CA1132281A - Glass size compositions - Google Patents
Glass size compositionsInfo
- Publication number
- CA1132281A CA1132281A CA287,293A CA287293A CA1132281A CA 1132281 A CA1132281 A CA 1132281A CA 287293 A CA287293 A CA 287293A CA 1132281 A CA1132281 A CA 1132281A
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- glass fiber
- polyester resin
- sizing composition
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An aqueous glass fiber sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer, substantially insoluble in styrene and having a silane level of from about 1 to about 7 weight percent is disclosed. Glass fibers coated with the sizing composition and molding compositions comprising a thermo-setting resin and the coated glass fibers are also disclosed.
The sizing composition serves to facilitate the handling of glass fibers and to form bonds between the glass fibers and molding compositions.
An aqueous glass fiber sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer, substantially insoluble in styrene and having a silane level of from about 1 to about 7 weight percent is disclosed. Glass fibers coated with the sizing composition and molding compositions comprising a thermo-setting resin and the coated glass fibers are also disclosed.
The sizing composition serves to facilitate the handling of glass fibers and to form bonds between the glass fibers and molding compositions.
Description
113Z~81 This invention relates generally to a size composition.
In one of its more specific aspects, this invention relates to a size composition suitable for use with glass fibers incorporated in molding compositions for strength improvement.
The use of molding compounds, both sheet and bulk, is well known. Generally such molding compounds comprise a thermosetting resin such as a polyester and various fillers and reinforcements in combination with a crosslinking monomer.
The molding composition is pliable and is subjected to molding pressures under elevated temperatures. Under these conditions, crosslinking of the resin occurs and a thermoset composition is produced.
It is customary to incorporate into the molding compounds various fillers and reinforcements which provide bulk and strength. Principal among such reinforcements are glass flbers which generally have diameters of about .00025 to .00075 inch and lengths of about 0.13 to about 2.00 inch.
In order to facilitate the handling of the glass fibers, it is customary that they be sized immediately upon forming. It is advantageous if the size composition serves not only to facilitate the handling of the glass fibers but also if the size acts to create a bond between the glass fibers and the resin such -that the strength properties of the molded resin are improved. The glass size composition of this invention possesses such properties.
According to a broad aspect of this invention, there is provided an aqueous glass fiber sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from :~13~
about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substan-tially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
By another aspect of the present invention there is provided a glass fiber having at least a portion of its surface in contact with a residue formed upon removal of water from an aqueous sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substantially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
According to another aspect of this invention, there is provided a molding composition containing glass fibers sized with the size of this invention.
In the size composition of this invention, any suitable unsaturated, water-emulsifiable polyester resin can be employed. On particularly suitable unsaturated, water-emulsifiable polyester resin is orthophthalic polyester resin, available commercially under the trade name designation E-400 from Owens-Corning Fiberglas. Another suitable unsatur-ated, water-emuls:ifiable polyester resin, designated E-108, is commercially available from Owens-Corning Fiberglas.
E-108 is neopentyl glycol polyester resin.
The unsaturated, water-emulsifiable polyester resin suitably is employed in the size in an amount within the range of from about 1 to about 13 weight percent of the ~3Z2~31 aqueous size.
Any suitable ethylene vinyl acetate emulsion can be used. Some suitable ethylene v:inyl acetate emulsions are commercially available. The ethylene vinyl acetate emulsion suitably is employed in the size in an amount within the range of from 1 to . - 2a -~F :
~L~3Z~281 about 10 weight percent.
Any suitable polyvinyl acetate-organo silane copolymer having a high insolubility in styrene and a silane level of from about 1 to about 7 weight percent can be used. One particularly suitable polyvinyl acetate-organo silane copolymer is available from National Starch and Chemical Corporation under the trade name National Starch 78-3724. National Starch 78-3724 is a copo-lymer of vinyl acetate and gamma-methacryloxy-propyltrimethoxy-silane (A-174 from Union Carbide) and has about a 2 percent silane level.
The polyvinyl acetate-organo silane copolymer suitably is employed in the size in an amount within the range of from about 1 to about 15 weight percent.
The glass size composition of this invention preferably includes at least one lubricant and at least one coupling agent.
