CA1124926A - Composition and method for coating glass fibers and the fibers obtained - Google Patents
Composition and method for coating glass fibers and the fibers obtainedInfo
- Publication number
- CA1124926A CA1124926A CA295,290A CA295290A CA1124926A CA 1124926 A CA1124926 A CA 1124926A CA 295290 A CA295290 A CA 295290A CA 1124926 A CA1124926 A CA 1124926A
- Authority
- CA
- Canada
- Prior art keywords
- organo
- silane
- sizing
- methoxy
- propoxy
- 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
-
- 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
- C03C25/40—Organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
Abstract
ABSTRACT
The present invention concerns aqueous compositions for the coating of glass fibers used particularly for textiles. It also concerns both a method for manufacturing glass fiber having great tensile strength, by which method the aforementioned aqueous compositions are applied to the fibers, and the finished fibers.
The present invention concerns aqueous compositions for the coating of glass fibers used particularly for textiles. It also concerns both a method for manufacturing glass fiber having great tensile strength, by which method the aforementioned aqueous compositions are applied to the fibers, and the finished fibers.
Description
~24~
The present invention concerns aqueous compositions for the coating of glass fibers used particularly for textiles. It also concerns both a method for manufacturing glass fibers having great tensile strength, by which method the aforementioned aqueous compositions are applied to the fibers, and the finished fibers.
The glass fibers are manufactured in a known manner by the attenuation of molten glass threads flowing from die orifices. These glass threads are thinned down in order to form continuous filaments by means of an attenuation brought about by having these filaments rolled on a support on a winder turning at great speed, before which rolling, however, the filaments are gathered in the form of a strand. Before being gathered in the form of a strand, the filaments are coated with a sizing by being passed onto a continuously fed sizing component.
The sizing is applied in order to prevent the mutual abrasion and the rupture of the individual filaments when the strand is submitted to a certain number of transformations during its formation or during its utilization. Particularly, in order that the strand can withstand friction during its speedy passage through guide components during various textile operations, such as twisting, cabling, warping, pirn winding or weaving, it must be coated with a sizing having protective and lubricating properties. The sizing also provides for the adhesion or sufficiently strong cohesion of the individual filaments to provide an integer strand. The properties providing protection against abrasion and providing for integrity are essential when the strand must be submitted to all the operations and textile transformations previously mentioned.
df- '' ~ 1 From another angle, where the strands or webs are used for the reenforcement of plastic materials, the sizing must be compatible with the matrices to be reenforced and must improve the adhesion of the strands to these matrices so that laminations with good mechanical and dielectrical properties are obtained.
Generally the sizing is a solution or an a~ueous dispersion composed essentially of: one or several adhesive or film forming agents, contributing to the integrity of the strands; lubricants, for protecting the filaments and strands against abrasion; and possibly binding agents favoring adhesion of the filaments to plastic matrices.
Various additives, such as products stabilizing the emulsions, antistatic products, fungicides or softening agents, can also be added to these sizing compositions, depending on the ultimate range of application of the strands.
The present invention relates particularly to sizings permitting the fabrication of strands capable of supporting the substantial tensions to which they are submitted during their transformations or ultimate applications, such as twisting, cabling, sectional warping, pirn winding or weaving. These sizings are conducive to strands with firm integrity and allow for a considerable reduction in the number of filament breakages, which in turn improves the yields during the aforesaid operations and transformations.
The invention relates to compositions containing, in addition to starch and the constituents usually used for coating glass fibers, at least one component from an organo-silane family, the formula for which is given hereafter in the description and one particular characteristic of which is that it considerably increases the tensile strength of the strands without affecting their other properties and, particularly, their behavior during textile operations.
It is well known to use aqueous sizings for coating glass fibers which contain:
- adhesive agents such as polyvinyl acetate, acrylic resins, polyesters, epoxy resins, polyurethanes;
- lubricating agents;
- and components of the organo-silane type.
The purpose of these fibers thus generally is to reenforce plastic materials; in this context the organo-silanes serve as binding or bridging agents between the glass and the organic resins by assuring in this manner compatibility of the fibers with the resins to be reenforced.
However, the organo-silanes used most often in these sizings, such as ~ -aminopropyltriethoxysilane, vinyltriace-toxysilane, ~ ~ -amino-ethyl ~ - amino-propyltrimethoxy-silane, ~ -methacryloxypropyl-trimethoxysilane, phenyltri-methoxysilane, vinyl-tri-~-methoxyethoxysilane), practically do not improve the tensile strength of the sized strands and provide only the property of adhesion to the matrices to be reenforced. This is also the case for other organo-silanes from prior art more rarely used such as polyaminopropyl-trimethoxysilane or ~
(3,4-epoxy cyclohexyl~ethyl-trimethoxysilane, or para-aminophenyltrihydroxysilane. In addition, when the strands coated with these known sizings are first woven in order to be used in the form of webbing for reenforcing plastic materials, the various organo-silanes incorporated do not allow for obtaining strands possessing integrity, sliding ability and tensile strength which is strong enough for the twisting,winding on a warp beam and weaving ,c;'6 operations to be carried out without filament breakage or without other difficulties. These difficulties considerably decrease the yields from the operation.
For this same application, the publication of French patent 2 259 127 also proposed aqueous sizings containing a partially baked starch, a parafin wax, an emulsifier, a cationic lubricant and an organo-silane of the formula:
CH O
1 3 ll H2C=C - C - O - NH - CH2 - CH2 - NH - (CH2)3 - Si(OCH3)3 However, the preceding composition seems to be the only one capable of obtaining sjtrands conducive to satisfactory results during textile operations. In fact it is stated specifically that the replacement of this organo-silane with another silane such as ~ -methacryloxypropyltrimethoxysilane totally spoils the capability of the strands to withstand textile operations. Also, the addition of this component of the organo-silane type in sizings does not seem to result in an improvement of the tensile strength of the strands contrary to the use of the particularly active organo-silanes proposed by the present invention.
