CA1090939A

CA1090939A - Non-discoloring glass strand size

Info

Publication number: CA1090939A
Application number: CA286,995A
Authority: CA
Inventors: Thomas A. Coakley; John E. Rubadue; Carl E. Forman; Robert A. Schweizer
Original assignee: Owens Corning Fiberglas Corp
Current assignee: Owens Corning
Priority date: 1976-11-12
Filing date: 1977-09-19
Publication date: 1980-12-02
Also published as: GB1594817A; DK500977A; BR7706800A; DE2750198A1; FI773408A; AU2913677A; FR2370703A1; SE7712709L; JPS5361787A; ZA775667B; NO773855L; FI62045B; NL7710638A; BE860034A; IT1087792B; FI62045C; FR2370703B3; MX148498A; AU512477B2

Abstract

ABSTRACT OF THE DISCLOSURE
A non-discoloring glass strand size comprises a polyurethane latex emulsion produced by the chain extension of an NCO-terminated prepolymer. The prepolymer is prepared by the reaction of an aliphatic or cycloaliphatic diisocyanate with a polyalkylene ether polyol and is particularly suitable for glass incorporated in polyamide resins.

Description

109()~3~

This invention relates to a non-discoloring glass strand sizing.
In one of its more specific aspects, this invention pertains to sizings for glass used for incorporation in poly-amides.
Glass reinforced polyamides, such as nylon, are pre-sently being injection molded into many articles in the automo-tive and appliance industry. To obtain the best improvement in properties, the composition with which the glass is sized must be compatable with the polyamides.
It is known that polyurethanes based on aromatic di-isocyantes provide sizes having outstanding adhesion between glass and polyamdies. However, such sizes have a tendency to discolor laminates produced from the resulting glass-reinforced nylons, the laminates not possessing a white color but rather a green or brown discoloration.
A large number of these polyurethanes are based on toluene derivatives such as toluene diisocyanate, an aromatic diisocyanate which results in discolored laminates.
It has now been discovered that glass sizes suitable for use on glass incorporated in polyamides can be produced by employing therein polyurethanes based on aliphatic or cycloali-phatic diisocyanates. The employment of the latter materials largel~ eliminate such discoloration while not adversely affec-ting the quality of the finished product.
According to this invention, there is provided a glass fiber, at least a portion of the surface of which is in contact with the residue formed upon the removal of waterfrom an aaueous composition comprising: a thermoplastic polyurethane latex emul-sion produced by the chain extension of an NCO-terminated pre-D

109093~3 polymer prepared by the reaction product of an aliphatic or cycl-oaliphatic diisocyanate with a polyalkylene ether polyol, and;
a silane coupling agent.
This invention also provides polyamide resins rein-forced with glass fibers of this invention.
A particularly suitable polyurethane latex emulsion based on aliphatic or cycloaliphatic diisocyanates, employable in this invention, is designated X1042H*, a thermoplastic, non-aromatic polyurethane derived from cyclohexanediisocyanate commerically available from BASF Wyandotte, Wyandotte, Michigan.
U. S. Patents Nos. 3,401,133 issued September 10, 1968 to Wyandotte Chemicals Corp. and 3,563,943 issued February 16, 1971 to the same company describe in detail the preparation of X1042H.
The polyurethane latex emulsion will be employed in the size in an amount within the range of from about 3 to about 20 parts per 100 parts by weight.
Any suitable coupling agent comprising an organo silane can be employed. Preferably an organo silane such as gamma-aminopropyltrimethoxysilane will be used. A suitable coupliny agent of this type is designated AllO0* available from Union Carbide.
The coupling agent will be employed in the size in an amount within the range of from about 0.2 to about 4 parts * Trade Mark

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10~3~3~3 per 100 parts by weight.
Any suitable lubricant can be employed. A preferred lubricant is the cationic condensation product of dimethylamino-proplyamine and pelargonic acid. This material will have a specific gravity of about 1, a viscosity of about 500 cps. at 25C and a pH (5~ aqueous solution) of from about 5.5 to about 7. A preferred lubricant of these characteristics is available from Emery Industries as Emerstat 6665 (trade mark). Another suitable lubricant is an amide substitute polyethyleneamine such as Emery 6717 (trade mark) availablP from Emery Industries.
Emery 6717 is a fatty amide of a polyethylenimine.
The lubricant is employed in the size in an amount up to about 5 parts per 100 parts by weight.
The size of this invention is prepared by conventional methods such as described below. It can be applied to any glass fibers conventionally employed as molding compound reinforcement, being applied during the forming operation such that the fibers possess, upon drying, a solids content within the range of from about 0.3 to about 2.0 weight percent based upon loss on ignition.
The best mode for carrying out the invention is demonstrated by the following examples.
EXAMPLE I
This example demonstrates the preparation of approxi-mately 100 gallons of a size composition of this invention.
About 40 gallons of demineralized water where added to a main mix tank.
About 8 pounds of gamma-aminopropyltrimethoxysilane (Union Carbide AllO0) were mixed with about 10 galls of deminera-lized water in a first premix kettle until the resulting solu-tion was clear (about 10 minutes) and the solution was

