Aqueous treating composition for glass fiber strands used to produce mats for thermoplastics

Claim 2

In a method of forming glass fibers that are gathered into strands including the steps of forming glass fibers from molten cones of glass at the tips of orifices in a bushing by attenuation; sizing said glass fibers with an aqueous sizing composition; gathering said fibers into one or more strands; and collecting one or more glass fiber strands, the Improvement comprising: sizing said glass fibers with an aqueous sizing composition comprising: a. a combination of two organic silane coupling agents in an amount of about 0.5 to about 10 weight percent of the aqueous sizing composition, wherein one organic silane coupling agent is a vinyl containing organic silane coupling agent in an amount of about 60 to about 99 weight percent of the amount of the combined silane coupling agents and the other is a saturated amino organic silane coupling agent present in an amount of about 1 to about 40 weight percent of the combined silane coupling agents, b. about 0.125 to about 7.6 percent by weight of a nonionic surfactant, c. about 0.001 to about 1 percent by weight of a glass fiber lubricant, d. about 0.1 to about 6 percent by weight of an organic peroxide free radical initiator having a half life exceeding 60 hours at 212° F. (100° C.) and 20 minutes at 300° F. (149° C.), e. about 0.5 to about 15 weight percent of a film forming polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone and vinyl acetatemetholacrylamide copolymers, and f. water in an amount to give a total solids in the range of about 1 to about 20 weight percent.

Claim 3

Method of claim 1 wherein the vinyl-containing silane coupling agent is selected from the group consisting of vinyl-tris-(bethamethoxyethoxy) silane, vinyl triethoxysilane, gammamethacryloxy propyl trimethoxysilane, vinyltri-acetoxysilane.

Claim 4

Method of claim 1 wherein the saturated amino silane coupling agent is selected from gamma aminopropyl triethoxy silane, N-beta-(amino ethyl), gamma aminopropyl trimethoxysilane and the amino functional silane having the structural formula ##STR2##

Claim 5

Method of claim 1 wherein the nonionic surfactant is octylphenoxy polyethyoxy ethanol.

Claim 6

Method of claim 1 wherein the softening agent is a 50/50 anionic-cationic methyl sulfate quaternary salt of a fatty acid.

Claim 7

Glass fiber strands produced by the method of claim 1.

Claim 8

A needled continuous glass fiber strand mat prepared from the glass fiber strands of claim 6.

Claim 9

Glass mat reinforced thermoplastic article having the mat of claim 7 combined with an overlay and underlay of thermoplastic polymer wherein the combination is heated under pressure to produce the article.

Claim 10

Article of claim 8 wherein the thermoplastic polymer is polypropylene or chemically coupled polypropylene.

Claim 11

Method of claim 1 wherein there is present an effective amount of pigment.

Claim 12

A needled mat of glass fiber strands for use in reinforcing thermoplastic polymers to give the reinforced thermoplastic polymers improved stampability, where the needled mat is comprised of: a. a plurality of glass fiber strands distributed in a mat structure where the mat has sufficient integrity provided by needling, and b. a coating on a substantial portion of the surface of the glass fibers in the strands, wherein the coating is of an aqueous sizing composition comprising: (a) a combination of organic silane coupling agents present in the aqueous treating composition in an amount of about 0.5 to about 10 percent by weight, wherein one silane is a vinyl-containing organic silane coupling agent present in an amount of about 60 to about 99 weight percent of the combined silanes and another silane coupling agent is a saturated amino-organic silane coupling agent in an amount in the range of about 1 to about 40 weight percent of the combined silanes, (b) about 0.5 to about 15 percent by weight of a film forming polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone and vinylacetatemetholacrylamide copolymers, (c) about 0.125 to about 7.6 percent by weight of a nonionic surfactant, (d) about 0.001 to about 1 percent by weight of a glass fiber lubricant, (e) about 0.1 to about 6 percent by weight of a heat stable organic peroxide free radical initiator, and (f) an amount of water to give a total solids for the composition in the range of about 1 to about 20 weight percent.

