obtained.
[0575] The thickness of the intermediate layer is not particularly limited, but is, for example, in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 2 to 15 nm, and even more preferably 3 to 10 nm.
[0576] The compounds, compositions, and articles of the present disclosure have been described in detail above. However, the compounds, compositions, and articles of the present disclosure are not limited to those exemplified above.
[0577] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
[0578] In the following examples, the number of repeating units n of the siloxane is: 1 Calculated by H-NMR.
[0579] (Synthesis Example 1) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 5.0 g of COOH, 92 mg of 2-propen-1-amine, 31 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 13 mg of 4-dimethylaminopyridine, and 20 mL of dichloromethane were mixed and stirred at room temperature for 16 hours. The reaction solution was washed with hydrochloric acid and water, and then concentrated under reduced pressure to obtain compound (1) CH 3 CH 2 CH 2 CH 2 Si(CH3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 CONHCH 2 CH=CH 2 5.28 g of (n≈59) was obtained.
[0580] 1 H-NMR (400 MHz, chloroform-D) δ [ppm] 6.59-6.71 (br), 5.80-5.91 (m), 5.12-5.24 (m), 3.91-3.97 (m), 3.45-3.50 (t), 1.58-1.69 (m), 1.24-1.36 (m), 0.86-0.91 (t), 0.51-0.58 (m), -0.10-0.30 (m)
[0581] Synthesis Example 2 2.0 g of compound (1), 10 mL of toluene, 47 μL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and 113 μL of aniline were added, followed by the addition of 210 μL of trimethoxysilane and stirring at 40° C. for 3 hours. Thereafter, purification was carried out to obtain compound (2) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 1.74 g of (n≈59) was obtained.
[0582] 1H-NMR (400 MHz, chloroform-D) δ [ppm] 6.62-6.70 (br), 3.92 (s), 3.53-3.62 (m), 3.43-3.49 (t), 3.27-3.33 (q), 1.58-1.72 (m), 1.24-1.35 (m), 0.85-0.92 (t), 0.63-0.69 (t), 0.50-0.57 (m), -0.13-0.32 (m)
[0583] (Synthesis Example 3) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n - (CH 2 ) 3 -OCH 2 —COOH (10 g), 2,2-diallyl-4-penten-1-amine (1.71 g), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.98 g), 4-dimethylaminopyridine (84 mg), and dichloromethane (30 mL) were mixed and stirred at room temperature for 16 hours. The mixture was diluted with dichloromethane, washed with hydrochloric acid and water, and then concentrated under reduced pressure to obtain compound (3) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n - (CH 2 ) 3 -OCH 2 -CONH-CH 2 C(CH 2 CH=CH 2 ) 3 The average number of repeating units n was 55.
[0584] 1 H-NMR (CDCl 3, 400MHz) δ [ppm]: -0.10-0.30 (m), 0.52-0.59 (m, 4H), 0.88 (t, J = 6.9Hz, 3H), 1.26-1.33 (m, 4H), 1.61-1.69 (m, 2H), 2.05 (d, J =7.3Hz, 6H), 3.22 (d, J = 6.4Hz, 2H), 3.47 (t, J = 6.6Hz, 2H), 3.93 (s, 2H), 5.08-5.13 (m, 6H), 5.82-5.92 (m, 3H), 6.75 (brs, 1H)
[0585] Synthesis Example 4 Compound (3) (5 g), toluene (5 mL), a xylene solution of Karstedt's catalyst (2%, 0.24 mL), aniline (38 mg), and trimethoxysilane (1.19 mL) were mixed. The mixture was stirred at room temperature for 16 hours and then concentrated under reduced pressure to give compound (4) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n - (CH 2 ) 3 -OCH 2 -CONH-CH 2 C{CH 2 CH 2 CH 2 Si(OCH 3 ) 3} 3 The average number of repeating units n was 55.
[0586] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: -0.13-0.32 (m), 0.54-0.63 (m, 10H), 0.90 (t, J=7.1Hz, 3H), 1.23-1.37 (m, 16H), 1.62 -1.69 (m, 2H), 3.17 (d, J=5.9Hz, 2H), 3.47-3.50 (m, 2H), 3.56-3.63 (m, 27H), 3.94 (s, 2H), 6.54 (brs, 1H)
[0587] Synthesis Example 5 3.02 g of 22-tricosenoic acid, 26 mL of toluene, and 17 mL of methanol were added, and then 20 mL of trimethylsilyldiazomethane was added dropwise thereto, followed by stirring at room temperature for 3 hours. Thereafter, the mixture was concentrated under reduced pressure to obtain 3.11 g of compound (5).
