DE1942034A1 - Reinforced nylon preparation - Google Patents

Description

The present invention relates to preparations containing a reinforcing Filling material included Polyethylene to improve certain physical properties *

The preparations or mixtures according to the invention are used in injection molding, Extruded and transfer molded components in many industrial applications Objects and precision parts for many different purposes. The preparations according to the invention deliver after shaping or extrusion Objects with high heat resistance, iwhar dimensional stability, high Young's modulus, high tensile strength, high flexural strength, high impact resistance and low shrinkage during deformation. You are as End products in particular as electrical connection parts, fuse boxes and heating cables as well as electrical components and parts in systems, such as instrument housings, propellers, bowls, tablets and fuel rings usable

009310/1769

* 4 ·. ». '. , 1 «■ ■ - ■; ■,,., - *, .., .. _: . ■ ".., - ^; ..;., Ι JaltfüJVfc k ^ M-iiifrfefc. ^.

Nylon, which is a term for certain polyamide resins, is in principle

available in about 4 to 6 main types, such as nylon 6/6, nylon 6, nylon 6/10 _r nylon 11 and to some extent the nylon resins 7 »8, 9 and 12. The through. Condensation of a diamine with an adipic acid made nylon resins are nylon 6/6 and 6/10 (for example, the reaction of hexamethylenediamine and adipic acid gives polyhexamethylene adipamide - nylon 6/6) , while others are made by polymerizing amino acids or derivatives, such as caprolactam (nylon 6). In like manner, nylon produced by polymerization of ll-aminoundecanoic 11 "nylon resins have been used for many years for many different purposes, such as textiles and as molding resins. Although they generally have good properties such as toughness and stiffness (stiffness being a function of molecular weight and crystalline structure), tensile and flexural strengths have yet to be improved and, in fact, many attempts have been made to produce such reinforced nylons. Some published tensile and bending

2 strengths for nylon 6 630 and 756 kg / cm

according to ASIM D-633 or D-790. From these literature values, which erf in = » were essentially confirmed in accordance with the present invention, it can be seen that one more further out open to improvements in the physical properties of nylon is.

Technology knows the reinforcement of nylon with certain types of filling » materials β like glass fibers and asbestos fibers «Glass fibers have long been considered Reinforcing materials to improve the physical properties of such Base resins such as nylon have been used. She has use of fiberglass However, the cost of the reinforced material increases significantly «Opposite is Asbestos is used to improve the physical properties of nylon without sacrificing the cost of the reinforced material over the base resin have been increased. Which used with some success! Asbestos"? rfcen

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include chrysotile (3Mg.2SiD ₂ .2H ₂ O), crocidolite (Na ₂ O.Fe ₂ O ₂ - ^ eO.8SiO ₂ H ₂ O), anthophyllite ((MgFe) ₇ Si ₈ O ^ (OH) ₂ , tremolite (Ca ₂ Mg ₅ -Si ₈ O ₂₂ (OH) ₂ ) and. Actinolite (Ca ₂ (MgFe) ₁ -Si ₈ O ₂₂ (OH) ₂ ). Although chgsotile asbestos is most common, it is versatile and widely used as an asbestos fiber can, even with chrysotile asbestos, 'the reinforcing properties' have never been found on the order of magnitude that glass fibers have in nylon preparations. ,

The reduction in the cost of making reinforced nylon with the known types of asbestos was insufficient to make the worse physical Properties of the known, asbestos-reinforced nylon resins in comparison to glass-reinforced nylons. Hence there was no economic one Reason for the end user, the well-known lit asbestos-filled nylons to buy instead of the glass reinforced nylon resins.

In contrast to the well-known asbestos-reinforced nylon preparations, the Preparations according to the invention have about the same tensile strength and flexural strength and other physical properties such as glass-filled nylons but cheaper.

The preparation according to the invention therefore consists of an intimate mixture of about 50-85 wt. $ nylon; and about 50-15 wt consists essentially of a highly pure chrysotyl glass best, i.e. a chiysotile asbestos with at least 95 pounds of chrysotile fiber.

