IP Library › Granted Patent US 10,767,048
Granted Patent B2
US 10,767,048 · App. 16/104,035 · Granted Sep 8, 2020

Reinforced polyamide molding compounds having low haze and molded bodies therefrom

Inventors: Etienne Aepli (Domat/Ems, CH); Botho Hoffmann (Domat/Ems, CH); Thomas Wiedemann (Domat/Ems, CH); Heinz Hoff (Tamins, CH)
Assignee: EMS-Patent AG
C08L77/06B32B27/34C08G69/265C08L2205/025
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Quick Facts
Patent No.
US 10,767,048
App. No.
16/104,035
Granted
Sep 8, 2020
Kind
B2
Abstract

The present invention relates to a polyamide molding compound comprising the following components or consisting of these components: (A) 50 to 95 wt % of a mixture comprising the specific polyamides (A1) and (A2); (B) 5 to 50 wt % of at least one glass filler having a refractive index in the range from 1.540 to 1.600; (C) 0 to 10 wt % of at least one additive; wherein the weight proportions of the components (A) to (C) add up to 100% by weight; wherein the content of (A1) in the mixture (A) is >50 wt %, if the ratio is Δ2/Δ1>1 and the content of (A2) in the mixture (A) is >50 wt %, if the ratio is Δ2/Δ1≤1, where Δ1=n(A1)−n(B) applies and Δ2=n(B)−n(A2) applies; wherein the transparent polyamides (A1) and (A2) have a transparency of at least 90% and a haze of at most 3%; and wherein the mixture (A) has a transparency of at least 88% and a haze of at most 5%. The present invention additionally relates to molded bodies composed of these polyamide molding compounds.

Claims (97)

1. A polyamide molding compound comprising the following components:

(A) 50 to 95 wt % of a mixture consisting of the polyamides (A1) and (A2), wherein

(A1) is at least one transparent, semi-aromatic polyamide having more than 35 mol % of monomers having aromatic structural units, related to the total quantity of diamines and dicarboxylic acids in the polyamide (A1) that is amorphous or microcrystalline; and

(A2) is at least one transparent, semi-aromatic polyamide having at most 35 mol % of monomers having aromatic structural units, related to the total quantity of diamines and dicarboxylic acids in the polyamide (A2) that is amorphous or microcrystalline;

(B) 5 to 50 wt % of at least one glass filler having a refractive index in the range from 1.540 to 1.600; and

(C) 0 to 10 wt % of at least one additive;

wherein the weight proportions of the components (A) to (C) add up to 100% by weight;

wherein the content of (A1) in the mixture (A) is >50 wt %, if the ratio is Δ2/Δ1>1 and the content of (A2) in the mixture (A) is >50 wt %, if the ratio is Δ2/Δ1≤1, where Δ1=n(A1)−n(B) and Δ2=n(B)−n(A2) applies; n being the refractive index measured according to ISO 489 (1999 April),

wherein the polyamide molding compound has a transparency of at least 80% and a haze of maximum 40%;

wherein the transparency and haze of the polyamide molding compound are measured in accordance with ASTM D1003 on a molded plate of the polyamide molding compound having a dimension of 60 mm×60 mm×2 mm.

2. The polyamide molding compound in accordance with claim 1 , wherein

the polyamide mixture (A) comprises 51 to 95 wt of polyamide (A1) and 5 to 49 wt % of polyamide (A2) if Δ2/Δ1>1;

or

the polyamide mixture (A) comprises 51 to 95 wt % of polyamide (A2) and 5 to 49 wt % of polyamide (A2) if Δ2/Δ1≤1.

3. The polyamide molding compound in accordance with claim 1 , wherein the transparent polyamides (A1) are made up of the following monomers:

(a-A1) 10 to 100 mol % of cycloaliphatic diamines, with respect to the total quantity of diamines;

(b-A1) 0 to 90 mol % of diamines having aromatic structural units, with respect to the total quantity of diamines;

(c-A1) 0 to 90 mol % of open-chain cycloaliphatic diamines, with respect to the total quantity of diamines;

(d-A1) 0 to 65 mol % of open-chain aliphatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;

(e-A1) 35 to 100 mol % of aromatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;

(f-A1) 0 to 65 mol % of cycloaliphatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids; and

(g-A1) 0 to 40 wt % of lactams and/or aminocarboxylic acids having 6 to 12 carbon atoms, with respect to the total quantity of the monomers (a-A1) to (g-A1),

where the sum of the diamines (a-A1), (b-A1), and (c-A1) produces 100 mol %;

where the sum of the dicarboxylic acids (d-A1), (e-A1), and (f-A1) produces 100 mol %; and

where the sum of the monomers (b-A1) and (e-A1) amounts to more than 35 mol %, with respect to the sum of the total diamines and of the total dicarboxylic acids in the polyamide (A1).

