NL8006696A - METHOD FOR REDUCING FIBER REINFORCED POLYMERIC MATERIALS UNDER THERMAL AGING CONDITIONS, ANTIOXY DANCE EMULSION, AQUEOUS COATING MATERIALS FOR THE PROCESSING OF GLASS FIBERS, PREPARED FOR THE MANUFACTURING OF GLASS FABRICS, OF FIBERGLASS. - Google Patents

Description

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Process for reducing fibrous reinforced polymeric materials under thermal aging conditions, anti-oxidant emulsion, aqueous coating material for treating glass fibers, method for manufacturing glass fibers, and method for preparing an emulsion suitable for use in a coating material for treating glass fibers.

The invention is directed to approaches to improve the properties of fiber-reinforced polymers under aging conditions, including the use of oil-in-water emulsions of antioxidants that are insoluble in water or immiscible with water or limited have water solubility in which the emulsions have a small particle size and good stability.

More particularly, the present invention is directed to methods and materials for improving the performance of glass fiber reinforced polymers under thermal aging conditions. The materials include the use of oil-in-water emulsions of anti-oxidants which are insoluble in water or immiscible with water or have limited solubility in water and which have low volatility and good thermal stability and are not discolor, for use in the treatment of glass fibers. The oil-in-water emulsion provides a method of reducing chemical degradation of polymers reinforced with glass fibers containing coating materials.

To stabilize polymers against degradation due to oxygen and ozone, various hindered phenol and diarylamine antioxidants are included in polymer compositions. Another type of degradation that can occur with polymers is degradation due to various chemicals other than oxygen and ozone that the polymers can come into contact with. Such chemical degradation can occur when the materials are reinforced with material treated with various chemicals to provide effective processing of the materials and to provide compatibility of the materials with the 800 6 69 6 - 2 - I * polymers. When producing reinforcing materials containing treatment chemicals, such as glass fiber coatings, care should be taken to avoid any problem of interaction between the chemistry on the reinforcing material and the polymers. Any possible interaction between the various chemical agents in the system or reaction or deposition products of these chemical agents with the polymer may degrade the polymer to some extent. This deterioration or degradation decreases the mechanical properties of the reinforced polymer with time and in particular under thermal aging conditions. When the reinforced polymer is subjected to elevated temperatures for a period of time, ie, thermal aging, degradation of the polymer can be accelerated due to thermal auto-oxidation and increased chemical interaction reaction rates. This degradation detracts from the useful properties of the reinforced polymer, which usually has improved properties due to the presence of the reinforcement.

Antioxidants added to polymeric compositions to be used in the preparation of reinforced polymers are also added in the form of the antioxidant as a solid or liquid only. Antioxidants have also been added to latex compositions, such as rubber latices, in the form of emulsion and dispersions. For example, the anti-oxydance "Age Rite Resin D" can be obtained from R.T. Vanderbilt

Company, Inc. which is the antioxidant polymerized 1,2-dihydro-2,2,4-trimethylquinoline, are prepared in a 30% emulsion by melting the "Age Rite Resin D" antioxidant in light process oil and oleic acid at 304 ° C and remove of the mixture 30. from the heating source and adding xylene. Then, the emulsifier is diluted nonylphenoxy-poly (ethyleneoxy) ethanol, available from GAF Corporation Chemical Products under the trade designation "Igepal CO-630". Dissolved potassium hydroxide granules are mixed with the emulsifying agent and the mixture is heated to about 88 ° C. The emulsifier mixture is then added to the antioxidant mixture with vigorous stirring to provide 8006696 & i -v - 3 - Λ an emulsion with about 32.1% oil in 31.8% water. Other similar emulsions and dispersions are available in the publication "Vanderbilt News" volume 34, number 2, 1972, pages 13-24.

An emulsion is a two-phase system, consisting of two incompletely miscible liquids, one of which is dispersed in the form of fine droplets in the other, while a suspension is a two-phase system in which the dispersed phase is a solid. As indicated above, both emulsions and dispersions of anti-oxidants have been used in rubber latex compositions. The stability of anti-oxidant emulsions depends on the factors for emulsions in general: (1) particle size, (2) difference between the densities of the material in the internal phase, which is the droplet broken liquid, and the material in the external phase, which is the surrounding material, (3) the viscosity of the emulsion concentrate, (4) the charges on the particles, (5) the choice of the emulsifier type and the amount of the emulsifier used, and (6) storage conditions, such as agitation, temperature, dilution and evaporation.

Further uses of antioxidant emulsions can be developed if the emulsions have a small average particle size of about 1.5 µm and a sufficiently narrow particle size distribution. Such further application can be found in the coating industry in which coating or treatment solutions for various materials would benefit from an antioxidant emulsion with a small average particle size and a fairly narrow particle size distribution. Antioxidants which would be particularly useful in a small average particle size emulsion and fairly narrow particle size distribution would be those which have low volatility and / or are heat resistant and / or do not discolour.

An object of the present invention is to provide an oil-in-water emulsion of an antioxidant dance, in particular antioxidants of low volatility and / or heat-resistant and / or non-coloring, with an average particle size of less than 1.5 µm9 a fairly narrow particle size distribution, 8 00 6 69 6% - 4 - good stability and good dilutability to a low concentration.

A further object of the invention is to provide a glass fiber treatment material to be used to reinforce various polymeric materials and to degrade the reinforced polymer due to interaction between the chemicals in the treatment material or the reaction or decomposition products thereof and reduce the polymeric material.

A further object of the invention is to provide a method of reducing degradation of a glass fiber reinforced polymer due to any interaction between the materials contained in the coated glass fiber strand and / or reaction or thermal decomposition products thereof under thermal aging conditions, thereby to reduce any deterioration in mechanical properties of the reinforced polymer due to such degradation.

According to the invention, the foregoing and other purposes arising from discussion 20 below are achieved by a method of reducing chemical degradation of polymers due to chemical interaction between chemicals in the reinforcing material coating material and / or chemical reaction or thermal decomposition products of said chemicals and the polymer by adding an antioxidant or to the treatment material for the reinforcing material. or adding an amount of one or more antioxidants with low volatility and good heat resistance to the polymeric material.

The treatment material for the reinforcing material, such as coating materials used with glass fibers, has the antioxidant present in the form of an oil-in-water emulsion with a small average particle size and a fairly fine particle size distribution so that the treating material 35 the surface of the reinforcing material material well covered. The treating material may contain other components conventionally used in glass fiber treatment materials.

8006696 * i. 'i ♦ -5-

Non-exclusive examples of this include coupling agents, film-forming agents, lubricants, surfactants and the like.

The oil-in-water emulsion of the antibody dance allows for high concentrations, up to about 60% by weight of the aqueous emulsion, of the water-immiscible or water-insoluble or limited water-soluble and miscible hindered phenol or low volatility diarylamine antioxidant with good thermal resistance and good compatibility with the polymer.

The emulsion also has an organic solvent that volatilizes just above ambient temperatures to temperatures above those just above the temperature used to treat and process the reinforcing material treated with the emulsion. The emulsion also has one or more emulsifying agents or an emulsifying agent mixture 15 wherein the hydrophilic / lipophilic balance (HLB) for the mixture is in the range of about 12 to about 27.

Low volatility indicates that the antioxidant has a weight loss percentage, measured by thermogravimetric analysis (TGA), of less than about 20% when about 20 6 mg of the antioxidant is heated to 250 ° C and held at said temperature for 30 minutes. This ensures the presence of a sufficient amount of antioxidants in the reinforced polymer.

The good heat or thermal resistance or stability of the antioxidant indicates that the antioxidant does not decompose in any way that would cause it to lose its effectiveness at temperatures below about 93 ° C.

The compatibility between the antioxidant and the polymer to be reinforced indicates that the antioxidant is capable of forming secondary bonds, such as hydrogen bond, Van der Waals bond and dipole interactions and ionic bond with the polymers. If the antioxidant is highly compatible with the polymer and has a high degree of at least secondary bonds, the volatility of the antioxidant may approach the upper limit of weight loss.

In general, the method of the invention includes the following. The oil-in-water antioxidant emulsion is prepared. The aqueous treatment solution containing the emulsion is prepared with at least a film-forming agent and a coupling agent and optionally a lubricant and other conventional coating material additives used to treat glass fibers. The glass is formed into glass fiber strands and the aqueous treatment solution is applied to the glass fibers during formation. The treatment solution, also known as a coating material, in contact with the glass is dried to remove moisture and vaporizing organic solvent. The dried, treated glass fibers are used in any form as reinforcing material for polymeric materials.

