Polyimide composite material and film thereof

Patent metadata

Field	Value
Publication number	US-9540487-B2
Application number	US-74493408-A
Country	US
Kind code	B2
Filing date	Nov 27, 2008
Priority date	Nov 30, 2007
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

A polyamic acid solution includes a polyamic acid, a solvent (C) in which the polyamic acid (PAA1) is dissolved, and a substance (M) that can release at least one metal selected from groups 1 and 2 of the periodic table as a metal ion, or a substance (m) that contains the substance (M). A polyimide composite is produced from the polyamic acid solution. The polyimide composite can provide a greatly improved glass transition temperature without impairing the intrinsic physical properties of the polyimide.

First claim

The invention claimed is:

1. A polyamic acid solution (S2) comprising:
a polyamic acid (PAA1) having the following general formula (1);

wherein in the formula (1), X denotes a divalent organic group, and Y denotes a tetravalent organic group,
a solvent (C) in which the polyamic acid (PAA1) is dissolved; and
a substance (M) selected from the group consisting of calcium hydroxide, magnesium hydroxide, and strontium hydroxide, wherein the amount of substance (M) is from 1.4 to 14 equivalents per 100 equivalents of a constitutional repeating unit of the polyamic acid (PAA1) having the formula (1).

2. The polyamic acid solution (S2) according to claim 1 , wherein the solvent (C) is an aprotic polar solvent (C).

3. A method for producing the polyamic acid solution (S2) according to claim 1 , comprising the following steps 1 and 2 of:
(step 1) producing a polyamic acid solution (S1) produced from the polyamic acid (PAA1) having the general formula (1) wherein X denotes a divalent organic group, and Y denotes a tetravalent organic group and the solvent (C) in which the polyamic acid (PAA1) is dissolved, the polyamic acid (PAA1) being produced from a tetracarboxylic acid anhydride (A) and a diamine compound (B); and

(step 2) adding 1.4 to 14 equivalents of the substance (M) selected from the group consisting of calcium hydroxide, magnesium hydroxide, and strontium hydroxide per 100 equivalents of a constitutional repeating unit of the polyamic acid (PAA1) having the formula (1) to the polyamic acid solution (S1) produced in the step 1 to produce the polyamic acid solution (S2), wherein the solution viscosity (V1) of the polyamic acid solution (S1) before the addition of the substance (M) (E-type viscosity measured at 25° C.) and the solution viscosity (V2) of the polyamic acid solution (S2) after the addition of the substance (M) (E-type viscosity measured at 25° C.) satisfy the following formula (I)
( V 2/ V 1)×100 ≧120%  (I).

4. A polyimide composite (PIC) produced from the polyamic acid solution (S2) according to claim 1 .

5. (The polyimide composite (PIC) according to claim 4 produced by a production method comprising the following steps 1 to 3 of:
(step 1) producing a polyamic acid solution (S1) produced from the polyamic acid (PAA1) having the general formula (1) wherein X denotes a divalent organic group, and Y denotes a tetravalent organic group, and the solvent (C) in which the polyamic acid (PAA1) is dissolved, the polyamic acid (PAA1) being produced from a tetracarboxylic acid anhydride (A) and a diamine compound (B);

(step 2) adding 1.4 to 14 equivalents of the substance (M) selected from the group consisting of calcium hydroxide, magnesium hydroxide, and strontium hydroxide per 100 equivalents of a constitutional repeating unit of the polyamic acid (PAA1) having the formula (1) to the polyamic acid solution (S1) produced in the step 1 to produce the polyamic acid solution (S2), wherein the solution viscosity (V1) of the polyamic acid solution (S1) before the addition of the substance (M) (E-type viscosity measured at 25° C.) and the solution viscosity (V2) of the polyamic acid solution (S2) after the addition of the substance (M) (E-type viscosity measured at 25° C.) satisfy the following formula (I); and
( V 2/ V 1)×100≧120%  (I)

(step 3) producing the polyimide composite (PIC) by imidization of a polyamic acid (PAA2) contained in the polyamic acid solution (S2) produced in the step 2 and removal of the solvent (C).

6. The polyimide composite (PIC) according to claim 5 , wherein the glass transition temperature (Tg1) of a polyimide (PI) produced not through the step 2 but through the step 3 using the polyamic acid solution (S1) produced in the step 1 and the glass transition temperature (Tg2) of the polyimide composite (PIC) satisfy the following formula (II) (K means absolute temperature)
Tg2−Tg1≧5 K   (II).

7. The polyimide composite (PIC) according to claim 4 , wherein a polyimide contained in the polyimide composite (PIC) has a constitutional unit having the following general formula (2)

wherein in the formula (2), X denotes a divalent organic group, and Y denotes a tetravalent organic group.

8. The polyimide composite (PIC) according to claim 7 , wherein X in the constitutional unit having the general formula (2) is at least one divalent alicyclic group selected from the group consisting of

or at least one bivalent aromatic group selected from the group consisting of

wherein X 1 to X 5 are selected from

and X 2 to X 5 may be the same or different from one another, and
Y in the constitutional unit having the general formula (2) is at least one tetravalent aromatic group selected from the group consisting of

or at least one tetravalent alicyclic group selected from the group consisting of

9. The polyimide composite (PIC) according to claim 7 , wherein X in the constitutional unit having the general formula (2) is a divalent alicyclic group containing 4 to 15 carbon atoms, and Y is a tetravalent aromatic group containing 6 to 27 carbon atoms.

10. The polyimide composite (PIC) according to claim 7 , wherein X in the constitutional unit having the general formula (2) is a divalent aromatic group containing 6 to 51 carbon atoms, and Y is a tetravalent alicyclic group containing 4 to 12 carbon atoms.

11. The polyimide composite (PIC) according to claim 7 , wherein X in the constitutional unit having the general formula (2) is a divalent alicyclic group containing 4 to 15 carbon atoms, and Y is a tetravalent alicyclic group containing 4 to 12 carbon atoms.

12. The polyimide composite (PIC) according to claim 7 , wherein X in the constitutional unit having the general formula (2) is a divalent aromatic group containing 6 to 51 carbon atoms, and Y is a tetravalent aromatic group containing 6 to 27 carbon atoms.

13. The polyimide composite (PIC) according to claim 7 , wherein the polyimide composite (PIC) has a glass transition temperature of 200° C. or more and a coefficient of linear expansion below 50 ppm/K at a temperature in the range of 100° C. to 200° C.

14. The polyimide composite (PIC) according to claim 7 , wherein the polyimide composite (PIC) has a glass transition temperature of 200° C. or more, a total light transmittance of 80% or more, and a coefficient of linear expansion below 50 ppm/K at a temperature in the range of 100° C. to 200° C.

15. The polyimide composite (PIC) according to claim 4 , wherein the polyimide composite (PIC) has a glass transition temperature of 200° C. or more.

16. A polyimide composite film manufactured from the polyim

Assignees

• Fukukawa Kenichi
• Sakata Yoshihiro
• Fujio Ichiro
• Yamashita Wataru
• Mitsui Chemicals Inc

Inventors

• Fukukawa Kenichi
• Sakata Yoshihiro
• Fujio Ichiro
• Yamashita Wataru

Classifications

• C09D179/08

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

• H05K1/0373

  containing additives, e.g. fillers (H05K1/036 takes precedence) · CPC title

• C08G73/1039

  comprising halogen-containing substituents · CPC title

• C08L79/08

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

• Y10T428/31681

  Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.] · CPC title