4. The polyamide molding compound in accordance with claim 1 , wherein the transparent polyamide (A1) comprises at least 36 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids in the polyamide (A1).

5. The polyamide molding compound in accordance with claim 1 , wherein the transparent polyamides (A2) are made up of the following monomers:

(a-A2) 20 to 100 mol % of cycloaliphatic diamines, with respect to the total quantity of diamines;

(b-A2) 0 to 70 mol % of diamines having aromatic structural units, with respect to the total quantity of diamines;

(c-A2) 0 to 80 mol % of open-chain aliphatic diamines, with respect to the total quantity of diamines;

(d-A2) 20 to 100 mol % of open-chain aliphatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;

(e-A2) 0 to 70 mol % of aromatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;

(f-A2) 0 to 70 mol % of cycloaliphatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids; and

(g-A2) 0 to 40 wt % of lactams and/or aminocarboxylic acids having 6 to 12 carbon atoms, with respect to the total quantity of the monomers (a-A2) to (g-A2),

where the sum of the diamines (a-A2), (b-A2), and (c-A2) produces 100 mol %;

where the sum of the dicarboxylic acids (d-A2), (e-A2), and (f-A2) produces 100 mol %; and

where the sum of the monomers (b-A2) and (e-A2) amounts to at most 35 mol %, with respect to the sum of the total diamines and of the total dicarboxylic acids in the polyamide (A2).

6. The polyamide molding compound in accordance with claim 1 , wherein the transparent polyamide (A2) comprises at most 33 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids in the polyamide (A2).

7. The polyamide molding compound in accordance with claim 1 , wherein the monomers having aromatic structural units for the transparent polyamides (A1) and (A2) are selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic acid, p-terphenylene-4,4″-dicarboxylic acid, 2,5-pyridine dicarboxylic acid, xylylenediamine, and mixtures thereof.

8. The polyamide molding compound in accordance with claim 1 , wherein

the transparency of the molded plate is at least 85%; and/or

the haze of the molded plate amounts to a maximum of 35%; and/or

the molded plate produced from the polyamide molding compound, wherein the glass filler is in the form of glass fibers, has an arithmetical mean roughness Ra determined in accordance with DIN EN ISO 4287 (2010 July) by means of a MarSurf XR1 Surface Measuring Station of at most 0.12 μm, and/or has a surface roughness R z of at most 1.50 μm.

9. The polyamide molding compound in accordance with claim 3 , wherein

the cycloaliphatic diamine (a-A1) is selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, 2,6-norbornane diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophorone diamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4′-diaminodicyclohexyl)propane, and mixtures thereof;

and/or

the aromatic diamine (b-A1) is selected from xylylenediamines;

and/or

the diamine (c-A1) is selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, hexanediamines, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, nonanediamines, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-trideceanediamine, 1,14-tetradecanediamine, 1,18-octadecanediamine, and mixtures thereof;

and/or

the aliphatic dicarboxylic acid (d-A1) is selected from the group consisting of 1,6-apidic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12 dodecanedioic acid, 1,13-tricanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof;

and/or

the aromatic dicarboxylic acid (e-A1) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, and 4,4-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic acid, p-terphenylene-4,4″-dicarboxylic acid, and 2,5-pyridinedicarboxylic acid, and mixtures thereof;

and/or

the cycloaliphatic dicarboxylic acid (f-A1) is selected from the group consisting of 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 2,6-norbornanedicarboxylic acid, and mixtures thereof;

and/or

the lactam and/or the α,ω-aminocarboxylic acid (g-A1) is selected from the group consisting of m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminoheptanoic acid, α,ω-aminooctanoic acid, α,ω-aminononanoic acid, α,ω-aminodecanoic acid, α,ω-aminoundecanoic acid (AUA), laurolactam (LL), and α,ω-aminododecanoic acid (ADA).

