# US 10,767,047 B2 · Reinforced polyamide molding compounds having low haze and molded bodies therefrom

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- Number: US 10,767,047 B2
- Document ID: US10767047B2
- Status: Granted
- Kind: B2
- Application number: 16/104,028
- Filed: 2018-08-16
- Published: 2019-02-21
- Granted: 2020-09-08
- Earliest claimed: 2017-08-18
- Assignees: Ems-Patent AG
- Applicants: Ems-Patent AG
- Inventors: Etienne Aepli; Botho Hoffmann; Heinz Hoff
- Web page: https://patentgrep.com/patent/US10767047B2

## CPC

- C08L 77/06: Polyamides derived from polyamines and polycarboxylic acids (C08L77/10 takes precedence)
- B32B 7/02: Physical, chemical or physicochemical properties
- B32B 27/08: of synthetic resin
- B32B 27/18: characterised by the use of special additives
- B32B 27/20: using fillers, pigments, thixotroping agents
- B32B 27/22: using plasticisers
- B32B 27/34: comprising polyamides
- C08G 69/265: {from at least two different diamines or at least two different dicarboxylic acids}
- C08G 69/36: derived from amino acids, polyamines and polycarboxylic acids
- B32B 2250/02: 2 layers
- B32B 2250/03: 3 layers
- B32B 2250/24: All layers being polymeric
- B32B 2262/101: Glass fibres
- B32B 2264/101: Glass
- B32B 2307/3065: Flame resistant or retardant, fire resistant or retardant
- B32B 2307/412: Transparent
- B32B 2307/538: Roughness
- B32B 2307/54: Yield strength; Tensile strength
- B32B 2307/558: Impact strength, toughness
- B32B 2307/71: Resistive to light or to UV
- B32B 2307/714: Inert, i.e. inert to chemical degradation, corrosion
- B32B 2439/00: Containers; Receptacles
- B32B 2451/00: Decorative or ornamental articles
- B32B 2457/00: Electrical equipment
- B32B 2605/00: Vehicles
- B32B 2607/00: Walls, panels
- C08L 2201/10: Transparent films; Clear coatings; Transparent materials
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## 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 1.510 to 1.539; (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 furthermore relates to molded bodies composed of these polyamide molding compounds.

## Claims

### Claim 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 at least 25 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 polyamide having less than 25 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 1.510 to 1.539; 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) applies and Δ2=n(B)−n(A2) applies; n being the refractive index measured according to ISO 489 (1999-04),
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%.

### Claim 2 (depends on 1)

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 (A1) if Δ2/Δ1≤1;
and/or
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 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 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 components (A) to (C).

### Claim 3 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein the transparent polyamides (A1) are made up of the following monomers:
(a-A1) 20 to 100 mol % of cycloaliphatic diamines, with respect to the total quantity of diamines;
(b-A1) 0 to 80 mol % of diamines having aromatic structural units, with respect to the total quantity of diamines;
(c-A1) 0 to 80 mol % of open-chain cycloaliphatic diamines, with respect to the total quantity of diamines;
(d-A1) 0 to 75 mol % of open-chain aliphatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;
(e-A1) 25 to 100 mol % of aromatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;
(f-A1) 0 to 75 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),
wherein the sum of the diamines (a-A1), (b-A1), and (c-A1) produces 100 mol %;
wherein the sum of the dicarboxylic acids (d-A1), (e-A1), and (f-A1) produces 100 mol %; and
wherein the sum of the monomers (b-A1) and (e-A1) amounts to at least 25 mol %, with respect to the sum of the total diamines and of the total dicarboxylic acids in the polyamide (A1).

### Claim 4 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein the transparent polyamide (A1) comprises at least 27 mol %, and in the range from 25 to 100 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids in the polyamide (A1).

### Claim 5 (depends on 1)

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 less than 50 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 less than 50 mol % of aromatic dicarboxylic acids, with respect to the total quantity of dicarboxylic acids;
(f-A2) 0 to 80 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);
wherein the sum of the diamines (a-A2), (b-A2), and (c-A2) produces 100 mol %;
wherein the sum of the dicarboxylic acids (d-A2), (e-A2), and (f-A2) produces 100 mol %; and
wherein the sum of the monomers (b-A2) and (e-A2) amounts to less than 25 mol %, with respect to the sum of the total diamines and of the total dicarboxylic acids in the polyamide (A2).

### Claim 6 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein the transparent polyamide (A2) comprises at most 23 mol % of monomers having aromatic structural units, with respect to the total quantity of diamines and dicarboxylic acids in the polyamide (A2).

