Mixed-type photosensitive resin and preparation method therefor

• US 10,642,155 B2
• Filed: 01/11/2019
• Issued: 05/05/2020
• Est. Priority Date: 07/13/2016
• Status: Active Grant

• Current Assignee: Changzhou Tronly Advanced Electronic Materials Co., Ltd., Changzhou Tronly New Electronic Materials Co., Ltd.
• Original Assignee: Changzhou Tronly Advanced Electronic Materials Co., Ltd.
• Inventors: Qian, Xiaochun
• Primary Examiner(s): Carcanague, Daniel R
• Application Number:
  US16/246,379
• Publication Number:
  US 20190391491A1
• Time in Patent Office: 480 Days
• Field of Search: 549510
• CPC Class Codes: C07D 305/06 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
• CPC Class Codes: C08F 20/68 Esters
• CPC Class Codes: C08F 22/20 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 135/02 Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09J 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: G03F 7/0045 with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/028 with photosensitivity-increasing substances, e.g. photoinitiators
• CPC Class Codes: G03F 7/029 Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021

Abstract

A hybrid photosensitive resin having a structure represented by general formula (I) and contains an oxetanyl functional group and a (meth)acryloxy functional group. The functional groups are coordinated with each other and the functionality is adjustable and controllable. The hybrid photosensitive resin is highly suitable for radical-cation photocuring systems, there is no problem of polymerization inhibition by oxygen, and its cured film has high hardness, good flexibility, excellent adherence, and excellent heat resistance.

Claims

1. A hybrid photosensitive resin, wherein the hybrid photosensitive resin has a structure represented by general formula (I):

2. The hybrid photosensitive resin according to claim 1, wherein R₁ represents a C₁-C₄₀ linear m-valent alkyl group, a C₁-C₄₀ branched m-valent alkyl group, a C₂-C₁₀ linear m-valent alkenyl group, a C₂-C₁₀ branched m-valent alkenyl group, or a C₆-C₃₀ m-valent aryl group, wherein —

CH₂—

can be substituted with an oxygen atom, —

NH—

, or a 1,4-phenylene group, provided that two —

O—

'"'"'s are not directly connected; and

wherein, one or more hydrogen atoms in these groups can be each independently substituted with a group selected from an alkyl group, a halogen, and a nitro group.

3. The hybrid photosensitive resin according to claim 1, wherein R₁ is selected from the following structures:

a C₁-C₁₂ linear or branched 1-to-4-valent alkyl group,

4. The hybrid photosensitive resin according to claim 1, wherein R₂ represents a C₁-C₁₀ linear alkylene group, a C₁-C₁₀ branched alkylene group, wherein —

CH₂—

in the main chain can be substituted with an oxygen atom, provided that two —

O—

'"'"'s are not directly connected.

5. The hybrid photosensitive resin according to claim 1, wherein R₃ represents hydrogen, a C₁-C₁₀ linear alkyl group, a C₁-C₁₀ branched alkyl group, a C₃-C₁₀ cycloalkyl group, a C₄-C₁₀ cycloalkylalkyl group, a C₄-C₁₀ alkylcycloalkyl group, a C₂-C₈ alkenyl group, or a phenyl group.

6. The hybrid photosensitive resin according to claim 1, wherein m is an integer of 1-6.

7. A preparation method of the hybrid photosensitive resin of claim 1, wherein a hydroxy-containing compound represented by R₁OH)_m and an oxetanyl-containing compound represented by

8. The preparation method according to claim 7, wherein said first catalyst is selected from one or a combination of two or more of an alkali metal hydroxide, an alkali metal salt of an alcohol, an alkali metal carbonate, an alkali metal bicarbonate, an alkyl metal lithium compound, and a lithium amide compound.

9. The preparation method according to claim 7, wherein the intermediate is subjected to esterification reaction with (meth)acrylic acid or transesterfication reaction with (meth)acrylate to obtain the product;

said second catalyst used in the esterification reaction is an inorganic acid or an organic acid, and the catalyst used in the transesterfication reaction is a titanate-based compound.

10. The hybrid photosensitive resin according to claim 1, wherein R₂ represents a C₁-C₆ linear alkylene group or a C₁-C₆ branched alkylene group, wherein —

CH₂—

in the main chain can be substituted with an oxygen atom, provided that two —

O—

'"'"'s are not directly connected.

11. The hybrid photosensitive resin according to claim 1, wherein R₃ represents a C₁-C₄ linear alkyl group, a C₁-C₄ branched alkyl group, or a C₄-C₈ cycloalkylalkyl group.

12. The hybrid photosensitive resin according to claim 1, wherein m is an integer of 1-4.