Photosensitive resin composition and method for producing cured relief pattern

Patent metadata

Field	Value
Publication number	US-2022011669-A1
Application number	US-202117480648-A
Country	US
Kind code	A1
Filing date	Sep 21, 2021
Priority date	Aug 22, 2016
Publication date	Jan 13, 2022
Grant date	—

Abstract

A negative-type photosensitive resin composition that has a satisfactory imidization rate and can yield a resin layer with high chemical resistance, even under low-temperature curing conditions of 200° C. or below, the negative-type photosensitive resin composition containing a photopolymerization initiator (B) in a proportion of 0.1 part by mass to 2.0 parts by mass with respect to 100 parts by mass of a polyimide precursor (A), the polyimide precursor (A) being a polyamic acid ester or polyarnic acid salt with a specific structure, and the weight-average molecular weight (Mw) of the polyimide precursor (A) being 3,000 or greater and less than 16,000, in terms of polystyrene, according to gel permeation chromatography (GPC)

First claim

1 . A negative-type photosensitive resin composition containing a photosensitive polyimide precursor, wherein:
a backbone on the end of a main chain repeating unit of the photosensitive polyimide precursor is a backbone derived from a monomer having carboxy group or a backbone derived from a monomer having animo group; the photosensitive polyimide precursor has a main chain end substituent on the end of the main chain which is a reactive substituent that reacts by heat or light, and a side chain substituent which is a substituent of —CO— corresponding to carboxylic acid end of the side chain of the main chain; the main chain end substituent is a substituent of —CO— corresopnding to carboxy group end when the end of the main chain is the backbone derived from a monomer having carboxy group, or a substituent of —NH— corresponding to amino end when the end of the main chain is the backbone derived from a monomer having amino group; the main chain end substituent and the side chain substituent are different substituents; and the negative-type photosensitive resin composition has a viscosity of 80 poise or lower as measured at 25 ° C. using an E-type viscotneter.

2 . The photosensitive resin composition according to claim 1 , wherein the reactive substituent includes at least one selected from the group consisting of the following groups:
acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanato, cyanate, cycloalkyl, epoxy, oxetanyl, carbonate, hydroxyl, mercapto, methylol, and alkoxyalkyl groups.

3 . The photosensitive resin composition according to claim 2 , wherein the reactive substituent includes at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl groups.

4 . The photosensitive resin composition according to claim 3 , wherein the reactive substituent includes a methacryl group.

5 . The photosensitive resin composition according to claim 1 , wherein the photosensitive polyimide precursor is a photosensitive polyimide precursor including a structure represented by the following formula (A1):

wherein in formula (A1), X is a tetravalent organic group, Y is a divalent organic group, R 5 and R 6 are each independently
a hydrogen atom,
a monovalent organic group represented by the following formula (R1):

wherein in formula (R1), R 7 , R 8 and R 9 are each independently
a hydrogen atom or an organic group of 1 to 3 carbon atoms, and p is an integer selected from 1 to 10, or

a saturated aliphatic group of 1 to 4 carbon atoms, with the proviso that R 5 and R 6 are not both hydrogen, and
wherein at least one end of the main chain of the photosensitive polyimide precursor has a structure of the following formula (E1) or (F1);

wherein in formula (E1), a1 includes at least one group that is an amide bond, imide bond, urea bond, or urethane bond, b1 is a reactive substituent that crosslinks by heat or light, e1 is a monovalent organic group of 1 to 30 carbon atoms, R 11 and R 14 are each independently hydrogen atom or a. monovalent organic group ofl to 30 carbon atoms, and R 12 and R 13 are each independently hydrogen atom, a monovalent organic group of 1 to 30 carbon atoms, or part of an aromatic ring or an aliphatic ring, and R 12 or R 13 directly or indirectly binds to a main chain backbone of the polyimide precursor, with the proviso that R 12 and R 13 are not both hydrogen;

wherein in formula (F1), f1 includes at least one group that is an amide bond, imide bond, urea bond, urethane bond, or ester bond, g1 is a reactive substituent that crosslinks by heat or light, R 15 -R 19 are each independently hydrogen atom, a monovalent organic group of 1 to 30 carbon atoms, or part of an aromatic ring or an aliphatic ring, and any of R 16 , R 17 and R 18 directly or indirectly binds to a main chain backbone of the polyimide precursor, with the proviso that R 16 , R 17 and R 18 are not all hydrogen.

6 . The negative-type photosensitive resin composition according to claim 5 , wherein b1 and g1 are reactive substituents having double bonds at their ends.

7 . The negative-type photosensitive resin composition according to claim 5 , wherein at least one end of the main chain of the photosensitive polyimide precursor includes the structure of formula (F1).

8 . The negative-type photosensitive resin composition according to claim 7 , wherein f1 includes at least one group from among amide, imide, urea, and urethane groups.

9 . The photosensitive resin composition according to claim 5 , wherein b1 includes at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanato, cyanato, cycloalkyl, epoxy, oxetanyl, carbonate, hydroxyl, mercapto, methylol, and alkoxyalkyl groups.

10 . The photosensitive resin composition according to claim 9 , wherein b1 includes at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl groups.

11 . The photosensitive resin composition according to claim 10 , wherein the reactive substituent that crosslinks by heat or light b1 includes a methacryl group.

12 . The photosensitive resin composition according to claim 5 , wherein the reactive substituent that crosslinks by heat or light gl includes at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, ethynyl, imino, isocyanato, cyanato, cycloakyl, epoxy, oxetanyl, carbonate, hydroxyl, mercapto, methylol, and alkoxyalkyl groups.

13 . The photosensitive resin composition according to claim 12 , wherein the reactive substituent that crosslinks by heat or light g1 includes at least one selected from the group consisting of acryl, methacryl, vinyl, alkenyl, cycloalkenyl, alkadienyl, cycloalkadienyl, styryl, and ethynyl groups.

14 . The photosensitive resin composition according to claim 13 , wherein the reactive substituent that crosslinks by heat or light g1 includes a methacryl group.

15 . The negative-type photosensitive resin composition according to claim 5 , wherein in formula (A1), X contains at least one tetravalent organic group selected from among the following formulas (B1) to (B3):

and Y is at least one divalent organic group selected from among the following formulas (C1) to (C3):

wherein in formula (C1), R 10 -R 13 are hydrogen atoms or monovalent aliphatic groups of 1 to 4 carbon atoms, which may be different from each other or the same:

wherein in formula (C3), R 14 -R 21 are hydrogen acorns, halogen atoms or monovalent organic groups of 1 to 4 carbon atoms, which may be different from each other or the same.

Assignees

• Asahi Chemical Ind

Inventors

• Yorisue Tomohiro
• Hirata Tatsuya
• Sasaki Takahiro

Classifications

• C08L79/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/128

  the unsaturated precursors containing heterocyclic moieties in the main chain · CPC title

• C08G73/1003 Primary

  Preparatory processes · CPC title

• G03F7/0387 Primary

  Polyamides or polyimides · CPC title

• G03F7/2012

  using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps · CPC title