Patent ID: 11866608
Assignee: DAICEL CORPORATION
Field: Macromolecular chemistry, polymers (Chemistry)
Classification: CPC C  B  Y | IPC C

Claim 0:
1. A weather-resistant hard coat composition for a metal, the composition comprising a polyorganosilsesquioxane having a constituent unit represented by Formula (1):

[R1SiO3/2]  (1)

wherein R1 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 R1 groups are the groups containing the active energy ray-curable functional group; and

a constituent unit represented by Formula (II):

[RbSiO2/2(ORc)]  (II)

wherein Rb 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 Rc represents a hydrogen atom or an alkyl group having from 1 to 4 carbons; and
provided that at least some of the Rb groups are the groups containing the active energy ray-curable functional group;

wherein a molar ratio [(constituent unit represented by Formula (I))/(eonstituent unit represented by Formula (II))] of the constituent unit represented by Formula (I) to the constituent unit represented by Formula (11) is from 5 to 500;
wherein a ratio of a total amount of the constituent unit represented by Formula (1) wherein R1 is the group containing the active energy ray-curable functional group and the constituent unit represented by Formula (II) wherein Rb is the group containing the active energy ray-curable functional group is from 55 to 100 mol % with respect to a total amount (100 mol %) of siloxane constituent units;
wherein the composition further comprises a compound having one or more thermally- polymerizable functional groups and one or more photopolyrnerizable functional groups; and
wherein the compound having one or more thermally-polymerizable functional groups and one or more photopolyrnerizable functional groups per molecule comprises at least one compound 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 number average molecular weight of the polyorganosilsesquioxane is from 1000 to 50000;
wherein a molecular weight dispersity (weight average molecular weight/ntunber average molecular weight) of the polyorganosilsesquioxane is from 1.0 to 4 0;
wherein a content of the polyorganosilsesquioxane is 70 wt. % or greater, and less than 100 wt. % relative to a total amount of the weather-resistant hard coat composition excluding solvent;
wherein the active energy ray-curable functional group in R1 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;
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; and
wherein a first cured product has a pencil hardness of not less than H, a color difference (ΔE) of less than 20, and a glossiness retention rate of not less than 15%;
wherein the first cured product is obtained by curing the weather-resistant hard coat composition under conditions including pre-baking at 150° C. for 5 minutes followed by UV radiation at a dosage of 400 mJ/cm2 and a radiation intensity of 260 mW/cm2, followed by aging at 120° C. for 0.5 hours;
wherein the pencil hardness is measured in accordance with JIS K5600-5-4 with a 750 g load;
wherein the color difference (ΔE) is determined from an initial hue value from the first cured product and a hue value from a second cured product, and the glossiness retention rate is determined from an initial glossiness value from the first cured product and a glossiness value from the second cured product;
wherein the second cured product is produced by exposing the first cured product to a high luminance xenon weatherometer test;
wherein the color difference (ΔE) is calculated based on the following equation according to CIELAB standard:

ΔE=[(difference in “L” between the first cured product and the second cured product)2+(difference in “a” between the first cured product and the second cured product)2+(difference in “b” between the first cured product and the second cured product)2]1/2;

wherein the glossiness retention rate (%) is calculated from the following equation:

Glossiness Retention Rate (%)=(Glossiness of the second cured product)/(Glossiness of the first cured product)×100;

wherein the high luminance xenon weatherometer test is measured at 63° C., 50% RH with 18 minutes of rain per 120 minutes, a radiation illuminance of 100 W/m2 at 300 to 400 nm, a radiation time of 3000 hours, and using a wavelength filter where an inside and outside of the wavelength filter are made of borosilicate type S glass;

wherein the rain is in accordance with JIS B 7754 at an atomizing water pressure of 0.1 MPa and a water flow rate of 0.24 L/min;
wherein the inside of the wavelength filter has an outer diameter of 12 mm and a length of 140 mm; and
wherein the outside of the wavelength filter made of borosilicato typo S/borosilicato typo has an outer diameter of 24 mm and a length of 180 mm.