Search

CN-122029236-A - Curable composition, cured product, hard coating agent, hard coating layer, article, and laminate

CN122029236ACN 122029236 ACN122029236 ACN 122029236ACN-122029236-A

Abstract

A curable composition comprising a polysiloxane represented by formula (1) and having a content of 0.1% by mass or more and less than 10% by mass relative to the total solid content of the curable composition, and a cured product obtained by curing the curable composition, a hard coat agent, a hard coat layer, an article and a laminate each using the curable composition. At least 1 of R 1 is a monovalent organic group having a polymerizable group, R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom, w represents a positive number, v, x, y, and z each independently represents 0 or a positive number, at least one of x and y represents a positive number, and when x is 0, the composition represented by the following formula (S) is contained, and n represents a number of 3 or more.

Inventors

  • IWASAKI AKIRA
  • Ogata Narumi
  • Kimura Chongkuan

Assignees

  • 东亚合成株式会社

Dates

Publication Date
20260512
Application Date
20241008
Priority Date
20231013

Claims (12)

  1. 1. A curable composition comprising a polysiloxane represented by the following formula (1), wherein the content of the polysiloxane is 0.1 mass% or more and less than 10 mass% and x/(v+w+x+y+z) is less than 0.6 with respect to the total solid content of the curable composition, [ Chemical formula 1] , In the formula (1), R 1 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group, at least one of R 1 is a monovalent organic group having a polymerizable group, the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in R 1 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkoxy group, and an oxy group, and R 2 each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom, R 3 、R 4 and R 5 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group, and the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in R 3 、R 4 and R 5 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkoxy group, and an oxy group, w represents a positive number, v, x, y, and z each independently represent 0 or a positive number, at least any one of x and y represents a positive number, and in the case where x is 0, the structure represented by the following formula (S) is contained, [ Chemical formula 2] , N represents a number of 3 or more.
  2. 2. The curable composition according to claim 1, wherein, Which comprises, in addition to the polysiloxane represented by the formula (1), a polysiloxane represented by the following formula (2), [ Chemical formula 3] , In the formula (2), R 6 、R 7 and R 8 each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group, at least one of R 6 、R 7 and R 8 is a monovalent organic group having a polymerizable group, and the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in R 6 、R 7 and R 8 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkoxy group, and an oxy group, q represents a positive number, and p, R, and s each independently represent 0 or a positive number.
  3. 3. The curable composition according to claim 1 or 2, wherein, The polymerizable group in R 1 in the formula (1) is at least one selected from the group consisting of an acryl group, a methacryl group, an epoxy group, an oxetanyl group, a vinyl group, and an allyl group.
  4. 4. The curable composition according to claim 1 or 2, wherein, The value of (x+y)/(v+w+x+y+z) in the formula (1) is 0.20 to 0.80.
  5. 5. The curable composition according to claim 1 or 2, further comprising a polymerization initiator.
  6. 6. A cured product obtained by curing the curable composition according to claim 1 or 2.
  7. 7. A hard coat agent comprising the curable composition according to claim 1 or 2.
  8. 8. A hard coating layer obtained by curing the hard coating agent according to claim 7.
  9. 9. An article provided with the hard coat layer of claim 8.
  10. 10. A laminate having the hardcoat layer of claim 9 and a substrate.
  11. 11. The cured product according to claim 6, wherein, The cured product obtained on the steel sheet has a pencil hardness of 5H or more and a dynamic friction coefficient of 0.35 or less.
  12. 12. The cured product according to claim 6, wherein, The decrease rate of the water contact angle before and after the abrasion test using the absorbent cotton impregnated with acetone, the abrasion test using the absorbent cotton impregnated with hexane, and the abrasion test using the steel wool was 10% or less.

Description

Curable composition, cured product, hard coating agent, hard coating layer, article, and laminate Technical Field The present disclosure relates to curable compositions, cured products, hard coats, hard coatings, articles, and laminates. Background Displays of various devices for displaying images are provided with a transparent coating layer excellent in scratch resistance and hardness as a surface protective layer. In order to prevent the visibility from being lowered due to contamination of the display surface, the coating layer preferably has stain resistance. Particularly for a display having a touch panel function, it is desirable to prevent sebum adhesion and to easily remove it. For this reason, leveling agents, which are substances having low surface free energy, are added to the coating layer of many display surfaces, thereby improving the smoothness of the surfaces and imparting stain resistance. As such leveling agents, fluorine resins and silicone resins have been conventionally used. However, these leveling agents are not chemically fixed to the resin as a base material, and have problems such as bleeding, falling off due to repeated use, and loss of function. In order to solve such problems, a leveling agent having a polymerizable functional group and a fluorinated alkyl group or a silicon chain is used. The conventional leveling agents include those described in patent documents 1 to 4. Patent document 1 discloses a composition for forming a hard coating layer, which contains a nonionic fluorine-containing compound as a leveling agent in a polyorganosilsesquioxane having a polymerizable epoxy group. Patent document 2 discloses a leveling agent obtained by polymerizing a monomer having 2 or more groups having a radical polymerizable double bond and containing at least 1 nitrogen atom and having a fluorine atom, and a composition comprising the leveling agent and a polyorganosilsesquioxane. Patent document 3 discloses a composition for a hard coating layer, which comprises a polymer having at least one of a silicon group and a perfluoropolyether group and a reactive group in a side chain as a leveling agent, and a polyorganosilsesquioxane having a polymerizable group. Patent document 4 discloses a composition for forming a hard coating layer, which contains polysilsesquioxane having a perfluoropolyether group. Prior art literature Patent literature Patent document 1 International publication No. 2021/193173 Patent document 2 International publication No. 2019/235108 Patent document 3 International publication No. 2020/059726 Patent document 4 International publication No. 2021/193478 Disclosure of Invention Problems to be solved by the invention In particular, in a display in direct contact such as a touch panel, from the viewpoints of physical strength and durability, It is desired that the leveling agent having uneven distribution on the surface of the coating layer has excellent hardness and weather resistance in addition to high antifouling property. Patent document 1 discloses a composition for a hard coating layer, in which a nonionic fluorine-containing compound is added to a polymerizable epoxy-based polyorganosilsesquioxane as a leveling agent, but in a hard coating layer obtained by curing the composition, there is no covalent bond between the silsesquioxane as a main agent and the leveling agent, and thus, there is a problem that the performance is degraded due to bleeding of the leveling agent or the like. Patent document 2 discloses a leveling agent in which a monomer having 2 or more groups having a radical polymerizable double bond and containing at least 1 nitrogen atom is polymerized and which has a fluorine atom, but in a hard coating layer obtained by curing the composition, there is no covalent bond between silsesquioxane as a main agent and the leveling agent, and therefore, performance degradation such as bleeding of the leveling agent is caused. Further, since the leveling agent has nitrogen atoms in the molecule, there is a possibility that deterioration may be increased in long-term use from the viewpoint of hydrolysis of a hard coating obtained by curing the composition. Patent document 3 discloses a composition for a hard coating, in which a leveling agent having a polymerizable functional group and silicon or perfluoropolyether is added to a polysilsesquioxane derivative, but the leveling agent has a low crosslinking density, and the hardness of the coating surface may be lowered. Patent document 4 discloses a composition for forming a hard coat layer as follows. The composition for forming a hard coat layer contains polysilsesquioxane having a perfluoropolyether group, but fails to achieve both surface hardness and low dynamic friction coefficient (i.e., high surface smoothness). The present disclosure has been made in view of the above problems, and an object thereof is to provide a curable composition which is excellent in durability of a cured product obtained a