Any suitable lubricant can be employed. A preferred lubricant is the cationic condensation product of dimethylamino-propylamine and pelargonic acid. This material has 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 abou-t 7. A pre-ferred lubricant of these characteristics is available from Emery Industries under the trade name Emerstat 6664. Another suitable lubricant is an amide-substituted polyethyleneamine, such as Emery 6717 available from Emery Industries. The lubri-cant is employed in the size in an amount within the range of from about 0.02 to about 1.0 weight percent.
Any suitable coupling agent comprising an organo-silane can be employed. Preferably, an organo-silane such as gamma-methacryloxypropyltrimethoxysilane will be used. A suitable coupling agent of this type is available as A-174 from Union .,-~L3~281 Carbide. Other suitable coupling agents are vinyl-tris (2 methoxyethoxy~ silane available as A-172 from Union Carbide and gamma-aminopropyltriethoxysilane available as A-1100 from Union Carbide. The coupling agent is employed in the size in an amount within the range of from about 0.1 to about 1.0 weight percent.
The glass size composition of this inven-tion can also comprise up to 0.05 weight percent of an acid suitable to adjust the pH of the size composition to enable silane hydrolysis prior to the addition of the silane coupling agent. A suitable acid is glacial acetic acid.
The size of this invention is prepared by conventional ~ethods such as that described below. It can be applied to any glass fibers conventionally employed as molding compound rein-forcement, being applied during the forming operation such that the fibers possess, upon drying, a solids content within the range of from about 1.2 to about 3.0 weight percent, based upon loss on ignition.
Examples of carrying out the present invention will now be demonstrated by means of the following specific examples:
EXAMPLE I
This example demonstrates the preparation of approxi-mately 100 gallons of a size composition of this invention.
About 39 pounds of orthophthalic polyester resin (OCP
E-400) were mixed with about 20 gallons of deminerallzed water in a first premix kettle for a period of about 4 hours. The resulting solution was introduced into a main mix tank contain-ing about 20 gallons of demineralized water.
~ :
. . .
.. ~ . ~ . .. ,; .. . .. ..
L3228i About 75 pounds of polyvinyl acetate-organo silane copolymer (N~tional Starch 78-3724) were introduced into a second premix kettle and about 10 gallons of demineralized water were added thereto. The composite was mixed for about 5 minutes and the resulting mixture was introducecl into the contents of the main mix tank.
About 25 pounds of ethylene vinyl acetate (Airflex 400) and about 5 gallons of demineralized water were added to a third premix tank. The composite was mixed for about 5 minutes and the resulting mixture was introduced into the contents of the main mix tank.
About 10 gallons of demineralized water were added to a fourth premix tank and about 0.25 pound of glacial acetic acid added thereto. Mixing was started and about 3.5 pounds of gamma-methacryloxypropyltrimethoxysilane (A-174) were added at the rate of about one pound per every 30 seconds. Mixing was continued for about 25 minutes and the resulting mixture was introduced into the contents of the main mix tankn About 2 gallons of demineralized water were added to a fifth 20 premix tank and heated to about 155F. About 36 millileters of glacial acetic acid were added to the water and then about 0.8 pound of lubricant (Emery 6717). The composite was mixed 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 and the addition of sufficient water to bring the volume of the size to about 100 gallons, will have a solids content within the range of from about 8 to about 12 weight percent and a pH within the range of from about 4 to 6.
The size prepared in the above manner was applied to 1~32281 individual glass fibers by conventional application methods and at rates such that the strand solids, on drying, amounted to about 2 weight percent. Preferably, the size is supplied to the applicator at a temperature of about 60F.
EXAMPLE II
Glass fibers having a diameter within the range of from about .00025 to about .00075 inch, sized on forming with the size of this invention, were incorporated in a sheet molding compound of the following approximate composition.