Respecting the starch base sizings for strands specifically for textiles subsequently submitted to the various textile operations of twisting, cabling, warping, pirn winding, weaving and desizing, the prior art compositions essentially contain starch, a non-ionic lubricant, such as an oil or a wax and an emulsifier and a cationic lubricant, but do not usually contain components of the organo-silane type. In fact, it may be noted that, generally speaking, these components are detrimental to the textile operations because they may be the originators of filament rupturing, the presence of hairs, or the C
tangling of the strands. Moreover, for these sizings for "te~tile strands", the addition of organo-silanes, the essential function of which is to assure the adhesion of glass with a synthetic resin, bears no particular interest since the webs must be desized before being finished and used as decorative fabrics or for reinforcement of high performance laminations (with very strict dielectric limits).
According to the present invention, the addition of one or several specific silanes, constituting the group defined hereafter, to the sizing compositions - for glass fibers surprisingly improves the tensile strength of the sized strands, that is the values for resistance to breakage by pulling, by between 20% and 60%, depending on the types of strands and the components of the sizing without detracting from the other properties of these strands.
The aqueous compositions which are objects of the invention essentially contain the following elements, whose rates are expressed, throughout the whole of the description, in weight portions of active materials per 100 parts of the total:
~ 0.5 to 15% of at least one starch;
- O.Q5 to 5% of non~ionic lubricant;
- 0.03 to 2% of a cationic lubricant;
- 0.02 to 1% of an emulsifier;
- 0.1 to 2% of at least one organo-silane from the group made up of the organo-silanes comprising an organic chain of the polyazamide type and of the organo-silanes whose organic chain contains at least one phenyl radical and at least one secondary or tertiary amine group;
iB 5 1~2~2~
- 0 to 7% of at least one supplementary film forming material;
- 0 to 1% of another organo-silane;
- complement: demineralized water The organo silanes with an organic chain of the proposed polyazamide type are of the following formulas:
The present invention concerns aqueous compositions for the coating of glass fibers used particularly for textiles. It also concerns both a method for manufacturing glass fibers having great tensile strength, by which method the aforementioned aqueous compositions are applied to the fibers, and the finished fibers.
The glass fibers are manufactured in a known manner by the attenuation of molten glass threads flowing from die orifices. These glass threads are thinned down in order to form continuous filaments by means of an attenuation brought about by having these filaments rolled on a support on a winder turning at great speed, before which rolling, however, the filaments are gathered in the form of a strand. Before being gathered in the form of a strand, the filaments are coated with a sizing by being passed onto a continuously fed sizing component.
The sizing is applied in order to prevent the mutual abrasion and the rupture of the individual filaments when the strand is submitted to a certain number of transformations during its formation or during its utilization. Particularly, in order that the strand can withstand friction during its speedy passage through guide components during various textile operations, such as twisting, cabling, warping, pirn winding or weaving, it must be coated with a sizing having protective and lubricating properties. The sizing also provides for the adhesion or sufficiently strong cohesion of the individual filaments to provide an integer strand. The properties providing protection against abrasion and providing for integrity are essential when the strand must be submitted to all the operations and textile transformations previously mentioned.
df- '' ~ 1 From another angle, where the strands or webs are used for the reenforcement of plastic materials, the sizing must be compatible with the matrices to be reenforced and must improve the adhesion of the strands to these matrices so that laminations with good mechanical and dielectrical properties are obtained.
Generally the sizing is a solution or an a~ueous dispersion composed essentially of: one or several adhesive or film forming agents, contributing to the integrity of the strands; lubricants, for protecting the filaments and strands against abrasion; and possibly binding agents favoring adhesion of the filaments to plastic matrices.
Various additives, such as products stabilizing the emulsions, antistatic products, fungicides or softening agents, can also be added to these sizing compositions, depending on the ultimate range of application of the strands.
The present invention relates particularly to sizings permitting the fabrication of strands capable of supporting the substantial tensions to which they are submitted during their transformations or ultimate applications, such as twisting, cabling, sectional warping, pirn winding or weaving. These sizings are conducive to strands with firm integrity and allow for a considerable reduction in the number of filament breakages, which in turn improves the yields during the aforesaid operations and transformations.
The invention relates to compositions containing, in addition to starch and the constituents usually used for coating glass fibers, at least one component from an organo-silane family, the formula for which is given hereafter in the description and one particular characteristic of which is that it considerably increases the tensile strength of the strands without affecting their other properties and, particularly, their behavior during textile operations.
It is well known to use aqueous sizings for coating glass fibers which contain:
- adhesive agents such as polyvinyl acetate, acrylic resins, polyesters, epoxy resins, polyurethanes;
- lubricating agents;
- and components of the organo-silane type.
The purpose of these fibers thus generally is to reenforce plastic materials; in this context the organo-silanes serve as binding or bridging agents between the glass and the organic resins by assuring in this manner compatibility of the fibers with the resins to be reenforced.
However, the organo-silanes used most often in these sizings, such as ~ -aminopropyltriethoxysilane, vinyltriace-toxysilane, ~ ~ -amino-ethyl ~ - amino-propyltrimethoxy-silane, ~ -methacryloxypropyl-trimethoxysilane, phenyltri-methoxysilane, vinyl-tri-~-methoxyethoxysilane), practically do not improve the tensile strength of the sized strands and provide only the property of adhesion to the matrices to be reenforced. This is also the case for other organo-silanes from prior art more rarely used such as polyaminopropyl-trimethoxysilane or ~
(3,4-epoxy cyclohexyl~ethyl-trimethoxysilane, or para-aminophenyltrihydroxysilane. In addition, when the strands coated with these known sizings are first woven in order to be used in the form of webbing for reenforcing plastic materials, the various organo-silanes incorporated do not allow for obtaining strands possessing integrity, sliding ability and tensile strength which is strong enough for the twisting,winding on a warp beam and weaving ,c;'6 operations to be carried out without filament breakage or without other difficulties. These difficulties considerably decrease the yields from the operation.
