CA1049678A - Forming size - Google Patents
Forming sizeInfo
- Publication number
- CA1049678A CA1049678A CA228,513A CA228513A CA1049678A CA 1049678 A CA1049678 A CA 1049678A CA 228513 A CA228513 A CA 228513A CA 1049678 A CA1049678 A CA 1049678A
- Authority
- CA
- Canada
- Prior art keywords
- percent
- weight
- size
- gamma
- solids
- 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
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- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
Abstract of the Disclosure A glass fiber forming size utilized to produce glass fiber strands is described in which the forming size is an aqueous mixture of polyvinyl acetate, fatty acid lubricant, methacrylate chronic chloride and gamma (ethylene diamine) propyl trimethoxy silane, the mixture being adjusted to pH between 6.1 and 6.5. The size composition is applied to glass fibers during forming. The strands produced utilizing this forming size find particular utility when formed into roving and produce a particularly effective gun roving product.
Description
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; ~ I Background of the Invention ~ ~ :~
. Fiber glass has been utilized for many years in the prepara- ' :~
tion of palyester resin fiber glass reinforced articles. One of the :
more important systems utilized in preparing fiber glass reinforced ~articles is the spray-up process. In.this process a spray gan and a flber glass roving chopper are combined so that the palyester re~in : to be utilized and roving are sprayed simultaneously onto a mold from ~, :
',' ~ ~
.
.
., .
, ~9L967~
a spray gun which i~as built into it a chopper. Fiber glass utilized ~or tllese purposes is provided in the form of roving and should possess goo-l wet-out characteristics. Thus, the application of a satisfactory Eorming size on the surEace of the glass flber utilized to prepare the flber glass roving for this use is important in providing a fiber glass product whicll is compatible wlth the polyester resins utilized in the spray-up process inclustry. Thus the sized roving must be capable of readily mixing with the resins used in the spray gun type applicator and should possess good laydown characteristics when sprayed on a mold in the manner conventionally employed in the spray-up industry.
The Invention In accordance with the present invention a novel forming size is providéd for glass fibers which is readily compatible with polyester resins which finds particular utility when formed into fiber glass roving for utilization in the spray-up process fiber glass reinforce-ment field. Thus, in accordance with the instant invention a fiber glass sizing composition is provlded which comprises an aqueous mixture of a polyvinyl acetate film former, a fatty acid lubricant, methacrylato chromic chloride, and gamma (ethylene diamine) propyl trimethoxy silane. The sizing mixture described above is provided with sufficient quantities of ingredients to provide a formuIation which results in an aqueous mixture containing between 7 aad 7.5 percent by weight solids. It is an important consideration in preparing the forming size of the instant invention that the pH of the aqueous mixture be adjusted to between 6.1 and 6.5, preferably that it be controlled between 6.2 and 6.~
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~a94967~3 In formlllating the novel sizing composition of the instant invention various textile lubricants are employed and are preferably cationic or non-ionic in character. Thus, commercially available solubilized Eatty acid amldes including both saturated and unsaturated Eatty acid amides wllere the acid group contains from 4 to 24 carbon atoms are typically employed. Also utilized are anhydrous acid solu-bilized polymers of lower molecular weight unsaturated Eatty acid amides.
A particularly effective material for utilization as a textile lubricant in the applicant's novel system is the pelargonic acid amide of tetra-ethylene pentamine. On a weight solids basis the sizing composition, this lubricant is used in amounts between 4 and 7 percent.
A maJOr ingredient of the size Eormulation of the instant invention is polyvinyl acetate film former (40 to 60 percent weight solids) and in the typical size formulations employed in the instant invention the polyvinyl acetate content of the aqueous size solution ranges between 70 to 90 percent by weight basis the total weight of the size solution solids.
A coupling-agent is employed in the preparation of the instant size and typical of the coupling agents employed are complex compounds of the Werner type in which a trivalent nuclear atom such as chromium is coordinated with organic acid such as methacrylic acid, i.e., a ~ -methacrylic acid complex of chromic chloride. Such agents are described in U. S. Patent 2,611,718. Other Werner type couplin~ agents having - vinyl allcyl, amino, epoxy, mercaptyl, thioalkyl, thioaryl and phenyl groups are also suitable for incorporation of the size of the instant invention. On the basis of the size ingredients other than water, this material is used in amounts of 2 to 6 percent by weight solids.
. .