Composition Weight Percent _ Polyester Resin Syrup 34 Glass fibers tl inch length) 30 Calcium Carbonate 34 Zinc Stearate 0.9 Magnesium Hydroxide Catalyst 0.1 A series of such blends was prepared, each blend containing glass fibers sized with a size composition of this invention and compared with a similar series of blends containing glass sized with a prior art size. Average strength test results on each series of blends, molded at about 1000 psi at a platen temperature within the range of from about 270F to about 300F with a cure cycle of up to about 1.5 to about 4 minutes, were as follows:
Glass Size Formulations _ Invention Prior Art Tensile Strength, M psi 12.78-14.03 12.32-12.52 Impact Strength, ft. pounds 16.66-18.03 13.90-17.69 Flexural Strength, M psi 28.61-31.38 28.06-30.43 .~ , 1 lL3ZZ~
It will be seen from the above data that glass sized with the size of the present invention acts to increase the mechanical strength of the sheet molding compounds into which the glass is incorporated to a greater extent than does glass sized with the prior art sizing.
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.
r` ~
.: `
In one of its more specific aspects, this invention relates to a size composition suitable for use with glass fibers incorporated in molding compositions for strength improvement.
The use of molding compounds, both sheet and bulk, is well known. Generally such molding compounds comprise a thermosetting resin such as a polyester and various fillers and reinforcements in combination with a crosslinking monomer.
The molding composition is pliable and is subjected to molding pressures under elevated temperatures. Under these conditions, crosslinking of the resin occurs and a thermoset composition is produced.
It is customary to incorporate into the molding compounds various fillers and reinforcements which provide bulk and strength. Principal among such reinforcements are glass flbers which generally have diameters of about .00025 to .00075 inch and lengths of about 0.13 to about 2.00 inch.
In order to facilitate the handling of the glass fibers, it is customary that they be sized immediately upon forming. It is advantageous if the size composition serves not only to facilitate the handling of the glass fibers but also if the size acts to create a bond between the glass fibers and the resin such -that the strength properties of the molded resin are improved. The glass size composition of this invention possesses such properties.
According to a broad aspect of this invention, there is provided an aqueous glass fiber sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from :~13~
about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substan-tially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
By another aspect of the present invention there is provided a glass fiber having at least a portion of its surface in contact with a residue formed upon removal of water from an aqueous sizing composition comprising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substantially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
According to another aspect of this invention, there is provided a molding composition containing glass fibers sized with the size of this invention.
In the size composition of this invention, any suitable unsaturated, water-emulsifiable polyester resin can be employed. On particularly suitable unsaturated, water-emulsifiable polyester resin is orthophthalic polyester resin, available commercially under the trade name designation E-400 from Owens-Corning Fiberglas. Another suitable unsatur-ated, water-emuls:ifiable polyester resin, designated E-108, is commercially available from Owens-Corning Fiberglas.
E-108 is neopentyl glycol polyester resin.
The unsaturated, water-emulsifiable polyester resin suitably is employed in the size in an amount within the range of from about 1 to about 13 weight percent of the ~3Z2~31 aqueous size.
Any suitable ethylene vinyl acetate emulsion can be used. Some suitable ethylene v:inyl acetate emulsions are commercially available. The ethylene vinyl acetate emulsion suitably is employed in the size in an amount within the range of from 1 to . - 2a -~F :
~L~3Z~281 about 10 weight percent.
Any suitable polyvinyl acetate-organo silane copolymer having a high insolubility in styrene and a silane level of from about 1 to about 7 weight percent can be used. One particularly suitable polyvinyl acetate-organo silane copolymer is available from National Starch and Chemical Corporation under the trade name National Starch 78-3724. National Starch 78-3724 is a copo-lymer of vinyl acetate and gamma-methacryloxy-propyltrimethoxy-silane (A-174 from Union Carbide) and has about a 2 percent silane level.
The polyvinyl acetate-organo silane copolymer suitably is employed in the size in an amount within the range of from about 1 to about 15 weight percent.
The glass size composition of this invention preferably includes at least one lubricant and at least one coupling agent.
Any suitable lubricant can be employed. A preferred lubricant is the cationic condensation product of dimethylamino-propylamine and pelargonic acid. This material has 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 abou-t 7. A pre-ferred lubricant of these characteristics is available from Emery Industries under the trade name Emerstat 6664. Another suitable lubricant is an amide-substituted polyethyleneamine, such as Emery 6717 available from Emery Industries. The lubri-cant is employed in the size in an amount within the range of from about 0.02 to about 1.0 weight percent.
