Modified polyimide resin and thermosetting resin composition containing the same

• US 6,335,417 B1
• Filed: 08/17/2000
• Issued: 01/01/2002
• Est. Priority Date: 01/14/1998
• Status: Expired due to Term

• Current Assignee: Ajinomoto Co., Inc.
• Original Assignee: Ajinomoto Co., Inc.
• Inventors: Yokota, Tadahiko, Orikabe, Hiroshi
• Primary Examiner(s): HAMPTON HIGHTOWER, PATRICIA
• Application Number:
  US09/581,543
• Time in Patent Office: 502 Days
• Field of Search: 528/353, 528/170, 528/173, 528/75, 528/65, 528/45, 528/176, 525/422, 525/440, 525/436, 525/434, 428/458
• US Class Current: 528/170
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/346 having four carboxylic acid groups
• CPC Class Codes: C08G 18/40 High-molecular-weight compounds C08G18/2805 takes precedence
• CPC Class Codes: C08G 18/69 Polymers of conjugated dienes hydrogenated polymers of conjugated dienes C08G18/6208
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: C08G 73/1035 from tetracarboxylic acids or derivatives and diisocyanates
• CPC Class Codes: C09D 175/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: H01L 23/49894 Materials of the insulating layers or coatings
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: H05K 1/023 using auxiliary mounted passive components or auxiliary substances printed passive components H05K1/16
• CPC Class Codes: H05K 1/0346 containing N
• CPC Class Codes: H05K 1/0393 Flexible materials H05K1/038 takes precedence; specific organic compositions are classified in H05K1/0313 and subgroups
• CPC Class Codes: H05K 3/285 Permanent coating compositions
• CPC Class Codes: Y10T 428/31681 Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Abstract

A novel modified polyimide resin having a polybutadiene sheleton and obtainable by reacting the following three (3) kinds of compounds, i.e., a bifunctional hydroxyl-terminal polybutadiene having a number average molecular weight of 800 to 5,000, a tetrabasic acid dianhydride, and a diisocyanate compound, imparts reduced shrinkage upon setting to a thermosetting resin composition comprising the same and also imparts heat resistance and pliability and the like to a hardened mass or article of such thermosetting resin composition. Therefore, such thermosetting resin composition is an excellent resin composition capable of fully satisfying the requirements with regard to the characteristics of an overcoat agent for a wiring circuit which should be pliable, such as a flexible wiring circuit substrate, a film carrier and the like.

Claims

1. A polyimide resin represented by Formula (2):

wherein

R₁ represents a residue obtainable by removing all the carboxyl groups from an organic compound having 4 carboxyl groups, R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl-terminal polybutadiene;

L1 represent the ratio of the number of the component polybutadiene units and M1 the ratio of the number of the component polyimide units, respectively, to the total number of both L1 and M1; and

n1 1 to 10,000, provided that L1+M1=1, 0<

L1<

1,0<

M1<

1.

2. A method of preparing the polyimide resin of claim 1, comprising:

reacting a bifunctional hydroxyl-terminal polybutadiene having a number average molecular weight of 800 to 5,000, a tetrabasic acid dianhydride represented by Formula (1);

wherein

R₁ represents a residue obtainable by removing all the carboxyl groups from an organic compound having 4 carboxyl groups, and a diisocyanate compound.

3. A method of preparing the polyimide resin of claim 1, comprising:

reacting X equivalents of an isocyanate group-containing product represented by the Formula (3);

wherein

R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl-terminal polybutadiene;

n2 represents 0-100 and Y equivalents of the tetrabasic dianhydride of the formula (1).

4. The method of claim 3, wherein said isocyanate group-containing product is obtained by reacting a bifunctional hydroxyl-terminal polybutadiene having a number average molecular weight of 800 to 5,000 and a diisocyanate compound with a isocyanate group ratio of 1:

1.5 to 2.5.

5. The method of claim 3, wherein Y<

X≦

Y/3,0<

X and 0<

Y.

7. The method of making the polyimide resin of claim 1, comprising:

reacting a compound of Formula (4);

wherein

R₁ represents a tetrabasic acid, R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl terminal polybutadiene;

L1 represent the ratio of the number of the component polybutadiene units and M1 the ratio of the number of the component polyimide units, respectively, to the total number of both L1 and M1 and n3 represents 1 to 1000, provided that L2+M2=1,0<

L2<

1,0<

M2<

1,

a compound of Formula (3);

wherein

R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl-terminal polybutadiene;

n2 represents 0-100; and

a diisocyante compound.

6. A polyimide resin represented by Formula (4):

wherein

R₁ represents a tetrabasic acid, R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl terminal polybutadiene;

L1 represent the ratio of the number of the component polybutadiene units and M1 the ratio of the number of the component polyimide units, respectively, to the total number of both L1 and M1 and n3 represents 1 to 1000, provided that L2+M2=1, 0<

L2<

1,0<

M2<

1.

8. A method of making the polyimide of claim 6, comprising reacting X equivalents of a compound of Formula (3):

wherein

R₂ represents a residue obtainable by removing all the isocyanate groups from an organic compound having 2 isocyanate groups, and R₃ represents a residue obtainable by removing the hydroxyl group from a hydroxyl-terminal polybutadiene;

n2 represents 0-100;

Y equivalents of a compound of Formula (1);

wherein

R₁ represents a residue obtainable by removing all the carboxyl groups from an organic compound having 4 carboxyl groups; and

Z equivalents of a diisocyanate compound;

wherein Y>

(X+Z)2Y/3,0.2<

(Z/X)≦

5,0<

X, 0<

Y and O≦

Z.

9. A resin composition comprising

(A) a polybutadiene polyol having a number average molecular weight of 1,000 to 8,000 and having 2 to 10 hydroxyl groups per molecule;

(B) the polyimide of claim 6; and

(C) a polybutadiene polyblock isocyanate having a number average molecular weight of 1,000 to 8,000 and having 2 to 10 block isocyanate groups per molecule;

wherein (A);

(B) is 40;

60 to 90;

10 by weight, and wherein the polybutadiene polyblock isocyanate is in an amount of 0.8 to 3.5 times the sum of the hydroxyl group equivalent number of (A) and the acid anhydride equivalent number of (B).

10. The resin of claim 9 further comprising rubber microparticles.

11. The resin of claim 9 further comprising polyimide microparticles.

12. A method of making a thermosetting insulating layer on a surface comprising applying the resin of claim 9 to said surface.

13. A method of making a flexible circuit overcoat on a surface comprising applying the resin of claim 9 to said surface.

14. A film carrier comprising an insulating film and a metal thin film pattern formed thereon, and an overcoat comprising the resin of claim 9.