. .. ~
9~7~3 The slze composition oE the instant inventi~n also contains gan~ma (ethylene diamine) propyl trialkoxy silanes. While it i9 contem-plated that various alkoxy groups may be linked to the sllica atom, the preferre(l materlal o~ thls character utilized ln the practice of the inventlon is gamma (ethylene diamine) propyl trimethoxy silane.
Silanes of thls partlcular type have been found to be particularly effective in producing the size composition of the instant invention and in particular in producing fiber glass strands which when made into roving provide a superior gun roving product for spray-up applications in the fiber glass resin reinforcement area. On the basis of the size ingredients other than water this material is used itl amounts of 3 to 6 percent by weight, preferably 4 to 5 percent by weight.
- In applying the formulations of the instant invention to glass fibers the g]ass fiber strand is formed by a multitude of fine fiber glass filaments which are drawn at a high rate of speed through molten cones of glass located at the tips of small orifices in a bushing such as is shown in ~. S. Patent ~o. 2,133,238. During formation the filaments are coated while they are moving at speeds on the order of 5,000 to 20,00~ feet per minute with the forming size of the instant invention. The size may be sprayed on the fibers as they are being -drawn or in the preferred embodiment the fibers may be drawn across the surface of a roller applicator on which the size is placed. The fibers after sizing are grouped into strands which are then wound typically onto forming packages utilizing a winder and an associated paper or plastic or other type forming tube located on the surface of the winder in the -conventional manner. The forming packages containing the fibe~ glass ' ~ ' .
~ _ 1814~7~
s~rand sized with the slzing composition of the instant invention may then be formed into roving by unwindlng a plurality o~ strands from several Forming packages positioned on a creel and combining the strands Ln paral:lel ~orm and winding the strands on tubular support in the con-ventional n~anner.
The size oE the instant invention is prepared by mixing the polyvinyl acetate latex with water in a mixing tank with stirring. To -the polyvinyl acetate - water mixture is added the gamma (ethylene diamine) propyl trialkoxy silane wilich has preferably been premixed with cold water. After mixing these ingredients the coupling agent is added slowly to the mix tank. After mixing the coupling agent into the mixing tank the Eiber glass lubricants are then added. The mixture is then diluted to final volume with water. The mixture is checked for its pH characteristics and sufficient acetic acid is added to control the p~ between 6.1 and 6.5.
The size of the instant invention is applied to the individual glass fibers as llas been stated during their formation. Thus, the size is applied to the individual fibers just after they emerge from the orifices in an electrically heated platinum alloy bushing containing the . .~
: molten glass. Further, the size is applied to the filaments prior to the time they are grouped together to form a strand and application of size ! ~ iS preferably by means of a roller applicator which is partially submerged in the size solution which is contained in the reservoir. Such an applicator i5 shown in more detail in U. S. Patent 2,728,972. The fibers after size is applied are then grouped into strands by using a ' graphite guide and wound around a rotating Eorming tube WtliCh produces s strand travel of approximately 5,000 to 20,000 feet per minute. Other g ~ ' ' ' ~` . , : ,, .
, ` '` ' .
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methods of applying the siæe to tlle strand of glass Eibers such as pad applicators may he ernployed and the strand may be ~ormed by means other tl~an winding on tlle rorming tube such as by means of a pair of rotating wheel pullers wl~icl~ direct strand into a suitable collecting device. ~ u AEter the fiber g:Lass strands have been wound on-the forming tube, they are then dried at approximately 240~. Eor a period of about 11 hours.
After drying, the ~strands are then processed in a conventional manner by placing the forming tubes on a balloon creel and combining the strands in parallel form and winding them on a tubular support to provide roving packages.
Upon drying subsequent to the application of the aqueous sizing mixture, glass ~ibers are provided which contain on the surface thereof a coating residue obtained by evaporation of the moisture on the surface of the glass fibers of the aqueous mixture of polyvinyl acetate, fatty acid lubricant, methacrylato chromic chloride and the gamma (ethylene -diamine) propyl trialkoxy silane.
The following example illustrates a typical preparation of the forming size of the instant invention.
- ~xample Parts by Weight (grams) Polyvinyl acetate (film former 56 percent solids 4500 in water) 1. Volan (Werner complex of methacrylic acid- 334 chromic chloride l9 percent solids in isopropanol) :. .
: :
:
: `
:
L04~67~
~ ~ ~`
~ :
: ` - . , .
