Polymer composite, method and polymer composition

• US 5,371,122 A
• Filed: 03/24/1993
• Issued: 12/06/1994
• Est. Priority Date: 03/24/1992
• Status: Expired due to Fees

• Current Assignee: Mitsuboshi Belting Limited
• Original Assignee: Mitsuboshi Belting Limited
• Inventors: Sayo, Koichi, Noguchi, Toru, Goto, Kazuo, Yamaguchi, Yoshio, Deki, Shigehito, Kawahara, Masahito
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): ZEMEL, IRINA SOPJIA
• Application Number:
  US08/036,502
• Time in Patent Office: 622 Days
• Field of Search: 524/88, 524/89, 524/90
• US Class Current: 524/88
• CPC Class Codes: C08K 5/00 Use of organic ingredients
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09B 67/0061 by grinding a dyed resin

Abstract

A polymer composite contains colorant molecules dispersed therein. The colorant molecules can be dispersed in the polymer or bound to the polymer molecules. When the polymer is a polyamide, the polyamide is in a noncrystalline state due to the inhibition of crystallization imparted by the size and shape of the colorant molecules because the colorant is separated on a molecular level. A high colorant availability is obtained. A method of producing the polymer composite includes the steps of forming a metastable polymer resin layer, applying a film of colorant to the layer, stabilizing the layer, dissolving the stable layer in a solvent, aspirating the solution to remove impurities and aggregates and then removing the solvent. A polymer composition can be produced by mixing the polymer composite with a polymer.

Claims

1. A polymer composite suitable for use as at least one of a dye, coloring agent and chemical indicator polymer, the polymer composite comprising a polymer resin and at least one colorant capable of being dispersed on a molecular level without aggregates in the polymer resin, the colorant is caused to migrate into the polymer resin by relaxation of a thermodynamically metastable polymer resin layer having a film of the colorant thereon to a thermodynamically stable state to form a polymer precursor.

2. The polymer composite in accordance with claim 1 wherein the polymer resin is a polyamide.

3. The polymer composite in accordance with claim 1 wherein the polymer resin has a cohesive energy density of at least about 2,000 cal/mol.

4. The polymer composite in accordance with claim 1 wherein the polymer resin has a cohesive energy density in the range of about 2,000 to about 6,000 cal/mol.

5. The polymer composite in accordance with claim 1 wherein the colorant is selected from the group consisting of azobenzene, 4-phenylazobenzene, 4-dimethylaminoazobenzene, 4-dimethylamino-4'"'"'-methylazobenzene, 4-nitro-4'"'"'-dimethylaminoazobenzene, 1-phenylazonaphthalene, 4-phenylazoazobenzene, (naphthylazo)-1,1'"'"'-azonaphthalene, trisazobenzene, stilbene, 4-dimethylamino-4'"'"'-nitrostilbene, coumarin, 4-methyl-7-dimethylaminocoumarin, 3,3'"'"'-diethyldicarbocyanine iodide, 3,3'"'"'-methyloxatricarbocyanine iodide, 3-ethyl-5-[4-(3-ethyl-2-benzothiazolylidene)-2-hexenylidene]rhodanine, squarilium, spiropyran, fulgide, indigo, anthracene, perylene and 1,4-benzoquinone.

6. The polymer composite in accordance with claim 1 wherein the colorant is selected from the group of porphyrin derivatives, metallo-porphyrin derivatives, phthalocyanine derivatives, metallo-phthalocyanine derivatives, naphthalocyanine derivatives and metallo-naphthalocyanine derivatives.

7. The polymer composite in accordance with claim 6 wherein the polymer resin is a polyamide resin.

8. The polymer composite in accordance with claim 7 wherein the colorant has at least one N--H group or metal group that is capable of bonding to a carbonyl group of the polyamide.

9. The polymer composite in accordance with claim 7 wherein the polyamide is in a noncrystalline state in the polymer composite.

10. The polymer composite in accordance with claim 1 wherein the colorant is selected from the group of porphyrin derivatives having the FORMULA I:

##STR7## wherein R1, R2, R3 and R4 are alike or different and are hydrogen, an alkyl group, an alkoxy group, an amino group, a cyano group, a phenyl group, a benzo group or a pyridyl group and R5 to R12 are alike or different and are hydrogen, an alkyl group, an alkoxy group, an amino group or a cyano group, metallo-porphyrin derivatives having the FORMULA II;

##STR8## wherein R1 to R12 are as described above in connection with FORMULA I and M represents a transition metal, an alkali metal, an alkaline earth metal, an element belonging to the Group IIIA or IVA of the second or lower period or a metal belonging to Group VA or VIA of the Periodic Table, phthalocyanine derivatives having the FORMULA III;

##STR9## wherein R5 to R12 are as described above in connection with FORMULA I, metallo-phthalocyanine derivatives having the FORMULA IV;

##STR10## wherein R5 to R12 are as described above in connection with FORMULA I and M is as described in connection with FORMULA II, naphthalocyanine derivatives having the FORMULA V;

##STR11## wherein R5 to R12 are as described above in connection with FORMULA I, and metallo-naphthalocyanine derivatives having the FORMULA VI;

##STR12## wherein R5 to R12 are as described above in connection with FORMULA I and M is as described in connection with FORMULA II.