Any suitable coupling agent comprising an organo-silane can be employed. Preferably, an organo-silane such as gamma-methacryloxypropyltrimethoxysilane will be used. A suitable coupling agent of this type is available as A-174 from Union .,-~L3~281 Carbide. Other suitable coupling agents are vinyl-tris (2 methoxyethoxy~ silane available as A-172 from Union Carbide and gamma-aminopropyltriethoxysilane available as A-1100 from Union Carbide. The coupling agent is employed in the size in an amount within the range of from about 0.1 to about 1.0 weight percent.
The glass size composition of this inven-tion can also comprise up to 0.05 weight percent of an acid suitable to adjust the pH of the size composition to enable silane hydrolysis prior to the addition of the silane coupling agent. A suitable acid is glacial acetic acid.
The size of this invention is prepared by conventional ~ethods such as that described below. It can be applied to any glass fibers conventionally employed as molding compound rein-forcement, being applied during the forming operation such that the fibers possess, upon drying, a solids content within the range of from about 1.2 to about 3.0 weight percent, based upon loss on ignition.
Examples of carrying out the present invention will now be demonstrated by means of the following specific examples:
EXAMPLE I
This example demonstrates the preparation of approxi-mately 100 gallons of a size composition of this invention.
About 39 pounds of orthophthalic polyester resin (OCP
E-400) were mixed with about 20 gallons of deminerallzed water in a first premix kettle for a period of about 4 hours. The resulting solution was introduced into a main mix tank contain-ing about 20 gallons of demineralized water.
~ :
. . .
.. ~ . ~ . .. ,; .. . .. ..
L3228i About 75 pounds of polyvinyl acetate-organo silane copolymer (N~tional Starch 78-3724) were introduced into a second premix kettle and about 10 gallons of demineralized water were added thereto. The composite was mixed for about 5 minutes and the resulting mixture was introducecl into the contents of the main mix tank.
About 25 pounds of ethylene vinyl acetate (Airflex 400) and about 5 gallons of demineralized water were added to a third premix tank. The composite was mixed for about 5 minutes and the resulting mixture was introduced into the contents of the main mix tank.
About 10 gallons of demineralized water were added to a fourth premix tank and about 0.25 pound of glacial acetic acid added thereto. Mixing was started and about 3.5 pounds of gamma-methacryloxypropyltrimethoxysilane (A-174) were added at the rate of about one pound per every 30 seconds. Mixing was continued for about 25 minutes and the resulting mixture was introduced into the contents of the main mix tankn About 2 gallons of demineralized water were added to a fifth 20 premix tank and heated to about 155F. About 36 millileters of glacial acetic acid were added to the water and then about 0.8 pound of lubricant (Emery 6717). The composite was mixed 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 and the addition of sufficient water to bring the volume of the size to about 100 gallons, will have a solids content within the range of from about 8 to about 12 weight percent and a pH within the range of from about 4 to 6.
The size prepared in the above manner was applied to 1~32281 individual glass fibers by conventional application methods and at rates such that the strand solids, on drying, amounted to about 2 weight percent. Preferably, the size is supplied to the applicator at a temperature of about 60F.
EXAMPLE II
Glass fibers having a diameter within the range of from about .00025 to about .00075 inch, sized on forming with the size of this invention, were incorporated in a sheet molding compound of the following approximate composition.
Composition Weight Percent _ Polyester Resin Syrup 34 Glass fibers tl inch length) 30 Calcium Carbonate 34 Zinc Stearate 0.9 Magnesium Hydroxide Catalyst 0.1 A series of such blends was prepared, each blend containing glass fibers sized with a size composition of this invention and compared with a similar series of blends containing glass sized with a prior art size. Average strength test results on each series of blends, molded at about 1000 psi at a platen temperature within the range of from about 270F to about 300F with a cure cycle of up to about 1.5 to about 4 minutes, were as follows:
Glass Size Formulations _ Invention Prior Art Tensile Strength, M psi 12.78-14.03 12.32-12.52 Impact Strength, ft. pounds 16.66-18.03 13.90-17.69 Flexural Strength, M psi 28.61-31.38 28.06-30.43 .~ , 1 lL3ZZ~
It will be seen from the above data that glass sized with the size of the present invention acts to increase the mechanical strength of the sheet molding compounds into which the glass is incorporated to a greater extent than does glass sized with the prior art sizing.