In addition to incorporating the antioxidant into the reinforced polymer by using the oil-in-water emulsion, the low-volatility heat-resistant antioxidant can be incorporated into the polymer during polymerization and / or dry mixing to prepare the fiber-reinforced polymer. This addition is in excess of the usual amount of that oxidant added to the polymer recipes. Usually, less than 1 part per 100 parts polymer up to about 3 parts per 100 parts polymer is added to polymer recipes. This addition protects the polymer during processing and in use from degradation due to oxygen, ozone and water. The additional amount in excess of the amount added for such protection protects a fiber-reinforced polymer from chemical degradation. The chemical degradation is that associated with interactions of chemicals in treatment solutions and / or reaction and / or thermal degradation products thereof used to treat the reinforcing material.

Although the theory of degradation of the reinforced polymer is not fully understood, it is believed that there is a chemical interaction between the chemical compounds of the coating material on the glass fibers or reaction products and / or thermal decomposition products of these chemicals and the polymer. This interaction leads to chemical degradation of the 8006696 A »- 7 polymer, which is associated with any degradation due to oxygen, ozone and / or water. This chemical degradation especially occurs when the reinforced polymer is subjected to elevated temperatures and thermal aging. It is believed that the degradation is more than thermal auto-oxidation, since the shaping of the fiber-reinforced polymers takes place in closed molds that reduce the amount of oxygen present, and since the reinforcement, such as glass fiber, contains little or no moisture because the glass fibers have been dried to reduce their moisture content before carrying out the shaping operation. It is further believed that certain types of compounds present in the treatment solution and on the dried treated glass fibers may be subject to thermal degradation at conditions milder than those causing polymer degradation. It is believed that an example of these compounds are the polyoxyalkylene type compounds which are used as nonionic emulsifiers in the treatment solution and.

It has been found that the addition or inclusion of hindered phenolic or diarylamine antioxidants of low volatility, good thermal stability and good polymer compatibility in the polymer or in an aqueous coating material for treating glass fibers during their formation increases the amount of chemical degradation. of the fiber-reinforced polymer. The reduction in chemical degradation improves the mechanical properties and the service life of the fiber-reinforced polymers, and this is especially true under conditions of thermal aging.

The types of hindered phenolic and / or diaryΙ-amine antioxidants that can be used include the non-exclusive examples of high molecular hindered phenolic compounds, high molecular hindered bisphenolic compounds, high molecular hindered phenolic amines, high molecular hindered monophenolic compounds; 3,5-di-tert-butyl-4-35 hydroxyhydrocinnamic acid triester with 1,3,5-tris (2-hydroxyethyl) bis triazine-2,4,6 (1H, 3H, 5H) -trion; alkylated phenols and 8006696 «**« 1 - δ-bis-phenols and phenol condensation products such as a 3: 1 condensate of 3-methyl-6-tert-butylphenol with crotonaldehyde; tetra-functional hindered phenols such as tetrakisOnethylene-S'S'SS'-di-t-butyl-4'-hydroxyphenyl (propionate) methane; octadecyl (di-t-5-butyl-hydroxyphenyl-propionate) and other such phenolic compounds having the structure of formula 1, wherein A has a value from 0 to 6 and B has a value from 2 to 30 and R hydrogen or hydroxy, such as the following compounds: 1,2-propylene glycol bis- / 3,5-di-t-butyl-4-hydroxyphenyl) propionate; ethylene glycol-10 bis / 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; neopentyl bis- / 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate /; ethylene bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate; glycerine / n-octadecanoate-2,3-bis- (3,5-di-t-butyl-4-hydroxyphenyl acetate); sorbitol -hexa- / 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate /; 2-hydroxyethyl 1-7- (3-15 methyl 5-t-butyl-4-hydroxyphenyl) heptanoate; N. N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy) -hydrocinnamamide and the like; polybutyl bisphenol; esters of ethoxylated arylphenols and bis-aryl phenols such as the acetate ester of the condensation product of 5 moles ethylene oxide with 1 mole of benzylphenol; the laurate ester 20 of the condensation product of 24 moles of ethylene oxide and 1 mole of bis-benzylphenol; the stearate ester of the condensation product of 10 moles of ethylene oxide and 1 mole of a-methyl-benzylphenol; neutral adipate esters of the condensation product of 2 moles of ethylene oxide with 1 mole of aja'-dimethylbenzylphenol; the dipelargonate ester 25 of the condensation product of 17 moles of ethylene oxide and 1 mole of bis-methyl-benzylphenol; the neutral malonate ester of the condensation product an 8 moles of ethylene oxide with 1 mole of a-phenylbenzyl-phenol; the palmitate ester of the condensation product of 3 moles of ethylene oxide with 1 mole of α-methylbenzylphenol and the like; Condensation products of oxalyl dihydrazide and 3-tertiary butyl-4-hydroxy-aryl-carbonyl compounds such as 3,5-ditertiary-butyl-4-hydroxybenzaldehyde. Particularly useful are the antioxidants such as tetrakis (methylene-3-3 ', 5'-di-t-butyl-4-hydroxyphenol) -propionate-methane, substituted diphenylamine such as 4,4' - / 2- (2-35 phenyl propyl / diphenylamine; 3: 1 condensate of 3-methyl-6-tertiary-butylphenol with crotonaldehyde and octadecyl-3- (3 ', 5'-di-tert-butyl-8006696-9-4-hydroxyphenyl) propionate and the like; condensation product of oxalyl dihydrazide and 3,5-di-tertiary-butyl-4-hydroxy-arylcarbonyl compounds; esters of ethoxylated arylphenols and 1,3,5-trimethyl-2,4,6-tris / 3,5-di-tert-butyl-4-hydroxybenzyl / -5 benzene. The aforementioned antioxidants that most benefit from the present invention are those that are immiscible with water or insoluble in water.

Any of the aforementioned anti-oxidant stabilizers have a high degree of compatibility with monomers polymerized to provide polymers to be reinforced with fibrous materials, the anti-oxidant stabilizer may be added directly to the polymer to aid in chemical degradation due to chemical compounds present on the fibrous reinforcement material or its chemical and / or thermal degradation products thereof.

Synthetic organic polymeric materials to be reinforced with fibrous materials useful in the present invention include the non-exclusive examples of vinyl polymers such as poly-α-olefins such as polyethylene, polypropylene, polybutene, polyisoprene and the like, including copolymers of poly-α-olefins; polyurethanes, such as are prepared from polyols and organic polyisocyanates; polyamides, such as polyhexamethylene adipamide; polyesters, such as polymethylene terephthalates and polybutalene terephthalates and polyethylene and polypropylene terephthalates; polycarbonates, polyacetals, polystyrene and copolymers, such as those of a high impact polystyrene containing copolymers of butadiene and styrene and those formed by the copolymerization of acrylonitrile, butadiene and / or styrene.

Generally, small amounts of the antioxidant stabilizers are added to the polymers during the polymerization, although larger amounts are added to the polymers during formulation, mixing and processing and final fabrication of the reinforced polymeric material. Generally, the antioxidants are used in an amount of from about 0.005% to about 3% by weight, based on the stabilized 8006696.

the material. In polypropylene, amounts of from about 0.01 to about 3 wt% are advantageous with particularly preferred amounts being from about 0.01 to about 1 wt%. Therefore, the amount of antioxidant stabilizer needed to overcome the chemical degradation of any of the compounds on the reinforcing material used to reinforce the polymer or the reaction and / or decomposition products of the compounds should be an additional amount in the range of about 0.25 to about 1.0 parts per 100 parts of polymer and reinforcement added to the polymer which may already contain amounts up to 3% of some type of oxidizing agent. This additional amount of antioxidant can be added to the polymer to be reinforced at any time prior to the final production of the reinforced polymeric material. It is most advantageous to add the extra amount of anti-oxidant to the polymerized polymer ready to be mixed with the reinforcement; preferably glass fibers are used to produce the reinforced polymeric material. The antioxidant can be added in any form, such as the solid form, liquid or as an emulsion or dispersion in aqueous or non-aqueous solvents.

When the additional amount of antioxidant is incorporated into the aqueous treatment solution or coating material applied to the reinforcing material, such as glass fibers, the antioxidant is added to the glass fiber treatment solution in the form of an oil-in-water emulsion. The aqueous emulsion is necessary to provide substantially even coating of the glass fibers as they are formed. To reduce the amount of degradation of polymeric materials that are reinforced with fibrous reinforcement with chemical agents thereon that cause chemical degradation in the polymer upon thermal aging, the amount of antioxidant present in the emulsion should range from about 5 to about 60 wt% of the emulsion.

The oil-in-water emulsion of the aforementioned antioxidants which are immiscible with water or are insoluble in water 800 6 6 9 6 - η - include, in addition to the antioxidant, one or more organic solvents and one or more emulsifying agents.