; ~ I Background of the Invention ~ ~ :~
. Fiber glass has been utilized for many years in the prepara- ' :~
tion of palyester resin fiber glass reinforced articles. One of the :
more important systems utilized in preparing fiber glass reinforced ~articles is the spray-up process. In.this process a spray gan and a flber glass roving chopper are combined so that the palyester re~in : to be utilized and roving are sprayed simultaneously onto a mold from ~, :
',' ~ ~
.
.
., .
, ~9L967~
a spray gun which i~as built into it a chopper. Fiber glass utilized ~or tllese purposes is provided in the form of roving and should possess goo-l wet-out characteristics. Thus, the application of a satisfactory Eorming size on the surEace of the glass flber utilized to prepare the flber glass roving for this use is important in providing a fiber glass product whicll is compatible wlth the polyester resins utilized in the spray-up process inclustry. Thus the sized roving must be capable of readily mixing with the resins used in the spray gun type applicator and should possess good laydown characteristics when sprayed on a mold in the manner conventionally employed in the spray-up industry.
The Invention In accordance with the present invention a novel forming size is providéd for glass fibers which is readily compatible with polyester resins which finds particular utility when formed into fiber glass roving for utilization in the spray-up process fiber glass reinforce-ment field. Thus, in accordance with the instant invention a fiber glass sizing composition is provlded which comprises an aqueous mixture of a polyvinyl acetate film former, a fatty acid lubricant, methacrylato chromic chloride, and gamma (ethylene diamine) propyl trimethoxy silane. The sizing mixture described above is provided with sufficient quantities of ingredients to provide a formuIation which results in an aqueous mixture containing between 7 aad 7.5 percent by weight solids. It is an important consideration in preparing the forming size of the instant invention that the pH of the aqueous mixture be adjusted to between 6.1 and 6.5, preferably that it be controlled between 6.2 and 6.~
:. :
',: :
~., , ... .
'' ' ::-:. , : : , : . -,::
.: . .
., .: . ., , : . . . .
: : , . ,, .. : . ,.: .
. .
~a94967~3 In formlllating the novel sizing composition of the instant invention various textile lubricants are employed and are preferably cationic or non-ionic in character. Thus, commercially available solubilized Eatty acid amldes including both saturated and unsaturated Eatty acid amides wllere the acid group contains from 4 to 24 carbon atoms are typically employed. Also utilized are anhydrous acid solu-bilized polymers of lower molecular weight unsaturated Eatty acid amides.
A particularly effective material for utilization as a textile lubricant in the applicant's novel system is the pelargonic acid amide of tetra-ethylene pentamine. On a weight solids basis the sizing composition, this lubricant is used in amounts between 4 and 7 percent.
A maJOr ingredient of the size Eormulation of the instant invention is polyvinyl acetate film former (40 to 60 percent weight solids) and in the typical size formulations employed in the instant invention the polyvinyl acetate content of the aqueous size solution ranges between 70 to 90 percent by weight basis the total weight of the size solution solids.
A coupling-agent is employed in the preparation of the instant size and typical of the coupling agents employed are complex compounds of the Werner type in which a trivalent nuclear atom such as chromium is coordinated with organic acid such as methacrylic acid, i.e., a ~ -methacrylic acid complex of chromic chloride. Such agents are described in U. S. Patent 2,611,718. Other Werner type couplin~ agents having - vinyl allcyl, amino, epoxy, mercaptyl, thioalkyl, thioaryl and phenyl groups are also suitable for incorporation of the size of the instant invention. On the basis of the size ingredients other than water, this material is used in amounts of 2 to 6 percent by weight solids.
. .
. .. ~
9~7~3 The slze composition oE the instant inventi~n also contains gan~ma (ethylene diamine) propyl trialkoxy silanes. While it i9 contem-plated that various alkoxy groups may be linked to the sllica atom, the preferre(l materlal o~ thls character utilized ln the practice of the inventlon is gamma (ethylene diamine) propyl trimethoxy silane.
Silanes of thls partlcular type have been found to be particularly effective in producing the size composition of the instant invention and in particular in producing fiber glass strands which when made into roving provide a superior gun roving product for spray-up applications in the fiber glass resin reinforcement area. On the basis of the size ingredients other than water this material is used itl amounts of 3 to 6 percent by weight, preferably 4 to 5 percent by weight.