-3-,. ~

1090~39 introduced into the contents of the main mix tank.
About 65 pounds of polyurethane latex emulsion (X1042H) were mixed with about 20 gallons of demineralized water in a second premix kettle for about 10 minutes and the resulting mixture was introduced into the contents of the main mix tank.
The contents of the main mix tank after complete mixing (about 15 minutes) had a solids content of about 4.7 weight percent and a pH of about 9.
The size prepared in the above manner was applied to individual glass fibers at conventional application methods and rates such that the strand solids, on drying, amounted to about 0.6 weight percent.
EXAMPLE II
This example demonstrates the preparation of approximately 100 gallons of a size composition of this invention.
About 25 gallons of demineralized water were added to a main mix tank.
About 8.3 pounds of gamma-aminopropyltrimethoxysilane (Union Carbide AllO0) were mixed with about 20 gallons of demineralized water in a first premix kettle until the resulting solution was clear (about 10 minutes) and the solution was introduced into the contents of the main mix tank.
About 45.9 pounds of polyurethane latex emulsion (X1042H) were mixed with about 20 gallons of demineralized water in a second premix tank for about 10 minutes and the resulting mixture was introduced into the main mix tank.
About 8.3 pounds of lubricant (Emery 6665) were mixed with about 10 gallons of demineralized water in a third premix ~ ,~

109t)5~39 kettle for about 10 minutes and the resulting mixture was introduced into the main mix tank.
The contents of the main mix tank after complete mixing (about 10 minutes) had a solids content within the range of from about 2.5 to about 4.5 weight percent and a pH within the range of from about 9 to about 10.
The size prepared in the above manner was applied to individual glass fibers at conventional application methods and rates such that the strand solids, on drying, amounted to about 0.6 weight percent.
EXAMPLE III
This example demonstrates the preparation of a molded article reinforced with glass fibers sized with the size composition of Example I.
- The size composition of Example I was applied to 816 "E" glass fibers having diameters of from about 0.00050 to about 0.00055 inch at forming using a roll-type applicator. The sized fibers were collected in the form of a strand. The strand was wound into a forming package and dried for about 16 hours at about 235F. The strand solids, on drying, amounted to about 0.6 weight percent.
Fifty forming packages of the sized strand were placed on a creel and the strands from the fifty packages were brought together through guide eyes to form a roving package which was then cured for about 6 hours at 235F. The roving was withdrawn from the roving package and chopped into approximately ~ inch length fibers.
About 3 parts by weight of chopped fibers were placed in a drum tumbler with about 7 parts by weight of nylon 6,6 having a melting index of 2 and a molecular weight of about ~090~39 100,000. The resulting mixture was then placed in a 2 1/2 inch Prodex (trade mark) Machine Screw Extruder and electrically heated to about 540F. Such extruders are made by HPM Corp. of Mt.
Gilead, Ohio, U.S.A. The mixture was extruded into 1/8 inch diameter cylindrical rods which were introduced into a Cumberland Pelletizer to form 1/4 inch long pellets. The pellets were, in turn, fed into an injection molding machine at a temperature of about 550F and formed into a standard ASTM D-638 dog bone test sample.
The test sample was white in color and found to have a tensile strength of about 26,000 psi., a modulus of elasticity of 1.2 x 106 psi. and an IZOD ~tched impact strength of 3.0 ft.
pounds/inch.
It will be evident from the foregoing that various modifications can be made to the present invention. Such, however, are considered as being within the scope of the invention.

I ..,

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A glass fiber, at least a portion of the surface of which is in contact with the residue formed upon the removal of water from an aqueous size composition comprising:
(a) a thermoplastic polyurethane latex emulsion pro-duced by the chain extension of an NCO-terminated prepolymer pre-pared by the reaction product of an aliphatic or cycloaliphatic diisocyanate with a polyalkylene ether polyol, and;
(b) a silane coupling agent.

2. The glass fiber of claim 1 in which said composi-tion comprises a lubricant.

3. The glass fiber of claim 2 in which said lubricant is a cationic condensation product of dimethylaminopropylamine and pelargonic acid.

4. The glass fiber of claim 2 or claim 3 in which said lubricant is employed in said aqueous composition in an amount up to about 5 parts per 100 parts by weight.

5. The glass fiber of claims 1, 2, or 3 in which said silane coupling agent is gamma-aminopropyltrimethoxysilane.

6. The glass fiber of claims 1, 2, or 3 in which said silane coupling agent is employed in said aqueous composition in an amount within a range of from about 0.2 to about 4 parts per 100 parts by weight.

7. The glass fiber of claims 1, 2 or 3 in which said polyurethane latex emulsion is employed in said aqueous composition in an amount within a range of from about 3 to about 20 parts per 100 parts by weight.

8. A polyamide resin containing at least one glass fiber at least a portion of the surface of which is in contact with the residue formed upon the removal of water from an aqueous size composition comprising; a thermoplastic polyurethane latex emulsion produced by the chain extension of an NCO-terminated prepolymer prepared by the reaction product of an aliphatic or cycloaliphatic diisocyanate with a polyalkylene ether polyol, and a silane coupling agent.

9. A polyamide resin containing at least one glass fiber at least a portion of the surface of which is in contact with the residue formed upon the removal of water from an aqueous size composition comprising: a thermoplastic polyurethane latex emulsion produced by the chain extension of an NCO-terminated prepolymer prepared by the reaction product of an aliphatic or cycloaliphatic diisocyanate with a polyalkylene ether polyol, and a silane coupling agent, and wherein said composition includes a lubricant.