Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength

Patent metadata

Field	Value
Publication number	US-10047246-B2
Application number	US-201515310292-A
Country	US
Kind code	B2
Filing date	Apr 20, 2015
Priority date	May 12, 2014
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

Provided is a varnish including 1 to 500 parts by weight of an aromatic tetracarboxylic acid diester (A) represented by General Formula (1), 1 to 450 parts by weight of 2-phenyl-4,4′-diaminodiphenyl ether (B), 1 to 100 parts by weight of a 4-(2-phenylethynyl)phthalic acid monoester (C) represented by General Formula (2), and 100 parts by weight of an organic solvent having a boiling point of 150° C. or less at 1 atmosphere or a mixture of two or more of the organic solvents (D). The components (A), (B), and (C) are dissolved in the varnish.

(In the formula, R 1 is an aromatic tetracarboxylic acid diester residue; R 2 and R 3 are the same or different and are an aliphatic organic group or an aromatic organic group.)

(In the formula, R 4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group).

First claim

The invention claimed is:

1. A varnish comprising components (A) to (D),
the components (A), (B), and (C) being dissolved in the varnish,
the component (A) being an aromatic tetracarboxylic acid diester represented by General Formula (1) and being contained in an amount of 1 to 500 parts by weight,
the component (B) being 2-phenyl-4,4′-diaminodiphenyl ether and being contained in an amount of 1 to 450 parts by weight,
the component (C) being a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) and being contained in an amount of 1 to 400 parts by weight, and
the component (D) being an organic solvent having a boiling point of 150° C. or less at 1 atmosphere selected from the group consisting of acetone, tetrahydrofuran, 1,4-dioxane, and methyl ethyl ketone, and being contained in an amount of 100 parts by weight; wherein

General Formula (1) is

where R 1 is an aromatic tetracarboxylic acid diester residue; R 2 and R 3 are the same or different and are an aliphatic organic group or an aromatic organic group; R 2 and R 3 are located in a cis configuration or a trans configuration; and the compound is optionally a single isomer or a mixture of two isomers and
General Formula (2) is

where R 4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group; and one of R 4 and R 5 is an aliphatic organic group or an aromatic organic group.

2. The varnish according to claim 1 , wherein the aromatic tetracarboxylic acid diester residue represented by R 1 in General Formula (1) is a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid.

3. The varnish according to claim 1 , wherein the aromatic tetracarboxylic acid diester residue represented by R 1 in General Formula (1) is a tetravalent residue of a 3,3′,4,4′-biphenyltetracarboxylic acid.

4. The varnish according to claim 1 , wherein two or more of a tetravalent aromatic tetracarboxylic acid diester represented by General Formula (1) in which R 1 is a tetravalent residue of a 1,2,4,5-benzenetetracarboxylic acid, an aromatic tetracarboxylic acid diester represented by General Formula (1) in which R 1 is a tetravalent residue of a 3,3′,4,4′-biphenyltetracarboxylic acid, and an aromatic tetracarboxylic acid diester represented by General Formula (1) in which R 1 is a tetravalent residue of a bis(3,4-carboxyphenyl) ether are used in combination.

5. The varnish according to claim 1 , wherein 2-phenyl-4,4′-diaminodiphenyl ether and an additional divalent aromatic diamine are used in combination.

6. A solid imide resin composition represented by General Formula (3), obtained by heating the varnish according to claim 1 to remove the organic solvent:
General Formula (3) is

where R 6 and R 7 are a hydrogen atom or a phenyl group; one of R 6 and R 7 is a phenyl group; R 8 and R 9 are the same or different and are a divalent aromatic diamine residue; R 10 and R 11 are the same or different and are a tetravalent aromatic tetracarboxylic acid residue; m and n satisfy relations of m≥1, n≥0, 1≤m+n≤10, and 0.05≤m/(m+n)≤1; and repeating units are optionally arranged in a block sequence or a random sequence.

7. A molded article of a polymerized imide resin composition, wherein the polymerized imide resin composition is obtained by heating the solid imide resin composition according to claim 6 in a molten state.

8. The molded article according to claim 7 , wherein the polymerized imide resin composition has a glass transition temperature (Tg) of 300° C. or more.

9. A film obtained from the molded article according to claim 7 , having a tensile elongation at break of 10% or more.

10. A prepreg comprising:
the varnish according to claim 1 , and fibers,
wherein the varnish is infiltrated in the fibers.

11. An imide prepreg obtained by further heating the prepreg according to claim 10 .

12. A fiber-reinforced composite material obtained by stacking the prepregs according to claim 10 and thermally curing the stacked prepregs.

13. The fiber-reinforced composite material according to claim 12 , having a glass transition temperature (Tg) of 300° C. or more.

14. A method for producing the varnish according to claim 1 , the method comprising:
heating an aromatic tetracarboxylic anhydride and 4-(2-phenylethynyl)phthalic anhydride and dissolving the aromatic tetracarboxylic anhydride and the 4-(2-phenylethynyl)phthalic anhydride in an organic solvent having a boiling point of 150° C. or less at 1 atmosphere, to prepare an aromatic tetracarboxylic acid diester represented by General Formula (1);
preparing a solution of an organic solvent having a boiling point of 150° C. or less at 1 atmosphere, which contains the aromatic tetracarboxylic acid diester represented by General Formula (1) and a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2);
adding a diamine including 2-phenyl-4,4′-diaminodiphenyl ether to the solution; and
uniformly dissolving, in the solution, the diamine including 2-phenyl-4,4′-diaminodiphenyl ether.

15. The varnish according to claim 1 , wherein the component (D) comprises a mixture of two or more of the organic solvents.

16. A varnish comprising components (A) to (D),
the components (A), (B), and (C) being dissolved in the varnish,
the component (A) being an aromatic tetracarboxylic acid diester represented by General Formula (1) and being contained in an amount of 1 to 500 parts by weight,
the component (B) being 2-phenyl-4,4′-diaminodiphenyl ether and being contained in an amount of 1 to 450 parts by weight,
the component (C) being a 4-(2-phenylethynyl)phthalic acid monoester represented by General Formula (2) and being contained in an amount of 1 to 400 parts by weight, and
the component (D) being a mixture of two or more of the organic solvents having a boiling point of 150° C. or less at 1 atmosphere selected from the group consisting of acetone, tetrahydrofuran, 1,4-dioxane, and methyl ethyl ketone, and being contained in an amount of 100 parts by weight; wherein

General Formula (1) is

where R 1 is an aromatic tetracarboxylic acid diester residue; R 2 and R 3 are the same or different and are an aliphatic organic group or an aromatic organic group; R 2 and R 3 are located in a cis configuration or a trans configuration; and the compound is optionally a single isomer or a mixture of two isomers and
General Formula (2) is

where R 4 and R 5 are a hydrogen atom, an aliphatic organic group, or an aromatic organic group; and one of R 4 and R 5 is an aliphatic organic group or an aromatic organic group.

Assignees

• Kaneka Corp
• Japan Aerospace Exploration

Inventors

• Miyauchi Masahiko
• Ishida Yuichi
• Ogasawara Toshio
• Yokota Rikio

Classifications

• C08G73/105

  with oxygen only in the diamino moiety · CPC title

• C08J2379/08

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

• C08G73/101

  containing chain terminating or branching agents · CPC title

• C08G73/1071

  Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain · CPC title

• C08G73/10

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