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.
r` ~
.: `
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous glass fiber sizing composition com-prising from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of any ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substan-tially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
2. An aqueous glass fiber sizing composition as defined in claim 1, wherein said unsaturated, water-emulsifiable polyester resin is an orthophthalic polyester resin.
3. An aqueous glass fiber sizing composition as defined in claim 1, wherein said unsaturated, water-emulsifiable polyester resin is a neopentyl glycol polyester resin.
4. An aqueous glass fiber sizing composition as defined in claim 1, 2 or 3, wherein said polyvinyl acetate-organo silane copolymer is a copolymer of vinyl acetate and gamma-methacryloxpropyltrimethoxysilane.
5. An aqueous glass fiber sizing composition as defined in claim 1, including from about 0.02 to about 1.0 weight percent of a lubricant and from about 0.1 to about 1.0 weight percent of a coupling agent.
6. An aqueous glass fiber sizing composition as defined in claim 5, wherein said lubricant is selected from the group consisting of: a cationic condensation product of dimethylaminopropylamine and pelargonic acid and an amide-substituted polyethyleneamine.
7. An aqueous glass fiber sizing composition as defined in claim 5 or 6, wherein said coupling agent is selected from the group consisting of: gamma-methacryloxy-propyltrimethoxysilane, vinyl-tris (2 methoxyethoxy) silane and gamma-aminopropyltriethoxysilane.
8. An aqueous glass fiber sizing composition as defined in claim 1 or 5, including glacial acetic acid, the amount of which does not exceed 0.05 weight percent.
9. A glass fiber having at least a portion of its surface in contact with a residue formed upon removal of water from an aqueous sizing composition comprising: from about 1 to about 13 weight percent of an unsaturated, water-emulsifiable polyester resin, from about 1 to about 10 weight percent of an ethylene vinyl acetate emulsion, and from about 1 to about 15 weight percent of a polyvinyl acetate-organo silane copolymer which is substantially insoluble in styrene and has a silane level of from about 1 to about 7 weight percent.
10. A glass fiber as defined in claim 9, wherein said residue is from about 1.2 to about 3.0 weight percent.
11. A glass fiber as defined in claim 9, wherein said unsaturated, water-emulsifiable polyester resin is an orthophthalic polyester resin.
12. A glass fiber as defined in claim 9, wherein said unsaturated, water-emulsifiable polyester resin is a neopen-tyl glycol polyester resin.
13. A glass fiber as defined in claim 9, 11 or 12, wherein said polyvinyl acetate-organo silane copolymer is a copolymer of vinyl acetate and gamma-methacryloxypropyl-trimethoxysilane.
14. A glass fiber as defined in claim 9, wherein said aqueous sizing composition includes from about 0.02 to about 1.0 weight percent of a lubricant and from about 0.1 to about 1.0 weight percent of a coupling agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75222276A | 1976-12-20 | 1976-12-20 | |
| US752,222 | 1985-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132281A true CA1132281A (en) | 1982-09-21 |
Family
ID=25025409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA287,293A Expired CA1132281A (en) | 1976-12-20 | 1977-09-22 | Glass size compositions |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5378396A (en) |
| AU (1) | AU513440B2 (en) |
| BE (1) | BE860259A (en) |
| BR (1) | BR7706977A (en) |
| CA (1) | CA1132281A (en) |
| DE (1) | DE2752810A1 (en) |
| DK (1) | DK568777A (en) |
| FI (1) | FI61180C (en) |