The organic solvent will vary with the different antioxidants used in such a way that if the antioxidant is predominantly aliphatic, the organic solvent will have a low kaurobutanol value, such as from about 10 to about 50 and a boiling range within the range of ambient temperatures up to about 250 ° C where the boiling point is above the use temperature of the emulsion, that is, the temperature at which the glass fibers are treated with aqueous coating materials. If the antioxidant has more than about 60% aromaticity, the acceptable organic solvent will have a kauri-butanol value of about 50 to about 100, with a boiling range within the range of about ambient temperature to about 250 ° C and which above the operating temperature of the emulsion. The use of organic solvents with a boiling point above 250 ° C is not advantageous since the solvent must be removed after the reinforcing material has been treated. When the organic solvent 20 has a boiling point below about 100 ° C to about 150 ° C, the use of suction equipment to control the escaping vapor is necessary.

The kauri-butanol number is a measure of the dissolving power of petroleum diluents, where the value 25 is equal to the number of ml of solvent required to cause cloudiness when adding 20 g of a solution of kauri-gum in butanol . The solution is prepared in the ratio of 100 g of cow gum and 500 g of butanol. Low aromatic solvents are strong precipitants for the resin and therefore give half low values. Conversely, the solvents with a high aromaticity give high values. The kauri-butanol numbers are preferably determined relative to one of two standards, the one standard being a one-degree toluene having a value of 105, used when the organic solvent has a kauri-butanol-35 value above 60, and the other standard is a mixture of 75% n-heptane and 25% toluene, when the organic solvent is AA Λ Λ (O Λ £ t *.

- 12 - has a cowaur-butanol number of 40. This is discussed in ASTM Standard D.1133-54T.

Organic solvents from which the low and high kauri-butanol value solvents are selected are solvents such as aliphatic hydrocarbons, aromatic hydrocarbons, esters, ethers, alcohols, ketones, petroleum distillates and coal tar distillates and mixtures thereof. Examples of organic solvents with low cowyl butanol numbers which are useful when the antioxidant contains a substantial amount of aliphatic components are the isopraffinic hydrocarbon solvents. Suitable examples are those from the range of commercially available isoparaffinic hydrocarbon solvents sold by EXXON Company USA under the trade name "ISOPAR" or Philips Petroleum under the trade name "SOLTROL" 15 which have boiling ranges within the above ranges. Examples of high kauri-butanol organic solvents include the solvent commercially available under the trade name "HI-S0L-10" or "HI-SOL-15" available from Ashland Chemical Company, Ohio. The "HI-SOL-10" solvent has a boiling point of 150 ° C, a flash point of 40.6 ° C and an evaporation rate of 25.0 using an ether base of 1. Also, the organic solvent contained in the is marketed by EXXON Company USA, Division of EXXON Corp. Co. are used under the name "S0LVESS0 150" or "S0LVESS0 100". Further examples of organic solvents that can be used in forming the antioxidant oil-in-water emulsion of the invention are the following non-exclusive examples: xylene, methyl ethyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, toluol, ethyl cellosolve, toluene, butyl carbitol acetate, butyl cellosolve acetate, trichlorethylene, methylene chloride, amyl acetate, ethyl acetate and the like.

The ratio of the antioxidant to the organic solvent will vary depending on the particular antioxidant and solvent used, but generally the ratio will be in the range of at least about 60 to about 40 of the antioxidant to the solvent and preferably 8006696 - 13 - running to about 40:60 and most preferably about 50 to about 60. Less solvent will be needed if the organic solvent has a higher kauri-butanol number, if the antioxidant has significant aromaticity, and if the kauri-5-butanol approaches number 50 when the antioxidant has a significant amount of aromatic character. The amount of the organic solvent used in preparing the emulsion of the antioxidant will generally vary within the range of about 1 to about 50% by weight of the emulsion. More solvent can always be added, but there is no advantage in such practice as the solvent is usually removed at a later time.

The emulsifying agent or emulsifying agents according to the invention is either selected from non-ionic emulsifying agents or a mixture of one or more non-ionic emulsifying agents with an anionic emulsifying agent. When using more than one emulsifying agent, the emulsifying agents form an emulsion mixture of at least two emulsifying agents. The emulsifying agents are selected to provide a hydrophilic-lipophilic balance (HLB-20 value) for the emulsifying agent or emulsifying mixture in the range of about 12 to about 27. Non-exclusive examples of chemical types of emulsifying agents for use in the mixture of emulsifying agents are non-ionic emulsifiers such as ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids, ethoxylated fatty esters and oils, fatty esters, glycerol esters, glycol esters, monoglycerides and derivatives, sorbitan derivatives, sucrose esters and alkyl alcohol polyol ether, alkyl alcohol oxide alkyl condensates. Non-exclusive examples of the anionic emulsifiers include alkyl sulfonates, phosphate esters, polyaminocarboxylic acids and related sequestering agents, sucin sulfate derivatives, alcohol sulfates, ethoxylated alcohol sulfates, sulfates and sulfonates of ethoxylated alkyl phenols, oils and fatty esters and the like. The amount of the emulsifying agent or emulsifying mixture added to the emulsion is in the range of about 3 to about 15% by weight of the emulsion.

s η n «6 a 6 - 14 -

In addition to the antioxidant, the organic solvent and one or more emulsifying agents, the emulsion contains an amount of water necessary to make the emulsion into an oil-in-water emulsion, which generally ranges from about 28 to is about 70% by weight. If the emulsion has to be transported over a significant distance, it is most practical to add just the amount of water needed to make the emulsion an oil-in-water emulsion, which is in fact a concentrated emulsion, which can be further diluted at the site of use.

In preparing the emulsion of the invention, one or more of the aforementioned antioxidants are dissolved in one or more of the volatilizing organic solvents suitable for the specific antioxidants involved. Also, the antioxidant or the antioxidants can be melted and then added to the volatilizing organic solvent. The mixture of the one or more antioxidants with one or more organic solvents can be subjected to moderately elevated temperatures to facilitate solubilization of the antioxidants. The mixture of the antioxidant dissolved in the organic solvent contains the one or more emulsifiers added thereto, and this mixture is emulsified using standard techniques, conditions and equipment. Such standard techniques include the direct method of preparing an emulsion or the indirect method of preparing an emulsion in which water is added until the oil inverts to an oil-in-water emulsion. The amount of water added to the organic solution of the antioxidant and emulsifying agent mixture is that which provides an emulsion containing about 28 to about 70% by weight water. The homogenizing action can be performed in a variety of equipment which can subject the aqueous organic mixture to high shear. An example of such equipment is an Eppenbach colloid mill with a distance setting of 20. A Manton-Gaulin homogenizer can also be used at pressures from 210 to 420 kg per cm. The emulsifier or emulsifier mixture can be added to the mixture of one or more antioxidants and one or more organic solvents by separately adding the emulsifier to the mixture or by adding any combination of the emulsifying agents. After the emulsifying agents have been added, the resulting mixture is slowly diluted with water using the invert emulsion technique, where the water may be at ambient or elevated temperature. The water is added slowly until the emulsion inverts to an oil-in-water emulsion and then the emulsion is cooled to ambient conditions. Additional water is added during cooling or afterwards to bring the emulsion to the desired concentration. The amount of water added to the emulsion is at least about 28% by weight of the emulsion composition.

One use for the antioxidant emulsion that is particularly beneficial is use in a glass fiber treatment solution. The emulsion has a fine droplet size or particle size sufficient to allow a substantially uniform coating of the treating solution on the glass fiber surface. The oil-in-water oxide dance emulsion can be formed into an aqueous treatment solution or, as mentioned in the art, a coating material for glass fibers by combining the emulsion with coating material components, such as film formers, coupling agents, lubricants and perhaps additional components, such as plasticizers, wetting agents, anti-foaming agents and further surfactants. This formation may involve slow addition of the emulsion to an aqueous mixture containing one or more coupling agents and optional lubricants or plasticizers and film-forming agents and the residual water to form the aqueous coating material. It is also possible to add the one or more coupling agents, lubricants, plasticizers, film-forming agents or other coatings to a mixture containing the emulsion alone or the emulsion and one or more of the aforementioned coating material components. Once the emulsion of the invention has been prepared, the aqueous coating material can be made by any means known to those skilled in the art. For example, the amounts of coupling agents, lubricants, film-forming agents and other coating material constituents can generally be in the following range: 5% by weight of the aqueous coating material coupling agent about 0.5 to about 10 lubricant about 0.001 to about 1 film-forming medium about 0.5 to about 15

The aqueous coating material is applied to individual glass fibers during their formation by any conventional method of applying coating materials to glass fibers. The glass fibers are drawn from molten streams of glass, which may be an E glass or 621 glass material or any slightly contaminating derivative thereof. Such methods are described in U.S. Pat. No. 4,027,071.