The preparation according to the invention has a tensile strength of at least 1050 kg / m 2 (according to ASIM D-638) and a flexural strength (according to ASIH D-790) of at least 1260 kg / ca * This mixture can also optionally be made of polyethylene in

a length of about 0.5-10 Jt, based on the combined weight of /

Be cugeigt nylon and asbestos * Dit Polyäthylenzugabe gives a ·

• 4 · * ■ *

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low brittleness as measured by an empirical test, i.e. the im the following test with the falling ball. These physical properties are the corresponding properties of other nylon compounds using known types of asbestos fillers and about the same or better than the glass-filled nylon preparations.

According to the invention, any nylon can be mixed with / certain types of asbestos fibers, as described here, in the proportions given above for the purpose of improving tensile and flexural strengths and other physical

be used

Properties of nylon / As is particularly evident from the following examples, the physical properties of nylon 6 and 6/6 in particular can be improved. Nylon resins are commercially available and manufactured on an industrial scale by various major companies. Particularly suitable according to the invention are the types of nylons which are commercially available under the names "Ylon", "Zytel", etc. Their strength properties can be noticeably improved by mixing with highly pure chrysotile asbestos.

The choice of the type of asbestos used in the present invention is extremely critical. It has been found that the only highly pure for the inventive preparation suitable asbestos material chrysotile asbestos is (at least 95 1 "chrysotile). In addition to its purity, this Chryeotilasbest differs from other Chrysotilen by a high surface area, a high degree of fiber release (little or no Faseraggloraerate) and a very low magnetite · Particularly preferably, highly pure chrysotile asbestos containing at least 98 £ chrysotile and less than 0.5 1 “ Magnetite, with a high concentration of completely free fibrils. These highly pure chrysotile asbestos materials are being mined in Coalinga, California and possibly elsewhere in the world. They are under the name "Atlas Coalinga Asbestos AZ-20" (Huxley Development Corporation) and "Calidria R-GlA ^ Asbestos" (Union Carbide Corporation).

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The preparation according to the invention consists in the most preferred form from an intimate mixture of 6-80 wt .- # nylon and 40-20 wt .- # high-grade chrysotile asbestos and has the following minimum physical properties:

Properties ASTM method value

2 '

Tensile strenght; kg / cm D-638 1190

Flexural strength; kg / cm ² D-790 1400

ο 70000

Modulus of elasticity; kg / cm D-638

Heat resistance temperature for D-64Q 182

18.48 kg / cm; ⁰ C.

The use of nylon 6/6 as the resin in the reinforced preparation results in a heat resistance temperature of at least 215 ° C under a load of 18.48 kg / cm. -

The preparations described above can be made by using nylon and highly pure chrysotile asbestos and other optional components, including polyethylene, dry into a uniform mixture, e.g. by melt blending in an ordinary equipment such as an extruder, a Banbury mixer, etc.

The properties of the various types of asbestos fibers used so far for reinforcement of plastics is in "Modern Plastics Encyclopedia" 1967, pages 595-598, described · The specified tensile strengths in kg / cm

^Sittd: kg / cm ²

Amosite 1120-11900

Anthophyllite 280 and less

Chrysotile 5600-7000

Crooidolit 70OO-35OOO

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- 6 - Although amosite asbestos fibers had equal tensile strengths and crocidolite asbestos fibers usually had better tensile strengths than chrysotile asbestos fibers (other than those used in the present invention), the following data show that only highly pure chrysotile asbestos fibers in asbestos-reinforced nylon resins

superior tensile strengths resulted in: * '

Tensile strength in kg / cra of a prep

Asbestos type rates made of 20% asbestos and 80 % nylon Anthophyllite (1) 672 (£ 40 asbestos : 60 # nylon) Amosite (2) 791 Crocidolite (3) 923 Chrysotile W 569 . - highly pure chrysotile (5) 1260

(1) = as "Aplex 101" from Asbestos Corp. of America in trade

(2) - as "KM / AA" from Asbestos Corp. of America in trade

(3) = as "ACOA-H" from the. Asbestoa Corp. of America in trade. (4) = as ⁿ CRL8i "vnn of Asbestos Corp. of America in trade

(5) = as "Atlas AZ-20" from Huxley Development Corp. in trade

As mentioned, there is an option of adding polyethylene to the mix for a substantial improvement the brittleness properties of the preparation are also used. The choice of the particular type of polyethylene is not decisive; and it can Low density polyethylene, i.e. with a nominal density of 0.910-0.939t or highly dense polyethylene, i.e. with a density of 0.939-0.975, or a modified polyethylene with carboxylic acid salt groups or mixtures thereof can be used in the preparation according to the invention.