- In applying the formulations of the instant invention to glass fibers the g]ass fiber strand is formed by a multitude of fine fiber glass filaments which are drawn at a high rate of speed through molten cones of glass located at the tips of small orifices in a bushing such as is shown in ~. S. Patent ~o. 2,133,238. During formation the filaments are coated while they are moving at speeds on the order of 5,000 to 20,00~ feet per minute with the forming size of the instant invention. The size may be sprayed on the fibers as they are being -drawn or in the preferred embodiment the fibers may be drawn across the surface of a roller applicator on which the size is placed. The fibers after sizing are grouped into strands which are then wound typically onto forming packages utilizing a winder and an associated paper or plastic or other type forming tube located on the surface of the winder in the -conventional manner. The forming packages containing the fibe~ glass ' ~ ' .
~ _ 1814~7~
s~rand sized with the slzing composition of the instant invention may then be formed into roving by unwindlng a plurality o~ strands from several Forming packages positioned on a creel and combining the strands Ln paral:lel ~orm and winding the strands on tubular support in the con-ventional n~anner.
The size oE the instant invention is prepared by mixing the polyvinyl acetate latex with water in a mixing tank with stirring. To -the polyvinyl acetate - water mixture is added the gamma (ethylene diamine) propyl trialkoxy silane wilich has preferably been premixed with cold water. After mixing these ingredients the coupling agent is added slowly to the mix tank. After mixing the coupling agent into the mixing tank the Eiber glass lubricants are then added. The mixture is then diluted to final volume with water. The mixture is checked for its pH characteristics and sufficient acetic acid is added to control the p~ between 6.1 and 6.5.
The size of the instant invention is applied to the individual glass fibers as llas been stated during their formation. Thus, the size is applied to the individual fibers just after they emerge from the orifices in an electrically heated platinum alloy bushing containing the . .~
: molten glass. Further, the size is applied to the filaments prior to the time they are grouped together to form a strand and application of size ! ~ iS preferably by means of a roller applicator which is partially submerged in the size solution which is contained in the reservoir. Such an applicator i5 shown in more detail in U. S. Patent 2,728,972. The fibers after size is applied are then grouped into strands by using a ' graphite guide and wound around a rotating Eorming tube WtliCh produces s strand travel of approximately 5,000 to 20,000 feet per minute. Other g ~ ' ' ' ~` . , : ,, .
, ` '` ' .
:~4~;7~
methods of applying the siæe to tlle strand of glass Eibers such as pad applicators may he ernployed and the strand may be ~ormed by means other tl~an winding on tlle rorming tube such as by means of a pair of rotating wheel pullers wl~icl~ direct strand into a suitable collecting device. ~ u AEter the fiber g:Lass strands have been wound on-the forming tube, they are then dried at approximately 240~. Eor a period of about 11 hours.
After drying, the ~strands are then processed in a conventional manner by placing the forming tubes on a balloon creel and combining the strands in parallel form and winding them on a tubular support to provide roving packages.
Upon drying subsequent to the application of the aqueous sizing mixture, glass ~ibers are provided which contain on the surface thereof a coating residue obtained by evaporation of the moisture on the surface of the glass fibers of the aqueous mixture of polyvinyl acetate, fatty acid lubricant, methacrylato chromic chloride and the gamma (ethylene -diamine) propyl trialkoxy silane.
The following example illustrates a typical preparation of the forming size of the instant invention.
- ~xample Parts by Weight (grams) Polyvinyl acetate (film former 56 percent solids 4500 in water) 1. Volan (Werner complex of methacrylic acid- 334 chromic chloride l9 percent solids in isopropanol) :. .
- 2. Gamma (ethy:Lene diamine) propyl trimethoxy 226 silane in rnethanol (40 percent volume by wt.) Z-6026
3. Cationic fatty acid amide (~mery 4046D) 24
4. Pelargonic acid amide of tetraethylene112 ` pentamine (C-]85~) Water (sufficient to provide 10 gallons of size mix) ~cetic acid - amolmt necessary to control pH at 6.3 ~ 0.2 ' . . . :
:~9L967~3 1. "Volan" methacrylic acid complex of chromic cllloride sold by E. I. Du Pont.
2. ~-602fi - methanolic solution of gamma (ethylelle diamine) trimethoxy silane sold by Dow Corning.