For this same application, the publication of French patent 2 259 127 also proposed aqueous sizings containing a partially baked starch, a parafin wax, an emulsifier, a cationic lubricant and an organo-silane of the formula:
CH O
1 3 ll H2C=C - C - O - NH - CH2 - CH2 - NH - (CH2)3 - Si(OCH3)3 However, the preceding composition seems to be the only one capable of obtaining sjtrands conducive to satisfactory results during textile operations. In fact it is stated specifically that the replacement of this organo-silane with another silane such as ~ -methacryloxypropyltrimethoxysilane totally spoils the capability of the strands to withstand textile operations. Also, the addition of this component of the organo-silane type in sizings does not seem to result in an improvement of the tensile strength of the strands contrary to the use of the particularly active organo-silanes proposed by the present invention.
Respecting the starch base sizings for strands specifically for textiles subsequently submitted to the various textile operations of twisting, cabling, warping, pirn winding, weaving and desizing, the prior art compositions essentially contain starch, a non-ionic lubricant, such as an oil or a wax and an emulsifier and a cationic lubricant, but do not usually contain components of the organo-silane type. In fact, it may be noted that, generally speaking, these components are detrimental to the textile operations because they may be the originators of filament rupturing, the presence of hairs, or the C
tangling of the strands. Moreover, for these sizings for "te~tile strands", the addition of organo-silanes, the essential function of which is to assure the adhesion of glass with a synthetic resin, bears no particular interest since the webs must be desized before being finished and used as decorative fabrics or for reinforcement of high performance laminations (with very strict dielectric limits).
According to the present invention, the addition of one or several specific silanes, constituting the group defined hereafter, to the sizing compositions - for glass fibers surprisingly improves the tensile strength of the sized strands, that is the values for resistance to breakage by pulling, by between 20% and 60%, depending on the types of strands and the components of the sizing without detracting from the other properties of these strands.
The aqueous compositions which are objects of the invention essentially contain the following elements, whose rates are expressed, throughout the whole of the description, in weight portions of active materials per 100 parts of the total:
~ 0.5 to 15% of at least one starch;
- O.Q5 to 5% of non~ionic lubricant;
- 0.03 to 2% of a cationic lubricant;
- 0.02 to 1% of an emulsifier;
- 0.1 to 2% of at least one organo-silane from the group made up of the organo-silanes comprising an organic chain of the polyazamide type and of the organo-silanes whose organic chain contains at least one phenyl radical and at least one secondary or tertiary amine group;
iB 5 1~2~2~
- 0 to 7% of at least one supplementary film forming material;
- 0 to 1% of another organo-silane;
- complement: demineralized water The organo silanes with an organic chain of the proposed polyazamide type are of the following formulas:
2 n Rl C]x ~[NH-(CH2)n~N~R3~C] -NH (CH ) N
l2 Si(R)3 (I) in which:
0 5 ~ x S 15; 2~ n~6 and preferably n = 2 or 3.
R is a methoxy, ethoxy, propoxy, n-butoxy or ~ -methoxyethoxy radical.
Rl and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms.
R2 is a substituted or non-substituted divalent cycloaliphatic aromatic or aliphatic radical.
The various methods for fabricating these compositions, the nature of the radicals and the values of x and y as a function of the method used are specifically described in U.S. patent 3,746,738.
Organo-silanes whose organic chain includes one phenyl radical and at least one secondary or tertiary amine grouping causing a particularly important improvement in the tensile strength of the sized strands are of the following formulas:
L~
.
Cl ~ CH - NH - (CH2)n - NH - ( CH 2 ) m 3 ( I I ) <~3-NH - (CH2)m - Si (R) 3 (III) Cl H2C = CH~>CH2 - NH - (CH2)n - NH - (CH2)m - Si(R)3 (IV) in which: 2~ n ~6, preferably n = 2 or 3 1~ m ~10, preferably 1~ m ~4 R is a methoxy, ethoxy, propoxy, n-butoxy or~ -methoxyethoxy radical.
The unexpected gain in the tensile strength of the strands with the addition of at least one of the proposed organo-silanes is obtained independently of the constituents forming the base of the sizing, despite the different nature of these constituents, which depend on the ultimate use of the strands. On the other hand, there is no bad effect on such properties as strand integrity, appearance of the strands, their adhesion to the matrices to be reenforced, their resistance to abrasion or their ability to withstand the ultimate operations or textile transformations --properties which naturally vary depending on the various sizing compositions used.
With respect to the above, there is a considerable and surprising advantage which proves to be particularly interesting when the strands are to be submitted to very substantial strains and tensions, particularly in the course of textile transformation operations. It has been observed, in fact, that the strands sized with the compositions which are objects of the invention withstand these operations with a decrease in the number of filament breakages, of the quantity of hairs, and of the tanglings B~
4~
of the strands during their passage through guide components.
This reduction in the number of breaks during twisting, cabling or weaving allows for faster operations, consequently resulting in an improvement in yields.
These improvements also result in webs with better appearance and possessing, as do the strands or assemblies of strands which are used for their construction, higher tensile strength.
From another angle, for sizings for strands whose application includes a further desizing, the presence of the organo-silanes does not increase the difficulty of the desizing step.
Another characteristic of the invention presenting particularly surprising results consists of combining, in sizing formulas with a starch base, at least one of the silanes which are ob]ects of the invention with another organo-silane usually used as an organic glass resin binding agent for the reenforcement of plastic materials. In fact, although these binding agents are generally detrimental to the ability of the strands to withstand textile operations, Applicants have found that their introduction in the form of this combination does not cause this detrimental effect and maintains the advantages of the greater tensile strengths.
Among all the sizing compositions conducive to sized strands possessing in particular high tensile strength, a good ability to withstand textile operations and having to be further desized, the combination of the sizing constituents described in Canadian Application No. 279,175 filed May 26, 1977 with at least one organo-silane having the previously indicated chemical formula, represents a preferred form of the invention.