It has been found that a high density polyethylene is used in the present invention

Preparations gives particularly good results, which is why it is preferred.

e.g.

Low density polyethylene is made / by a high pressure polymerization process of US Pat. No. 3,293,233; High density polyethylene

. e.g. -

is / produced in a low pressure process according to US Pat. No. 2,832,759, and the modified polyethylene with carboxylic acid salt groups is e.g.

009810/1769

prepared by a method of US Pat. No. 3,355,319. In the Preparations according to the invention can also contain copolymers of ethylene other olefins, with ethylene being the main component, can be used.

Although the incorporation of about 0.1J-10 # polyethylene in the highly pure chrysotile asbestos-nylon formulation significantly reduces its brittleness, the preferred range is 1-5 # polyethylene. Levels above 5 % polyethylene provide tensile strength With quantities above 10 % polyethylene, tensile strength and flexural strength are noticeably reduced · At concentrations below 0.5 % polyethylene there is no noticeable improvement in the brittleness of the preparation.

Other components that can also be mixed into the inventive preparations include pigments, gloss-reducing agents, plasticizers, flame retardants and other materials known in the art for modifying the chemical and physical properties of finished, reinforced nylon resins. It has been found that the addition of $ 0.01-5.0, based on the weight of the final preparation, of certain pigments, such as aluminum pigment, improves the physical properties, including brittleness, of the preparation of the present invention. The preparations according to the invention can even be mixed with other plastic materials the nylon for the purpose of substantial modification of the physical and chemical.

Features included.

In the following examples are the tensile and flexural strengths and others physical properties of the preparations according to the invention indicated and with compared to those of known materials. The magnitude of the increase in tensile and flexural strength etc. of the preparations according to the invention compared to the known materials was completely unexpected as the known preparations include nylon with other asbestos fibers, including chrysotile asbestos,

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which has essentially the same physical properties as the highly pure chrysotile asbestos used in the present invention.

In the following examples, the following soldering methods were used to measure physical properties: Property ASTM method

Tensile strenght; kg / cm ² D-638

Strain; <f> (»at yield»; on failure) Young's modulus D-638

Flexural strength; kg / cm ² D-? ° O Flexural modulus; kg / cm D-? k? Izod impact strength cmkg / cm D-256

Heat-setting temperature at 18.48 kg / cm ² ; ⁰ C. ·

.spec. Weight D-792

Water absorption. after 2k hours; $ D-570

example

The filled nylon preparations shown in Table 1 were made according to the following General Procedure. First, the components of each of the in Preparations evaluated in this example in a dry mixer for processing a homogeneous powder and then filled into a twin screw extruder by means of a vibrating funnel · The feed for example ' was as follows: 15.9 kg of nylon 6 (as "Plaskon 8202" from Allied Chemical Corp. in stores) 6.8 kg of highly pure Chryeotile asbestos, i.e. "resin grade" IW, and 0.4-Γ kg of an external lubricant (as "Carbowax 400" by the Union Carbide Corp. in trade).

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The following Table 1 shows the physical properties of injection-molded samples of the asbestos-reinforced nylon preparation according to the invention, which contained about 70 pounds by weight of nylon and 30 pounds by weight of asbestos.

Tabel

feed
Nylon, wt .- #
Asbestos, wt

Physical Properties

2 -

Tensile strenght; kg / cm

Strain; / 6 in the event of failure, modulus of elasticity
Flexural strength; kg / cm flexural modulus; kg / cm
Izod impact strength cmkg / cra heat resistance ;; temperature at 18.48 kg / cm ² ; ⁰ C.

spec. weight

Water absorption after 24 hours; ^ Flucht.Components in the filler material; Ash content; £

Filler content; £

Eg game 2

1350 2.55 117376 1892 100352

182

1.32 2.39 12.5 24.8 28.4

Example 1 was repeated except that the extrusion conditions were changed and Hjlon 6 as well as nylon 6/6 were used. Table 2 shows the data of the preparations obtained.