Coated glass fibers are dried to remove moisture and an evaporable organic solvent. Drying can be accomplished by air drying or by drying in a heated oven. The dried coated glass fibers can be used in any form such as fibers, strands, wet or dry strands, mats and the like to reinforce polymers such as polyamides such as Nylon-6; polyesters, such as polybutylene terephthalate; polyolefins, such as polyethylene, polypropylene and copolymers thereof, and the like. .

In the preferred embodiment of the present invention, the antioxidant used to overcome chemical degradation of a reinforced polymer material due to chemical interaction between chemical compounds present on the fibrous reinforcement or the reaction or thermal degradation products of the compounds and the polymer is added to the aqueous treatment solution for the fibrous material, which preferably consists of glass fibers. It is preferable to include the antioxidant in the aqueous treatment solution by combining the oil-in-water antioxidant emulsion with other components to prepare the aqueous treatment solution.

In the preferred oil-in-water emulsion 8006696 1 * -17-, the antioxidants used have reasonably low volatility, good thermal stability and good polymer compatibility. The preferred emulsion uses from about 5 to 60 and most preferably from about 5 to about 25 weight percent octadecyl-3- (3 ', 5'-di-5 tert-butyl-4-hydroxyphenyl propionate) available from Ciba Geigy Corporation under the brand name "IRGANOX 1076". This antioxidant, which is a white crystalline free-flowing powder with a melting range between 50 and 55 ° C and a molecular weight of about 531, is preferably dissolved in a ratio of about 10 µl with xylene. About 3 to about 15, preferably 3 to about 12, weight percent of an emulsifier mixture is added to this mixture. It is preferred that the emulsifying agent mixture be a combination of three emulsifying agents which when used at certain weight ratios relative to each other give a total HLB for the emulsifying mixture in the range of about 12 to about 27. It is preferred that one emulsifying agent has a high HLB value, in the range from about 12 to about 27. Another emulsifier has a lower HLB value, in the range from about 6 to about 12, and yet another emulsifier has a HLB value in the mid range from about 9 to about 18. It is particularly useful to use the emulsifiers in equal amounts, although any ratio of the various emulsifiers can be used to provide the desired HLB range.

It is most preferred to have a first emulsifying agent which is a trimethylnonylpolyethylene glycol ether, such as those commercially available from Union Carbide Corporation under the trade name "TERGITOL TMN-6" with an HLB of 11.7. This ether is used in an amount of about 30 to about 5% by weight of the emulsion. The ether emulsifiers are combined with another emulsifier, which is a nonylphenoxypolyethyleneoxyethanol, commercially available from GAF Corporation Chemical Products under the trade name "IGEPAL C0-630" with an HLB of 13 and used in an amount from about 3 to about 5% by weight of the aqueous emulsion. These two emulsifiers are combined and stirred to clarity.

8006696 - 18 -

Then an emulsifier, which is a condensate of ethylene oxide with hydrophilic bases, formed by condensing propylene oxide with propylene glycol and commercially available from BASF Wyandotte Industrial Chemical Corporation under the trade name 5 "Pluronic-P-65" which HLB of 17, and is used in an amount from about 1 to about 5 weight percent of the aqueous emulsion material.

It is preferable to add the emulsifying agent mixture in the following manner. A mixture of the ether-10 emulsifier and ethanol emulsifier is combined with the mixture of the antioxidant and organic solvent. The polyoxyalkylene oxide block copolymer emulsifier is split into two parts, preferably about equal parts, the first part being added to the mixture of the emulsifying agents, antioxidant and solvent, and the second part being added to water, at preferably in a mixing ratio of 50:50, and then this portion of the oxide block copolymer emulsifying agent in water is combined with the mixture of emulsifying agent, antioxidant and solvent. The final mixture is then stirred adding an amount of warm water from about 25 to about 30 ° C in the range from about 15 to about 30 weight percent of the aqueous emulsion. Then, an amount of cold water is added to provide an amount of active antioxidant in the range of about 5 to about 25 wt.% To provide the aqueous emulsion.

In an alternative embodiment, the antioxidant tetrakis (methylene-3-3 ', 5'-di-t-butyl-4'-hydroxy-phenyl) -propionate-methane available from Ciba Geigy Corporation under the trade name "IRGANOX 1010" antioxidant is dissolved in an amount of from about 5 to about 20 weight percent of the emulsion in the organic solvent methyl ethyl ketone. The amount of methyl ethyl ketone used is about 1: 1 with the antioxidant. The emulsifier mixture is combined with the mixture by one of the aforementioned methods of addition. The emulsifying agent mixture 35 comprises the emulsifying agent polyoxyethylene (4) sorbitan monolaurate (Tween 21 from ICI Americas, Inc.) in which the amount of the 8006696-19 monolaurate emulsifying agent is from about 1 to about 5% by weight.

Another emulsifier used is a condensate of ethylene oxide with hydrophilic bases formed by condensation of propylene oxide and propylene glycol, which is available from 5 BASF Wyandotte under the trade name "Pluronic F-85" with an HLB of 24 and used in an amount of about 1 to about 5% by weight. Another emulsifying agent used is the polyethoxylated vegetable oil available from GAF Corporation under the trade name "EMULPHOR EL-719" with an HLB of 13.6 and used in an amount from about 1 to about 5 wt. %. In addition to the antioxidant, the methyl ethyl ketone and the emulsifiers, an amount of polyalkylene polyol lubricant of the trade name "Pluracol V-10" from BASF Wyandotte Corporation is added to the emulsion in an amount of about 1 to about 5% by weight. This lubricant is added to give the emulsion extra stability. This lubricant can also be added to the coating material instead of the emulsion. The polyalkylene glycol "Pluracol V-10" is a viscous, high molecular weight liquid with a density of 1.089 at 25/25 ° C according to the BWC test with a flash point of 265 ° C according to ASTM D92-52. To the mixture of the antioxidant, methyl ethyl ketone, monolaurate, oxide glycol condensate and vegetable oil emulsifiers and polyol lubricant, the required amount of water is added to provide an oil-in-water emulsion as for the preferred antioxidant discussed above.

Another alternative embodiment is the use of a substituted diphenylamine antioxidant 4,4 '- / 2- (2-phenyl) -propyl / diphenylamine available from Uniroyal Chemical Corporation under the trade name "NAUGARD 445" in an amount preferably of about 5 to about 25% by weight dissolved in acetone, used in an amount of about 1: 1 with the antioxidant. To this antioxidant and solvent mixture, the emulsifying agent mixture is added by any of the methods discussed in the preferred antioxidant emulsion. The emulsifiers 35 comprise the condensate of ethylene oxide with hydrophobic bases formed by condensation of propylene oxide and propylene glycol, 8006696 -20- available from BASF Wyandotte Corporation under the trade name "Pluronic F-87" with an HLB of 24 and used in an amount of about 0 From 5 to about 5 wt% together with another ethylene oxide-propylene oxide glycol condensate available under 5 under the trade name "Pluronic P-65" which has an HLB of 17 and is available in paste form. Another emulsifier used is GAF's polyethoxylated vegetable oil under the trade name "EMULPHOR EL-719" with an HLB of 13.6. A required amount of water is added to this mixture by one of the methods, regardless of which discussed above for the preferred embodiment.

Another alternative embodiment is the use of an antioxidant which is a 3: 1 condensate of 3-methyl-6-tertiary butylphenol with crotonaldehyde, available from ICI 15 US, Ine. under the trade name "TOPANOL CA" in an amount of from about 5% to about 25% by weight of the emulsion. This antioxidant, which is a fine white crystalline powder with a melting point of 182.5 to 188 ° C, is dissolved in cyclopentanone which is used in an amount of about 1: 1 with the antioxidant. To this mixture, an emulsifying agent mixture is added by any of the methods used in the preferred embodiment, wherein the emulsifying agent mixture comprises an octylphenoxy polyethoxyethanol emulsifying agent available from Rohm &

Haas Company under the trade name "TRITON X-100", which is used in an amount of from about 1% to about 5% by weight of the emulsion. Another octylphenoxy polyethoxyethanol emulsifier used is available from Rohm & Haas Company under the trade name "TRITON X-45" and is used in the same amounts as the TRITON X-100 emulsifier. The X-100 has a 30 HLB of .13.5 and the X-45 an HLB of 10.4. In addition to the antioxidant, solvent, emulsifier mixture, an amount of epoxy resin such as Epon 828 epoxy resin from Shell Chemical Company can be added to the emulsion in an amount of up to about 40% by weight of the emulsion. This mixture is then emulsified by the indirect method by adding water to invert the oil into an oil-in-water emulsion. The amount of water added 8006696 4-21 and the method according to which it is added is similar to that discussed for the preferred embodiment. This emulsion of the antioxidant with the solvent and emulsifying agents and epoxy resins allows simultaneous emulsifying agent 5 of the antioxidant and the epoxy resin.