~ ~ 1422B
~t2~
The sizing compositions used ~expressed in parts in weight per 100 parts of aqueous solution) are the following:
% of active materials 5. - modified starch.................... 0~5 to 10%
- acrylic polymer......... ~.......... 0.1 to S~
- mineral oil with emulsifier........ l to 5%
- polyethy?ene wax................... 0.2 to 2%
- ca~ionic emulsifier of lO. polyethylene wax................... 0.03 to 0.6%
- organo-silane with an organic chain containing a phenyl radical and at least one secondary or tertiary amine group............... 0.1 to 2%
15. - other organo-silane................ 0 to l~
- demineralized water..... to 100 These compositions axe particularly interesting because they possess all the characteristics and advantages described in the above application and because 20. they not only allow for obtaining a uniform and regular distribution of the sizing on the strand, a low rate of migration, excellent unity of the strand and complete and rapid desizing but also effect, in addition, an improvement of about 20~ to 60~ in tensile strength.
25. Another form of the invention comprises sizings with a non-modified starch base or a mixture of non-modified starch and substituted starch according to the weight composition hereafter:
~9 1~
~ of active materials - starch high in amylose ~............... 2 to 8%
- cationic starch........................ 0.2 to 1%
- hydrogenated vegetable oil............. 0.10 to 5%
- emulsifier............................. 0.02 to 1%
- cationic lubricant..................... 0.05 to 2%
- softening agent........................ 0 to 0.3%
- supplementary film forming material.... 0 to 5%
- organo-silane with an organic chain of the polyazamide type lo or with an organic chain containing a phenyl radical and at least one substituted amine group ..... 0.1 to 2%
- other organo-silane.......... 0 to 1%
- demineralized water ......... to loa It is ~uite possible to cite a large number of other currently used sizing formulas for textile glass fibers in which the addition of the organo-silanes according to the present invention has the effect of substantially increasing the tensile strength of the sized strands.
Among the non-ionic lubricants generally used in the compositions, those that may be mentioned are, for example, waxes or natural or synthetic oils, (animal, mineral or vegetables~, polyethylene emulsions, and non-ionic derivatives of polyethyleneglycol. Most often used as cationic lubricants are condensates of fatty acids on polyethoxylated amino alcohols, or amine derivatives of fatty bodies.
l2 Si(R)3 (I) in which:
0 5 ~ x S 15; 2~ n~6 and preferably n = 2 or 3.
R is a methoxy, ethoxy, propoxy, n-butoxy or ~ -methoxyethoxy radical.
Rl and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms.
R2 is a substituted or non-substituted divalent cycloaliphatic aromatic or aliphatic radical.
The various methods for fabricating these compositions, the nature of the radicals and the values of x and y as a function of the method used are specifically described in U.S. patent 3,746,738.
Organo-silanes whose organic chain includes one phenyl radical and at least one secondary or tertiary amine grouping causing a particularly important improvement in the tensile strength of the sized strands are of the following formulas:
L~
.
Cl ~ CH - NH - (CH2)n - NH - ( CH 2 ) m 3 ( I I ) <~3-NH - (CH2)m - Si (R) 3 (III) Cl H2C = CH~>CH2 - NH - (CH2)n - NH - (CH2)m - Si(R)3 (IV) in which: 2~ n ~6, preferably n = 2 or 3 1~ m ~10, preferably 1~ m ~4 R is a methoxy, ethoxy, propoxy, n-butoxy or~ -methoxyethoxy radical.
The unexpected gain in the tensile strength of the strands with the addition of at least one of the proposed organo-silanes is obtained independently of the constituents forming the base of the sizing, despite the different nature of these constituents, which depend on the ultimate use of the strands. On the other hand, there is no bad effect on such properties as strand integrity, appearance of the strands, their adhesion to the matrices to be reenforced, their resistance to abrasion or their ability to withstand the ultimate operations or textile transformations --properties which naturally vary depending on the various sizing compositions used.
With respect to the above, there is a considerable and surprising advantage which proves to be particularly interesting when the strands are to be submitted to very substantial strains and tensions, particularly in the course of textile transformation operations. It has been observed, in fact, that the strands sized with the compositions which are objects of the invention withstand these operations with a decrease in the number of filament breakages, of the quantity of hairs, and of the tanglings B~
4~
of the strands during their passage through guide components.
This reduction in the number of breaks during twisting, cabling or weaving allows for faster operations, consequently resulting in an improvement in yields.
These improvements also result in webs with better appearance and possessing, as do the strands or assemblies of strands which are used for their construction, higher tensile strength.
From another angle, for sizings for strands whose application includes a further desizing, the presence of the organo-silanes does not increase the difficulty of the desizing step.
Another characteristic of the invention presenting particularly surprising results consists of combining, in sizing formulas with a starch base, at least one of the silanes which are ob]ects of the invention with another organo-silane usually used as an organic glass resin binding agent for the reenforcement of plastic materials. In fact, although these binding agents are generally detrimental to the ability of the strands to withstand textile operations, Applicants have found that their introduction in the form of this combination does not cause this detrimental effect and maintains the advantages of the greater tensile strengths.
Among all the sizing compositions conducive to sized strands possessing in particular high tensile strength, a good ability to withstand textile operations and having to be further desized, the combination of the sizing constituents described in Canadian Application No. 279,175 filed May 26, 1977 with at least one organo-silane having the previously indicated chemical formula, represents a preferred form of the invention.
~ ~ 1422B
~t2~
The sizing compositions used ~expressed in parts in weight per 100 parts of aqueous solution) are the following:
% of active materials 5. - modified starch.................... 0~5 to 10%
- acrylic polymer......... ~.......... 0.1 to S~
- mineral oil with emulsifier........ l to 5%
- polyethy?ene wax................... 0.2 to 2%
- ca~ionic emulsifier of lO. polyethylene wax................... 0.03 to 0.6%
- organo-silane with an organic chain containing a phenyl radical and at least one secondary or tertiary amine group............... 0.1 to 2%
15. - other organo-silane................ 0 to l~
- demineralized water..... to 100 These compositions axe particularly interesting because they possess all the characteristics and advantages described in the above application and because 20. they not only allow for obtaining a uniform and regular distribution of the sizing on the strand, a low rate of migration, excellent unity of the strand and complete and rapid desizing but also effect, in addition, an improvement of about 20~ to 60~ in tensile strength.