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Attempt no.

Gau Nylon; Wt .- ^ Asbestos ^ ¹ V wt. -4 Physical properties Tensile strength; kg / cm o Izod impact strength; cmkg / cm

^ Heat-resistant kaitsterap ,; at 18.48 kg / cm ² ; ⁰ C.

° ■ '■' + ■ = Nylon 6 ^ J 4+ ■ Nylon 6/6 P> (1) = "Atlas AZ-20" Asbestos to

Table 2 2 3 4th 5 6th 1 7O ⁺ 8O ⁺ + 8O ⁺ + 8O ⁺ + TO ⁺ 30th 20th 20th 20th 30th 30th 1602 1227 1499 1541 153? 1546 6.3 M. 4.83 5.16 4.40 6.0 189 220 242 228 237 189

example

Table 3 shows the physical properties of preparations according to the invention after mixing different types of nylon with two types of commercially available, high-grade chrysotile asbestos. The procedure of Example 1 was followed. applied·

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Attempt no 7th Tabel 3 9 10 feed 8th * Nylon; Weight #
Asbestos; Weight-56
physical properties > 8O ⁺ 20 « ²⁾ Tensile strenght; kg / approx ² 1361 TD ⁴⁺
3O <2) 1413 1334 Strain; # on failure 2.38 1525 2.90 1.63 Flexural strength; kg / e » 1763 1.86 1806 1137 O Ieod impact strength i cmkg / cm 5.0 1999 5.38 3.48 (O
co Heat resistance temperature
at 18.48 kg / cm ² ; ⁰ C. 226 6.0 189 231 / Ot spot. Weight .'.'"' 1.27 188 1.26 1.27 -a Water absorption after 24 hours i * 1.47 1.35 1.44 1.25 CD
CO I.52

+ == Nylon 6/6, as "Xylon 66N1" from the Fiberfil Division of Dart Industry, Inc., iui Handel ++ = Nylon 6, as "Plaskon 82020 Nylon from Allied Chemical Corp. in the volume '+ * + * Nylon 6/6, as "Zytel 101" by the EI duPont de Nemours & Co. in trade (1} = as "Resin-Grade I44 ⁿ Asbestos by the Union Carbide Corp. in trade (2) = as" Atlas AZ- 20 ^ff Asbosi from Huxley Development Corp. in trade

The following table shows higher-feeding and physical properties of various comparison tests for the production of preparations with different, non-inventive asbestos materials. In experiments 11-18 shown in the table, nylon 6 "Plaskon 8202" was used in each case. The data in table k can be compared with those of the previous examples, in particular test 9 (table 3) with tests 12-16 (table k) and test 8 (table 3) with tests 11 and 17 (table k)

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Attempt no.

Tabel 4th 13th 14 ' 15th 16 17th 11th 12th 20th
0 20th 20th 20th
80 (5) 30th
0 ΊΟ
6Ο < ² > 20th
B ₀ O) 793 923 991 569 711 672 791 3.13 2.65 2.55 6.96 3.63 2.79 2.68 1030 1320 1327 785 989 1040 1107 3.75 3.42 3.75 2.88 2.67 3.10 3.10 120 181 182 96 108 188 174 1.27 1.29 1.29 'ί.34' 1.35 1.50 1.34 1.35 1.61 1.38 2.32 1.67 1.72 1.38 17.2 17.4 18.7 23.3 25.7 40.9 20.4

feed
Nylon 6; Wt .- ^ asbestos; Weight #

Treatment aids; Physical properties by weight

Tensile strenght; kg / cm

ο stretching; £ in case of failure CO 2

co flexural strength; kg / cm

Q Itod impact strength; cmkg / cm *** rolling strength temperature at ^ 18.48 kg / cm ² ; ⁰ C.

apes · weight
co * ^

Water absorption after 24 hours; j>

Ash content; $

(1) = "Carbowax 400" based on * the combined weight of nylon and asbestos

(2) * "A-Plex'lOl" anthophyllite

(3) = "KM / AA" araositol

(4) a "ACOA-H" crocidolite

(5) = "CRL81" chrysotile

T ^ SFKmVZB

Table 5 shows the. published physical properties for nylon 6 and nylon. 6, which is reinforced with 10 or 20% by weight glass fiber.