Claim 13

A needled mat of glass fiber strands for use in reinforcing thermoplastic polymers to give the reinforced thermoplastic polymers improved stampability, where the needled mat is comprised of: a. a plurality of glass fiber strands distributed in a mat structure where the mat has sufficient integrity provided by needling, and b. a coating on a substantial portion of the surface of the glass fibers in the strands, wherein the coating is of an aqueous sizing composition comprising: (a) a combination of organic silane coupling agents present in the aqueous treating composition in an amount of about 0.5 to about 10 percent by weight, wherein one silane is a vinyl-containing organic silane coupling agent present in an amount of about 60 to about 99 weight percent of the combined silanes and another silane coupling agent is a saturated amino-organic silane coupling agent in an amount in the range of about 1 to about 40 weight percent of the combined silanes, (b) about 0.5 to about 15 percent by weight of a film forming polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone and vinylacetatemetholacrylamide copolymers, (c) about 0.125 to about 7.6 percent by weight of a nonionic surfactant, (d) about 0.001 to about 1 percent by weight of a glass fiber lubricant, (e) about 0.1 to about 6 percent by weight of a heat stable organic peroxide free radical initiator, and (f) an amount of water to give a total solids for the composition in the range of about 1 to about 20 weight percent.

Claim 14

Mat of claim 11 wherein the amount of saturated amino organic silane coupling agent is around 15 to 25 weight percent of the weight of the combined silane coupling agents.

Claim 15

Mat of claim 11 where the film forming polymer is present in an amount of about 0.5 to about 8 weight percent.

Claim 16

Mat of claim 13 wherein the film forming polymer is a polyvinylacetate homopolymer.

Claim 17

Mat of claim 11 which includes an effective amount of a softener.

Claim 18

Mat of claim 14 wherein the effective amount of softener is in the range of about 0.1 to about 1 weight percent of the aqueous treating composition.

Claim 19

Mat of claim 11 or 12 wherein the softener is a 50/50 anionic-cationic methylsulfate quaternary fatty ester compound.

Claim 20

Mat of claim 11 wherein the nonionic surfactant is an octyl phenoxy polyethyoxy ethanol having an HLB of 13.5.

Claim 21

Mat of claim 11 that has needled continuous glass fiber strands.

Claim 22

Mat of claim 11 that has continuous glass fiber strands.

Claim 23

Mat of claim 11 that has chopped glass fiber strand.

Claim 24

Needled glass fiber strand mat of claim 11 wherein the thermoplastic polymers are selected from the group consisting of polyolefins including chemically coupled polyolefins, nylons, and polyalkylene terephthalates.

Claim 25

Thermoplastic laminate reinforced with needled glass fiber strand mat having improved stampability, where the laminate is produced by combining the needled glass fiber strand mat with an overlay and underlay of the thermoplastic polymer and the combination is heated under pressure, comprising: a. needled glass fiber strand mat, wherein the glass fibers have a coating of a dried residue having around 2 to 10 percent moisture content, where the dried residue is of an aqueous sizing composition, comprising: (a) a combination of organic silane coupling agents present in the aqueous treating composition in an amount of about 0.5 to about 10 percent by weight, wherein one silane is a vinyl-containing organic silane coupling agent present in an amount of about 60 to about 99 weight percent of the combined silanes and another silane coupling agent is a saturated amino-organic silane coupling agent in an amount in the range of about 1 to about 40 weight percent of the combined silanes, (b) about 0.5 to about 15 percent by weight of a film forming polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone, and vinylacetatemetholacrylamide copolymers, (c) about 0.1 to about 7.6 percent by weight of a nonionic surfactant, (d) about 0.001 to about 1 percent by weight of a glass fiber lubricant, (e) about 0.1 to about 6 percent by weight of a heat stable organic peroxide free radical initiator, and (f) an amount of water to give a total solids in the range of about 1 to about 20 weight percent, b. thermoplastic polymer selected from the group consisting of polyolefins, polyamides, polyalkylene terephthalate chemically coupling polypropylene, polypropylenes with small amounts of polyethylenes and homopolymeric and copolymeric substances such as (1) vinyl resins formed by the polymerization of vinyl halides or by the copolymerization of vinyl halides with unsaturated polymerizable compounds, e.g. vinyl esters; alpha, beta-unsaturated acids; alpha, beta-unsaturated esters; alpha, beta-unsaturated ketones; alpha, beta-unsaturated aldehydes; and unsaturated hydrocarbons such as butadienes and styrenes; (2) polyalpha-olefins such as polyethylene, polypropylene, polybutylene, polyisoprene and the like, including copolymers of polyalpha-olefins; (3) phenoxy resins; (4) poly amides such as polyhexamethylene adipamide, polyalphacaprolactam and the like, including copolymers of polyamides; (5) polysulfones; (6) polycarbonates; (7) polyacetals; (8) polyethylene oxide; (9) polystyrene, including copolymers of styrene with monomeric compounds such as acrylonitrile and butadiene; (10) acrylic resins as exemplified by the polymers of methyl acrylate, acrylamide, methylol acrylamide, acrylonitrile and copolymers of these with styrene, vinyl pyridines, ect.; (11) neoprene; (12) polyphenylene oxide resins; and (13) cellulose esters including the nitrate, acetate and propionate.