25. Another form of the invention comprises sizings with a non-modified starch base or a mixture of non-modified starch and substituted starch according to the weight composition hereafter:
~9 1~
~ of active materials - starch high in amylose ~............... 2 to 8%
- cationic starch........................ 0.2 to 1%
- hydrogenated vegetable oil............. 0.10 to 5%
- emulsifier............................. 0.02 to 1%
- cationic lubricant..................... 0.05 to 2%
- softening agent........................ 0 to 0.3%
- supplementary film forming material.... 0 to 5%
- organo-silane with an organic chain of the polyazamide type lo or with an organic chain containing a phenyl radical and at least one substituted amine group ..... 0.1 to 2%
- other organo-silane.......... 0 to 1%
- demineralized water ......... to loa It is ~uite possible to cite a large number of other currently used sizing formulas for textile glass fibers in which the addition of the organo-silanes according to the present invention has the effect of substantially increasing the tensile strength of the sized strands.
Among the non-ionic lubricants generally used in the compositions, those that may be mentioned are, for example, waxes or natural or synthetic oils, (animal, mineral or vegetables~, polyethylene emulsions, and non-ionic derivatives of polyethyleneglycol. Most often used as cationic lubricants are condensates of fatty acids on polyethoxylated amino alcohols, or amine derivatives of fatty bodies.
3.121~
Adding organo-silanes, as defined in this invention, to the sizings in proportions going beyond the upper limit of 2% in weight brings no further improvement with respect to tensile strength, and can cause either a substantial modification of the stiffness of these strands, or a decrease of the protection of the strand, causing the appearance of broken filaments during the ultimate transformation operations.
Of course, the use of these organo-silanes for over-sizing or coating strands having previously received a standard sizing from a die presents similar advantages.
In the following examples relating to a few of embodiments demonstrating certain advantages of the invention, the tensile strength of the strands has been expressed independently of the area or of the size of these strands, that is in the form of values for the resistance to rupture by pulling. Each value corresponds to a mean established from several tests.
Example l A sizing is prepared using the components forming the basis of example l in Canadian Application No. 279,175 mentioned, but a preliminarily hydrolyzed organo-silane encompassing a polyazamide type of chain ;s introduced into the composition. This organo-silane has the general formula (I) in which:
y = 0.92; R = methoxy radical; n = 2 Rl = R3 = ethylene radical . ~13 ~ 2~26 R2 = hydroxy-cyclohexyl-ethylene, the cyclohexyl radical being tied to the nitrogen and the ethylene to the silicon atom.
This sizing contains the following components (whose quantities are expressed in parts by weight per 100 parts of sizing):
~ active materials - corn starch with 26% amylose liquified by acid and etherified lo by propylene oxide (containing 0.035 ether grouping per anhydro-glucose grouping) . . . . . . . . . . . . . . . . . 3.90 - acrylonitrile, acrylamide and acrylic acid, acrylic copolymer in the respective proportions of 40%, 55%, 5% . . . . . . . . . . . . 0.36 : - emulsifiable vaseline oil . . . . . . . . . . . . 1.83 containing (-80% by weight of vaseline oil ( (viscosity 3 Engler at 20C) (-20~ in weight of emulsifier:
. (product of the condensation (of stearylamine (with eight ethylene oxide molecules - cationic aqueous emulsion with polyethylene 25% of active materials . . . . . . . . . . . . . . 1.73 containing (-20% by weight of polyethylene (fusion point = 115C, density =
(0.93 (norm ASTM D 1505), (high molecular weight, viscosity (at 140 C = 200 cPo (-5% by weight of cationic emulsifier:
(amine quaternized with chain length (of from 12 to 16 carbon atoms (containing essentially dimethyl-lauryl ammonium ~ active materials - organo-silane with an organic chain of the polyazamide type : Y 5987~ (Union Carbide) of the preceding formula . . . . . . . . . . . . . . . . . . . . 0.15 - demineralized water . . . . . . . . . . . . . . to 100 The starch suspension is first prepared in a tank by the addition of the starch to 1/3 of the total volume of demineralized water which has been brought to 40C; it is then thermally treated in a continuous oven with the lo injection of steam at a temperature of 95C for 25 seconds, the condition corresponding to a total bursting of the starch granules. The viscosity of the obtained paste is on the order of 10 cPo with an 8% concentration at 90C.
In a second tank, the acrylic copolymer, neutralized to pH = 7 by an equimolecular mixture of triethanolamine and sodium hydroxide is added to around 1/10 of the total volume of demineralized water brought to 75C.
This is agitated until a clear and transparent liquid is obtained, then cooled by the addition of demineralized water until the temperature is 40C.
The acrylic copolymer used in this example is totally soluble in water; in solution it has a pH of 7 and at a 20% con-centration, a viscosity of 45,000 cPo at 22C measured by the Brookfield viscosimeter, type JJ.V.F., speed 10, module 6. A 2%
solution has a viscosity of 6.5 cPo at 22C.
The starch paste coming out of the oven is continuously introduced into the acrylic copolymer solution and the entire solution is cooled to 40C.
Elsewhere, in a third tank, an emulsion of the lubricants is formed using l/lo of the total volume of demineralized water and by successively adding, under moderate agitation,
Adding organo-silanes, as defined in this invention, to the sizings in proportions going beyond the upper limit of 2% in weight brings no further improvement with respect to tensile strength, and can cause either a substantial modification of the stiffness of these strands, or a decrease of the protection of the strand, causing the appearance of broken filaments during the ultimate transformation operations.
Of course, the use of these organo-silanes for over-sizing or coating strands having previously received a standard sizing from a die presents similar advantages.
In the following examples relating to a few of embodiments demonstrating certain advantages of the invention, the tensile strength of the strands has been expressed independently of the area or of the size of these strands, that is in the form of values for the resistance to rupture by pulling. Each value corresponds to a mean established from several tests.
Example l A sizing is prepared using the components forming the basis of example l in Canadian Application No. 279,175 mentioned, but a preliminarily hydrolyzed organo-silane encompassing a polyazamide type of chain ;s introduced into the composition. This organo-silane has the general formula (I) in which:
y = 0.92; R = methoxy radical; n = 2 Rl = R3 = ethylene radical . ~13 ~ 2~26 R2 = hydroxy-cyclohexyl-ethylene, the cyclohexyl radical being tied to the nitrogen and the ethylene to the silicon atom.