Any of these aforementioned oil-in-water emulsions and preferably the emulsion with the octadecyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate antioxidant can be incorporated into a coating material for the treatment of glass fibers. This processing preferably takes place by addition to an aqueous material containing a coupling agent which is preferably a mixture of coupling agents such as an organodiamino silane coupling agent and an epoxy organosilane coupling agent, both of which are present in an amount of about 0.5 to about 10% by weight of the aqueous coating material. Film formers, such as epoxy resin, are also added to this mixture in an amount of from about 0.5 to about 12 weight percent of the aqueous coating material. In an alternative embodiment, other coating ingredients can be added, such as lubricants, such as Pluracol V-10 lubricant, wetting agents and additional surfactants and cationic agents. The amount of water in the aqueous coating material usually ranges from about 70 to about 99% by weight of the coating material. The aqueous coating material is applied to individual glass fibers during their formation according to the method described in US Pat. No. 4,027,071, and the coated glass fibers are then dried to remove the moisture and organic solvent. The oil-in-water antioxidant emulsion, used in the aforementioned coating material, with a mixture of silanes and a film-forming agent, reduces the chemical degradation of polymers reinforced with these glass fibers, especially at exposures to greatly elevated temperatures during final use. This is particularly beneficial when these coated glass fibers are used to reinforce polyesters, such as polybutylene terephthalate.

8006696 - 22 -

The aqueous emulsions of the invention will be further illustrated by the following examples. Example I

An emulsion was prepared by the following method.

First, 180 g (8.7 wt% of the emulsion) of a 3: 1 condensate of 3-methyl-6-tertiary butylphenol with crotonaldehyde antioxidant was available from ICI U.S. Pat. Ine. when Topanol CA antioxidant was dissolved in an epoxy resin solution at 49 ° C. The solution contained 540 g (26.2 wt%) epoxy resin available Ciba Products Corporation under the trade name "Araldite 540 X90" and 100 g (4.9 wt%) methyl ethyl ketone and 140 g (6.8 wt. %) trichlorethylene.

Then, two emulsifiers which are condensates of ethylene oxide with hydrophobic bases, formed by condensing propylene oxide with propylene glycol, were mixed with the anti-oxide dance emulsion. One emulsifier was Pluronic L-35 with an HLB of 18.5 used in an amount of 66 g (3.2 wt%) and the other emulsifier was Pluronic F-127 emulsifier, with an HLB of 22 and used in a amount of 33 g (1.6 wt%). Both emulsifiers are available from BASF Wyandotte 20 Industrial Chemical Group. The emulsifier mixture had a combined HLB of 19.6. Both were mixed in the anti-oxidant mixture until the F-127 emulsifier was completely melted.

The mixed mixture was cooled before being homogenized in an Eppenbach homogenizer with slow addition of 1000 g of water at room temperature.

This emulsion could be used in a glass fiber coating material.

Example II

Using the same preparation procedure 30, another emulsion was prepared having the following composition: 8006696

a

- 23 -

Wt% g A. Epoxy resin (Araldite 540 X90) 25.4 540

Antioxydans (Naugard 445) 8.5 180

Trichlorethylene 6.6 140 5 Methyl isobutyl ketone 4.7 100

Mixed with A

Pluronic condensate emulsifier1 L-35 5.2 110 F-127 2.4 52 10 water 47.1 1000

Example III

Using the same preparation procedure as in Example I, an emulsion of the following composition was prepared: 15 A. Wt% g

Epoxy resin (Araldite 540X90) 29.6 685

Antioxydance (Naugard 445) 7.8 180

Methyl ethyl ketone 4.3 100

Butyl Cellosolve Acetate 4.3 100 20 1,1,1-trichloroethane 6.0 140 B.

Non-ionic emulsifier 3.0 70 (Pluronic L-35)

Non-ionic emulsifier 1.6 36 25 (Pluronic F-l08)

Water 43.3 1000

This mixture with three solvents and two emulsifiers provided an emulsion with good stability. Example IV

Using the same preparation procedure as in Example I, an emulsion was prepared having the following composition: 8006696 - 24 -

Parts by weight A. Epoxy resin (Araldite 540X90) 25.4 540

Antioxydans (Naugard 445) 8.5 J80

Methylcarbitol Acetate 9.4 200 5 Methyl Ethyl Ketone 4.7 100

Non-ionic emulsifier 3.3 70

Pluronic L-35

Non-ionic emulsifier 1.6 35

Pluronic F-127 10 Cold water 47.1 1000

The inversion occurred with the addition of 700 g of water and the whole remainder of the water was added to produce a stable emulsion.

Example V

J5 An amount of 720 g (25.8 wt) of the aqueous emulsion of antioxidant tetrakis / methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate / methane Xrganox 1010 was dissolved in a mixture of 720 g (25.8 wt.%) cyclohexane. This effervescence took place at a temperature of from 26 to 33 ° C. 45 g (1.6 wt. Z) of the non-ionic emulsifier Tergitol TMN-6 and 45 g (1.6 wt. Z) of the non-ionic emulsifier Igepal CO-630 and 65 g were mixed with this mixture. (2.3 wt. Z) non-ionic emulsifying agent Triton N-401. The emulsifier mixture had an overall HLB of 19.7. To emulsify into an oil-in-water emulsion, 1200 g (42.9 wt.%) Of water was added with shear mixing. A stable emulsion was produced with a fine to medium particle size distribution with hardly any coarse particles.

Example VI

The emulsion of Example V was used to prepare a coating material used to treat glass fibers. The coating material contained: 35 8 00 6 69 6

É A

- 25 -

Wt% g

Epoxy resin (Genepoxy 370 H55 8.3 2730 55% solid)

Emulsion (30.6% solids) 6.7 2210 5 Film-forming agent (Poly 24.2 7980 urethane resin Wyandotte X-1042 50%, available from BASF Wyandotte)

Diamino Organosilane 9.1 3000 10 Water 18.2 6000

Epoxy-containing silane 0.5 150

Water 32.8 10,800

Acetic acid 0.18 60 0.01 5 The bubble-making material was prepared by hydrolyzing the silanes in the indicated amounts of water and combining. The antioxidant emulsion was combined with the silane mixture and the polyurethane resin was added to this mixture. The General Mills Company epoxy resin was added to the mixture. This coating material is hereinafter referred to as coating material 1.

The coating material was used to treat K-37 1/0 glass fibers in a wet chopping process to provide 3.18 mm chopped glass fibers.

Example VII

An amount of 313 g (7.9 wt% of the emulsion) of antioxidant Naugard 445 was dissolved in acetone. The amount of acetone was 500 g (12.7 wt%) yielding an antioxidant to solvent ratio of 0.6: 1. This mixture was added to 1250 g (31.6 wt%) of warm epoxy resin (Epon 828 resin). To this mixture was added 48 g (1.2 wt%) of the Pluronic F-87 nonionic emulsifier and 82 g (2.1 wt%) of the Pluronic P-65 nonionic emulsifier and 32 g ( 0.8 wt%) of the non-ionic emulsifier Emulphor EL-719. The latter emulsifier is a polyoxyethylated vegetable oil available from GAF Corporation. This gives a total HLB

8006696 * - 26 - for the emulsion mixture of 18.4.

The mixture was heated to remove the acetone, although the acetone could also be evaporated before the addition of the emulsifier mixture.

Once about 90 to 95% of the acetone had been removed, emulsification was started using Eppenbach equipment. The water was added gradually until all water was added. The emulsion mixture was again cooled to room temperature.

Examples VIII, IX and X

The emulsion of Example VII was used in preparing three glass fiber coatings. Their compositions are shown in Table A below.