[0588] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 1.249-1.649(m), 2.005-2.061(m), 2.279-2.316(t), 1.567-1.622(m), 3.662(s), 4.904-5.015(m), 5.760-5.862(m)
[0589] Compound (5)
[0590] Synthesis Example 6: 1.25 g of compound (5), 20.0 mL of toluene, 0.1 mL of pyridine, and 0.65 mL of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the dropwise addition of 1.01 g of tris(trimethylsilyloxy)silane. After stirring at room temperature for 16 hours, the mixture was purified to obtain 1.36 g of compound (6).
[0591] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 0.013-0.142 (m), 0.408 (t), 1.137-1.378 (m), 1.591 (quin), 2.275 (t), 3.639 (s)
[0592] Compound (6)
[0593] Synthesis Example 7 0.64 g of compound (6), 2.8 mL of allylamine, and 0.12 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene were added, and the mixture was stirred for 3 hours at 75° C. Thereafter, the mixture was washed with an aqueous hydrochloric acid solution, dehydrated with magnesium sulfate, and concentrated under reduced pressure to obtain 0.68 g of compound (7).
[0594] 1 H-NMR (CDCl 3, 400MHz) δ [ppm]: 0.011-0.217 (m), 0.407 (t), 1.153-1.378 (m), 1.612 (qu in), 2.163 (t), 3.865 (tt), 5.090-5.182 (m), 5.409 (br), 5.770-5.866 (m)
[0595] Compound (7)
[0596] Synthesis Example 8 0.56 g of compound (7), 10.0 mL of toluene, 0.022 mL of aniline, and 0.46 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 0.2 mL of trimethoxysilane and stirring for 2 hours at 45° C. The mixture was then purified to obtain 0.57 g of compound (8).
[0597] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 0.010-0.141 (m), 0.408 (t), 0.629 (t), 1.150-1.376 ( m), 1.519-1.652 (m), 2.121 (t), 3.172 (q), 3.516-3.589 (m), 5.607 (br)
[0598] Compound (8)
[0599] Synthesis Example 9: 0.50 g of compound (5), 10.0 mL of toluene, 0.05 mL of pyridine, and 0.3 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the dropwise addition of 1.2 mL of 1,1,1,3,5,5,5-heptamethyltrisiloxane. After stirring at room temperature for 17 hours, the mixture was purified to yield 0.87 g of compound (9).
[0600] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 0.033-0.241 (m), 0.438-0.550 (m), 1.191-1.413 (m), 1.607-1.642 (m), 2.242-2.325 (m), 3.669 (s)
[0601] Compound (9)
[0602] Synthesis Example 10 0.86 g of compound (9), 5.0 mL of allylamine, and 0.20 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene were added, and the mixture was stirred for 3 hours at 75° C. Thereafter, the mixture was washed with an aqueous hydrochloric acid solution, dehydrated with magnesium sulfate, and concentrated under reduced pressure to obtain 0.72 g of compound (10).
[0603] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 0.076-0.128 (m), 0.413-0.465 (t), 1.183-1.1.404 (m), 1.604- 1.677 (m), 2.173-2.248 (t), 3.841-3.942 (m), 5.122-5.210 (m), 5.809-5.877 (m)
[0604] Compound (10)
[0605] Synthesis Example 11: 0.72 g of compound (10), 6.0 mL of toluene, 0.04 mL of pyridine, and 0.26 mL of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 1.4 mL of trimethoxysilane and stirring at room temperature for 16 hours. Thereafter, purification was carried out to obtain 0.48 g of compound (11).
[0606] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: 0.054-0.149 (m), 0.425-0.464 (t), 0.628-0.681 (m) , 1.181-1.402 (m), 1.544-1.768 (m), 2.125-2.164 (t), 3.558-3.646 (m)
[0607] Compound (11)
[0608] Synthesis Example 12 Tris(trimethylsilyloxy)silane (0.7 g), 18-octadecen-1-ol (1.0 g), tris(pentafluorophenyl)borane (0.24 g), and toluene (10 mL) were added and stirred under heating for 2 hours at 70° C. Thereafter, the reaction solution was filtered through a silica gel column, and the filtrate was concentrated to obtain 1.2 g of compound (12).
[0609] 1 H-NMR (400 MHz, chloroform-D) δ 5.87-5.76 (m, 1H), 5.02-4.91 (m, 2H), 3.64 (t, J = 6.6 Hz, 2H), 2.07-2.01 (m, 2H), 1.55-1.50 (m, 2H), 1.41-1.26 (m, 26H), 0.15-0.07 (m, 18H), 0.03 (s, 3H)
[0610] (Compound 12)
[0611] Synthesis Example 13 Compound (12) (1.0 g), Karstedt's catalyst (0.13 g, xylene solution containing 2% platinum), trimethoxysilane (0.75 g), pyridine (22 mg), and toluene (10 mL) were added, stirred at room temperature for 4 hours, and then concentrated under reduced pressure to obtain 1.09 g of compound (13).
