Poly-amic acid, photo-sensitive resin composition, dry film, and circuit board

Patent metadata

Field	Value
Publication number	US-9410017-B2
Application number	US-201314115201-A
Country	US
Kind code	B2
Filing date	May 3, 2013
Priority date	May 3, 2012
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

The present invention relates to a novel polyamic acid introduced with an imidazolyl group in the polymer chain, a photosensitive resin composition including the polyamic acid and that is capable of providing a photosensitive material that satisfies the characteristics of an excellent bending property and low stiffness and also exhibits excellent heat resistance and coating resistance, a dry film obtained from the photosensitive resin composition, and a circuit board including the dry film.

First claim

What is claimed is:

1. A polyamic acid comprising a repeating unit of the following Chemical Formula 1:

wherein X 1 is a tetravalent organic group,
X 2 is an aromatic ring-containing trivalent or tetravalent organic group,
n is an integer of 0 or 1, and
P 1 and P 2 are the same or different, and are each an organic functional group containing an imidazolyl group, and
wherein each of P 1 and P 2 is a functional group of the following Chemical Formula 2:
—(R 1 ) a —(R 2 ) b —Y  [Chemical Formula 2]

wherein R 1 is

a is 0 or 1,
R 2 is a straight or branched alkylene group having 1 to 10 carbon atoms,
b is 0 or 1, and
Y is an imidazolyl group that is substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms.

2. The polyamic acid according to claim 1 , wherein X 2 is one tetravalent organic group selected from the group consisting of the following Chemical Formula 11 to 15, or one trivalent organic group selected from the group consisting of the following Chemical Formulae 16 to 20:

in Chemical Formula 12, Y 1 is a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 13, Y 2 and Y 3 are the same or different, and are each a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 14, Y 4 , Y 5 , and Y 6 are the same or different, and are each a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 17, Y 1 is a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 18, Y 2 and Y 3 are the same or different, and are each a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 19, Y 4 , Y 5 , and Y 6 are the same or different, and are each a direct bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

3. The polyamic acid according to claim 1 , wherein each of P 1 and P 2 includes a carbonyl group and an imidazolyl group-binding functional group at the end.

4. The polyamic acid according to claim 1 , wherein X 1 is one tetravalent organic group selected from the group consisting of the following Chemical Formulae 21 to 35:

in Chemical Formula 22, Y 1 is a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 23, Y 2 and Y 3 are the same or different, and are each a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2 and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 24, Y 4 , Y 5 , and Y 6 are the same or different, and are each a single bond, —O—, —CO—, —S—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —CONH—, —COO—, —(CH 2 ) n1 —, —O(CH 2 ) n2 O—, or —OCO(CH 2 ) n3 OCO—, and n1, n2, and n3 are an integer of 1 to 10, respectively,

in Chemical Formula 26 and 27, * indicates the bonding point of a functional group,

5. The polyamic acid according to claim 1 , further comprising a repeating unit of the following Chemical Formula 3:

wherein X 3 is a tetravalent organic group and X 4 is a divalent organic group.

6. The polyamic acid according to claim 5 , comprising 0.1 to 50 mol % of the repeating unit of Chemical Formula 1, and 50 to 99.9 mol % of the repeating unit of Chemical Formula 3.

7. The polyamic acid according to claim 1 , wherein its weight average molecular weight is 5000 to 200,000.

8. A photosensitive resin composition comprising a polymer resin including the polyamic acid of claim 1 , a photocrosslinking agent, an organic solvent, and a photopolymerization initiator.

9. The photosensitive resin composition according to claim 8 , wherein the photocrosslinking agent includes a (meth)acrylate-based compound containing a double bond between carbons.

10. The photosensitive resin composition according to claim 8 , wherein the photopolymerization initiator includes one or more compounds selected from the group consisting of an acetophenone-based compound, a biimidazole-based compound, a triazine-based compound, and an oxime-based compound.

11. The photosensitive resin composition according to claim 8 , wherein the solid content of the polymer resin is 15 to 90% by weight, based on the total weight of the photosensitive resin composition.

12. The photosensitive resin composition according to claim 8 , further comprising one or more additives selected from the group consisting of a thermal crosslinking agent, a curing accelerator, a photocrosslinking sensitizer, a curing accelerator, a phosphorus-based flame retardant, a defoaming agent, a leveling agent, and an anti-gelling agent.

13. A dry film comprising a cured product of the photosensitive resin composition of claim 8 .

14. The dry film according to claim 13 , wherein the cured product includes a crosslinked product of polyamic acid containing a repeating unit of the following Chemical Formula 1-1 and a photocrosslinking agent:

Assignees

• Lg Chemical Ltd

Inventors

• Kim Jung-Hak
• Kyung You-Jin
• Kim Hee-Jung
• Lee Kwang-Joo

Classifications

• G03F7/037

  the binders being polyamides or polyimides · CPC title

• G03F7/40

  Treatment after imagewise removal, e.g. baking · CPC title

• H05K2201/0154

  Polyimide · CPC title

• H05K3/287

  Photosensitive compositions · CPC title

• C08G73/10 Primary

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