Photo-curable organic-inorganic hybrid resin composition

Patent metadata

Field	Value
Publication number	US-9469763-B2
Application number	US-201414161778-A
Country	US
Kind code	B2
Filing date	Jan 23, 2014
Priority date	Aug 3, 2011
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

The present invention relates to a photo-curable organic-inorganic hybrid composition, more particularly to a photo-curable organic-inorganic hybrid resin composition having superior physical properties such as UV resistance, chemical resistance, light transmittance, adhesive property, insulating property, heat resistance, flatness and water resistance and in particular, having excellent heat resistance and adhesive property enabling the composition to endure a thermal deformation caused by a processing temperature change during post-process after a film is cured. Thus, the composition of the invention is suitable for use as an insulating material and an encapsulating material for a protective film of optical devices including display devices and semiconductors.

First claim

The invention claimed is:

1. A photo-curable organic-inorganic hybrid resin composition comprising:
(1) a poly aliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group of chemical formula 1:

wherein R 1 to R 4 each independently represent a hydrogen atom; or an alkyl group or alkoxy group of C 1-20 substituted or unsubstituted with an ethylenically unsaturated group of C 2-20 , a fluorine, or an aromatic group of C 6-20 , wherein at least one of R 1 to R 4 is the alkyl group or alkoxy group containing an ethylenically unsaturated group, and at least one of R 1 to R 4 is the alkyl or alkoxy group of C 1-20 containing a fluorine,
n is an integer of 1-30, and
R 5 to R 8 are each independently a hydrogen atom, or an alkyl or alkoxy group of C 1-20 ;
(2) a reactive monomer containing at least one unsaturated group in the molecule;
(3) an organic silane compound of chemical formula 2:
R 9 4-m -Q p -Si—(OR 10 ) m   [Chemical formula 2]

wherein R 9 is selected from the group consisting a phenyl group, an amino group, a (meth)acryl group, a vinyl group, an epoxy group and a combination thereof,
R 10 is selected from the group consisting of an alkyl group of C 1-5 , a cycloalkyl group of C 3-10 , an aryl group of C 6-12 , —OCR′, —CR′═N—OH, and a combination thereof, wherein R′ is an alky group of C 1-6 ,
Q is an alkylene group of C 2-6 or an alkyleneoxy group of C 2-6 ,
m is an integer of 0 to 4, and
p is an integer of 0 or 1; and
(4) a photo initiator,
wherein the reactive monomer containing at least one unsaturated group in the molecule of (2) is a reactive monomer containing a (meth)acryl group, or an epoxy group together with at least one unsaturated group; and
wherein the photo-curable organic-inorganic hybrid resin composition further comprises a reactive monomer containing at least one fluorine group in the molecule.

2. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the photo-curable organic-inorganic hybrid resin comprises
(1) 30 to 80 parts by weight of the poly aliphatic aromatic silsesquioxane containing an ethylenically unsaturated group and a fluorine group of chemical formula 1;
(2) 5 to 50 parts by weight of the reactive monomer containing at least one unsaturated group in the molecule;
(3) 5 to 50 parts by weight of the organic silane compound of chemical formula 2; and
(4) 0.1 to 10 parts by weight of the photo initiator with regard to 100 parts by weight of the total sum amount of (1), (2), and (3) components.

3. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the poly aliphatic aromatic silsesquioxane of (1) is a compound having a ladder or cage structure of weight average molecular weight of 1,000 to 200,000.

4. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the reactive monomer containing a fluorine group is at least one selected from the group consisting of perfluorohexylethylene, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropylmethacrylate, 3-perfluorohexylhydroxylpropylmethacrylate, trifluoroethylmethacrylate, tetrafluoropropylmethacrylate, 2-perfluorohexylethylacrylate, 3-perfluoromethylbutyl-2-hydroxypropylacrylate, and derivatives thereof.

5. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the reactive monomer containing a (meth)acryl group is at least one selected from the group consisting of methylmethacrylate, ethylmethacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methylacrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methyl cyclo hexylmethacrylate, dicyclopentenylacrylate, dicyclopentanylacrylate, dicyclopentenylmethacrylate, dicyclopentanylmethacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethylmethacrylate, isoboronylmethacrylate, cyclohexylacrylate, 2-methyl cyclohexylacrylate, dicyclopentanyloxyethylacrylate, isoboronylacrylate, phenylmethacrylate, phenylacrylate, benzylacrylate, 2-hydroxy ethylmethacrylate, and 1,6-hexanedioldiacrylate.

6. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the reactive monomer containing an epoxy group is at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate, α-n-butylglycidyl acrylate, acrylic acid-β-methyl glycidyl, methacrylic acid-β-methyl glycidyl, acrylic acid-β-ethyl glycidyl, methacrylic acid-β-ethyl glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy heptyl, acrylic acid-3,4-epoxy cyclohexylmethyl, methacrylic acid-3,4-epoxy cyclohexylmethyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidylether, and p-vinylbenzylglycidylether.

7. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the organic silane compound of (3) is an organic silane compound containing a phenyl group, an amino group, a (meth)acryl group, a vinyl or an epoxy group.

8. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 7 , wherein the organic silane compound is at least one selected from the group consisting of (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, 3-(methacryloxy)proppyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxysilane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

9. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the photo initiator of (4) is at least one selected from the group consisting of diphenyl-(2,4,6-trimethylbenzoyl)phosphineoxide, methylbenzoylformate, ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate, 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p-(diethylamino)benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,2-bis(2-chlorophenyl)-4,4,5,5-tetraphenyl-1,2-diimidazole.

10. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the photo-curable organic-inorganic hybrid resin composition further comprises a surfactant selected from the group consisting of polyoxyethyleneoctylphenylether, polyoxyethylenenonylphenylether, and a combination thereof.

11. The photo-curable organic-inorganic hybrid resin composition as claimed in claim 1 , wherein the photo-curable organic-inorganic hybrid resin composition is a composition for the protective film of display devices.

12. A pattern formation method using the photo-curable organic-inorganic hybrid resin composition of claim 1 .

13. An encapsulation method using the photo-curable organic-inorganic hybrid resin composition of

Assignees

• Dongjin Semichem Co Ltd

Inventors

• Yoo Jae-Won
• Nam Dong-Jin
• Kim Doo-Shick
• Park Kyung-Min

Classifications

• H10W74/40

  characterised by their materials · CPC title

• C08G77/442

  containing vinyl polymer sequences · CPC title

• C08L83/10 Primary

  Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) · CPC title

• C09J4/00

  Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16} · CPC title

• C08G77/24

  halogen-containing groups · CPC title