[0612] 1 H-NMR (400 MHz, chloroform-D) δ 3.74-3.53 (m, 11H), 1.56-1.50 (m, 2H), 1.43-1.25 (m, 30H), 0.67-0.62 (m, 2H), 0.26-0.07 (m, 18H), 0.04 (q, J = 4.4 Hz, 3H)
[0613] (Compound 13)
[0614] (Synthesis Example 14) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 105.01 g of COOH, 15.0 g of tetrahydrofuran, 0.99 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.047 g of 4-dimethylaminopyridine, and 0.38 mL of allylamine were added, and the mixture was stirred at room temperature for 16 hours. Then, the mixture was purified to obtain compound (14) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH=CH 2 (n≈16) 4.80 g was obtained.
[0615] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: -0.124-0.279(m), 0.486-0.523(t), 1.243-1.269(m), 1 .617 (bs), 2.161-2.196 (t), 3.859 (bs), 5.083-5.175 (m), 5.781-5.848 (m)
[0616] (Synthesis Example 15) Compound (14) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH=CH 24.34 g of the compound, 13.09 g of toluene, 0.035 g of triacetoxymethylsilane, and 0.15 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 0.61 mL of trichlorosilane, heating to 60°C and stirring for 4 hours. After that, the volatile matter was distilled off under reduced pressure, and then a mixed solution of 0.280 g of methanol and 6.340 g of trimethyl orthoformate was added, followed by heating to 50°C and stirring for 3 hours. Thereafter, purification was carried out to obtain compound (15)CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n≈16) 4.24 g was obtained.
[0617] 1 H-NMR (CDCl 3 , 400MHz) δ [ppm]: -0.010-0.157 (m), 0.495-0.666 (m), 1.251-1.274 (m) , 1.578-1.654 (m), 2.123-2.312 (m), 3.218-3.267 (m), 3.420-3.605 (m)
[0618] The following compound (16) was used to prepare surface treatment agent 7. Compound (16): MCR-XT11 (triethoxysilylethyl-terminated polydimethylsiloxane, Mw=600-900), manufactured by Gelest.
[0619] (Synthesis Example 17) (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) n - (CH 2 ) 10 -CON (CH 2 CH=CH 2 ) 2(2 g), toluene (10 mL), a xylene solution of Karstedt's catalyst (2%, 0.20 mL), aniline (32 mg), and trimethoxysilane (1.00 mL) were mixed and stirred at room temperature for 16 hours. The mixture was then concentrated under reduced pressure to give compound (17) (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) n - (CH 2 ) 10 -CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 The average number of repeating units n was 19.
[0620] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.20-0.31 (m), 0.42-0.65 (m, 6H), 1.10-1.40 (m, 14H), 1.63-1.71 (m, 6H), 2.26 (t, 2H, 7.2 Hz), 3.19 (t, 2H, 7.6 Hz), 3.27 (t, 2H, 7.6 Hz), 3.45-3.65 (m, 18H).
[0621] (Synthesis Example 18) [(CH 3 ) 3 SiO] 2 CH 3 SiO(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CONHCH 2 CH (CH 2 CH=CH 2 ) 2 2.00 g of (n≈26), 10 ml of toluene, 0.05 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, and 0.01 ml of aniline were added and stirred, and 0.24 ml of trimethoxysilane was added dropwise at room temperature, followed by heating to 45°C and stirring for 2 hours. Thereafter, the volatile components were distilled off under reduced pressure, and the resulting mixture was purified to give compound (18) [(CH 3 ) 3 SiO] 2 CH 3 SiO(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CONHCH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 2.0 g of (n≈26) was obtained.
[0622] 1 H-NMR (CDCl 3, 400MHz) δ [ppm]: -0.089-0.207 (m), 0.492-0.531 (m), 0.595-0.635 (t), 1.200-1.308 (m), 1.378- 1.681 (m), 2.123-2.160 (t), 3.157-3.187 (t), 3.517-3.592 (m), 3.494-3.602 (m), 5.465-5.492 (m)
[0623] Synthesis Example 19: 4.03 g of 22-tricosenoic acid perfluorophenol and 5.0 ml of THF were added and stirred, and then 1.30 ml of dimethylchlorosilane and 0.080 ml of a xylene solution containing 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added at room temperature, followed by stirring at room temperature for 16 hours. Thereafter, the volatile components were distilled off under reduced pressure, and the mixture was purified to obtain 4.6 g of compound (19-1), chlorodimethylsilyl tricosenoic acid ester.
