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CN-121991588-A - Surface treatment agent, article, and film forming method

CN121991588ACN 121991588 ACN121991588 ACN 121991588ACN-121991588-A

Abstract

The present invention provides a non-fluorine-based (i.e., having no fluorine atom in the molecule) surface treatment agent capable of forming a cured film excellent in water repellency, slidability, dirt erasure and abrasion resistance even on various substrates, particularly on substrates having at least a resin surface, an article surface-treated with the surface treatment agent, and a film forming method for applying the surface treatment agent to a substrate. A non-fluorine-containing surface treatment agent comprising (A) a non-fluorine-containing hydrocarbon terminal group-containing compound and/or a partial reaction condensate thereof, wherein the non-fluorine-containing compound has at least one linear, branched or cyclic monovalent hydrocarbon group having 4 to 32 carbon atoms at the terminal of the molecular chain and at least one reactive silyl group at the terminal of the other molecular chain, and (B) a compound having a functional group and a silanol group or a hydrolyzable silyl group at the terminal of the molecular chain or a compound having a silanol group or a hydrolyzable silyl group at both terminals of the molecular chain, wherein the total of the components (A) and (B) is 1 to 50 mass%.

Inventors

  • Takasuke

Assignees

  • 信越化学工业株式会社

Dates

Publication Date
20260508
Application Date
20251104
Priority Date
20241105

Claims (18)