10. The polyamide molding compound in accordance with claim 1 , wherein

the polyamide (A1) is selected from the group consisting of PA MACMI/12, PA MACMI/1012, PA MACMT/12, PA MACMI/MACMT/12, PA MACMI/MACMT, PA MACMI/MACMT/MACM12, PA 6I/6T/MACMI/MACMT, PA 6I/6T/MACMI/MACMT/12, PA 6I/MACMI, PA 6I/6T/PACMI/PACMT, PA 6I/612/MACMI/MACM12, PA 6T/612/MACMT/MACM12, PA 6I/6T/612/MACMI/MACMT/MACM12, PA 6I/6T/MACMI/MACMT/PACMI/PACMT, PA 6I/6T/MACMI/MACMT/PACMI/PACMT/12, PA MACMI/MACMT/MACM36, PA MACMI/MACM36, PA MACMT/MACM36, PA 12/PACMI, PA 12/MACMT, PA 6/PACMT, PA 6/PACMI, PA MXDI, PA MXDI/MXD6, PA MXDI/MXD10, PA MXDI/MXDT, PA MXDI/MACMI, PA MXDI/MXDT/MACMI/MACMT, PA 6I/6T/BACI/BACT, PA MACMI/MACMT/BACI/BACT, PA 6I/6T/MACMI/MACMT/BACI/BACT and mixtures thereof, wherein these polyamides comprise more than 35 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids; and/or

the polyamide (A2) is selected from the group consisting of PA MACM9, PA MACM10, PA MACM11, PA MACM12, PA MACM13, PA MACM14, PA MACM15, PA MACM16, PA MACM17, PA MACM18, PA MACM36, PA PACM9, PA PACM10, PA PACM11, PA PACM12, PA PACM13, PA PACM14, PACM15, PA PACM16, PACM17, PA PACM18, PA PACM36, PA TMDC9, PA TMDC10, PA TMDC11, PA TMDC12, PA TMDC13, PA TMDC14, PA TMDC15, PA TMDC16, PA TMDC17, PA TMDC18, PA TMDC36 or copolyamides PA MACM10/1010, PA MACM10/PACM10, PA MACM12/1012, PA MACM14/1014, PA PACM10/1010, PA PACM12/1012, PA PACM14/1014, PA MACM12/PACM12, PA MACM14/PACM14, PA MACMI/MACMT/MACM12, PA 6I/612/MACMI/MACM12, PA 6T/612/MACMT/MACM12, PA 6I/6T/612/MACMI/MACMT/MACM12, PA MACMI/MACMT/MACM36, PA MACMI/MACM36, PA MACMT/MACM36, PA MACMI/MACM12, PA MACMT/MACM12, PA MACMI/MACMT/10I/10T/1012, PA 6I/6T/612/PACMI/PACMT/PACM12, PA 6I/612/MACMI/MACM12, PA 6T/612/MACMT/MACM12, PA 10T/1012/MACMT/MACM12, PA 10I/1012/MACMI/MACM12, PA6I/6T/MACMI/MACMT/PACMI/PACMT/MACM12/PACM12, PA MACMI/PACMI/MACM12/PACM12, PA MACMT/PACMT/MACM12/PACM12, PA MACMI/PACMT/MACM12/PACM12, PA MACMI/MACM36, PA MACMI/MACMT/MaCM36, PA 1012/MACMI, PA 1012/MACMT, 1010/MACMI, PA 1010/MACMT, PA 612/MACMT, PA 610/MACMT, PA 612/MACMI, PA 610/MACMI, PA 1012/PACMI, PA 1012/PACMT, PA 1010/PACMI, PA 1010/PACMT, PA 612/PACMT, PA 612/PACMI, PA 610/PACMT, PA 610/PACMI and mixtures thereof;

wherein these polyamides have at most 35 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids.

11. The polyamide molding compound in accordance with claim 1 , wherein the at least one glass filler (B) is selected from the group consisting of glass fibers, ground glass fibers, glass particles, glass flakes, glass spheres, hollow glass spheres, and combinations thereof.

12. The polyamide molding compound in accordance with claim 1 , wherein the glass type of the at least one glass filler (B) is selected from the group consisting of E-glass, E-CR-glass, R-glass, AR-glass, and mixtures of glass having substantially the same refractive index.

13. The polyamide molding compound in accordance with claim 1 , wherein the at least one additive (C) is selected from the group consisting of inorganic and organic stabilizers, monomers, plasticizers, less than 5 wt % with respect to the total mass of the polyamide molding compound of semi-crystalline polyamides, impact modifiers, lubricants, colorants, marking means, photochromic agents, demolding means, condensation catalysts, chain regulators, anti-foaming agents, anti-blocking agents, optical brighteners, non-halogen flame retardants, natural sheet silicates, synthetic sheet silicates, nanoscale fillers having a particle size of a maximum of 100 nm, and mixtures thereof.