[0624] Compound (19-1)
[0625] In a separate reactor, 1.33 g of hexamethyldisiloxane and 10 ml of THF were added and stirred, and then 2.57 ml of a 15% n-butyllithium hexane solution was added in a 30°C water bath. After cooling in an ice bath, 17.79 g of hexamethylcyclotrisiloxane and 20 ml of THF were added as a solution, and the mixture was stirred for an additional 8 hours. While cooling in an ice bath, 2.3 g of the previously synthesized compound (19-1) chlorodimethylsilyltricosenoate ester and 10 ml of THF were added as a solution, and the mixture was stirred for 1 hour. Further, 1.50 g of 2-allylpent-4-en-1-amine was added, and the mixture was stirred for 16 hours while immersed in the ice bath. A portion of the reaction mixture was then purified to obtain compound (19-2) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CONH-CH 2 CH [CH 2 CH=CH 2 ] 2 The average value of n was 57.
[0626] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.089 - 0.211 (m), 0.494 - 0.533 (t), 1.242 - 1.335 (m), 1.586 - 1.623 (m), 1.692 - 1.758 (m), 2.000 - 2.160 (m), 3.193 - 3.224 (t), 5.023 - 5.077 (m), 5.455 (br), 5.728 - 5.832 (m)
[0627] Synthesis Example 20 2.74 g of compound (19-2), 5.5 mL of toluene, 14 μL of pyridine, and 70 μL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 0.29 mL of trimethoxysilane, and the mixture was stirred at room temperature for 16 hours. After that, purification was carried out to obtain compound (20) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CONH-CH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 The average number of repeating units of dimethylsiloxane was 57.
[0628] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.104-0.196 (m), 0.498(t), 0.604 (t), 1.226-1.339 (m), 1.404(quin), 1.568-1.664 (m), 2.130 (t), 3.160(t), 3.496-3.584 (m), 5.471 (br)
[0629] (Synthesis Example 21) CH 3 CH 2 CH 2CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 -C(CH 2 CH 3 ) (CH 2 OH) 2 After adding 2.0 g of methylparaben (average molecular weight 4,700) and 0.49 mL of (3-isocyanatopropyl)trimethoxysilane, the mixture was stirred at 40°C for 2.5 hours, then at 55°C for 3.5 hours, and then at 60°C for 6 hours. After washing with methanol and concentrating, compound (21)CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 -C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 The average number of repeating units of dimethylsiloxane was 63.
[0630] 1H-NMR (400 MHz, CHLOROFORM-D) δ 4.83 (s, 2H), 4.01-3.94 (m, 6H), 3.57-3.49 (m, 18H), 3.32-3.24 (m, 2H), 3.16-3.12 (m, 4H), 1.60-1.54 (m, 6H), 1.40-1.24 (m, 6H), 0.90-0.82 (t, 6H), 0.66-0.58 (m, 4H), 0.54-0.47 (m, 4H), 0.21 - -0.09 (m)
[0631] (Synthesis Example 22) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 CH 2 After adding 2.0 g of 3-isocyanatopropyltrimethoxysilane (average molecular weight 4,800) and 0.48 mL of (3-isocyanatopropyl)trimethoxysilane, the mixture was stirred at 55°C for 1 hour, then at 65°C for 3 hours, and then at 70°C for 5 hours. After washing with methanol and concentrating, compound (22)CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 The average number of repeating units of dimethylsiloxane was 60.
[0632] 1H-NMR (400 MHz, CHLOROFORM-D) δ 4.87 (s, 1H), 4.20-4.18 (t, 2H), 3.60-3.53 (m, 9H), 3.43-3.40 (t, 2H), 3.30-3.26 (t, 2H), 3.18-3.13 (m, 2H), 1.75-1.69 (m, 2H), 1.64-1.58 (m, 2H), 1.34-1.24 (m, 4H), 0.89-0.85 (t, 3H), 0.69-0.60 (m, 2H), 0.54-0.49 (m, 4H), 0.21 - -0.09 (m)
[0633] Synthesis Example 23 20.10 g of 22-tricosenoic acid, 200 mL of dichloromethane, and 10.20 g of 1,1′-carbonyldiimidazole were added, stirred at room temperature for 2 hours, and then purified to obtain 20.25 g of compound (23).
[0634] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: 1.219-1.445 (m), 1.803 (quin), 2.040 (q), 2.856 (t), 4.880-5.054 (m), 5.745-5.888 (m), 7.105 (s), 7.483 (s), 8.165 (s)
[0635] Compound (23)
[0636] Synthesis Example 24 5.0 g of compound (23), 29 mL of toluene, 4 μL of pyridine, and 0.55 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the dropwise addition of 5.05 mL of 1,1,1,3,3,5,5-heptamethyltrisiloxane. After stirring at room temperature for 16 hours, the mixture was purified to yield 7.58 g of compound (24).
[0637] 1H NMR (CDCl3, 400 MHz) δ[ppm]: -0.129-0.251 (m), 0.526 (t), 1.115-1.430 (m), 1802 (quin), 2.855 (t), 7.104 (s), 7.480 (s), 8.173 (s)
[0638] Compound (24)
[0639] Synthesis Example 25 4.03 g of compound (24), 14 mL of toluene, and 0.58 mL of allylamine were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, purification was carried out to obtain 1.17 g of compound (25).