Claim 26

Thermoplastic laminate reinforced with needled glass fiber strand mat having improved stampability, where the laminate is produced by combining the needled glass fiber strand mat with an overlay and underlay of the thermoplastic polymer and the combination is heated under pressure, comprising: a. needled glass fiber strand mat, wherein the glass fibers have a coating of a dried residue having around 2 to 10 percent moisture content, where the dried residue is of an aqueous sizing composition, comprising: (a) a combination of organic silane coupling agents present in the aqueous treating composition in an amount of about 0.5 to about 10 percent by weight, wherein one silane is a vinyl-containing organic silane coupling agent present in an amount of about 60 to about 99 weight percent of the combined silanes and another silane coupling agent is a saturated amino-organic silane coupling agent in an amount in the range of about 1 to about 40 weight percent of the combined silanes, (b) about 0.5 to about 15 percent by weight of a film forming polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyvinylpyrrolidone, and vinylacetatemetholacrylamide copolymers, (c) about 0.1 to about 7.6 percent by weight of a nonionic surfactant, (d) about 0.001 to about 1 percent by weight of a glass fiber lubricant, (e) about 0.1 to about 6 percent by weight of a heat stable organic peroxide free radical initiator, and (f) an amount of water to give a total solids in the range of about 1 to about 20 weight percent, b. thermoplastic polymer selected from the group consisting of polyolefins, polyamides, polyalkylene terephthalate chemically coupling polypropylene, polypropylenes with small amounts of polyethylenes and homopolymeric and copolymeric substances such as (1) vinyl resins formed by the polymerization of vinyl halides or by the copolymerization of vinyl halides with unsaturated polymerizable compounds, e.g. vinyl esters; alpha, beta-unsaturated acids; alpha, beta-unsaturated esters; alpha, beta-unsaturated ketones; alpha, beta-unsaturated aldehydes; and unsaturated hydrocarbons such as butadienes and styrenes; (2) polyalpha-olefins such as polyethylene, polypropylene, polybutylene, polyisoprene and the like, including copolymers of polyalpha-olefins; (3) phenoxy resins; (4) poly amides such as polyhexamethylene adipamide, polyalphacaprolactam and the like, including copolymers of polyamides; (5) polysulfones; (6) polycarbonates; (7) polyacetals; (8) polyethylene oxide; (9) polystyrene, including copolymers of styrene with monomeric compounds such as acrylonitrile and butadiene; (10) acrylic resins as exemplified by the polymers of methyl acrylate, acrylamide, methylol acrylamide, acrylonitrile and copolymers of these with styrene, vinyl pyridines, ect.; (11) neoprene; (12) polyphenylene oxide resins; and (13) cellulose esters including the nitrate, acetate and propionate.

Claim 27

Method according to claim 1 wherein the sized glass fibers are dried to a moisture content of around 2 to 10 percent.

Claim 28

Needled mat of claim 11 wherein the coated glass fiber strands have a moisture content of about 2 to 10 percent.

Claim 29

Reinforced thermoplastic polymeric article prepared from the mat of claim 11 combined with an overlay and underlay of thermoplastic polymer and heated under pressure to place these components in close association.

Claim 30

The thermoplastic laminate of claim 23, wherein the film forming polymer is a polyvinylacetate homopolymer.

Claim 33

Method of claim 28, wherein the strands are collected into a forming package and a plurality of the forming packages are dried so that the dried glass fiber strand has a moisture content of around 2 to about 10 weight percent and a plurality of the dried forming packages are used to provide the plurality of glass fiber strands for dispersing onto a moving conveyor to form a continuous mat.

Claim 34

Method of claims 1 or 28, wherein the aqueous size has present about 0.1 to about 1 weight percent of a softening agent.