3. I~`mery ~l046D - cntionic fatty acld amide sold by Fmery Industries.
4. C-:l85A - pelargonic acld amide of tetraethylene pentaDline sold by Imperial Chemlcal Industries.
The siæe preparation liste~ above is prepared by mixing the polyvinyl acetate with about 35 percent of the total water to be used in preparing the final size solution volume. The gamma (ethylene diamine) propyl trimethoxy silane is then mixed with a small quantity of cold water and added to the mixing tcmk Çollowed by tlle addition of the anti-static agent. The cationic fatty acid am:ide and the pelargonic acid amide of tetraethylene pentamine are mixed in hot water and added to the size ingredients wlth continuous mixing. The mixing tank is then diluted to the final volume of lO gallons. The pll is then measured and acetic acid is added in sufficient quantity to control the pH at 6.3 + 0.2.
It is preferred that the p~l of the final size be maintained at 6.3.
After mixing the forming size of Rxample I it is applied to the individual glass fibers during their formation. The size is applied to the individual fibers after they emerge from the orifices in the electrically heated platinum alloy bushing containing the molten glass and the size is applied to the filaments prior to the timc they are grouped together to form a strand by means of a roller applicator such as the type shown in U. S. Patent No. 2,728,972. The fibers are collected on a collet operating at speeds of about 6,000 revolutions. per minute and the roller ~:, ' ' .
, ~_ , . ....... . _ -.: . :
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~)4~
applicator speed is maintained at approximately 145 revolutions per minute. The Eorming packages are baked for a period of 11 hours at 240F. and are then placed on an appropriate balloon creel and wound on a roving winder to provide a fiber glass roving product containing the dried residlle oE the aqueous si~e composition placed on the fibers during formation. The dried residue on the glass Eibers represents a coating of between 1.25 and 1.55 percent by weight basis the bare glass.
Roving produced by fibers si~ed with this quantity of the si~ing of the instant invention has been found particularly effective in producing sp~ray-up fiber glass reinforced resin products. ~ -While the invention has been described with reference to certain specific examples and illustrative embodiments, it is not intended to be limited thereby ex~ept iDsofar as appesrs ;D .he sccompsnying cltim~.
.` ' ' :':'1` ' ' ' ' : ' , . . , .. , .. _ ._ _ . , --- ... -- .--. ~ . : . . . . : .. , , ~ , ~ . ;
', ~.' "' ~' ''` '' ' ~ ' ', '' " ;.' '
:~9L967~3 1. "Volan" methacrylic acid complex of chromic cllloride sold by E. I. Du Pont.
2. ~-602fi - methanolic solution of gamma (ethylelle diamine) trimethoxy silane sold by Dow Corning.
3. I~`mery ~l046D - cntionic fatty acld amide sold by Fmery Industries.
4. C-:l85A - pelargonic acld amide of tetraethylene pentaDline sold by Imperial Chemlcal Industries.
The siæe preparation liste~ above is prepared by mixing the polyvinyl acetate with about 35 percent of the total water to be used in preparing the final size solution volume. The gamma (ethylene diamine) propyl trimethoxy silane is then mixed with a small quantity of cold water and added to the mixing tcmk Çollowed by tlle addition of the anti-static agent. The cationic fatty acid am:ide and the pelargonic acid amide of tetraethylene pentamine are mixed in hot water and added to the size ingredients wlth continuous mixing. The mixing tank is then diluted to the final volume of lO gallons. The pll is then measured and acetic acid is added in sufficient quantity to control the pH at 6.3 + 0.2.
It is preferred that the p~l of the final size be maintained at 6.3.
After mixing the forming size of Rxample I it is applied to the individual glass fibers during their formation. The size is applied to the individual fibers after they emerge from the orifices in the electrically heated platinum alloy bushing containing the molten glass and the size is applied to the filaments prior to the timc they are grouped together to form a strand by means of a roller applicator such as the type shown in U. S. Patent No. 2,728,972. The fibers are collected on a collet operating at speeds of about 6,000 revolutions. per minute and the roller ~:, ' ' .
, ~_ , . ....... . _ -.: . :
. :: . : , . . ~:
~, .. - . .-. .. . .
~)4~
applicator speed is maintained at approximately 145 revolutions per minute. The Eorming packages are baked for a period of 11 hours at 240F. and are then placed on an appropriate balloon creel and wound on a roving winder to provide a fiber glass roving product containing the dried residlle oE the aqueous si~e composition placed on the fibers during formation. The dried residue on the glass Eibers represents a coating of between 1.25 and 1.55 percent by weight basis the bare glass.
Roving produced by fibers si~ed with this quantity of the si~ing of the instant invention has been found particularly effective in producing sp~ray-up fiber glass reinforced resin products. ~ -While the invention has been described with reference to certain specific examples and illustrative embodiments, it is not intended to be limited thereby ex~ept iDsofar as appesrs ;D .he sccompsnying cltim~.