Tabel

feed locr 90 80 Nylon 6, wt .- # 0 1O ⁺ 2O ⁺ Filling material; Weight # Physical Properties 630 924 1131 Tensile strenght; kg / cm ² 4.0 - - Strain; # on failure 266ÖCl - - modulus of elasticity 756 1512 1918 Flexural strength; kg / cm 18410 . 45500 63000 Bending module 6.9 5.9 7.9 Izod impact strength; cmkg / cm 14th 80 104 18.48 kg / cm ^ ⁰ C. + * Glass fibers Example 4

Table 6 shows two preparations according to the invention which contain black pigment or Contains aluminum pigments. In experiment 18, the black pigment compound "999 Carbon Black ** in pearl form (Columbian Carbon Corp ·) was used in the amounts shown in Table 6. In attempt 19 was the aluminum pigment compound "Silex 2110" from Silberline Manufacturing Cor.

attempt

Table 6 18. 19

Loading nylon; Geir.- £ asbestos; Gev.-jt pigment

80 < ¹ >

ao < ² > ₂ <3)

80 ^ 20 ⁽²⁾

1.5

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attempt

Table 6 continuation 18th 19th 1382 1418 2.38 2.74 107 # 0 94976 1572 1831 81410 71480 4.0 5.2 * 217 224 1.29 1.27 1.48 1.40

physical properties tensile strength; kg / cm ² elongation; # in the event of failure, modulus of elasticity, flexural strength; kg / cm ² flexural modulus; kg / cm ² '

Izod impact strength cmkg / cm

Heat set temperature at an average of 18.48 kg / cm ² ; ⁰ C * 217

spec. weight Water absorption after 24 hours;

(1) = nylon 6/6 * ~~

(2) = "Atlas AZ-20" asbestos,

(3 - "999 Carbon Black" pigment, amount based on the dish of nylon> (4) = "Silex 2110" pigment, amount based on the weight of nylon

Example 5

This example shows another embodiment of the present invention, in which the beneficial effect of the addition of polyethylene to the preparations Nylon and highly pure chzyaatil asbestos is shown.

The preparation was hergetteHts a dry mixture of 36.3 kg as follows Nylon 6/6 (traded as "Xylon 66N1"), 9.1 kg of highly pure chryeotile asbestos (as "Atlas AZ-20" from Huxley Development Corp. in HaMei) and 0.91 kg high density "polyethylene (ale" Dylan 7120? From Sijiclair-Koppers Comp, in trade) were smelted in a twin snail tetrangpreeae. The preparation obtained was then injection-molded and pieces of tea. The ASIM tests showed the following physical properties. 1

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2 - JTr

Tensile strenght; kg / cm " 1260

Strain; $ 1.0

Modulus of elasticity; kg / cm 77000

Flexural strength; kg / cm 1680 Flexural modulus; kg / cm 63,000 Izod impact strength; cmkg / cm 4, 9 Thermal strength temperature at

18.46 kg / cm ² ; ⁰ c. 227

Water absorption; % 1.5

spec. Weight 1.3

Mold shrinkage ^ '; cm / cm - ^ 0.0085

(1) = linear shrinkage of a standard ASTM test stick for an average 3 Kim cut after deformation of the test stick and cooling at room temperature. The units for this test are inches of shrinkage per cm test stick.

To test the brittleness properties (test with falling ball) was a 0.4-5 kg steel ball from a height of 4-5 cm on the bottom of an injection molded container about 5 cm wide, 10 cm long and 1.6 cm deep and about Dropped 0.245 cm wall thickness. In this test, the containers deformed from the above preparation showed only cracks at the point of impact, while the containers made from preparations without polyethylene broke into pieces. Specimens containing 20 pounds of glass fiber reinforced nylon 6/6 cracked or broke.