[0640] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.129-0.237 (m), 0.525 (t), 1.180-1.1.404 (m), 1.635 (quin), 2.192 (t), 3.891 (tt), 5.117-5.209 (m), 5.469 (br), 5.781-5.892 (m)
[0641] Compound (25)
[0642] Synthesis Example 26: 1.17 g of compound (25), 3.0 mL of toluene, 0.046 mL of pyridine, and 0.22 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 0.72 mL of trimethoxysilane and stirring at room temperature for 4 hours. Thereafter, purification was carried out to obtain 1.06 g of compound (26).
[0643] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.133-0.234 (m), 0.523 (t), 0.649 (t), 1.166-1.402 (m), 1.582-1.675 (m), 2.149 (t), 3.239 (q), 3.486-3.664 (m),5.677 (br)
[0644] Compound (26)
[0645] Synthesis Example 27 3.55 g of compound (24), 12 mL of toluene, and 0.85 g of 2-allylpent-4-en-1-amine were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, purification was carried out to obtain 1.64 g of compound (27).
[0646] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.130-0.236 (m), 0.525 (t), 1.180-1.1.404 (m), 1.612 (quin), 1.736 (quin), 2.071 (q), 2.157 (t), 3.217 (t), 5.033-5.087 (m), 5.510 (br), 5.738-5.841 (m)
[0647] Compound (27)
[0648] Synthesis Example 28: 1.64 g of compound (27), 5.0 mL of toluene, 0.058 mL of pyridine, and 0.27 mL of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by the addition of 1.83 mL of trimethoxysilane and stirring at room temperature for 4 hours. Thereafter, purification was carried out to obtain 1.77 g of compound (28).
[0649] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.134-0.232 (m), 0.522 (t), 0.626 (t), 1.103-1.388 (m), 1.388-1.449 (m), 1.538-1.690 (m), 2.156 (t), 3.182 (t), 3.383-3.741 (m),5.534 (br)
[0650] Compound (28)
[0651] Synthesis Example 29 2.11 g of 22-tricosenoic acid, 95 ml of toluene, and 1.26 g of 1,1′-carbonyldiimidazole were added and stirred at room temperature for 1 hour. After that, purification was carried out to obtain compound (29) CH2 =CH(CH 2 ) 20 CO(C 3 H 4 N 2 ) 2.22 g was obtained.
[0652] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: 1.250 (s), 1.333-1.426 (m), 1.761-1.836 (m), 2.007-2.061 (dd), 2.837-2.875 (t), 4.909-5.016 (m), 5.761-5.863 (m), 7.104 (s), 7.481 (s), 8.174 (s)
[0653] Compound (29)
[0654] (Synthesis Example 30) Compound (29) CH 2 =CH(CH 2 ) 20 CO(C 3 H 4 N 2 ) 1.38 g, toluene 24.9 g, CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 After adding 6.12 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 0.56 ml of a xylene solution containing 2% Pt complex, the mixture was heated to 60°C and stirred for 12 hours. After that, the mixture was purified to obtain compound (30) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CO(C 3 H 4 N 2 ) 6.86 g was obtained. The average value of n is 26.
[0655] 1H NMR (CDCl3, 400 MHz) δ[ppm]: -0.076-0.223 (m), 0.505-0.543 (t), 1.253 (br s), 1.767-1.841 (m), 2.857-2.894 (t), 7.124 (s), 7.497 (s), 8.273 (s)
[0656] Compound (30) n=26
[0657] (Synthesis Example 31) Compound (30) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CO(C 3 H 4 N 2 6.86 g of bis[3-(trimethoxysilyl)propyl]amine, 6.86 g of heptane, and 1.48 g of bis[3-(trimethoxysilyl)propyl]amine were added, and the mixture was stirred at 60° C. for 3 hours. After that, the mixture was purified to obtain compound (31)CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 The average value of n was 26.
[0658] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.109-0.216 (m), 0.499-0.537 (t), 0.559-0.612 (m), 1.245 (br s), 1.570-1.630 (m), 2.256-2.295 (t), 3.182-3.221 (t), 3.264-3.301 (t),3.556 (br s),3.575 (br s)
[0659] (Synthesis Example 32) CH 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 Compound (32) CH 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 22 CON [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 The average value of n is 34.
[0660] 1 H NMR (CDCl3, 400 MHz) δ[ppm]: -0.109-0.216 (m), 0.499-0.537 (t), 0.559-0.612 (m), 1.245 (br s), 1.570-1.630 (m), 2.256-2.295 (t), 3.182-3.221 (t), 3.264-3.301 (t),3.556 (br s),3.575 (br s)
[0661] (Synthesis Example 33) CH 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 Compound (33) CH 3 [Si(CH 3 ) 2 O] 48 Si(CH 3 ) 2 (CH 2 ) 22 CON [(CH 2 ) 3 Si(OCH 3 ) 3 ]2 The average value of n is 48.