This sizing contains the following components (whose quantities are expressed in parts by weight per 100 parts of sizing):
~ active materials - corn starch with 26% amylose liquified by acid and etherified lo by propylene oxide (containing 0.035 ether grouping per anhydro-glucose grouping) . . . . . . . . . . . . . . . . . 3.90 - acrylonitrile, acrylamide and acrylic acid, acrylic copolymer in the respective proportions of 40%, 55%, 5% . . . . . . . . . . . . 0.36 : - emulsifiable vaseline oil . . . . . . . . . . . . 1.83 containing (-80% by weight of vaseline oil ( (viscosity 3 Engler at 20C) (-20~ in weight of emulsifier:
. (product of the condensation (of stearylamine (with eight ethylene oxide molecules - cationic aqueous emulsion with polyethylene 25% of active materials . . . . . . . . . . . . . . 1.73 containing (-20% by weight of polyethylene (fusion point = 115C, density =
(0.93 (norm ASTM D 1505), (high molecular weight, viscosity (at 140 C = 200 cPo (-5% by weight of cationic emulsifier:
(amine quaternized with chain length (of from 12 to 16 carbon atoms (containing essentially dimethyl-lauryl ammonium ~ active materials - organo-silane with an organic chain of the polyazamide type : Y 5987~ (Union Carbide) of the preceding formula . . . . . . . . . . . . . . . . . . . . 0.15 - demineralized water . . . . . . . . . . . . . . to 100 The starch suspension is first prepared in a tank by the addition of the starch to 1/3 of the total volume of demineralized water which has been brought to 40C; it is then thermally treated in a continuous oven with the lo injection of steam at a temperature of 95C for 25 seconds, the condition corresponding to a total bursting of the starch granules. The viscosity of the obtained paste is on the order of 10 cPo with an 8% concentration at 90C.
In a second tank, the acrylic copolymer, neutralized to pH = 7 by an equimolecular mixture of triethanolamine and sodium hydroxide is added to around 1/10 of the total volume of demineralized water brought to 75C.
This is agitated until a clear and transparent liquid is obtained, then cooled by the addition of demineralized water until the temperature is 40C.
The acrylic copolymer used in this example is totally soluble in water; in solution it has a pH of 7 and at a 20% con-centration, a viscosity of 45,000 cPo at 22C measured by the Brookfield viscosimeter, type JJ.V.F., speed 10, module 6. A 2%
solution has a viscosity of 6.5 cPo at 22C.
The starch paste coming out of the oven is continuously introduced into the acrylic copolymer solution and the entire solution is cooled to 40C.
Elsewhere, in a third tank, an emulsion of the lubricants is formed using l/lo of the total volume of demineralized water and by successively adding, under moderate agitation,
4~26 mineral oil containing emulsifier, then the cationic emulsion of polyethylene wax. At the end of preparation, the mixture of the lubricants in emulsion has a pH of 7.4 and a temperature of 23C; it is introduced into the bath already containing the starch paste and the acrylic copolymer.
In another bath, the organo-silane is added to 1/20 of the total volume of water at around 18C with a pH that has been adjusted to 3.5 by acetic acid. The agitation lo is maintained until the hydrolysis of the silane is complete.
The product is thus transferred into the bath already containing the mixture of starch, acrylic copolymer and lubricants. After the addition of the remainder of the water, the pH is adjusted to 7.2 and the temperature controlled at 35C, a temperature which is maintained both for holding the sizing and during application.
The resulting sizing has a viscosity of 10 cPo at 35C and a dry extract of 5.6% by weight, measured after evaporation at 82C for 1 hour and then drying for 10 minutes at 105C. This sizing is applied at a temperature of 35C during the fiberization of standard glass by means of sizing apparatus of the type with a rubberized belt.
In this example, the strands are formed from 9 micron filaments and rolled on their supports during the fiberization operation in order to form reels called "cakes". The quantity of dry sizing deposited on the strand is determined by loss by burning at 625C until there is a constant weight. The first 1,000 meters of strand at the exterior of the cakes presents a dry sizing rate above 0.80% of the weight of the strand and are not used for the final operations, while the rest of the strand possesses a very regular dry sizing rate of ~S.,~
`926 0.75% + 0.05~. The strand is then submitted to a first twisting of 40 turns per meter and the tensile strength is measured in the standard way by the method described by the B.I.S.F.A. (International Bureau for the Standardization of Rayon and Synthetic Fibers). The simple strands, having undergone a twisting of 20 or 40 turns per meter have a tensile strength of 169 kgf/mm2.
Control Example Tl In order to show the increase in tensile strength with the addition of organo-silane, a sizing prepared as described above but not containing organo-silane Y 5987 is applied in the same manner to 9 ~1 m filaments.
The resulting strand possesses a dry sizing rate of 0.74~, that is a rate very near that of example 1, and there is obtained, after the strand has undergone an identical twisting of 20 to 40 turns per meter, a tensile strength of 131 kgf/mm2.
Therefore it may be concluded from the comparison of these results that the introduction in the composition of the organo-silane Y 5987 in a hydrolyzed form increases by 29% the tensile strength of the simple strands.
The comparison of the sized strands shows that the strand with the sizing containing the hydrolyzed organo-silane Y 5987 possesses an improved integrity as compared with the strand coated with the sizing of example Tl, which appears to be attributable to the film forming qualities of this organo-silane.
On the other hand, it is interesting to note that the suitability for the textile operations of 1~ S
warping, pirn winding, and weaving is not completely destroyed with the addition of this organo-silane, contrary to what might be concluded with respect to other organo-silanes such as those employed in example 12 herebelow.