| FR (1) | FR2374269A1 (en) |
| GB (1) | GB1590409A (en) |
| IT (1) | IT1088964B (en) |
| MX (1) | MX148499A (en) |
| NL (1) | NL7710951A (en) |
| NO (1) | NO148343C (en) |
| SE (1) | SE422249B (en) |
| ZA (1) | ZA776033B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4338234A (en) | 1980-06-04 | 1982-07-06 | Ppg Industries, Inc. | Sizing composition and sized glass fibers and strands produced therewith |
| US4477496A (en) * | 1981-06-15 | 1984-10-16 | Ppg Industries, Inc. | Process for preparing sized glass fiber roving |
| US4410645A (en) | 1981-06-15 | 1983-10-18 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
| US4435474A (en) | 1981-06-15 | 1984-03-06 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
| US4338233A (en) | 1981-06-15 | 1982-07-06 | Ppg Industries, Inc. | Aqueous sizing composition and sized glass fibers and method |
| US4394418A (en) | 1981-12-24 | 1983-07-19 | Ppg Industries, Inc. | Aqueous sizing composition and glass fibers made therewith for reinforcing thermosetting polymers |
| US4457970A (en) * | 1982-06-21 | 1984-07-03 | Ppg Industries, Inc. | Glass fiber reinforced thermoplastics |
| JPS62501852A (en) * | 1985-02-13 | 1987-07-23 | ブリツジズ コ−ポレ−シヨン ピ−テイ−ワイ エルテイ−デイ− | Modified polyester thermosetting resin composition |
| US4808478A (en) * | 1986-09-05 | 1989-02-28 | Ppg Industries, Inc. | Chemically treated glass fibers for reinforcing thermosetting polymers |
| CA1340052C (en) * | 1988-03-31 | 1998-09-22 | Narasimhan Raghupathi | Chemically treated glass fibers for reinforcing thermosetting polymer matrices |
| US4927869A (en) * | 1988-09-15 | 1990-05-22 | Ppg Industries, Inc. | Chemically treated glass fibers for reinforcing polymers |
| US7169463B2 (en) * | 2004-06-21 | 2007-01-30 | Owens Corning Fiberglas Technology, Inc. | Sizing composition for sheet molding compound roving |
-
1977
- 1977-09-22 CA CA287,293A patent/CA1132281A/en not_active Expired
- 1977-09-29 AU AU29244/77A patent/AU513440B2/en not_active Expired
- 1977-09-29 MX MX170744A patent/MX148499A/en unknown
- 1977-10-06 NL NL7710951A patent/NL7710951A/en unknown
- 1977-10-07 GB GB41850/77A patent/GB1590409A/en not_active Expired
- 1977-10-07 ZA ZA00776033A patent/ZA776033B/en unknown
- 1977-10-19 BR BR7706977A patent/BR7706977A/en unknown
- 1977-10-26 FR FR7732316A patent/FR2374269A1/en active Granted
- 1977-10-28 BE BE182170A patent/BE860259A/en not_active IP Right Cessation
- 1977-10-31 IT IT29219/77A patent/IT1088964B/en active
- 1977-11-22 JP JP14058077A patent/JPS5378396A/en active Granted
- 1977-11-26 DE DE19772752810 patent/DE2752810A1/en not_active Withdrawn
- 1977-12-15 SE SE7714252A patent/SE422249B/en not_active IP Right Cessation
- 1977-12-19 NO NO774356A patent/NO148343C/en unknown
- 1977-12-20 DK DK568777A patent/DK568777A/en not_active Application Discontinuation
- 1977-12-20 FI FI773874A patent/FI61180C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| MX148499A (en) | 1983-04-27 |
| SE422249B (en) | 1982-02-22 |
| NO148343B (en) | 1983-06-13 |
| DE2752810A1 (en) | 1978-06-29 |
| FR2374269A1 (en) | 1978-07-13 |
| NO774356L (en) | 1978-06-21 |
| AU2924477A (en) | 1979-04-05 |
| BR7706977A (en) | 1978-08-08 |
| FI61180C (en) | 1982-06-10 |
| IT1088964B (en) | 1985-06-10 |
| DK568777A (en) | 1978-06-21 |
| GB1590409A (en) | 1981-06-03 |
| SE7714252L (en) | 1978-06-21 |
| FI61180B (en) | 1982-02-26 |
| NL7710951A (en) | 1978-06-22 |
| BE860259A (en) | 1978-02-15 |
| NO148343C (en) | 1983-09-21 |
| FI773874A (en) | 1978-06-21 |
| JPS6140694B2 (en) | 1986-09-10 |
| FR2374269B3 (en) | 1980-07-11 |
| JPS5378396A (en) | 1978-07-11 |
| ZA776033B (en) | 1978-05-30 |
| AU513440B2 (en) | 1980-12-04 |
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