Silicone-modified polyimide resin composition of solvent free type

Patent metadata

Field	Value
Publication number	US-2017355825-A1
Application number	US-201715621358-A
Country	US
Kind code	A1
Filing date	Jun 13, 2017
Priority date	Jun 14, 2016
Publication date	Dec 14, 2017
Grant date	—

Abstract

Disclosed herein is a silicone-modified polyimide resin composition of solvent free type. The composition is suitable for use as an adhesive and a coating material which are capable of hardening upon irradiation with ultraviolet rays and/or visible rays. Also, it is saved from drooling even in the case of light filling with an inorganic compound and it is saved from bubble entrapment and nonuniformity at the time of application with heavy filling. It further exhibits good moldability due to its thixotropic properties. Moreover, it exhibits improved adhesion to polyolefin resins without impairing the past properties. Finally, it gives rise to a cured product which is not excessively hard, with a low elastic modulus, despite filling with an inorganic compound. The composition of the present invention includes components (A) to (B) listed below and is characterized by being fluid at 25° C. and free of solvent:
(A) silicone-modified polyimide resin; (B) polymerizable compound; (C) polymerization initiator, (D) hydrophobic fumed silica; and (E) adhesion auxiliary agent.

First claim

1 . A silicone-modified polyimide resin composition of solvent free type which is fluid at 25° C. and free of solvent, the composition comprising:
(A) 100 parts by weight of a silicone-modified polyimide resin which is represented by the formula (1) below:
E e -F f -G g   (1)

in the formula (1), E, F, and G are randomly bonded repeating units, E is a divalent residue derived from diamino-modified silicone represented by the formula (2) below, F is a residue derived from tetracarboxylic acid dianhydride represented by the formula (3) below, and G is a divalent residue derived from diamine, and the sum of e+f+g is 100 mol %, the molar ratio of f/(e+g) is from 0.8 to 1.2,

in the formula (2), R A is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 and R 2 are each, independent from each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 and R 4 are each, independent from each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 5 and R 6 are each, independent from each other, an organic group selected from a substituted or unsubstituted alkyl group, aryl group, or aralkyl group, having 1 to 16 carbon atoms, and each of m, n, and o is an integer from 0 to 20, n+o≧1 and m+n+o=1 to 60,
—I m —X—I m —  (3)

in the formula (3), I m is a cyclic group having a cyclic imide structure at its end, and X is a single bond, oxygen, sulfur, sulfide group, sulfonic group, carbonyl group, —NR N — (wherein R N is a straight, branched, or cyclic monovalent hydrocarbon group having 1 to 12 carbon atoms), —CR B 2 — (wherein R B is, independent form each other, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms), —R Ar h — (wherein R Ar is a divalent arylene group having 6 to 12 carbon atoms, and h is an integer of 1 to 6), a trivalent or tetravalent group derived from an arylene group with one or two hydrogen atoms eliminated, —R Ar h (OR Ar ) i — (wherein R Ar and h are defined as above and i is an integer of 1 to 5), a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, a trivalent group derived from the alkylene group with one hydrogen atom eliminated, or a divalent to tetravalent organic group selected from arylenealkylene groups;
(B) a polymerizable compound: 100 to 2,000 parts by weight,
(C) a polymerization initiator: 0.1 to 30 parts by weight per 100 parts by weight of the total content of the components (A) and (B),
(D) a hydrophobic fumed silica: 1 to 50 parts by weight per 100 parts by weight of the total content of the components (A) and (B), and
(B) an adhesion auxiliary agent: 0.1 to 5 parts by weight per 100 parts by weight of the total content of the components (A) and (B).

2 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , wherein I m is selected from the groups shown below:

wherein the bonding hands marked with a wavy line function such that the one bonding to the nitrogen atom bonds to E or G and the other bonds to X.

3 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , wherein the component (B) is a radical-polymerizable compound.

4 . The silicone-modified polyimide resin composition of solvent free type of claim 3 , wherein the component (B) is a (meth)acrylate ester compound.

5 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , wherein the component (C) is a radical initiator capable of thermal decomposition or an initiator to be activated by irradiation.

6 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , wherein the component (D) is hydrophobic fumed silica having a bulk density no higher than 1 g/mL, a mean primary particle diameter of from 1 to 100 nm, and a BET specific surface area of from 100 to 300 m 2 /g.

7 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , wherein the component (E) is a compound represented by the formula (4) below:
I-(J-K) jk -J-I  (4)

in the formula (4), I is a monovalent unsaturated hydrocarbon group having a polymerizable group at each end and having 6 to 20 carbon atoms, J is a divalent siloxane unit represented by the formula (5), K is a divalent hydrocarbon group having 6 to 20 carbon atoms, and jk is an integer from 1 to 10,

in the formula (5), R 1 , R 2 , R 5 , and R 6 are defined as above, p is an integer from 1 to 60, and q is an integer from 0 to 60, with p+q≦1 and p+q=1 to 60.

8 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , having a viscosity of from 3 to 1,000 Pa·s at 25° C.

9 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , further comprising (F) a modifying additive.

10 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , further comprising (G) a leveling agent.

11 . The silicone-modified polyimide resin composition of solvent free type of claim 1 , further comprising (H) a dye as the component.

12 . An adhesive composed of the composition defined in claim 1 .

13 . A coating agent composed of the composition defined in claim 1 .

14 . A cured product of silicone-modified polyimide resin which is obtained from the silicone-modified polyimide resin composition of solvent free type of claim 1 , by curing with ultraviolet rays and/or visible rays,
wherein coating film formed by the cured product has a storage elastic modulus of from 1 to 500 MPa.

15 . A cured product of silicone-modified polyimide resin which is obtained from the silicone-modified polyimide resin composition of solvent free type of claim 1 by curing with ultraviolet rays and/or visible rays,
wherein coating film formed by the cured product has a light transmittance at least 80% in the visible region and also has a color specified by the L*a*b* colorimetric system such that L* is at least 80%, a* is at least −10% and lower than 10%, and b* is at least −10% and lower than 10%.

Assignees

• Shinetsu Chemical Co

Inventors

• Hattori Hatsuhiko
• Yoneda Yoshinori
• KANAI Tomoya

Classifications

• C08F290/065

  Polyamides; Polyesteramides; Polyimides · CPC title

• C09D151/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08L51/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C09J151/08

  grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08G77/12

  containing silicon bound to hydrogen · CPC title