  1. 1. A non-fluorine-based surface treatment agent comprising: (A) A non-fluorine-containing hydrocarbon terminal group-containing compound having at least one straight, branched or cyclic monovalent hydrocarbon group having 4 to 32 carbon atoms at the molecular chain terminal and at least one reactive silyl group at the other molecular chain terminal, and/or a partially reactive condensate thereof, and (B) The total of the component (A) and the component (B) is 1 to 50 mass% of a compound having a functional group and a silanol group or a hydrolyzable silyl group at the molecular chain end or a compound having a silanol group or a hydrolyzable silyl group at both molecular chain ends.
  2. 2. The surface treatment agent according to claim 1, wherein the monovalent hydrocarbon group in the hydrocarbon terminal group-containing compound of the component (a) is a group selected from an alkyl group having 6 to 32 carbon atoms and an aryl group having 6 to 32 carbon atoms.
  3. 3. The surface treatment agent according to claim 1, wherein the hydrocarbon terminal group-containing compound of the component (a) has 2 or more monovalent hydrocarbon groups and has 3 or more linking groups that combine the 2 or more monovalent hydrocarbon groups with at least one reactive silyl group.
  4. 4. The surface treatment agent according to claim 1, wherein the hydrocarbon-terminal-group-containing compound of the component (a) is a hydrocarbon-terminal-group-containing compound represented by the following general formula (1): [ chemical 1] Wherein R 1 is independently a monovalent hydrocarbon group of 4 to 32 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, may be linear, branched or cyclic or a combination thereof, R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group or a monovalent hydrocarbon group of 1 or 2 carbon atoms, U is a carbon atom, a silicon atom, a nitrogen atom or an organic group of 3 or 4 carbon atoms, V is independently a single bond or a hydrocarbon group of 2 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom or an organic group of 3 to 8 carbon atoms, Y is independently a hydrocarbon group of 2 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, A is independently a group represented by the following general formula (2) or the following general formula (3), k1 is an integer of 1 to 3, k2 is 0, k3 is an integer of 1 to 3, k3 is an integer of 1 to k3 is 1 to k 4, [ Chemical 2] Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, [ Chemical 3] Wherein n ́ ́ is a number of 0 to 3, and n ́ is (3-n ́ ́)/2.
  5. 5. The surface treatment agent according to claim 4, wherein in the formula (1), k1 is 2 or 3.
  6. 6. The surface treatment agent according to claim 4, wherein in the formula (1), R 1 is any one group represented by the following formula, [ Chemical 4] Wherein R A is independently a monovalent hydrocarbon group of 4 to 32 carbon atoms which may be linear, branched or cyclic or a combination thereof, Q is independently a 2-valent group selected from the group consisting of an oxygen atom, a sulfur atom, a 2-valent cyclic hydrocarbon group of 6 to 8 carbon atoms, a diorganosilylene group, a silylene structure or a silylene structure, and a linear or 3 to 10 branched or cyclic 2-valent organopolysiloxane residue of 2 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amido group, a carbamate group, a urea group, a 2-valent nitrogen-containing heterocyclic group, Q ́ is independently a group of 3 valency selected from a nitrogen atom, a cyclic hydrocarbon group of 3 valency of 6 to 8, a branched or cyclic 3 valency organopolysiloxane residue of 3 to 10 silicon atoms, an amido group of 3 valency, a nitrogen-containing heterocyclic group of 3 valency, Q ́ ́ is independently a group of 4 valency selected from a cyclic hydrocarbon group of 6 to 8 carbon atoms, a branched or cyclic 4 valency organopolysiloxane residue of 3 to 10 silicon atoms, a linear or branched or cyclic 2 valency of 1 to 29 carbon atoms, R B is independently a single bond or a linear, branched or cyclic hydrocarbon group of 4 valency, R C is independently R A or a hydrogen atom, and p is an integer of 0 to 10, however, the total number of carbon atoms in each structure is 32 or less.
  7. 7. The surface treatment agent according to claim 4, wherein in the formula (1), R 1 is independently a monovalent hydrocarbon group having 11 to 32 carbon atoms which may contain at least one kind selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, and which may be linear, branched or cyclic or a combination thereof.
  8. 8. The surface treatment agent according to claim 4, wherein in the formula (1), Y is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, an alkylene group having 1 to 10 carbon atoms which contains an arylene group having 6 to 8 carbon atoms, a group having 1 to 8 carbon atoms of which solution is a 2-valent group bonded by a diorganosilylene group, a silylene structure or a nitrogen-containing heterocyclic group, and a group having 2-valent group to which an alkylene group having 1 to 10 carbon atoms is bonded to a bonding end of a linear or 3 to 10 silicon atom-containing organopolysiloxane residue having 2 to 10 silicon atoms.
  9. 9. The surface treatment agent according to claim 4, wherein in the formula (1), Z is a single bond, or a 3-to 8-valent cyclic hydrocarbon group selected from a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, a 3-to 4-valent cyclic hydrocarbon group having 6 to 8 carbon atoms, a 3-valent group represented by-SiR 3 = 3, a 3-valent group represented by-CR 4 = 3, a 2-to 10-valent linear or 3-to 10-valent branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, a 3-valent amido group, a 3-valent carbamate group, a 3-to 4-valent urea group, and a 3-to 8-valent nitrogen-containing heterocyclic group, wherein R 3 is a hydroxyl group, a 1-to 3-valent alkyl group, or a 1-to 3-valent alkoxy group, and R 4 is a hydrogen atom, a hydroxyl group, or a 1-to 3-valent alkyl group.
  10. 10. The surface treatment agent according to claim 4, wherein in the formula (1), U is a 3-or 4-valent group selected from a carbon atom, a silicon atom, a nitrogen atom, a 3-or 4-valent cyclic hydrocarbon group having 6 to 8 carbon atoms, a branched or cyclic 3-or 4-valent organopolysiloxane residue having 3 to 10 silicon atoms, a 3-valent amido group, a 3-valent urethane group, a 3-or 4-valent urea group, and a 3-or 4-valent nitrogen-containing heterocyclic ring-containing group having 2 to 10 silicon atoms.
  11. 11. The surface treatment agent according to claim 1, wherein the functional group of the compound having a functional group and a silanol group or a hydrolyzable silyl group at a molecular chain end of the component (B) is an amino group, an epoxy group, a thiol group, an acryl group or a methacryl group.
  12. 12. The surface treatment agent according to claim 1, wherein the compound having a functional group and a silanol group or a hydrolyzable silyl group at the molecular chain end of the component (B) or the compound having a silanol group or a hydrolyzable silyl group at both molecular chain ends is a silane compound represented by the following general formula (4), [ Chemical 5] Wherein B is any one group represented by the following formulas (5 a) to (5 f), D is independently an alkylene group having 1 to 10 carbon atoms, E is independently-O-, -NH-, -S-, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, g is an integer of 0 to 3, but in the case where B is a group represented by the formula (5 f), g is an integer of 1 to 3, n is an integer of 1 to 3, [ Chemical 6] Wherein R' is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ́ ́ is independently an alkyl group having 1 to 3 carbon atoms, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer of 1 to 3.
  13. 13. An article surface-treated with the surface treating agent according to any one of claims 1 to 12.
  14. 14. The article of claim 13, wherein at least a surface of the article is a resin.
  15. 15. A method for forming a coating film, which comprises applying a surface treatment agent comprising a non-fluorine-containing surface treatment agent comprising (A) a non-fluorine-containing hydrocarbon terminal group-containing compound having at least one linear, branched or cyclic monovalent hydrocarbon group having 4 to 32 carbon atoms at the molecular chain terminal and having at least one reactive silyl group at the other molecular chain terminal and/or a partially reactive condensate thereof, and (B) a compound having a functional group and a silanol group or a hydrolyzable silyl group at the molecular chain terminal or a compound having a silanol group or a hydrolyzable silyl group at both molecular chain terminals, wherein the total of the components (A) and (B) is 1 to 50% by mass.
  16. 16. The method according to claim 15, wherein the monovalent hydrocarbon group in the hydrocarbon terminal group-containing compound of the component (A) is a group selected from the group consisting of an alkyl group having 6 to 32 carbon atoms and an aryl group having 6 to 32 carbon atoms.
  17. 17. The method for forming a coating film according to claim 15, wherein the hydrocarbon terminal group-containing compound of the component (A) has 2 or more monovalent hydrocarbon groups and has 3 or more linking groups for binding the 2 or more monovalent hydrocarbon groups to at least one reactive silyl group.
  18. 18. The method for forming a coating film according to any one of claims 15 to 17, wherein the hydrocarbon end group-containing compound of component (a) is a hydrocarbon end group-containing compound represented by the following general formula (1): [ chemical 7] Wherein R 1 is independently a monovalent hydrocarbon group of 4 to 32 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom, may be linear, branched or cyclic or a combination thereof, R 2 is a hydrogen atom, a halogen atom, a hydroxyl group, a siloxy group, an amino group, a thiol group or a monovalent hydrocarbon group of 1 or 2 carbon atoms, U is a carbon atom, a silicon atom, a nitrogen atom or an organic group of 3 or 4 carbon atoms, V is independently a single bond or a hydrocarbon group of 2 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom or an organic group of 3 to 8 carbon atoms, Y is independently a hydrocarbon group of 2 carbon atoms which may contain at least one member selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, A is independently a group represented by the following general formula (2) or the following general formula (3), k1 is an integer of 1 to 3, k2 is 0, k3 is an integer of 1 to 3, k3 is an integer of 1 to k3 is 1 to k 4, [ Chemical 8] Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, n is an integer of 1 to 3, [ Chemical 9] Wherein n ́ ́ is a number of 0 to 3, and n ́ is (3-n ́ ́)/2.

