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JP-2026076121-A - Polyorganosiloxane

JP2026076121AJP 2026076121 AJP2026076121 AJP 2026076121AJP-2026076121-A

Abstract

[Problem] To provide a polyorganosiloxane contained in a mold release agent that provides better release from resins and the like. [Solution] A polyorganosiloxane represented by formula (11) or formula (12). Each reference numeral is as described in the specification. [Selection Diagram] None

Inventors

  • 加藤 愛理
  • 石井 大貴
  • 中前 靖史
  • 植畑 秀一

Assignees

  • ダイキン工業株式会社

Dates

Publication Date
20260511
Application Date
20251010
Priority Date
20241023

Claims (20)

  1. Formula (11) below: [In the formula: Each R1 is independently a hydrogen atom or a monovalent organic group; Each of R2 is independently a hydrogen atom or a monovalent organic group; Each of R4 is independently a hydrogen atom or a monovalent organic group; Each of R5 is independently a hydrogen atom or a monovalent organic group; Each of R6 is independently either a hydrogen atom or a monovalent organic group; Each R Si is independently -(O-SiR 7 2 ) m -OSiR 1 2 R 2 ; Each R7 is independently a monovalent organic group or RSi ' ; R Si' is synonymous with R Si ; m is a non-negative integer; However, at least one of R1 , R2 , R4 , R5 , R6 , and R7 is given by formula (2): It is a base represented by; X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2; a is a non-negative integer; b is a non-negative integer; c is a non-negative integer; The sum of a, b, and c is an integer greater than or equal to 2; The order in which the repeating units labeled a, b, and c are enclosed in parentheses is arbitrary within the expression. Or, the following formula (12): [In the formula: Each of R4 is independently a hydrogen atom or a monovalent organic group; Each of R5 is independently a hydrogen atom or a monovalent organic group; However, at least one of R4 and R5 is a group represented by formula (2); d is an integer greater than or equal to 1. A polyorganosiloxane represented by [a specific symbol/method].
  2. The polyorganosiloxane according to claim 1, wherein a is an integer between 10 and 1,000.
  3. In equation (11), At least one of R1 , R2 , R4 , R5 , R6 , and R7 is given by equation (2): [In the formula: X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2. It is a base represented by, Among the other groups, R1 , R2 , R4 , R5 , and R6 are each independently monovalent organic groups that do not contain a hydrogen atom or a group represented by formula (2). Each R7 is independently a monovalent organic group that does not contain RSi ' or the group represented by formula (2). The monovalent organic group that does not contain the group represented by formula (2) above is a C1-20 alkyl group, a group having an aryl group, a group having a carbon-carbon double bond, a group having a phenyl group, SiR113 -C1-20 alkylene group-, or Rf-Z- C1-20 alkylene group-. Each R11 is independently a C1-20 alkyl group. Rf is a C1-16 alkyl group having at least one fluorine atom. Z is O, C(=O) NR9 , NR9 C(=O), C(=O)O, OC(=O), NR9 C(=O)O, OC(=O) NR9 , or NR9 C(=O) NR9 . R9 is independently a hydrogen atom, a phenyl group, or a C1-6 alkyl group. The polyorganosiloxane according to claim 1.
  4. In equation (11), At least one of R1 and R2 is given by equation (2): [In the formula: X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2. The base represented by The polyorganosiloxane according to claim 1.
  5. The polyorganosiloxane of formula (11) is given by formula (13): It is represented as, In formula (13): R1 , R2 , R6 , and RSi are all equivalent to those described above; Each of R 41 is independently a hydrogen atom or a C1-20 alkyl group; Each of R 51 is independently a hydrogen atom or a C1-20 alkyl group; R 42 is independently a group having an aryl group, a group having a carbon-carbon double bond, a SiR 11 3 -C 1-20 alkylene group-, or a Rf-Z-C 1-20 alkylene group-; Each of the R11 groups is independently a C1-20 alkyl group; Rf is a C1-16 alkyl group having at least one fluorine atom; Z is O, C(=O) NR9 , NR9 C(=O), C(=O)O, OC(=O), NR9 C(=O)O, OC(=O) NR9 , or NR9 