Example 2 A sizing is prepared in which the same components are introduced as in example 1 and in the identical proportions, but the organo-silane Y 5987 is replaced lo by 0.20~ in weight of an organo-silane containing a phenyl radical and two substituted amine groupings of the general formula tIV) in which:
R is a methoxy radical, n = 2, m = 3 Cl CH2 = CH - ~ - CH2 - NH - CCH2)2 - ~H (CH2)3 3 3 The sizing is prepared and applied, according to the same method and the same operatory conditions as those in example 1, to ~ m filaments. The mean dry sizing rate on the strand is 0.78% and the tensile strength obtained with the strand having undergone a first twisting of 20 or 40 turns per meter has a value of 180 kgf/mm2. The gain in tensile strength as compared to the same sizing without organo-silane (example Tl) here represents 37~ and the textile operations of warping and weaving are carried out without any difficulty.
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It is noted, however, that this organo-silane does not improve the integrity of the strands, contrary to the results in example 1.
Example 3 In the sizing composition of example 1, the organo-silane is replaced with 0.15~ of an organo-silane of formula (II) with R = methoxy radical, n = 2, m = 3:
Cl - CH2 - NH - (CH2)2 - NH - ~CH2)3 - Si (OCH3)3 The method for preparing the sizing is the same as that in example 1. The composition presents a dry extract of 4.93~ and the quantity of dry sizing deposited on the strand represents 0.65~ of the weight of the strand.
The tensile strength of the simple strand is raised to ~, 1~ 9~6 195 kgf/mm2, by which there is noted a gain of 49~ as compared with the same sizing without organo-silane (example T1). The textile operations are carried out with this strand without any difficulty, without rupture of the filaments nor tangling of the strand layers.
Example 4 A sizing is prepared and applied which is of the same type as that of example 1 but includes 0.15% of an organo-silane of the formula tIII) in which R is a methoxy group and m = 3, that is: ~ -NH - (CH2)3 -Si(OCH3~3.
The quantity of dry sizing deposited on the strands with 9~ m filaments is 0.70% and the tensile strength of the simple strand, having undergone a twisting of 20 or 40 turns per meter, has a value of 165 kgf/mm2.
In this case a gain of 26% in tensile strength is obtained as compared with the strand sized with the composition of example Tl. The final textile transformation operations take place quite normally, without tangling of the strands or rupture of the filaments, and very satis-factory wehs are obtained.
Examples 5 and 6 In the sizing composition for textile strands from example 1, the organo-silane with an organic chain of the polyazamide type (.Y 5987~ is replaced with 0.15 of an organo-silane with a smaller molecular weight, whose polyazamide organic chain responds to the general formula (I) in which:
~' -y = 8.86; R = methoxy radical; n = 2 Rl = R3 = ethylene radical, R2 = hydroxycyclohexyl-ethylene, the cyclohexyl radical being tied to the nitrogen and the ethylene to the silicon atom.
With this organo-silane, sold on the market as Y 5986, Union Carbide, a gain of 21% in the tensile strength is obtained, this strength being raised to 158 kgf/mm2 for a simple strand having a dry sizing rate of 0.72~.
An equivalent gain in the tensile strength as compared with example Tl is also reached by using, under the same conditions (that is in a hydrolyzed form), 0.15%
of a cationic organo-silane, Y 5922 (Union Carbide), with a polyazamide chain responding to the followingcharacteristics:
yx =9.25; R - methoxy radical, n = 2.
Rl = R3 = ethylene radical R2 = propylene radical Example 7 This example relates to a sizing for strands to be used specifically for textile applications and which contains the usual adhesive agents, lubricants and emulsifiers and encompasses, in addition, an organo-silane whose organic chain includes a phenyl radical and two secondary amine groups, one of which is in the form of hydrochlorate.
The sizing has the following composition:
~ of active materials - hybrid corn starch with 60% amylose . . . . . . . . . 3.81 - cationic derivative of corn starch high in amylose . . . . . . . . . . . . . . . . . . . 0.42 - vegetable oil: hydrogenated corn oil . . . . . . . . 1.27 - emulsifier: monooleate of sorbitan polyoxyethylene . . . . . . . . . . . . . . . . 0.13 - cationic lubricant: product of the condensation of pentamine tetraethylene with stearic acid solubilized by acetic acid . . . . . . . . . . . 0.21 - polyethylene glycol, molecular weight = 300 . . . . . . . . . . . . . . . . . . . . . 0.13 - softening agent: polyoxyethylenated nonylphenol (with 9 moles of ethylene oxide). . . 0.02 - organo-silane of formula (IV) with R = methoxy, n = 2, m = 3.
Cl CH2 = CH - ~ - CH2 - NH - (CH2)2 - NH- (CH2)3 - Si(OCH3)3 0.20 - tin tributyl oxide (fungicide) . . . . . . . . . . . . 0.01 - demineralized water . . . . . . . . . . to 100 To prepare this sizing the starches are dispersed in water and preheated to 80C for the preliminary swelling of the starch granules. Then the mixture is baked in a steam oven fed by steam at a pressure of around 7 bars and the temperature upon exit is regulated at about 100C;
under these conditions, there exists a certain portion of incompletely bursted starch granules. The polyethylene glycol and the cationic lubricant, after dilution, are directly introduced into the baked and cooled starch mixture. Another emulsion, consisting of vegetable oil in the presence of a softening agent and of an emulsifier, heated to around 70C, is prepared by the introduction of water and by violent agitation of the solution until there is a phase inversion. After passing through a cone homogenizer the emulsion is then added to the principal mixture and to the fungicide.
112~
In a separate tank, an organo-silane is diluted with demineralized water until a concentration is obtained which is below 3% and agitation is kept up until there is complete hydrolysis of this silane. The product brought to pH = 4.5 is then introduced into the preceding principal mixture and the preparation is brought to its final volume with the addition of the remaining water. The sizing, adjusted to pH = 4.75, must be kept at a temperature of 65C.
The sizing thus obtained presents a dry extract of 6%;
it is applied to the 9 ~m filaments at 65C during fiberization.
The quantity of dry sizing deposited on the strand rises to 1.50% of the weight of the strand. After twisting the strand shows a tensile strength of 192 kgf/mm2.
Control Example T
For a comparison, the same sizing is prepared but without the organo-silane type of component, and this sizing is applied to the filaments under the same conditions in order to form strands identical in yardage.
The resulting strands have a mean dry sizing rate of 1.4% in weight and display a tensile strength of 131 kgf/mm2 after a first twisting.