11. The polymer composite in accordance with claim 1 wherein the colorant is present in an amount in the range of about 0.1 to about 30 weight percent based on the total weight of the composite.

18. The polymer composite of claim 1 wherein the polymer precursor is dissolved by exposure to solvent to form a solution.

19. The polymer composite of claim 18 wherein the solution is filtered to form a filtrate and the filtrate is dried to form a polymer composite.

12. A polymer composite suitable for use as at least one of a dye, coloring agent and chemical indicator polymer, the polymer composite comprising a polymer resin and at least one colorant selected from the group of porphyrin derivatives, metallo-porphyrin derivatives, phthalocyanine derivatives, metallo-phthalocyanine derivatives, naphthalocyanine derivatives, metallo-naphthalocyanine derivatives azobenzene, 4-phenylazobenzene, 4-dimethylaminoazobenzene, 4-dimethylamino-4'"'"'-methylazobenzene, 4-nitro-4'"'"'-dimethylaminoazobenzene, 1-phenylazonaphthalene, 4-phenylazoazobenzene, (naphthylazo)-1,1'"'"'-azonaphthalene, trisazobenzene, stilbene, 4-dimethylamino-4'"'"'-nitrostilbene, coumarin, 4-methyl-7-dimethylaminocoumarin, 3,3'"'"'-diethyldicarbocyanine iodide, 3,3'"'"'--methyloxatricarbocyanine iodide, 3-ethyl-5-[4-(3-ethyl-2-benzothiazolylidene)-2-hexenylidene]rhodanine, squarilium, spiropyran, fulgide, indigo, anthracene, perylene and 1,4-benzoquinone dispersed without aggregates in the polymer resin by migration of a film of the colorant on a thermodynamically metastable polymer resin layer into the polymer resin layer by relaxation to a thermodynamically stable state to form a polymer precursor.

13. The polymer composite in accordance with claim 12 wherein the polymer resin has a cohesive energy density of at least about 2,000 cal/mol.

14. The polymer composite in accordance with claim 12 wherein the polymer resin has a cohesive energy density in the range of about 2,000 to about 6,000 cal/mol.

15. The polymer composite in accordance with claim 12 wherein the colorant is present in an amount in the range of about 0.1 to about 30 weight percent based on the total weight of the composite.

16. The polymer composite in accordance with claim 12 wherein the colorant is selected from the group of porphyrin derivatives having the FORMULA I:

##STR13## wherein R1, R2, R3 and R4 are alike or different and are hydrogen, an alkyl group, an alkoxy group, an amino group, a cyano group, a phenyl group, a benzo group or a pyridyl group and R5 to R12 are alike or different and can be hydrogen, an alkyl group, an alkoxy group, an amino group or a cyano group, metallo-porphyrin derivatives having the FORMULA II;

##STR14## wherein R1 to R12 are as described above in connection with FORMULA I and M represents a transition metal, an alkali metal, an alkaline earth metal, an element belonging to the Group IIIA or IVA of the second or lower period or a metal belonging to Group VA or VIA of the Periodic Table, phthalocyanine derivatives having the FORMULA III;

##STR15## wherein R5 to R12 are as described above in connection with FORMULA I, metallo-phthalocyanine derivatives having the FORMULA IV;

##STR16## wherein R5 to R12 are as described above in connection with FORMULA I and M is as described in connection with FORMULA II, naphthalocyanine derivatives having the FORMULA V;

##STR17## wherein R5 to R12 are as described above in connection with FORMULA I, and metallo-naphthalocyanine derivatives having the FORMULA VI;

##STR18## wherein R5 to R12 are as described above in connection with FORMULA I and M is as described in connection with FORMULA II.

17. The polymer composite in accordance with claim 12 wherein the polymer resin is a polyamide resin and the polyamide is in a noncrystalline state in the polymer composite.

20. A polymer composite suitable for use as at least one of a dye, coloring agent and chemical indicator polymer, the polymer composite comprising a polymer resin and at least one colorant dispersed in the polymer resin by the migration of the colorant into a thermodynamically metastable polymer resin layer from a film of the colorant thereon by relaxation to a thermodynamically stable state to form a polymer precursor, dissolution of the precursor in a solvent to form a solution, filtration of the solution to form a filtrate and solidification the filtrate to form a substantially aggregate free polymer composite.

21. A polymer composite suitable for use as at least one of a dye, coloring agent and chemical indicator polymer, the polymer composite comprising a polymer resin and at least one colorant capable of being dispersed on a molecular level without aggregates in the polymer resin by:

depositing a thermodynamically metastable polymer resin layer;

depositing a film of the at least one colorant onto the metastable layer;

relaxing the polymer layer to cause migration of the colorant into the polymer layer to disperse the colorant in the polymer layer; and

removing aggregates or impurities from the polymer resin layer having colorant dispersed therein using a solvent.

22. The polymer composite of claim 21 wherein the aggregates or impurities are removed by:

dissolving the polymer resin layer having colorant dispersed therein in a solvent;

centrifuging the solution to remove colorant aggregates; and

removing the solvent.