[0662] <Preparation of Surface Treatment Agent> Surface treatment agents were prepared as shown in Table 1.
[0663] <Na-Containing Intermediate Layer Forming Material> 2.2 g of sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 24 g of distilled water to obtain an 8.4 mass% sodium hydroxide aqueous solution. 24 g of this 8.4 mass% sodium hydroxide aqueous solution was mixed with 20 g of MS gel (MSGELD-100-60A (manufactured by AGC Si-Tech Co., Ltd.)), and the sodium hydroxide aqueous solution was absorbed into the MS gel. The MS gel that had absorbed the sodium hydroxide aqueous solution was dried at 25°C for 8 hours, then molded using a tablet molding machine (4 MPa for 1 minute) and baked at 1,000°C for 1 hour to obtain molded body 1 (pellet).
[0664] (SiO 2 Intermediate layer) The surface treatment agent prepared above was vacuum-deposited onto chemically strengthened glass (Corning Gorilla Glass, thickness 0.7 mm). Specifically, 0.1 g of the surface treatment agent was loaded into a molybdenum boat in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was pressurized to a pressure of 3.0 × 10 -3 The chamber was evacuated to a pressure of 100 Pa or less. A silicon dioxide film having a thickness of 5 nm was then formed, and the boat was then heated by resistance heating to form a surface treatment layer (i.e., a water-repellent layer). A heat treatment was then performed in an oven at 150°C for 2 hours, yielding a surface treatment layer.
[0665] (Na-containing SiO 2 Intermediate layer) The surface treatment agent prepared above was vacuum-deposited onto chemically strengthened glass (Corning Gorilla Glass, thickness 0.7 mm). Specifically, 0.1 g of the surface treatment agent was loaded into a molybdenum boat in a vacuum deposition apparatus, and the inside of the vacuum deposition apparatus was pressurized to a pressure of 3.0 × 10 -3 The chamber was evacuated to a pressure of 100 Pa or less. Subsequently, a silicon dioxide film containing Na was formed to a thickness of 5 nm by electron beam deposition using the molded body 1, and the boat was subsequently heated by resistance heating to form a surface treatment layer (i.e., a water-repellent layer). Subsequently, a heat treatment was performed in an oven at 150°C for 2 hours, thereby obtaining a surface treatment layer.
[0666] <Evaluation> [Measurement of water contact angle after film formation] The surface of the substrate with the surface treatment layer prepared by the above method was thoroughly wiped with Kimwipe S-200 (product name, manufactured by Nippon Paper Crecia) soaked in ethanol, and then the static contact angle of water was measured.
[0667] (Contact Angle Measurement) The contact angle was measured using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 25°C. Specifically, the substrate having the surface treatment layer to be measured was placed horizontally, 2 μL of water was dropped onto the surface from a microsyringe, and a still image was taken with a video microscope 1 second after the drop to measure the static contact angle. The static contact angle was measured at five different points on the surface treatment layer of the substrate, and the average value was calculated.
[0668] The criteria for the water contact angle measurement are as follows: 103° or more: ○ (good) Less than 103°: × (bad)
[0669] [Abrasion Resistance Evaluation] (Abrasion Method) The following friction element was brought into contact with the formed surface treatment layer, a load of 5 N was applied thereon, and the friction element was moved back and forth at a speed of 40 mm / sec while the load was applied. The static contact angle (°) of water was measured after 50 friction cycles. The method for measuring the contact angle was as described above.
[0670] Friction element The surface of the silicone rubber processed product shown below was covered with cotton soaked in artificial sweat of the composition shown below and used as a friction element. Composition of artificial sweat: Anhydrous disodium hydrogen phosphate: 2 g Sodium chloride: 20 g 85% lactic acid: 2 g Histidine hydrochloride: 5 g Distilled water: 1 kg Silicone rubber processed product: A silicone rubber stopper SR-51 manufactured by Tigers Polymer was processed into a cylindrical shape with a diameter of 1 cm and a thickness of 1 cm.
[0671] (Judgment criteria for water contact angle after abrasion test) 90° or more: ◎ (Excellent) 75° or more and less than 90°: ○ (Good) 60° or more and less than 75°: △ (Fair) Less than 60°: × (Bad)
[0672] [Measurement of Surface Composition] (XPS Measurement Method) The surface composition of the surface treatment layer applied to the substrate was measured using an X-ray photoelectron spectrometer (XPS, PHI5000VersaProbeII manufactured by ULVAC-PHI, Inc.). The measurement conditions for XPS analysis were as follows: X-ray source: monochromated AlKα radiation (25W) Photoelectron detection area: 1400 μm × 300 μm Photoelectron detection angle: 45 degrees Pass energy: 23.5 eV Measured elements: carbon (C1s) 278-298 eV, nitrogen (N1s) 390-410 eV, oxygen (O1s) 523-543 eV, fluorine (F1s) 680-698 eV, silicon (Si2p) 94-114 eV
[0673] The nitrogen concentration (atomic %) of the surface treatment layer was calculated from the peak shape and intensity obtained in each region.