### Claim 7 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein
the transparency measured in accordance with ASTM D1003 at a molded body (plate with the dimensions 60×60×2 mm) manufactured from the polyamide molding compound amounts to at least 80%; and/or
the haze measured in accordance with ASTM D1003 at a molded body (plate with the dimension 60×60×2 mm) manufactured from the polyamide molding compound amounts to a maximum of 40%; and/or
the arithmetical mean roughness Ra determined in accordance with DIN EN ISO 4287 (2010-07) at a molded body (plate with the dimension 60×60×2 mm) produced from the polyamide molding compound using a MarSurf XR1 Surface Measuring Station amounts to at most 0.12 μm, and/or has a surface roughness Rz of at most 1.50 μm.

### Claim 8 (depends on 3)

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-aminocylcohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5,-dimethylcyclohexyl)methane, 2,6-norbornane diamine, 2,6-bis-(aminomethyl)-norbornane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophorone diamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4′-diamonodicyclohexyl)propane, and mixtures thereof;
and/or
the diamine having aromatic structural unit (b-A1) is a xylylenediamine;
and/or
the open-chain aliphatic diamine (c-A1) is a hexanediamine,
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 dedecanedioic acid, 1,13-tridecanedioic 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, a naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid, 1,5-anthracene dicarboxylic acid, p-terphenylene-4,4″-dicarboxylic acid, 2,5-pyridine dicarboxylic 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 aminocarboxylic acid (g-A1) are 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).

### Claim 9 (depends on 1)

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-pyridinedicarboxylic acid, and xylylenediamine; and
the monomers having aromatic structural units for the transparent polyamides (A1) and (A2) are selected from the group consisting of terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, meta-xylylenediamine and mixtures thereof.

### Claim 10 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein
the polyamide (A1) is selected from the group consisting of PA MACMI/12, PA MACMT/12, PA MACMI/MACMT/12, 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/612MACMI/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;
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, PA PACM15, PA PACM16, PA 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, 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, MACMI/MACM12, PA MACMT/MACM12, PA MACMI/MACMT/MACM12, PA MACMI/MACMT/10I/10T/1012, PA 6I/6T/612/MACMI/MACMT/MACM12, 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, PA 6I/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;
and/or
the polyamide mixture (A) comprises or consists of the following combinations of the polyamides (A1) and (A2):
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM12; or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM10; or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM14; or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA PACM10; or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA PACM14; or
polyamide (A1) PA MACMI/MACMT/12 and polyamide (A2) PA MACM12; or
polyamide (A1) PA MACMI//12 and polyamide (A2) PA MACM12; or
polyamide (A1) PA 6I/6T/MACMI/MACMT/MACM12 and polyamide (A2) PA MACM12.

### Claim 11 (depends on 1)

The polyamide molding compound in accordance with claim 1, wherein the polyamide molding compound comprises the following components:
(A) 50 to 95 wt % of a mixture of
(A1) 25 to 48% polyamide PA MACMI/MACMT/12;
(A2) 52 to 75% polyamide PA MACM12;
(B) 5 to 50 wt % of at least one glass filler having a refractive index in the range from 1.510 to 1.539; and
(C) 0 to 10 wt % of at least one additive.

### Claim 12 (depends on 1)

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 mixtures thereof.

### Claim 13 (depends on 1)

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 S-glass, C-glass, and A-glass.

### Claim 14 (depends on 1)

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 or to the sum of the components (A) to (C), semi-crystalline polyamides, impact modifiers, lubricants, colorants, marking means, photochromic agents, antistatic agents, demolding means, condensation catalysts, chain regulators, anti-foaming agents, anti-blocking agents, optical brighteners, halogen flame retardants, non-halogen flame retardants, natural sheet silicates, synthetic sheet silicates, nanoscale fillers having a particle size (d90) of a maximum of 100 nm, and mixtures thereof.

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 1)

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

### Claim 17 (depends on 16)

The molded body in accordance with claim 16, wherein the molded body is a multilayer molded body.

### Claim 18 (depends on 5)

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-aminocylcohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5,-dimethylcyclohexyl)methane, 2,6-norbornane diamine or 2,6-bis-(aminomethyl)-norborane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophorone diamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4′-diamonodicyclohexyl)propane, and mixtures thereof;
and/or
the diamine having aromatic structural unit (b-A2) is a xylylenediamine;
and/or
the open-chain aliphatic diamine (c-A2) is a hexanediamine,
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 dedecanedioic acid, 1,13-tridecanedioic 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, a naphthalenedicarboxylic acid (NDA), biphenyldicarboxylic acid, 1,5-anthracene dicarboxylic acid, p-terphenylene-4,4″-dicarboxylic acid, 2,5-pyridine dicarboxylic 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 aminocarboxylic acid (g-A2) are selected from the group consisting of m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL), 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).