Photo-curable and thermo-curable resin composition, and dry film solder resist

Patent metadata

Field	Value
Publication number	US-9389504-B2
Application number	US-201314379720-A
Country	US
Kind code	B2
Filing date	Feb 20, 2013
Priority date	Feb 20, 2012
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

The present invention relates to a photo-curable and thermo-curable resin composition that can provide a dry film solder resist having a higher glass transition temperature and improved heat resistance reliability, and the dry film solder resist. Said resin composition may include an acid-modified oligomer including an iminocarbonate-based compound having a carboxy group (—COOH) and a photo-curable unsaturated functional group, a photo-polymerizable monomer having two or more photo-curable unsaturated functional groups, a thermo-curable binder having a thermo-curable functional group, and a photo-initiator.

First claim

What is claimed is:

1. A photo-curable and thermo-curable resin composition, comprising:
an acid-modified oligomer comprising an iminocarbonate-based compound having a carboxy group (—COOH) and a photo-curable unsaturated functional group;
a photo-polymerizable monomer having two or more photo-curable unsaturated functional groups;
a thermo-curable binder having a thermo-curable functional group; and
a photo-initiator,
wherein the iminocarbonate-based compound is formed by reacting (1) a cyanate ester-based compound, (2) a dicarboxylic acid compound or an acid anhydride thereof, and (3) a compound having a photo-curable unsaturated functional group and a hydroxy group or carboxy group, and
wherein the compound having a photo-curable unsaturated functional group and a hydroxy group or carboxy group comprises one or more compounds selected from the group consisting of acrylic acid, methacrylic acid, cinnamic acid, butenoic acid, hexenoic acid, 2-allylphenol, and hydroxystyrene.

2. The resin composition of claim 1 which, when cured, has a coefficient of thermal expansion (α1) of 10 to 35 ppm before a glass transition temperature (Tg) and a coefficient of thermal expansion (α2) of 150 ppm or lower after the glass transition temperature (Tg).

3. The resin composition of claim 1 , wherein the dicarboxylic acid compound is an aliphatic dicarboxylic acid compound, an alicyclic dicarboxylic acid compound, or an aromatic dicarboxylic acid compound.

4. The photo-curable and thermo-curable resin composition of claim 1 , wherein the dicarboxylic acid compound or the acid anhydride thereof is one or more compounds selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, norbornene dicarboxylic acid, a C5-C10 cycloalkane dicarboxylic acid, and acid anhydrides thereof.

5. The photo-curable and thermo-curable resin composition of claim 1 , wherein the dicarboxylic acid compound or the acid anhydride thereof is one or more compounds selected from the group consisting of phthalic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, succinic acid, imidazole dicarboxylic acid, pyridine dicarboxylic acid, and acid anhydrides thereof.

6. The photo-curable and thermo-curable resin composition of claim 1 , wherein the cyanate ester-based compound includes the bisphenol-based or novolak-based compound having a cyanide group (—OCN).

7. The photo-curable and thermo-curable resin composition of claim 1 , wherein the dicarboxylic acid compound or the acid anhydride thereof and the compound having a photo-curable unsaturated functional group and a hydroxy group or carboxy group are used in a molar ratio of 2:8 to 8:2 to be reacted with the cyanate ester-based compound.

8. The photo-curable and thermo-curable resin composition of claim 1 , wherein the acid-modified oligomer comprises an iminocarbonate-based compound having the following Formula (1):

wherein, in the above Formula (1), n is an integer of 1 to 100, R 1 is a functional group derived from the compound having a photo-curable unsaturated functional group and a hydroxy group or carboxy group, and R 2 is a functional group derived from the dicarboxylic acid compound or the acid anhydride thereof.

9. The photo-curable and thermo-curable resin composition of claim 8 , wherein R 1 of Formula (1) is

and said ‘*’ means a point of binding.

10. The photo-curable and thermo-curable resin composition of claim 1 , wherein the acid-modified oligomer is contained in an amount of 15 to 75% by weight based on the total weight of the resin composition.

11. The photo-curable and thermo-curable resin composition of claim 1 , wherein the photo-polymerizable monomer comprises an acrylate-based compound having two or more photo-curable unsaturated functional groups.

12. The photo-curable and thermo-curable resin composition of claim 1 , wherein the photo-polymerizable monomer comprises one or more compounds selected from the group consisting of acrylate-based compounds having a hydroxy group, water soluble acrylate-based compounds, polyester acrylate-based compounds, polyurethane acrylate-based compounds, epoxy acrylate-based compounds, and caprolactone-modified acrylate-based compounds.

13. The photo-curable and thermo-curable resin composition of claim 1 , wherein the photo-polymerizable monomer is contained in an amount of 5 to 30% by weight based on the total weight of the resin composition.

14. The photo-curable and thermo-curable resin composition of claim 1 , wherein the photo-initiator comprises one or more selected from the group consisting of benzoins and alkylethers thereof, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, α-aminoacetophenones, acylphosphine oxides, and oxime esters.

15. The photo-curable and thermo-curable resin composition of claim 1 , wherein the photo-initiator is contained in an amount of 0.5 to 20% by weight based on the total weight of the resin composition.

16. The photo-curable and thermo-curable resin composition of claim 1 , wherein the thermo-curable functional group is one or more selected from the group consisting of an epoxy group, an oxetanyl group, a cyclic ether group, and a cyclic thioether group.

17. The photo-curable and thermo-curable resin composition of claim 1 , wherein the thermo-curable binder is contained in an amount corresponding to 0.8 to 2.0 eq. with respect to 1 eq. of the carboxy group in the acid-modified oligomer.

18. The photo-curable and thermo-curable resin composition of claim 1 , which further comprises a solvent, and one or more selected from the group consisting of a thermo-curable binder catalyst, a filler, a pigment, and an additive.

Assignees

• Lg Chemical Ltd

Inventors

• Ku Se-Jin
• Choi Byung-Ju
• Jeong Woo-Jae
• Choi Bo-Yun
• Lee Kwang Joo
• Jeong Min-Su

Classifications

• C08G73/0655

  from polycyanurates · CPC title

• C09D179/04 Primary

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08G73/065

  Preparatory processes · CPC title

• C08G73/0644

  Poly(1,3,5)triazines · CPC title

• G03F7/032

  with binders · CPC title