Description

Surface treatment agent, article, and film forming method Technical Field The present invention relates to a surface treatment agent containing a hydrocarbon terminal group-containing compound, and more particularly, to a surface treatment agent which forms a coating film having excellent water repellency, slidability, scale erasure property, abrasion resistance, and further excellent adhesion to various substrates, particularly, substrates having at least a resin surface, an article surface-treated with the surface treatment agent, and a method for forming a coating film by applying the surface treatment agent to a substrate. Background In recent years, touch panels of displays such as smart phones and in-vehicle displays have been accelerated. However, the touch panel is in a state where the screen is completely exposed, and there are many opportunities for direct contact of fingers, cheeks, etc., and dirt such as sebum is likely to adhere to the touch panel. Therefore, in order to improve the appearance and visibility, the demands for techniques for making it difficult to attach fingerprints to the surface of a display and techniques for making dirt easily drop have been increasing year by year, and it has been desired to develop a material capable of satisfying these demands. In particular, fingerprint dirt is easily attached to the surface of the touch panel display, and thus it is desirable to provide a water-repellent and oil-repellent layer. However, the conventional water-repellent oil-repellent layer has problems such as high water repellency and oil repellency, excellent dirt erasure, insufficient abrasion resistance, and significant fingerprint adhesion. In general, a compound containing a fluoropolyether group has water-and oil-repellency, chemical resistance, lubricity, mold release property, stain resistance, and the like because of its very small surface free energy. By utilizing the properties, it is widely used in industry as a water-repellent, oil-repellent and stain-proofing agent for paper, fiber and the like, a lubricant for magnetic recording media, an oil-repellent agent for precision equipment, a mold release agent, a cosmetic, a protective film and the like. However, the properties of the coating film mean non-adhesion to other substrates and non-adhesion, and even if the coating film can be applied to the substrate surface, it is difficult to adhere the coating film. As a substance for binding the surface of a substrate such as glass or cloth to an organic compound, a silane coupling agent is known, and is widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organofunctional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group forms a film by self-condensation reaction due to moisture in the air or the like. The film is chemically/physically bonded to the surface of glass, metal, or the like by the hydrolyzable silyl group, and thus becomes a durable and strong film. Accordingly, there has been disclosed a composition which is capable of easily adhering to the surface of a substrate by using a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced into a fluoropolyether group-containing compound and which can form a coating film having water/oil repellency, chemical resistance, lubricity, mold release property, stain resistance and the like on the surface of the substrate (patent documents 1 to 6: japanese patent application laid-open No. 2008-534696, japanese patent application laid-open No. 2008-537557, japanese patent application laid-open No. 2012-072272, japanese patent application laid-open No. 2012-157856, japanese patent application laid-open No. 2013-136833, japanese patent application laid-open No. 2015-199906). However, fluorine-containing compounds such as fluoropolyether group-containing compounds have a characteristic of being hardly decomposed in nature and tend to accumulate in nature, and therefore, it is necessary to develop a surface protecting agent for non-fluorine-containing materials. In the development of a surface protective agent for a non-fluorine-based material, water repellency, slidability, dirt erasure property, and abrasion resistance are required, and further, adhesion to a substrate, particularly adhesion to a substrate having at least a surface of a resin, is required. Prior art literature Patent literature Patent document 1 Japanese patent application laid-open No. 2008-534696 Patent document 2 Japanese patent application laid-open No. 2008-537557 Patent document 3 Japanese patent application laid-open No. 2012-072272 Patent document 4 Japanese patent application laid-open No. 2012-157856 Patent document 5 Japanese patent laid-open publication No. 2013-136833 Patent document 6 Japanese patent application laid-open No. 2015-199906 Disclosure of Invention Problems to be solved by t