IP Library Granted Patent US 11,155,686
Granted Patent B2
US 11,155,686 · App. 16/085,694 · Granted Oct 26, 2021

Fiber-reinforced polyamide resin base, method for producing same, molded article containing same, and composite molded article

Inventors: Masayuki Koshi (Nagoya, JP); Hiroyuki Ome (Nagoya, JP); Ken Sudo (Nagoya, JP); Kenichi Utazaki (Nagoya, JP)
Assignee: TORAY INDUSTRIES, INC.
C08J5/042B29B15/08B32B7/12B32B27/08B32B27/34C08G69/14C08G69/26C08K3/046C08K7/02C08L77/00B29K2077/00B29K2309/08B32B2262/101C08J2377/02C08J2377/06
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Quick Facts
Patent No.
US 11,155,686
App. No.
16/085,694
Granted
Oct 26, 2021
Kind
B2
Abstract

A fiber-reinforced polyamide resin base material comprises continuous reinforcing fibers, or comprises a reinforcing fiber base material in which discontinuous reinforcing fibers are dispersed, impregnated with a polyamide resin. In the polyamide resin, at least part of the polymer constituting the polyamide resin is an end-modified polyamide resin having, at an end group of the polymer, a structure constituted by a structural unit different from a repeating structural unit constituting the backbone of the polymer. A fiber-reinforced polyamide resin base material having an excellent impregnation property and thermal stability, less void, and excellent surface quality is provided.

Claims (29)

1. A fiber-reinforced polyamide resin base material comprising continuous reinforcing fibers impregnated with a polyamide resin, wherein in the polyamide resin, at least part of the polymer constituting the polyamide resin is an end-modified polyamide resin having, at an end group of the polymer, a structure constituted by a structural unit different from a repeating structural unit constituting the backbone of the polymer, wherein the reinforcing fibers contain carbon fibers and wherein the reinforcing fibers are contained in an amount of 20 to 70% by volume with respect to the 100% by volume of the fiber-reinforced polyamide resin base material,

wherein the end-modified polyamide resin contains an end structure represented by the following General Formula (I):

—X—(R 1 —O) m —R 2   (I)

wherein in the General Formula (I), m represents a range of 2 to 100; R 1 represents a C 2 -C 10 divalent hydrocarbon group; R 2 represents a C 1 -C 30 monovalent hydrocarbon group; —X— represents —NH—, —N(CH 3 )—, or —(C═O)—; and the R 1 of m-pieces contained in General Formula (I) may be either the same or different,

wherein the end structure represented by the following General Formula (I) is present in an amount of 1 to 20% by mass with respect to 100% by mass of the end-modified polyamide resin,

wherein the end-modified polyamide resin further contains an end structure represented by the following General Formula (II):

—Y—R 3   (II)

wherein in the General Formula (II), R 3 represents a C 1 -C 30 monovalent hydrocarbon group; in cases where X in the General Formula (I) is —NH— or —N(CH 3 )—, —Y— in the General Formula (II) represents —(C═O)—; in cases where X in the General Formula (I) is —(C═O)—, Y in the General Formula (II) represents —NH— or —N(CH 3 )—, and

wherein the end structure represented by the General Formula (II) is present in an amount of 0.1 to 5% by mass with respect to 100% by mass of the end-modified polyamide resin.

2. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the reinforcing fibers are continuously aligned in one direction.

3. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the end-modified polyamide resin contains a total of 60 to 250 [mol/t] of the end structure represented by General Formula (I) and the end structure represented by General Formula (II), and wherein the ratio between the content [mol/t] of the end structure represented by General Formula (I) and the content [mol/t] of the end structure represented by General Formula (II) ((I)/(II)) is 0.3 to 2.5.

4. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the end-modified polyamide resin contains a total of 50 to 150 [mol/t] of amino end groups and carboxyl end groups, and wherein the ratio between the content [mol/t] of the amino end groups and the content [mol/t] of the carboxyl end groups (amino end groups/carboxyl end groups) is 0.5 to 2.5.

5. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the relative viscosity (η r ) of a solution of the end-modified polyamide resin at a resin concentration of 0.01 g/mL in 98% sulfuric acid at 25° C. is 1.3 to 3.0.

6. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the weight average molecular weight Mw of the end-modified polyamide resin as measured by gel permeation chromatography is 15,000 to 50,000.

7. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the melt viscosity of the end-modified polyamide resin at melting point+60° C. at a shear rate of 9728 sec −1 is not more than 30 Pa·s.

8. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the content retention rate of the end structure represented by General Formula (I) of the end-modified polyamide resin after 60 minutes of retention at melting point+60° C. ((content after retention/content before retention)×100) is not less than 80%.

9. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the weight average molecular weight retention rate of the end-modified polyamide resin after 60 minutes of retention at melting point+60° C. ((weight average molecular weight after retention/weight average molecular weight before retention)×100) is 80% to 120%.

10. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the melt viscosity retention rate of the end-modified polyamide resin after 60 minutes of retention at melting point+60° C. ((melt viscosity after retention/melt viscosity before retention)×100) is 80% to 120%.

11. The fiber-reinforced polyamide resin base material according to claim 1 , wherein the weight reduction rate of the end-modified polyamide resin after 40 minutes of retention under a nitrogen atmosphere at melting point+60° C. is not more than 4%.

12. A molded article comprising the fiber-reinforced polyamide resin base material according to claim 1 .

13. A composite molded article comprising the fiber-reinforced polyamide resin base material according to claim 1 and a molded article containing a thermoplastic resin that are at least partly bonded to each other.

14. A method for producing the fiber-reinforced polyamide resin base material according to claim 1 , the method at least comprising the steps of:

including, in polymerization of amino acid, lactam, and/or diamine and dicarboxylic acid, a terminal modification agent represented by the following General Formula (III):

H—X—(R 1 —O) m —R 2   (III)

at 1 to 20% by mass with respect to the total of the amino acid, lactam, diamine, and dicarboxylic acid, and allowing the terminal modification agent to bind to an end(s) of a polyamide resin to obtain an end-modified polyamide resin containing an end structure represented by the following General Formula (I):

—X—(R 1 —O) m —R 2   (I)

at 1 to 20% by mass; and

impregnating continuous reinforcing fibers, or a reinforcing fiber base material in which discontinuous reinforcing fibers are dispersed, with the end-modified polyamide resin;

wherein in the General Formulae (III) and (I), m represents a range of 2 to 100; R 1 represents a C 2 -C 10 divalent hydrocarbon group; R 2 represents a C 1 -C 30 monovalent hydrocarbon group; in the General Formula (III), —X— represents —NH—, —N(CH 3 )—, or —O(C═O)—; in the General Formula (I), —X— represents —NH—, —N(CH 3 )—, or —(C═O)—; and the R 1 of m-pieces contained in General Formula (III) may be either the same or different.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 25, 2018
From: KOSHI, MASAYUKI; OME, HIROYUKI; SUDO, KEN; UTAZAKI, KENICHI
To: TORAY INDUSTRIES, INC.
Reel/Frame 046959/0898 →
Priority Claims (2)
JP JP2016-067761 · Mar 30, 2016 · national
JP JP2016-067762 · Mar 30, 2016 · national
Continuity (1)
Related Publication 20190071549A1 · Mar 7, 2019
Cited By (1)
US 12,291,612