14. The polyamide molding compound in accordance with claim 1 , wherein

the proportion of component (A) in the polyamide molding compound is in the range from 55 to 90 wt % with respect to the sum of the components (A) to (C); and/or

the proportion of component (B) in the polyamide molding compound is in the range from 10 to 40 wt % with respect to the sum of the components (A) to (C); and/or

the proportion of component (C) in the molding compound is in the range from 0 to 7 wt % with respect to the sum of the components (A) to (C); and/or

the polyamide molding compound does not contain any other components than components (A) to (C).

15. The polyamide molding compound in accordance with claim 1 , wherein

component (A1) has a glass transition temperature determined in accordance with ISO 11357-2 of at least 135° C.; and/or

component (A2) has a glass transition temperature determined in accordance with ISO 11357-2 of at least 135° C.; and/or

mixture (A) has a glass transition temperature determined in accordance with ISO 11357-2 of at least 130° C.; and/or

the polyamide molding compound has a glass transition temperature determined in accordance with ISO 11357-2 of at least 130° C.

16. A molded body comprising a polyamide molding compound in accordance with claim 1 .

17. The molded body in accordance with claim 16 , which is a multilayer molded body.

18. The polyamide molding compound in accordance with claim 5 , wherein

the cycloaliphatic diamine (a-A2) is selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, 2,6-norbornane diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophorone diamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4′-diaminodicyclohexyl)propane, and mixtures thereof;

and/or

the aromatic diamine (b-A2) is selected from xylylenediamines;

and/or

the diamine (c-A2) is selected from the group consisting of 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, hexanediamines, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, nonanediamines, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-trideceanediamine, 1,14-tetradecanediamine, 1,18-octadecanediamine, and mixtures thereof;

and/or

the aliphatic dicarboxylic acid (d-A2) is selected from the group consisting of 1,6-apidic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12 dodecanedioic acid, 1,13-tricanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof;

and/or

the aromatic dicarboxylic acid (e-A2) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, and 4,4-diphenylsulfonedicarboxylic acid, 1,5-anthracene dicarboxylic acid, p-terphenylene-4,4″-dicarboxylic acid, and 2,5-pyridinedicarboxylic acid, and mixtures thereof;

and/or

the cycloaliphatic dicarboxylic acid (f-A2) is selected from the group consisting of 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 2,6-norbornanedicarboxylic acid, and mixtures thereof;

and/or

the lactam and/or the α,ω-aminocarboxylic acids (g-A2) are/is selected from the group consisting of m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminoheptanoic acid, α,ω-aminooctanoic acid, α,ω-aminononanoic acid, α,ω-aminodecanoic acid, α,ω-aminoundecanoic acid (AUA), laurolactam (LL), and α,ω-aminododecanoic acid (ADA).

19. The polyamide molding compound of claim 10 , wherein the polyamide mixture (A) comprises the following combination of polyamide (A1) and polyamide (A2):

polyamide (A1) 6I/6T/612/MACMI/MACMT/MACM12 and polyamide (A2) 6I/6T/612/MACMI/MACMT/MACM12;

polyamide (A1) 6I/6T/MACMI/MACMT and polyamide (A2) 6I/6T/612/MACMI/MACMT/MACM12;

polyamide (A1) 6I/6T/612/MACMI/MACMT/MACM12 and polyamide (A2) MACMI/MACMT/12;

polyamide (A1) 6I/6T/612/MACMI/MACMT/12/PACMI/PACMT and polyamide (A2) MACMI/MACMT/MACM12;

polyamide (A1) 6I/6T/MACMI/MACMT and polyamide (A2) MACMI/12; or

polyamide (A1) 6I/6T/612/MACMI/MACMT/MACM12 and polyamide (A2) MACMI/12.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 25, 2018
From: AEPLI, ETIENNE; HOFFMANN, BOTHO; WIEDEMANN, THOMAS; HOFF, HEINZ
To: EMS-PATENT AG
Reel/Frame 046944/0580 →
Priority Claims (1)
EP 17186920 · Aug 18, 2017 · regional
Continuity (1)
Related Publication 20190055405A1 · Feb 21, 2019
Cited By (3)
US 12,291,638 US 12,344,710 US 12,398,269