[0674] The evaluation criteria for the nitrogen concentration of the surface treatment layer were as follows: (Evaluation criteria for nitrogen concentration) 1.0 atomic % or more: ○ (Good) 0.5 atomic % or more and less than 1.0 atomic %: △ (Acceptable) Less than 0.5 atomic %: × (Unacceptable)
[0675] [Evaluation of Slipperiness] To evaluate the feel, the dynamic friction coefficient was measured using a Labthink FPT-F1. After forming the surface treatment layer, the excess on the surface was wiped off with ethanol, and then the dynamic friction coefficient was measured. The measurement conditions are as follows: Friction material: urethane sheet (thickness 2 mm) Contact surface: 2 cm Load: 200 gf Friction speed: 5 mm / sec
[0676] (Evaluation criteria) Less than 0.6: ○ (good) 0.6 or more: × (bad)
[0677] The results of the measurement of the N concentration, the water contact angle after film formation, and the water contact angle after the abrasion test are shown in Table 2. It was confirmed that the fluorine concentration was less than 0.01 atomic % in all examples.
[0678]
[0679] The measurement results of the N concentration, and the evaluation results of the water contact angle and slipperiness after film formation are shown in Table 3. It was confirmed that the fluorine concentration was less than 0.01 atomic % in all examples.
[0680]
[0681] The surface treatment agent of the present disclosure can be suitably used in a wide variety of applications.
Claims
1. A laminate comprising a substrate and a water-repellent layer located on the substrate, wherein the nitrogen concentration on the surface of the water-repellent layer is 0.01 atomic % or more and 10 atomic % or less, and the fluorine concentration on the surface of the water-repellent layer is less than 5 atomic %.
2. The laminate according to claim 1, wherein the silicon concentration on the surface of the water-repellent layer is 0.1 atomic % or more and 50 atomic % or less.
3. The laminate according to claim 2, wherein the silicon concentration on the surface of the water-repellent layer is 15 atomic % or more and 25 atomic % or less.
4. The water-repellent layer comprises a compound represented by the following formula (1): [In the formula: R S is a monovalent group containing one or more Si atoms to which no hydroxyl group or hydrolyzable group is directly bonded, and X 1 is a divalent to decavalent group, R Si is a monovalent group containing a Si atom to which a hydroxyl group or a hydrolyzable group is bonded, and α is an integer of 1 to 9.
5. R S is R 1 - (R S1 ) s1 -(SiR 2 2 ) s2 - (R Ar ) s3 -, and R 1 represents a hydrocarbon group, the following group A or group B, and the groups A and B are each a group represented by the following formula: [In the formula: R 51 are each independently R 53 -(SiR 53 2 -R 61 ) ma -, and R 61 are each independently a single bond, an oxygen atom, or C 1-6 is an alkylene group, R 53 are each independently a hydrocarbon group or R 51’ and R 51’ is R 51 Each ma is independently an integer of 1 to 5, provided that R 51 Medium, R 51’ The number of is 20 or less, and R 52 are each independently a hydrocarbon group, na is an integer of 1 to 3, and R 54 are each independently a hydrocarbon group, nb is an integer of 1 to 5, and z is 0 or 1. S1 are each independently a single bond or a group represented by the following formula: [In the formula: R 3 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 4 are each independently C 1-12 alkylene group, -R 6 -O-R 6 -, -R 8 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 7 -R 8 -, -R 8 -R 7 -R 9 -R 6 -R 9 -R 7 -R 8 - or -R 9 -R 6 -R 9 -R 7 -R 9 -R 6 -R 9 - and R 6 are each independently C 1-6 is an alkylene group, R 7 are each independently an optionally substituted arylene group, R 8 are each independently a single bond or C 1-6 is an alkylene group, R 9 are each independently a single bond or an oxygen atom, 5 are each independently a hydrocarbon group, x is an integer of 0 to 500, y is an integer of 0 to 500, z is an integer of 0 to 500, x + y + z is 1 or more, and the order of occurrence of the repeating units enclosed in parentheses with x, y, or z is arbitrary in the formula. 2 The laminate according to claim 4 , wherein each independently represents a hydrocarbon group; and s1, s2, and s3 are 0 or 1.