C(=O) NR9 ; R9 is independently a hydrogen atom, a phenyl group, or a C1-6 alkyl group; R 52 is independently a hydrogen atom, a C1-20 alkyl group, a group having an aryl group, a group having a carbon-carbon double bond, a group having a phenyl group, a SiR 11 3 - C1-20 alkylene group-, or a Rf-Z- C1-20 alkylene group-; R 43 is expressed independently in equation (2): It is a base represented by; X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2; Each of R 53 is independently a hydrogen atom, a C1-20 alkyl group, or a group represented by formula (2); a1 is a non-negative integer; a2 is a non-negative integer; a3 is an integer greater than or equal to 1; However, the sum of a1, a2, and a3 is a; a is 10 or greater; b and c are equivalent to the above; The order in which the repeating units a1, a2, a3, b, and c are enclosed in parentheses is arbitrary within the formula. The polyorganosiloxane according to claim 1.
  6. In equation (12), Of R4 and R5 , at least one is a group represented by formula (2), and the other groups are, independently, a hydrogen atom, a C1-20 alkyl group, a group having an aryl group, a group having a carbon-carbon double bond, a group having a phenyl group, SiR113 - C1-20 alkylene group-, or Rf- Z-C1-20 alkylene group-. Each R11 is independently a C1-20 alkyl group. Rf is a C1-16 alkyl group having at least one fluorine atom. Z is O, C(=O) NR9 , NR9 C(=O), C(=O)O, OC(=O), NR9 C(=O)O, OC(=O) NR9 , or NR9 C(=O) NR9 . R9 is independently a hydrogen atom, a phenyl group, or a C1-6 alkyl group. The polyorganosiloxane according to claim 1.
  7. The polyorganosiloxane according to claim 1, wherein d is an integer between 10 and 1,000.
  8. Each Y1 is independently represented as -(R 91 ) p1 -(X a ) q1 -R 92 -, R91 is a single bond, -( CH2 ) p2- or o-, m- or p-phenylene group, p2 is an integer between 1 and 20. X a represents -(X b ) q2- , Each X b independently represents a group selected from the group consisting of -O-, -S-, o-, m- or p-phenylene groups, -(OR 95 ) p4- , -C(O)O-, -Si(R 93 ) 2- , -(Si(R 93 ) 2O ) p5 -Si(R 93 ) 2- , -CONR 94- , -O-CONR 94- , -NR 94- , and -(CH 2 ) p6- . R 93 independently represents a phenyl group, a C1-6 alkyl group, or a C1-6 alkoxy group. R94 independently represents a hydrogen atom, a phenyl group, or a C1-6 alkyl group. Each of R95 is independently a C1-6 alkylene group. p4 are each an independent integer between 1 and 5. p5 are each an independent integer between 1 and 100. p6 are each an integer between 1 and 20, independently of each other. q2 is an integer between 1 and 10, and p1 is 0 or 1. q1 is either 0 or 1. The order of existence of each repeating unit, which is denoted as p1 or q1 and enclosed in parentheses, is arbitrary. Here, at least one of p1 and q1 is 1, R 92 represents a single bond, a -( CH2 ) p3- or o-, m- or p-phenylene group, p3 is an integer between 1 and 20. The polyorganosiloxane according to claim 1.
  9. The polyorganosiloxane according to claim 1, wherein Y1 does not contain a group represented by -NHC(=O)-.
  10. Y1 is a polyorganosiloxane according to claim 1, wherein Y1 does not contain an ester, secondary amine, amide, ether, thioether, or thioester.
  11. The polyorganosiloxane according to claim 1, wherein Y1 does not contain a group represented by -CH2 -N=CH-.
  12. The polyorganosiloxane according to claim 1, wherein Y1 is a C1-20 alkylene group.
  13. The polyorganosiloxane according to claim 1, wherein n1 is 3 or greater.
  14. A polyorganosiloxane according to claim 1, which does not contain fluorine atoms.
  15. The polyorganosiloxane according to claim 1, represented by any of the following: [In the formula, n is 34.] [In the formula, n = 34.] [In the equation, x = 27, y = 2, and z = 1.]
  16. A composition comprising the polyorganosiloxane described in claim 1.
  17. The composition according to claim 16, further comprising a solvent.
  18. The composition according to claim 17, wherein the solvent is an organic solvent.
  19. The composition according to claim 17, wherein the solvent is an aqueous medium.
  20. Furthermore, the composition according to claim 16, comprising an emulsifier.