Table A

15 Upholstery Material - Upholstery Upholstery Upholstery Composition Material 2 Material 3 Material 4 g / wt% g / wt% g / wt%

Emulsion concentration 50% epoxy resin / Naugard 445 20 Antioxydans 305 / 8.1 310 / 8.5 305 / 8.3

Film-forming agent:

Urea melamine resin (Resimene resin - Monsanto

Chem. Go.) 36 / 1.0 --- --- 25 Urethan latex

Witcoband W-210 (Witco Chemical Corp.) 200 / 5.3 - ---

Urethan latex Noptothane UOI

30 (Diamond Shamrock Chemical Co.) --- 100 / 2.7 ---

Urethan latex

(Wyandotte X-1042H

(BASF Wyandotte Corp.) --- --- 100 / 2.7

Water 957 / 25.5 1000 / 27.3 1000 / 27.3 35 Water 2176/58 2176 / 59.4 2176 / 59.5

Aminosilane (A-1100 Union Carbide Corp.) 60 / 1.6 60 / 1.6 60 / 1.6

Urea 18 / 0.5 18 / 0.5 18 / 0.5

Total solids 7.1% 7.0% 6.48% 40 No problems were encountered in applying the emulsions in the coating materials 2, 3 and 4.

800 6 69 6

a

- 27 -

These coating materials were used to treat glass fibers made from a glass bath melter used to make wet chopping glass fibers.

Example XI

An oil-in-water emulsion of Irganox 1010 antioxidant was prepared by dissolving 160 g (7.4 wt%) of the antioxidant in 160 g (7.4 wt%) methyl ethyl ketone at a temperature of up to 54 ° C. 50 g POE (4) sorbitan monolaurate (Tween 21 emulsifier from ICI Americas Inc.) and 10 50 g Emulphor EL-719 material, and 50 g Pluronic P-65 emulsifier and 50 g Pluronic F-87 were mixed in this mixture. emulsifying agent. The emulsifier mixture had a combined HLB of 17.

Also mixed in the mixture was 640 g (29.3 wt%) Epon 828 epoxy resin. The total mixture was emulsified using an Eppenbach mixer adding 1000 g (46.5 wt%) of water.

The stability of the emulsion is good when stored for 4 hours and 5 days. Although after 5 days of storage some surface film formed which may be due to solvent evaporation since the container was open to the atmosphere. Example XII

An oil-in-water emulsion of Irganox 1076 antioxidant was prepared by dissolving 160 g (7.4 wt%) of octadecyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate in 160 g (7.4 wt%) 25. toluene solvent at a temperature from 26 ° C to 33 ° C. 50 g POE (4) sorbitan monolaurate (Tween 21), 50 g Emulphor EL-719 material, 50 g Pluronic P-65 emulsifier and 50 g Pluronic F-87 emulsifier were added to this mixture. The emulsifying agent mixture had a combined HLB of 17. An epoxy resin, Epon 30828 resin, was stirred into the mixture and the resulting mixture was emulsified at a temperature of 43 ° C with the addition of 1000 g of water.

The storability and dilutability of the emulsion were good.

35 8 0 0 6 6 9 6 - 28 -

Example XIII

An oil-in-water emulsion of tetrakis (methylene-3-3 ', 5,5-di-t-butyl-4-hydroxyphenyl) propionate-methane was prepared with the following composition and in the following manner. An amount of 480 g of the antioxidant was dissolved in 49 g of methyl ethyl ketone at 49 ° C. 150 g POE (4) sorbitan monolaurate (Tween 21), 150 g Emulphor EL-719 material and 150 g Pluronic P-65 emulsifier and 50 g Pluracol V-10, a lubricant were mixed in with this mixture. The emulsifier mixture had a combined 10 HLB of 17 and the lubricant was added to improve the stability of the emulsion. After these materials were mixed, 1960 g of Epon 828 epoxy resin was stirred into the mixture. At a temperature of 41 ° C, the resulting mixture was emulsified with the addition of 6000 g of water.

15 The dispersibility and stability of the

emulsion were good. Stability was good after two days of storage. Example XIV

An oil-in-water emulsion of octadecell-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate was prepared in the same manner as in Example XIII. The emulsion had a greater amount of solids, 34%. The only exception in the method of preparation was the dissolution of the antioxidant in the toluene at room temperature. The composition was: w / wt% Octadecyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate 480 / 14.4

Toluene 480 / 14.4 POE (4) sorbitan monolaurate 105 / 3.1

Polyethoxylated vegetable oil 30 (Emulphor EL-719) 105 / 3.1

Condensates of ethylene oxide and propylene oxide with propylene glycol

Pluronic P-65 100 / 2.9

Pluronic F-87 100 / 2.9 35 Polyalkylene polyol (Pluracol V-10) 50 / 11.5

Water 1920 / 57.5 800 6 69 6 f - 29 -

The emulsion mixture had a total HLB of 16.8.

The emulsion had good stability and storability. When stored for 4 hours and two days, the emulsion was good.

Example XV

An oil-in-water emulsion of an antioxidant of 3: 1 condensate of 3-methyl-6-tertiary butylphenol with croton aldehyde was prepared. 160 g (6.9 wt%) of the antioxidant was dissolved in 160 g (6.8 wt%) of cyclopentanone. 100 g POE (4) sorbitan monolaurate 10 (Tween 21) and 100 g polyethoxylated vegetable oil (Emulphor EL-719) were mixed into this mixture. The emulsifier mixture had a total HLB of 13.4.

To this mixed mixture was added 655 g (27.9 wt%) of Epon 828 epoxy resin. The resulting mixture was emulsified with the addition of 1175 g (50 wt%) of water.

The emulsion had good dispersibility and good storability for 4 hours and 1 day.

Example XVI

An oil-in-water emulsion of octadecyl-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate was prepared. An amount of 20 288 g (17.7 wt%) of the antioxidant was dissolved in 288 g (17.7 wt%) xylene at about 43 ° C. To this mixture was added an emulsifier mixture of 18 g (1.1 wt%) trimethylnonyl polyethylene glycol ethers (Tergitol TMN-6 emulsifier from Union Carbide Corp.) and 18 g (1.1 wt%) nonylphenoxy polyethylene-25 oxyethanol (Igpal C0630 from GAF Corp.). Also, 18 g (1.1 wt%) condensate of ethylene oxide with hydrophilic bases was formed by condensing propylene oxide with propylene glycol (Pluronic P-65 emulsifier from BASF Wyandotte) combined with 200 g of warm water at 27 ° C and added to the antioxidant mixture . The emulsifier mixture had a total HLB of 13.7.

The resulting mixture was emulsified with the addition of 800 g (49.1 wt%) of water. The emulsion had good dispersibility and good storability.

Example XVII

The antioxidant tetrakis (methylene-3-31,5'-di-t-butyl-4-hydroxyphenyl) propionate methane was emulsified as follows.

800 6 SS δ * - 30 -

720 g (22.7 wt%) were dissolved in a mixture of petroleum solvent Hi-Sol-10 from Ashland Chemical Co.

in an amount of 720 g (22.7 wt%) and 80 g (2.5 wt%) of methyl ethyl ketone. The temperature was 66 ° C for solution in Hi-Sol-5 and the temperature was lowered to 32 ° C for the addition of methyl ethyl ketone.

To this mixture were added 45 g (1.4 wt%) of trimethylnonyl-polyethylene glycol ethers (Tergitol TMN-6) and 45 g (1.4 wt%) of nonylphenoxy polyethyleneoxyethanol (Igepal CO-630) and 10 65 g (2.0 wt%) nonylphenoxy polyethoxyethanol (Triton N-401 702) from Rohm and Haas Co. The emulsifier mixture had a combined HLB of 15.3.

The resulting mixture was emulsified with the addition of 1500 g (47.2 wt%) of water.

Example XVIII

The anti-oxidant which is a 3: 1 condensate of 3-methyl-6-tertiary-butyl-phenol with crotonaldehyde was emulsified by combining 315 g (16.8 wt%) of the anti-oxidant with 500 g ( 26.6 wt%) cyclohexanone at a temperature of about 40 ° C. To this mixture was added an emulsifying agent mixture comprising 32 g (1.7 wt%) of polyethoxylated vegetable oil (Emulphor EL 719) and 82 g (4.4 wt%) of a condensate of ethylene oxide with hydrophilic bases formed by condensing propylene oxide with propylene glycol (Pluronic 25 P-65) and 48 g (2.6 wt%) of another ethylene oxide condensate with hydrophilic bases formed by condensation of propylene oxide with propylene glycol (Pluronic F-87). The emulsion mixture has a total HLB of 18.4. The mixture was again cooled to 27 ° C and emulsified adding 900 g (47.9 wt%) of water.