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example

In a further embodiment of the present invention, a dry mixture of 18.1 kg nylon 6/6 (as "Xylon 66N1" from Fiberfil Division of Dart Industries, Inc., commercially), 4.5 kg highly pure Chrysotile asbestos (as "Atlas AZ-20" asbestos by Huxley Development Corp. commercially available) and 0.36 kg of high density polyethylene (commercially available as "Alathon 7050" from E.I. duPont de Nemours & Co.) in a twin screw extruder. The obtained preparation became test sticks

injection molded and exhibited the following physical properties: tensile strength; kg / cm ² _ ■ 1197

Strain; j> 2.5

Flexural strength; kg / cm 1680 Izod impact strength; cmkg / cm ' 5Λ

, Heat resistance temperature at

18.48 kg / cm ² ; ⁰ c. 232

spec. Weight 1.26

Was this preparation made after the test described above with the falling ball? tested, 7 of 10 samples cracked and 3 broke

Example 2

Another preparation was made according to an embodiment of the present invention Invention prepared by the method described above and then as in Example 2 deformed and tested, but with the preparation 0.8 wt .- #,: based on the weight of the final preparation, of red pigment were added. It was commercially available as a pigment from Harshaw Chemical Company located "Cadmium Red 15 * 40 ° is used. The physical properties of this material were:

00981071769

Tensile strenght; kg / cm ² * "* 1239

Strain; ή » 2.3

Flexural strength; kg / cm ² 1680

Izod impact strength; cmkg / cm 4-, 9

Heat resistance temperature at

18.48 kg / cm; ⁰ c. 227

spec. Weight - 1.28

In the test with the falling ball according to Example 5, out of 10 samples broke
2 samples failed, 6 cracked and 2 broke.

Example 8

In another embodiment of the present invention, according to
Did 6 hit a preparation with £ 1.2, based on da *? Weight of the final
Preparation made with aluminum pigment. The pigment used what
¹¹ Silex 2110 "from Silberline Manufacturing Comp.

This preparation had the following physical properties:

Tensile strenght; kg / cm 1260

Strain; 1" 2.3

Flexural strength; kg / cm ² 1729 Izod impact strength; cmkg / cm 4.9 Heat resistance temperature at,?

18.48 kg / cS ² ; ⁰ c. 22S ^

spec weight 1.28 ^,

During the test with the falling ball, did one of the 10 tested samples break ? not,,!, and 3 showed cracking. None of the samples tested had cracked. '"'

or completely broken.

The above examples showed the unexpected improvement in the physical properties in the preparations according to the invention la compared to those be. \ known preparations.

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Claims (1)

Claims lA preparation consisting of an intimate Misching from ijylon in an amount of about 50-85 GeWo- # and a filler consisting essentially of highly pure chrysotile asbestos in an amount of about 50-15 wt .- ^ van, wherein the preparation optionally in addition to the above components, polyethylene. in an amount of about 0.5-10 % based on the combined weight of nylon and asbestos 2.- preparation according to claim 1, characterized in that the preparation is a Tensile strength of at least 1050 kg / cm (ASTM D-638) and a flexural strength ) 2 at least 1260 kg / cm (ASTM D-790). 3.- preparation according to claim 1 and 2, characterized in that the nylon Is nylon 6 or nylon 6/6. 4.- preparation according to claim 1 to 3 »characterized in that the optional Polyethylene is high density polyethylene with carboxylic acid salt groups. 5.- preparation according to claim 1 to k _t, characterized in that polyethylene is present and the preparation additionally contains a pigment. 6, - Preparation according to claims 1 to 5 »characterized in that the high grade pure chrysotile asbestos contains at least $ 95 chrysotile fiber, "." Preparation according to claims 1 to 6, characterized in that the highly pure chrysotile asbestos contains at least 98 % chrysotile fibers and less than 0.5 $ magnetite BATH ORIGINAL 009810/1769 - 19A2034 Qj 8.- A method for producing a reinforced nylon preparation, characterized in that about 50-85 Gew .- ^ nylon una e- * wa 15-50 Gew .- / »of a filler material, which consists essentially of highly pure chrysotile asbestos, and optionally about 0.5-10 % polyethylene, based on the combined weight of nylon and asbestos, intimately mixed. 9.- The method according to claim 8, characterized in that the highly pure chrysotile asbestos at least 95 $%, preferably at least 98 #
Chrysotile fiber, and contains less than 0.5 # magnetite. 0 patent attorney: 009810/1769 BATH ORIGINAL