Description

This disclosure relates to polyorganosiloxanes. During the molding of synthetic resins, rubber, and other materials, a release agent is applied to the inner surface of the mold (die) beforehand to improve the release properties between the molded synthetic resin and the mold (for example, Patent Document 1). Japanese Patent Publication No. 2011-121367 As used herein, "monovalent organic group" means a monovalent group containing carbon. A monovalent organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A derivative of a hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at the terminal or in the molecular chain of a hydrocarbon group. In this specification, "hydrocarbon group" means a group containing carbon and hydrogen, from which one hydrogen atom has been removed from the molecule. Such hydrocarbon groups are not particularly limited, but may include hydrocarbon groups having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures. In the use herein, the substituents of the "hydrocarbon group" are not particularly limited, but include, for example, one or more groups selected from C1-6 alkyl groups, C2-6 alkenyl groups, C2-6 alkynyl groups, C3-10 cycloalkyl groups, C3-10 unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C6-10 aryl groups, and 5-10 membered heteroaryl groups, which may be substituted with one or more halogen atoms. In this specification, alkyl groups and phenyl groups may be unsubstituted or substituted. Substitutions of such groups are not particularly limited, but include, for example, one or more groups selected from halogen atoms, C1-6 alkyl groups, C2-6 alkenyl groups, and C2-6 alkynyl groups. [Polyorganosiloxane] The polyorganosiloxanes of this disclosure are given by the following formula (11): Or, the following formula (12): It is represented as follows. In equation (11), Each R1 is independently a hydrogen atom or a monovalent organic group; Each R2 is independently a hydrogen atom or a monovalent organic group; Each of R4 is independently either a hydrogen atom or a monovalent organic group; Each of R5 is independently a hydrogen atom or a monovalent organic group; Each of R6 is independently either a hydrogen atom or a monovalent organic group; Each R Si is independently -(O-SiR 7 2 ) m -OSiR 1 2 R 2 ; Each R7 is independently a monovalent organic group or RSi ' ; R Si' is synonymous with R Si ; m is a non-negative integer; However, at least one of R1 , R2 , R4 , R5 , R6 , and R7 is given by formula (2): It is a base represented by; X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2; a is a non-negative integer; b is a non-negative integer; c is a non-negative integer; The sum of a, b, and c is an integer greater than or equal to 2; The order in which the repeating units labeled a, b, and c are enclosed in parentheses is arbitrary within the formula. In equation (12), Each of R4 is independently either a hydrogen atom or a monovalent organic group; Each of R5 is independently a hydrogen atom or a monovalent organic group; However, at least one of R4 and R5 is given by equation (2): It is a base represented by; X1 is a hydrogen atom or a protecting group; Y1 is a single bond or a divalent to decavalent organic group; n1 is an integer greater than or equal to 2; d is an integer greater than or equal to 1. The above compound can be used by providing it on a substrate to form a surface treatment layer (cured layer), and then providing a resin such as a carbon fiber composite material on the surface treatment layer. When X1 is a hydrogen atom, it is thought that the oxygen atom of the group represented by formula (2) interacts with the surface portion of the substrate (e.g., metal). On the other hand, since the -Si-O- group of formula (11) or formula (12) is water-repellent, the bonding strength with the resin is not very good. Thus, the above compound can function as a release agent that suppresses the bonding between the substrate and the resin. Furthermore, due to its good adhesion to the substrate, it can function as a release agent that adheres to the substrate and suppresses the bonding between the substrate and the resin. Furthermore, if X1 is a protecting group, since this protecting group protects hydroxyl groups, the protective group is removed by some reaction before the surface treatment layer is formed. (Formula (11)) a is an integer greater than or equal to 0, preferably an integer between 0 and 1,000, more