Weather-resistant hard coat composition for glass-substitute substrate, cured product, and laminate

Patent metadata

Field	Value
Publication number	US-11898057-B2
Application number	US-201917295527-A
Country	US
Kind code	B2
Filing date	Nov 20, 2019
Priority date	Nov 21, 2018
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The purpose of the present invention is to provide a weather-resistant hard coat composition for a glass-substitute substrate capable of efficiently forming a coating film excelling in weather resistance, scratch resistance, and toughness. The present invention provides: a weather-resistant hard coat composition for a glass-substitute substrate, the composition containing a polyorganosilsesquioxane having a constituent unit represented by Formula (1); a cured product thereof; and a laminate having a glass-substitute substrate and a coating film formed on at least one surface of the glass-substitute substrate. The coating film is a layer of a cured product of the weather-resistant hard coat composition for a glass-substitute substrate. [In formula (1), R 1 represents a group containing an active energy ray-curable functional group.]

First claim

The invention claimed is:

1. A weather-resistant hard coat composition, the composition comprising a polyorganosilsesquioxane having a constituent unit represented by Formula (1):
[R 1 SiO 3/2 ]  (1)

wherein R 1 of the constituent unit of Formula (1) represents a group containing an active energy ray-curable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom;
provided that at least some of the R 1 groups are the groups containing the active energy ray-curable functional group; and
a constituent unit represented by Formula (II):
[R b SiO 2/2 (OR c )]  (II)

wherein R b represents a group containing an active energy ray-curable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom, and
wherein R c represents a hydrogen atom or an alkyl group having from 1 to 4 carbons; and
provided that at least some of the R b groups are the groups containing the active energy ray-curable functional group;
wherein the composition further comprises a compound having one or more thermally-polymerizable functional groups and one or more photopolymerizable functional groups per molecule;
wherein the compound having one or more thermally-polymerizable functional groups and one or more photopolymerizable functional groups per molecule comprises at least one selected from the group consisting of tripropylene glycol diglycidyl ether di(meth)acrylate and tripropylene glycol diglycidyl ether half(meth)acrylate;
wherein said tripropylene glycol diglycidyl ether di(meth)acrylate has the following formula:

wherein said tripropylene glycol diglycidyl ether half(meth)acrylate has the following formula:

wherein a molar ratio [(constituent unit represented by Formula (1))/(constituent unit represented by Formula (II))] of the constituent unit represented by Formula (1) to the constituent unit represented by Formula (II) is from 5 to 500;
wherein a ratio of a total amount of the constituent unit represented by Formula (1) wherein R 1 is the group containing the active energy ray-curable functional group and the constituent unit represented by the Formula (II) wherein R b is the group containing the active energy ray-curable functional group with respect to a total amount (100 mol %) of siloxane constituent units is from 55 to 100 mol %;
wherein a number average molecular weight of the polyorganosilsesquioxane is from 1000 to 50000;
wherein a molecular weight dispersity, weight average molecular weight/number average molecular weight, of the polyorganosilsesquioxane is from 1.0 to 4.0;
wherein the content of the polyorganosilsesquioxane is 70 wt,% or greater and less than 100 wt. % relative to a total amount of the hard coat composition excluding solvent;
wherein the active energy ray-curable functional group in R 1 is at least one selected from the group consisting, of an epoxy group, an oxetane group, a vinyl ether group, a vinyl phenyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, and a vinylthio group; and
wherein a content of the compound having one or more thermally-polymerizable functional groups and one or more photopolymerizable functional groups per molecule, as a solid content, is 1 to 100 parts by weight relative to 100 parts by weight of the total amount of active energy ray-curable compounds.

2. The weather-resistant hard coat composition according to claim 1 , wherein at least some of the R 1 groups represent a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.

3. The weather-resistant hard coat composition according claim 2 , wherein at least some of the R 1 groups represent a substituted or unsubstituted aryl group.

4. The weather-resistant hard coat composition according to claim 1 , wherein the active energy ray-curable functional group is an epoxy group.

5. The weather-resistant hard coat composition according to claim 1 , wherein the active energy ray-curable functional group is:
a group represented by Formula (1a):

wherein R 1a represents a linear or branched alkylene group;
a group represented by Formula (1b):

wherein R 1b represents a linear or branched alkylene group;
a group represented by Formula (1c):

wherein R 1c represents a linear or branched alkylene group; or
a group represented by Formula (1d):

wherein R 1d represents a linear or branched alkylene group.

6. The weather-resistant hard coat composition according to claim 1 , wherein the active energy ray-curable functional group is a (meth)acryloxy group.

7. The weather-resistant hard coat composition according to claim 1 , further comprising a photocuring catalyst.

8. The weather-resistant hard coat composition according to claim 7 , wherein the photocuring catalyst is a photocationic polymerization initiator.

9. The weather-resistant hard coat composition according to claim 7 , wherein the photocuring catalyst is a photoradical polymerization initiator.

10. The weather-resistant hard coat composition according to claim 1 , further comprising a second compound having one or more (meth)acryloxy groups per molecule.

11. The weather-resistant hard coat composition according to claim 1 , further comprising at least one compound selected from the group consisting of ultraviolet absorbers and antioxidants.

12. The weather-resistant hard coat composition according to claim 1 , further comprising a fluorine-containing photopolymerizable resin.

13. A cured product of the weather-resistant hard coat composition according to claim 1 .

14. A laminate comprising a substrate and a coating film formed on at least one surface of the substrate, wherein the coating film is a layer of the cured product according to claim 13 .

15. The laminate according to claim 14 , wherein a thickness of the coating film is from 0.1 to 1000 μm.

16. The laminate according to claim 14 , wherein the laminate is used for an automotive headlight cover or for an automotive window glass.

Assignees

• Daicel Corp

Inventors

• Shimizu Kunio
• Takahashi Hiroshi
• Shibamoto Akihiro

Classifications

• C09D183/06 Primary

  containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence) · CPC title

• C08G77/14

  containing silicon bound to oxygen-containing groups · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C08G77/70

  Siloxanes defined by use of the MDTQ nomenclature · CPC title

• Y10T428/26

  Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension · CPC title