Example XIX

Another composition of the 3: 1 condensate of 3-methyl-6-tertiary butyl phenol with crotonaldehyde antioxidant prepared in a manner similar to that of Example 18 is as follows: 35 800 6 69 6 ♦ - 31 -

Antioxydans 315 g 20 wt%

Cyclohexanone solvent 350 g 22.2 wt%

Polyethoxylated plant- 22 g 1.4 wt% nice oil 5 Condensate of ethylene oxide 54 g 3.4 wt% with hydrophilic base formed by condensation of propylene oxide with propylene glycol (Pluronic P-65) 10 Another condensate of 16 g 1 wt % ethylene oxide with hydrophilic base formed by condensing propylene oxide with propylene glycol 15 (Pluronic F-77)

Pluronic F-77 Emulsion in 15 g in 500 g 1 wt% in water 31.8 wt%

Water to complete 300 g of 19.1 wt% of the emulsion 20 The emulsifier which is a condensate of ethylene oxide with hydrophilic bases formed by condensing propylene oxide with propylene glycol and available as Pluronic F-77 was added to the antioxidant mixture by adding a first portion of the emulsifier directly to the antioxidant mixture containing the antioxidant, solvent and other emulsifying agents, which is preferably half, and then adding the second portion of the emulsifying agent to water and adding the diluted emulsifying agent to the antioxidant mixture .

The emulsion had a thin viscosity and a blue-white color.

Example XX

An emulsion of octadecyl-3- (3 ', 5'-di-tertiary-butyl-4-hydroxyphenyl) propionate was prepared by dissolving 160 g (20.8% by weight) of the antioxidant in 160 g (20 .8 wt.%) Of a petroleum solvent (Hi-Sol 10) at room temperature, but using heat to aid dissolution. To this mixture was added an emulsifying agent mixture of 25 g (3.2 wt.%) POE (4) sorbitan monolaurate emulsifying agent (Tween 40 21), and 12.5 g (1.6 wt.%) Condensate of ethylene oxide with hydrophilic bases formed by condensing propylene oxide with 8006696 * - 32 - propylene glycol (Pluronic P-65) and 12.5 g (1.6 wt%) of another ethylene oxide condensate with hydrophilic bases formed by condensing propylene oxide with propylene glycol (Pluronic F-87) diluted with 100 g (13 wt%) of water.

This mixture was emulsified with the addition of 300 g (39 wt%) of water. The emulsion had a thin viscosity and a blue-white color.

Example XXI

The emulsion of Example XIII was incorporated into a glass fiber coating material by taking 4080 g of a 32% concentrate of the emulsion and combining it with 1060 g of a polyurethane latex film former available from BASF Wyandotte Corp.. under the brand name WYANDOTTE X-1042H and with 4000 g of warm water at 43 ° C. 5000 g of water and 189 g of γ-aminopropyltriethoxy-silane were also added to this first mixture. The amount of the antioxidant emulsion in the coating material was about 9.1% by weight, based on the 32% concentration of the antioxidant emulsion. The amount of film-forming agent was 3.7 wt% based on the 50% concentrated polyurethane film former and the amount of silane in the coating material was 1.3 wt%.

The coating material had a total solids content of 32.3%.

The coating material was used to treat glass fibers formed by drawing molten streams of glass from small openings in a drawing plate obtained by a conventional method. An example of such a conventional method can be found in U.S. Pat. No. 4,027,071. The coated glass fibers were dried and chopped to lengths of 3.18 and 4.76 mm. Example XXII

The antioxidant emulsion of Example XIV was used to prepare a coating material for treating glass fibers. The coating material was composed as follows: 8006696 '4 ✓ - 33 - A)

Antioxidant emulsion 34.3% 3,794 g 25.6 wt% wet concentration

Polyurethan latex film-forming 3,059 g 7.1 wt% wet 5 mend (Wyandotte X-1042H) (50% solid)

Water, warm, approx. 43 ° C 4,800 g 32.3 wt.% Wet B)

Water 5,000 g 33.7 wt% wet 10 γ-aminopropyletriethoxy-189 g 1,3 wt% wet silane

Acetic acid adjustment of the pH to within the range of about 6.5 to about 7.0 The coating material contained 13% solids.

This coating material, hereinafter referred to as coating material No. 5, was used to treat glass fibers formed by drawing molten streams of glass from small openings in a drawing plate. An example of a conventional method for producing glass fibers is found in US Pat. No. 4,027,071. The coated glass fiber strands taken together were dried and chopped into 3.18 and 4.76 mm pieces. The chopped strands were tested for burnout weight loss and found to be 1.29%.

Example XXIII

An oil-in-water emulsion was prepared in a manner similar to that of Example V, having the following composition: g wt% 30 octadecyl-3- (3T, 51-di-tert-butyl-4'-hydroxyphenyl-) propionate antioxidant 720 25.8

Amyl acetate 720 25.8

Trimethyl-nonylpolyethylene-glycol ether (Tergitol TMNG) 45 1.6 35 Nonylphenoxy-polyethoxyethanol (Triton N-401) 65 2.3

Nonylphenoxy-poly (ethyleneoxy) ethanol (Igepal CO-630) 45 3.6

Cold water 1200 42.9 8006696 * - 34 -

This emulsion was incorporated into a coating material in a manner similar to that of Example VI.

The coating material had the following composition: g wt.% Epoxy resin (Genepoxy 370 H-55 of

General Mills Co. 55% solid 2,730 9.0

Antioxidant emulsion ie 27.6% solid 2,210 7.3

Polyurethan resin 10 (Wyandotte X-1042) 7,980 26.4

Water 6,000 18.2 γ-aminopropyltriethoxysilane

Water 10,800 35.8

Acetic acid 5 0.02 15 Epoxy silane 150 0.5

This coating material was used to treat glass fibers in a manner similar to that of Example XXI. The coated glass fibers were dried and chopped into 3.18 and 4.76 mm pieces.

Dried, coated glass fibers treated with the coating materials No. 1, 2, 3, 4 and 5 were used to reinforce polybutylene terephthalate. The reinforced polymer was obtained using 30 parts of the various coated glass fibers in the chopped form and 70 parts of polymer. This mixture was injected into a Newbury injection molding machine in an amount of 28 g at a time.

The reinforced polymeric materials were tested in an accelerated aging test known as thermal aging. This test was performed by placing tensile bars of the sample 30 in a high air velocity circulation oven at a temperature of 185 + 1 ° C for tests of Table B. Samples are removed at various intervals and tested for the mechanical property of tensile strength, measured in MPa on an Instron machine.

Polymeric material reinforced with dried coated glass fibers with coating material 1, 2, 3, 4 and 5 was thus tested. These reinforced polymeric materials were compared to reinforced materials containing commercially available glass fibers. The results are shown in Table B.

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Table B shows that the reinforced polybutylene terephthalate reinforced with glass fibers treated with a coating material containing the antioxidant emulsion of the invention fares much better than the commercial material. This better behavior can be reflected in higher initial tensile strength and higher tensile strength values in the first few weeks and comparable values after several weeks and / or comparable original values and higher values after several weeks.

Example XXIV

10 Examples focused on dry mixing.

In addition to testing the mechanical properties after accelerated aging tests for fiber glass reinforced polybutylene terephthalate in which the glass fibers are treated with a coating material containing the antioxidant emulsion, 15 accelerated aging studies with dry mixing were conducted. In the dry mix studies, the antioxidant was added to the polybutylene terephthalate and this polymer was compounded with 30 parts of chopped glass fibers commercially available from PPG Industries, Ine. The antioxidant added to the polymer 20 represents an additional amount over the amount already present in the commercial polymer.

The fiberglass, polybutylene terephthalate and antioxidant mixture was injection molded in the same Newbury apparatus as used in the previous examples.

The tensile rods obtained by injection molding were subjected to accelerated aging in a manner similar to that described in the previous examples at a temperature of usually 200 ± 3 ° C for tests 1 and 2 and 190 JH 1 ° C for tests 3 to 6 of Table C. Table C shows results of the mechanical property of tensile strength in MPa for the samples after various times under the accelerated aging conditions. Samples 4, 5 and 6 were compared with samples 2 and 3 containing glass fiber reinforced polybutylene terephthalate with the glass fibers used being commercially available from PPG Industries, Ine. Sample No. 1 was obtained in the same manner as the other samples except that no glass fibers were included in the polymer.

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Table C shows the improved tensile strength at longer durations under thermal aging conditions obtained by adding additional antioxidant with low volatility, good heat stability and good polymer compatibility.

In the above, oil-in-water anti-oxidant emulsions, aqueous fibrous reinforcement treatment materials containing the antioxidant emulsions, and a method of reducing the chemical degradation of fibrous-reinforced polymers have been described.