6. The laminate according to claim 4, wherein the compound represented by formula (1) is any one of the compounds shown below. CH 3 -[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 Si-O-[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 CH[CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -N[CH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [(CH 3 ) 3 SiO)] 2 (CH 3 )Si-(CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [(CH 3 ) 3 SiO)] 3 H. 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 3 [CH 3 CH 2 CH 2 CH 2 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 [CH 3 -[(Si(CH 3 ) 2 O)] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 2 -C[CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 ] 2 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -OC(=O)NHCH 2 CH 2 OC(=O)CH(CH 3 )CH 2 H. 3 ) 3 [CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 -(CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 H. 3 ) 3 [CH 3 -[Si(CH 3 ) 2 O] n1 H 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 3 C-CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 [CH 3 CH 2 CH 2 CH 2 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] [CH 3 -[(Si(CH 3 ) 2 O) ] n1 Si(CH 3 ) 2 - (CH 2 ) H1 -O-(CH 2 ) H2 -] 2 C(CH 2 CH 3 ) [CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (wherein, each n1 independently represents an integer of 0 to 100, and each H1 and H2 independently represents an integer of 1 to 50.) 7. The laminate according to claim 6, wherein n1 is independently 0 or 1, H1 is independently an integer from 8 to 40, and H2 is independently an integer from 1 to 10.
8. The laminate according to claim 6, wherein n1 is independently an integer of 5 to 100, H1 is independently an integer of 8 to 40, and H2 is independently an integer of 1 to 10.
9. The laminate according to claim 4, wherein the compound represented by formula (1) is any one of the compounds shown below. CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 OCH 2 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 40 to 70) CH 3 CH 2 CH 2 CH 2 Si(CH 3 ) 2 -(OSi(CH 3 ) 2 ) n - (CH 2 ) 3 -OCH 2 -CONH-CH 2 C{CH 2 CH 2 CH 2 Si(OCH 3 ) 3 「 3 (n is an integer from 40 to 70) CH 3 Si(CH 3 ) 2 O(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 10 CONHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 10 to 30) (CH 3 ) 3 Si-(OSi(CH 3 ) 2 ) n -(CH 2 ) 10 -CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 2 (n is an integer from 10 to 30) [(CH 3 ) 3 SiO] 2 CH 3 SiO(Si(CH 3 ) 2 O) n Si(CH 3 ) 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CONHCH 2 CH[CH 2 CH 2 CH 3 Si(OCH 3 ) 2 (n is an integer from 20 to 40) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CONH-CH 2 CH[CH 2 CH 2 CH 2 CH 3 Si(OCH 3 ) 3 2 (n is an integer from 40 to 70) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 [[ID=??]]CH 2 CH 2 -O-CH 2 -C(CH 2 CH 3 )[CH 2 OC(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 2 (n is an integer from 40 to 80) CH 3 CH 2 CH 2 CH 2 -[Si(CH 3 ) 2 O] n Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -O-CH 2 CH 2 O-C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (n is an integer from 40 to 80) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 2 (n is an integer from 20 to 40) CHIt should be noted that there is an unclear "??" in the original text which is maintained as is in the translation. Also, the translation is done strictly following the rules while keeping the original tags and line breaks. If there are any specific requirements for further improvement or correction, please let me know. 3 (Si(CH 3 ) 2 O) n Si(CH 3 ) 2 (CH 2 ) 22 CON[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (n is an integer from 20 to 50) CH 3 [Si(CH 3 ) 2 O] n Si(CH 3 ) 2 (CH 2 ) 22 CON[(CH 2 ) 3 Si(OCH 3 ) 3 ] 2 (n is an integer from 40 to 60) 10. The water-repellent layer contains a compound represented by formula (1) and a compound represented by formula (2): [In the formula: R A is a carbon chain containing at least one ethereal oxygen atom, and X A is a single bond or a divalent to decavalent group, R Si is R in the compound represented by formula (1). Si wherein each α1 is independently an integer of 1 to 9, and each β1 is independently an integer of 1 to 9.
11. The laminate according to any one of claims 1 to 10, wherein the water-repellent layer has a water contact angle of 103° or more.
12. An article comprising the laminate of any one of claims 1 to 11.
13. The article of claim 12, further comprising an intermediate layer between the substrate and the water-repellent layer, the intermediate layer comprising silicon oxide.
14. The article of claim 13, wherein the intermediate layer comprises alkali metal atoms.
15. The article of claim 14, wherein at least a portion of said alkali metal atoms are sodium atoms.
16. The article according to any one of claims 12 to 15, which is an optical element.
17. The article of any one of claims 12 to 16, which is a display.
18. A compound represented by the following formula: (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 CH [CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)N[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 2 (CH 3 ) 3 SiO—Si(CH 3 ) 2 O—Si(CH 3 ) 2 - (CH 2 ) H1 -C(=O)NHCH 2 C[CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ] 3 (In the formula, H1 is an integer from 11 to 50.)
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