Polyamide resin-type composite material and method for producing same

Patent metadata

Field	Value
Publication number	US-9688844-B2
Application number	US-201414528063-A
Country	US
Kind code	B2
Filing date	Oct 30, 2014
Priority date	Apr 12, 2011
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A xylylenediamine-based polyamide resin/fiber composite material and molding are provided that do not exhibit a decline in properties under high temperatures and high humidities, and that exhibit a high elastic modulus and present little warping, and exhibit better recycle characteristics, a better moldability, and a better productivity than for thermosetting resins. The polyamide resin-type composite material comprises a fibrous material (B) impregnated with a polyamide resin (A) wherein at least 50 mole % of diamine structural units derived from xylylenediamine, and having a number-average molecular weight (Mn) of 6,000 to 30,000, and containing a component of a molecular weight of not more than 1,000 at 0.5 to 5 mass %.

First claim

The invention claimed is:

1. A polyamide resin composite material, comprising:
a polyamide comprising a plurality of molecules having a number-average molecular weight (Mn) of 6,000 to 30,000; and
a fibrous material impregnated with the polyamide,
wherein the fibrous material has an average fiber length of at least 1 cm,
each of the molecules comprises a diamine structural unit and a dicarboxylic unit,
at least 50 mole % of the diamine structural units are derived from xylylenediamine, and
0.5 to 5 mass % of the molecules have a molecular weight of not more than 1,000.

2. The polyamide resin composite material of claim 1 , wherein the molecules comprise a cyclic compound formed by a salt produced from a diamine component having the diamine structural unit and a dicarboxylic acid component having the dicarboxylic unit in an amount of from 0.01 to 1 mass %.

3. The polyamide resin composite material of claim 1 , wherein the molecules have a molecular weight distribution (Mw/Mn) of from 1.8 to 3.1.

4. The polyamide resin composite material of claim 1 , wherein the polyamide has a melt viscosity of 50 to 1,200 Pa·s, when measured at a temperature of a melting point of the polyamide +30° C., at a shear rate of 122 sec −1 , and at a moisture content in the polyamide of not more than 0.06 mass %.

5. The polyamide resin composite material of claim 1 , wherein the polyamide has a flexural modulus retention rate of at least 85% when the polyamide absorbs moisture.

6. The polyamide resin composite material of claim 1 , wherein the polyamide has at least two melting points.

7. The polyamide resin composite material of claim 1 , wherein the xylylenediamine is meta-xylylenediamine, para-xylylenediamine, or a mixture thereof.

8. The polyamide resin composite material of claim 1 , wherein the fibrous material has a functional group at a surface of the fibrous material, and the functional group is derived from at least one compound selected from the group consisting of an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, and a titanate compound.

9. The polyamide resin composite material of claim 1 , wherein the fibrous material has a functional group at a surface of the fibrous material, and the functional group is derived from a silane coupling agent.

10. The polyamide resin composite material of claim 1 , wherein the fibrous material is at least one selected from the group consisting of a glass fiber, a carbon fiber, a plant fiber, an alumina fiber, a boron fiber, a ceramic fiber, a metal fiber, an aramid fiber, a polyoxymethylene fiber, an aromatic polyamide fiber, a polyparaphenylenebenzobisoxazole fiber, and an ultrahigh molecular weight polyethylene fiber.

11. The polyamide resin composite material of claim 1 , wherein an area ratio of the polyamide to the fibrous material in a cross section of the polyamide resin composite material is from 20/80 to 80/20.

12. The polyamide resin composite material of claim 1 , wherein a void area ratio in a cross section of the polyamide resin composite material is not more than 5%.

13. The polyamide resin composite material of claim 1 , further comprising:
short fibers having an average fiber diameter smaller than an average fiber diameter of the fibrous material.

14. A method for producing a molding, comprising:
heating the polyamide resin composite material of claim 1 ; and then
molding the heated polyamide resin composite material at a temperature of 70 to 150° C. in a die or with a roll.

15. The method of claim 14 , further comprising:
forming a polyamide resin layer on a surface of the molding.

16. A molding obtained by molding the polyamide resin composite material of claim 1 .

17. The molding of claim 16 , wherein an area ratio of the polyamide to the fibrous material in a cross section of the polyamide resin composite material is from 20/80 to 80/20.

18. The molding of claim 16 , wherein a void area ratio in a cross section of the molding is not more than 5%.

19. The polyamide resin composite material of claim 1 , wherein the fibrous material has an average fiber length of from 1 cm to 500 cm.

20. A method for producing a polyamide resin composite material, comprising:
converting a polyamide into a film or a fiber;
stacking a fibrous material and the polyamide that has been converted into the film or the fiber; and then
applying heat and pressure to the polyamide and the fibrous material, such that the polyamide is impregnated into the fibrous material,
wherein the fibrous material has an average fiber length of at least 1 cm,
the polyamide comprises a plurality of molecules each comprising a diamine structural unit and a dicarboxylic unit,
at least 50 mole % of the diamine structural units are derived from xylylenediamine,
the molecules have a number-average molecular weight (Mn) of 6,000 to 30,000, and
0.5 to 5 mass % of the molecules have a molecular weight of not more than 1,000.

21. The method of claim 20 , wherein the applying of heat and pressure to the polyamide and the fibrous material is carried out by applying pressure to the polyamide and the fibrous material with a plurality of rolls in a heated atmosphere.

22. The method of claim 20 ,
wherein the polyamide that has been converted into the film or the fiber has a heat capacity of crystallization of at least 5 J/g, and
the polyamide in the polyamide resin composite material has a heat capacity of crystallization of at least 5 J/g.

23. The method of claim 20 , wherein the polyamide that has been converted into the film or the fiber is a film and has a surface roughness (Ra) of from 0.01 to 1 μm.

24. The method of claim 20 , wherein the polyamide that has been converted into the film or the fiber is a multifilament fiber and has a monofilament fineness of from 1 to 30 dtex.

25. The method of claim 20 , wherein the polyamide that has been converted into the film or the fiber is a multifilament fiber and has a tensile strength of from 1 to 10 gf/d.

26. The method of claim 20 , wherein, in the converting, the polyamide is converted into the film by coextruding the polyamide and a polyolefin resin such that a film comprising a polyamide layer comprising the polyamide and a polyolefin resin layer comprising the polyolefin is formed, and separating the polyolefin resin layer from the polyamide layer to form the film.

27. The method of claim 20 , wherein the polyamide that has been converted into the film or the fiber has a moisture content of from 0.01 to 0.15 mass %.

Assignees

• Mitsubishi Gas Chemical Co

Inventors

• Mitadera Jun

Classifications

• B29K2307/04

  Carbon · CPC title

• C08K7/06 Primary

  Elements · CPC title

• B29K2995/0016

  Non-flammable or resistant to heat · CPC title

• C08L77/00

  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 title

• B29K2077/10

  Aromatic polyamides [polyaramides] or derivatives thereof · CPC title