.` ' ' :':'1` ' ' ' ' : ' , . . , .. , .. _ ._ _ . , --- ... -- .--. ~ . : . . . . : .. , , ~ , ~ . ;
', ~.' "' ~' ''` '' ' ~ ' ', '' " ;.' '
Claims (8)
IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A glass fiber containing on the surface thereof a coating residue obtained by drying on the surface of the glass fibers an aqueous sizing composition whose ingredients other than water consists essentially of:
70 to 90 percent by weight based on total weight of the size solution solids of a polyvinyl acetate film former; 4 to 7 percent by weight based on solids fatty acid amide lubricant; 3 to 6 percent by weight solids gamma-ethylene diamine propyl trialkoxy silane; and 2 to 6 percent by weight solids methacrylic acid chromic halide coupling agent; said sizing composition having been adjusted to a pH of about 6.2 to 6.4; and said composition having 7.0 to 7.5 percent by weight solids.
70 to 90 percent by weight based on total weight of the size solution solids of a polyvinyl acetate film former; 4 to 7 percent by weight based on solids fatty acid amide lubricant; 3 to 6 percent by weight solids gamma-ethylene diamine propyl trialkoxy silane; and 2 to 6 percent by weight solids methacrylic acid chromic halide coupling agent; said sizing composition having been adjusted to a pH of about 6.2 to 6.4; and said composition having 7.0 to 7.5 percent by weight solids.
2. The glass fibers of Claim 1 wherein the trialkoxy silane is gamma (ethylene diamine) propyl trimethoxy silane.
3. The glass fibers of Claim 2 wherein the gamma (ethylene diamine) propyl trimethoxy silane is between 4 to 5 percent by weight of the size ingredients exclusive of the water.
4. The glass fibers of claim 1 wherein the gamma (ethylene diamine) propyl trialkoxy silane is between 4 to 5 percent by weight of the size ingredients exclusive of the water.
5. An aqueous sizing composition for glass fiber strand whose ingredients other than water consists essentially of: 70 to 90 percent by weight based on total weight of the size solution solids of a polyvinyl acetate film former; 4 to 7 percent by weight based on solids fatty acid amide lubricant; 3 to 6 percent by weight solids gamma-ethylene diamine propyl trialkoxy silane; and 2 to 6 percent by weight solids methacrylic acid chromic halide coupling agent; said sizing composition having been adjusted to a pH of about 6.2 to 6.4, and said composition having 7.0 to 7.5 percent by weight solids.
6. The sizing composition of Claim 5 wherein the alkoxy silane is gamma (ethylene diamine) propyl trimethoxy silane.
7. The size composition of Claim 6 wherein the gamma (ethylene diamine) propyl trimethoxy silane is between 4 to 5 percent by weight basis the size ingredients exclusive of the water.
8. The size composition of Claim 5 wherein the gamma (ethylene diamine) propyl trialkoxy silane is between 4 to 5 percent by weight of the size ingredients exclusive of the water.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/491,730 US3933711A (en) | 1972-10-31 | 1974-07-23 | Forming size of aqueous polyvinylacetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049678A true CA1049678A (en) | 1979-02-27 |
Family
ID=23953421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA228,513A Expired CA1049678A (en) | 1974-07-23 | 1975-06-04 | Forming size |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5119894A (en) |
| CA (1) | CA1049678A (en) |
| IT (1) | IT1036334B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2076844A (en) * | 1980-05-29 | 1981-12-09 | Ppg Industries Inc | Aqueous sizing composition comprising vinyl acetate/acrylic copolymer, and sized glass fibers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE795964A (en) * | 1972-02-28 | 1973-08-27 | Johns Manville | COMPOSITION OF FIBERGLASS PRIMER AND ITS PREPARATION PROCESS FOR APPLICATION BY GUN OF FIBERGLASS BENCH BITS |
| US3816235A (en) * | 1972-08-18 | 1974-06-11 | Owens Corning Fiberglass Corp | Glass fiber size composition |
| JPS5116066B2 (en) * | 1972-10-27 | 1976-05-21 |
-
1975
- 1975-06-04 CA CA228,513A patent/CA1049678A/en not_active Expired
- 1975-06-19 IT IT6858175A patent/IT1036334B/en active
- 1975-06-23 JP JP50077472A patent/JPS5119894A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5119894A (en) | 1976-02-17 |
| IT1036334B (en) | 1979-10-30 |
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