# US 11,898,057 B2 · Weather-resistant hard coat composition for glass-substitute substrate, cured product, and laminate

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- Number: US 11,898,057 B2
- Document ID: US11898057B2
- Status: Granted
- Kind: B2
- Application number: 17/295,527
- Filed: 2019-11-20
- Published: 2022-01-20
- Granted: 2024-02-13
- Earliest claimed: 2018-11-21
- Assignees: Daicel Corporation
- Applicants: Daicel Corporation
- Inventors: Kunio Shimizu; Hiroshi Takahashi; Akihiro Shibamoto
- Web page: https://patentgrep.com/patent/US11898057B2

## CPC

- C09D 183/04: Polysiloxanes
- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- C08F 290/068: {Polysiloxanes}
- C08F 299/08: from polysiloxanes
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C09D 151/085: {on to polysiloxanes}
- C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- B05D 1/26: performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
- B05D 3/0209: {Multistage baking}
- B05D 3/0272: {with ovens}
- B05D 3/067: {Curing or cross-linking the coating}
- B05D 2518/12: Ceramic precursors (polysiloxanes, polysilazanes)
- C08G 77/04: Polysiloxanes
- C08G 77/38: Polysiloxanes modified by chemical after-treatment
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- Y10T 428/26: Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T 428/31: Surface property or characteristic of web, sheet or block
- Y10T 428/31663: As siloxane, silicone or silane
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## 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), R1 represents a group containing an active energy ray-curable functional group.]

## Claims

### Claim 1

A weather-resistant hard coat composition, the composition comprising a polyorganosilsesquioxane having a constituent unit represented by Formula (1):
[R1SiO3/2] (1)
wherein R1 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 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 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 R1 is the group containing the active energy ray-curable functional group and the constituent unit represented by the Formula (II) wherein Rb 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 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; 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.

### Claim 2 (depends on 1)

The weather-resistant hard coat composition according to claim 1, wherein at least some of the R1 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.

### Claim 3 (depends on 2)

The weather-resistant hard coat composition according claim 2, wherein at least some of the R1 groups represent a substituted or unsubstituted aryl group.

### Claim 4 (depends on 1)

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

### Claim 5 (depends on 1)

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 R1a represents a linear or branched alkylene group;
a group represented by Formula (1b):
wherein R1b represents a linear or branched alkylene group;
a group represented by Formula (1c):
wherein R1c represents a linear or branched alkylene group; or
a group represented by Formula (1d):
wherein R1d represents a linear or branched alkylene group.

### Claim 6 (depends on 1)

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

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 7)

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

### Claim 9 (depends on 7)

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

### Claim 10 (depends on 1)

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

### Claim 11 (depends on 1)

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.

### Claim 12 (depends on 1)

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

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 13)

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.

### Claim 15 (depends on 14)

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

### Claim 16 (depends on 14)

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