The aqueous emulsions include the antioxidant, organic solvents, one or more emulsifiers with an HLB in the range of about 12 to about 27. The aqueous treatment solutions for treating fibrous materials to be used as reinforcement in polymers, in particular especially glass fibers, include the antioxidant emulsion together with a film-forming agent and a coupling agent, although other coating ingredients known to those skilled in the art may also be used. The method of reducing the amount of chemical degradation of reinforced polymers, wherein the chemical degradation is due to an interaction between the chemistry and / or reaction and / or thermal decomposition products thereof of the reinforcement and the polymer means that an amount of antioxidant in excess of 3 parts per 100 parts of resin is added to the polymer or an amount of antioxidant in an oil-in-water emulsion of about 5 to about 60% by weight of the emulsion is added to the aqueous treatment solution. fibrous materials.

30 8 00 6 6 9 6

Claims (26)

1. A method of reducing chemical degradation of fiber-reinforced polymeric materials under thermal aging conditions, the chemical degradation being due to chemical interactions between the chemistry present on the fibrous reinforcement and / or reaction and / or or thermal decomposition products of said chemistry and the polymer, with the added advantage of including in the fiber-reinforced polymeric material an antioxidant of low volatility, good thermal stability and good compatibility with the polymer. 2. Process according to claim 1, characterized in that the antioxidant is incorporated into the polymer prior to the addition of the reinforcing materials and that the amount of antioxidant added is at least about 0.25 parts per 100 parts of the mixture of polymer and reinforcing material. . 3. Process according to claim 1, characterized in that the antioxidant is selected from hindered phenolic antioxidants and diarylamine antioxidants with a low volatility of less than 20% by weight loss as measured by thermogravimetric analysis. Method according to claim 1, characterized in that the antioxidant is incorporated into the aqueous treatment solution for the fibrous reinforcement material. Method according to one of the preceding claims, characterized in that the fibrous reinforcing material consists of glass fibers. 6. Oil-in-water emulsion of an antioxidant with low volatility and good thermal resistance, selected from hindered phenolic antioxidants and diarylamine antioxidants, characterized in that it comprises the following ingredients: a) about 5 to about 60 wt .% of the antioxidant which is a water-immiscible liquid or a water-insoluble solid, about 0.5 to about 50% by weight of an organic solvent or mixture of organic solvents having a kauri-butanol value of about 10 to about 50 in 8006696 4-40 - if the antioxidant is substantially aliphatic, or a kaurobutanol value of about 50 to about 100 if the antioxidant is essentially aromatic; b) about 3 to about 15% by weight of one or 5 more emulsifiers selected from the group of non-ionic and / or anionic emulsifiers, the emulsifier or emulsifier mixture having a total hydrophilic-lipophilic balance of about 12 to about 27 has. An aqueous emulsion according to claim 6, characterized in that the antioxidant is octadecyl-3- (31,5'-di-tert-butyl-4-hydroxyphenol) propionate and the organic solvent is xylene. An aqueous emulsion according to claim 6, characterized in that the antioxidant is tetrakis- (methylene-3-3 ', 5'-di-tert-butyl-4-hydroxyphenol) propionate-methane and the solvent is methyl ethyl ketone. An aqueous emulsion according to claim 6, characterized in that the antioxidant is the substituted diphenylamine 4,4 '- / 2- (2-phenyl) propyl / diphenylamine and the solvent is acetone. An aqueous emulsion according to claim 6, characterized in that the antioxidant is a 3: 1 condensate of 3-methyl-6-tertiary butyl phenol with crotonaldehyde and the solvent is cyclopentanone. An aqueous emulsion according to claim 6, characterized in that the emulsion mixture is trimethylnonylpolyethylene glycol ethers with an HLB of 11.7 and nonylphenoxy polyethyleneoxyethanol with an HLB of 13 and condensate of ethylene oxide with hydrophilic bases formed by condensing polypropylene oxide and poly-30 propylene glycol with an HLB of 16.5. An aqueous emulsion according to claim 6, characterized in that the emulsifying agent consists of polyethoxylated vegetable oil with an HLB of 13.6, condensate of ethylene oxide with hydrophilic bases formed by condensing propylene-oxide with propylene glycol with an HLB of 24 and polyoxyethylene (4) sorhitan monolaurate with an HLB of 13.3. 8006696 V 'i - 41 - wT An aqueous emulsion according to claim 6, characterized in that the emulsion mixture consists of condensate of ethylene oxide with hydrophilic bases formed by condensing propylene oxide with propylene glycol with an HLB of 24 and a condensate of ethylene oxide with hydrophilic bases formed by condensing propylene oxide with propylene glycol with an HLB of 17 and polyethoxylated vegetable oil with an HLB of 13.6. An aqueous emulsion according to claim 6, characterized in that the emulsion mixture consists of octylphenaxypolyethoxyethanol with an HLB of 13.5 and octylphenoxypolyethoxyethanol with an HLB of 12.5. An aqueous emulsion according to claim 6, characterized in that an epoxy resin is present in an amount of up to about 40% by weight of the emulsion to act as a carrier for the antioxidant. An aqueous emulsion according to claim 6, characterized in that a polyalkylene polyol is present in an amount from about 1 to about 5% by weight to help stabilize the emulsion. Aqueous coating material for treating glass fibers to provide additional protection against degradation of polymer reinforced with the treated glass fibers, characterized in that it comprises the following ingredients: a) about 0.5 to about 15% by weight of an oil-in-water emulsion of an antioxidant with low volatility and good thermal resistance, organic solvent with a boiling point above the processing temperature of glass fibers but sufficiently low to allow the solvent to evaporate at the temperature at which the glass fibers are dried and with a kuricuthanol value of about 10 to about 50 for the antioxidant which is substantially aliphatic and about 50 to about 100 for the antioxidant which is substantially aromatic, an emulsifying agent mixture of at least two emulsifying agents selected from the group of anionic, cationic and non-ionic emulsifiers with an HLB of about 12 to about 27, b) a film-forming agent in an amount of 8006696 * A. - 42 - about 0.5 to about 15 wt%, c) a coupling agent in an amount of about 0.5 to about 10 wt%. Coating material according to claim 17, 5, characterized in that it contains a lubricant in an amount from about 0.001 to about 1% by weight. Coating material according to claim 17, characterized in that the film-forming agent is an epoxy-containing resin and the coupling agent is an amino silane. Glass fibers treated with the coating material according to claim 17. Glass fibers treated with the coating material according to claim 19. Coating material according to claim 17, characterized in that the ratio of antioxidant to solvent is about 0.5 to about 1.5. 23. A process for forming glass fibers to reduce any chemical degradation of glass fiber reinforced polymers, the degradation resulting from chemical interaction of chemicals present on the glass fibers and the polymer at elevated temperatures or from chemical interaction of reaction products and / or decomposition products of said chemicals and polymers, characterized in that a) glass filaments are drawn from molten glass cones at a high speed; b) on the filaments during the formation thereof, apply an aqueous glass fiber coating material containing about 0.5 to about 15% by weight of an oil-in-water emulsion of an antioxidant with low volatility and good thermal resistance, organic solvent with a boiling point above the processing temperature of the glass fibers but sufficiently low to allow the solvent to evaporate at the temperature at which the glass fibers are dried and having a kauri-butanol value in the range of about 10 to about 50 for the antioxidant 35 is substantially aliphatic and about 50 to about 100 by the antioxidant which is essentially aromatic, and an emulsifier mixture of at least two emulsifiers selected from the group of anionic and nonionic emulsifiers, with an HLB of about 12 to about 27; c) a film-forming agent in an amount of from about 0.5 to about 15 wt. %; and d) a coupling agent in an amount from about 0.5 to about 10% by weight. 24. A process for the preparation of an oil-in-water emulsion suitable for use in a coating material for treating glass fibers, characterized in that a) an amount of from about 5 to about 60 wt. % of one or more hindered phenol or diphenylamine antioxidants having a weight loss of less than about 20 wt% 15 by thermogravimetric analysis mixes with one or more organic solvents in a ratio of about 0.19 to about 1.5 ( antioxidants to solvent), the solvent having a kauri-butanol value. about 10 to about -50 when the antioxidant is predominantly aliphatic and from about 50 to about 100 when the antioxidant is predominantly aromatic; b) the resulting mixture of (a) combines with an emulsifying agent mixture selected from one or more nonionic emulsifying agents or one or more anionic emulsifying agents or mixtures thereof wherein the emulsifying agent mixture has a hydrophilic lipophilic balance of from about 12 to about 27; and c) an amount of water from about 70 to about 99% by weight of the emulsion. 25. A method according to claim 24, characterized in that the emulsifier mixture is combined with the antioxidant and solvent mixture by adding one or more of the non-ionic emulsifying agents to the mixture and splitting another non-ionic emulsifying agent into two. portions where one portion is added to the mixture and the remaining portion is combined with water and the aqueous mixture is combined with the antioxidant-containing mixture. 26. Methods and articles essentially as / described in the description and / or the examples. i 8 00 6 6 9 6