It may be concluded, therefore, that there is a considerable gain in the tensile strength, reacing 47%
as compared with example T2, which results in noticeable decreases in the number of breaks of the filaments or of the strands in the final textile operations.
Example 8 While using the same operating conditions as in the preceding example, a sizing is prepared having the following composition:
% of active materials - hybrid corn starch with 60% amylose 3.81 - cationic derivative of corn starch high in amylose . . . . . . . . . . . . 0.42 - acrylonitrile, acrylamide and acrylic acid, acrylic copolymer in the respective proportions of 40%, 55%, 5% . . . . . . . 0.42 - hydrogenated corn oil . . . . . . . . . . 0.50 - emulsifier: sorbitan polyoxyethylene lo monooleate . . . . . . . . . . . . . . . 0.13 - cationic lubricant: product of the condensation of tetraethylene pentamine with stearic acid solubilized with acetic acid . . . . . . . 0.21 - polyethylene glycol, molecular weight = 300 0.13 - softening agent: nonylphenol polyoxyethylene with 9 moles ethylene oxide . . . . . . . . . 0.02 - organo-silane of formula (II) with R = methoxy, n = 2, m = 3:
Cl ~ - CH2 - NH - (CH2)2 - NH (CH2)3 3 3 0.15 - demineralized water . . . . . . . . . . . . . to 100 The acrylic copolymer, neutralized to pH = 7 by an equimolecular mixture of triethanolamine and sodium hydroxide, is introduced into the demineralized water brought to 75C in order to form a 10% solution. After agitation to a point when a clear and transparent liquid is obtained, it is cooled with the addition of water until the temperature is 65C. The copolymer in solution is then added to the starch mixture, baked and cooled as in example 7, before the addition of the polyethylene glycol and other components.
4~6 This sizing has a dry extract rate of 4.69%. It is applied at a temperature of 65C during the fiberization operation and, thus, strands are obtained with a sizing rate of 1.53~. The strands display, after a twisting of 20 to 40 turns per meter, a tensile strength of 195 kgf/mm .
Example 9 The organo-silane in example 8 is replaced with 0.15% of an organo-silane with a chain of the polyazamide o ( T 5987 Union Carbide) type. The sizing applied at a temperature of 65C results in strands possessing a dry sizing rate of 1.50% in weight. These strands, after twisting of 20 or 40 turns per meter, have a tensile strength of 171 kgf/mm2.
The strands sized with this composition have a better appearance than those in example 8, probably because of the improvement in their integrity brought about by the presence of organo-silane Y 5987. The final textile operations are carried out w;thout any rupture of the strands, thus leading to better fabrication yields.
Example 10 % of active materials - hybrid corn starch with 60% amylose 3.81 - cationic derivative of corn starch high in amylose ............................. 0.42 - acrylonitrile, acrylamide and acrylic acid copolymer in the respective proportions of 40%, 55%, 5% ................. 0.30 - hydrogenated corn oil ....................... 1.27 - emulsifier: sorbitan polyoxyethylene monooleate................................... o.l3 - cationic lubricant: product of the condensation of tetraethylene pentamine with stearic acid solubilized by acetic acid 0.21 2~
- polyethylene glycol, molecular weight = 300 . . . . . . . . . . . . . . . . . . . . . . 0.13 - softening agent: polyoxyethylenated nonyl-phenol (with 9 moles of ethylene oxide). . . . . . 0.02 - organo-silanes:
- glycidyl-oxypropyl-trimethoxysilane . . . . . 0.10 - silane with a polyazamide organic chain Y 5987 (Union Carbide) . . . . . . . . . . 0.10 This sizing composition is obtained under the same lo conditions as those for the sizings in examples 8 and 9 which only contain a single organo-silane. The two organo-silanes are introduced one after the other, after hydrolysis, into a mixture already containing the other products.
The final composition is applied to the 9~ m filaments at a temperature of 65C during the fiberization opera-tion. The dry sizing rate on the strands formed by the union of the filaments is 1.40%, and after a first twisting of 40 turns per meter, these strands possess a tensile strength of 176 kgf/mm2. As compared with strands sized with a similar composition not including organo-silane, the tensile strength is improved by 34%.
Respecting the textile operations, it is noted that the presence of these two silanes in combination in the sizing composition further facilitates warping.
Example 11 A sizing composition is prepared which is similar to that in example 7 and according to the same method i ;g~
and with the same operating conditions, but the organo-silane is replaced with the following mixture of two organo-silanes:
- 0.10% of glycidyl-oxypropyl-trimethoxysilane - 0.10% of N-vinyl-toluyl-ethyl-diamine-propyl-trimethoxy-silane (formula (IV):
Cl CH2 = CH - ~ - CH2 - NH - (CH2)2 - N~ - (CH2)3 3 3 The strands have a dry sizing rate of 1.41% of the weight of the strand and the tensile strength reaches 190 kgf/mm2, which represents a gain of 45~ as compared with the strands coated with the same sizing not containing this organo-silane, that is the composition of example T2. The strands sized with this composition behave as satisfactorily during the standard textile operations as they do in example 7.
This result is surprising because it was noted else-where that the use in this composition of ~-glycidoxypropyl-trimethoxysilane alone has a tendency to degrade the ability of the strand to withstand the textile operations.
On the contrary, this example shows that this detrimental effect is nullified by the presence of 0.1% of N-vinyl-toluyl-ethyl-diamine-propyl-tirmethoxysilane which carries with it the strong tensile strength value.
Example 12 In the sizing from example 1 the organo-silane is replaced with 0.15% of an organo-silane of the formula:
O - NH - CH2 - CH2 - NH - (CH2)3 3 3 ~4~
This organo-silane is used in the prior art in compositions with a starch base for the coating of glass fibers to be used for reenforcing plastic material in the form of webs such as described in the French Patent 2,259,127.
The sizing is applied at 35C and a strand is obtained having a dry sizing rate of 0.70~. After twist-ing, it is noted that the tensile strength of the strands only reached 100 kgf/mm2, a value below that obtained with the same sizing not containing organo-silane (example Tl).
This example shows that the addition of organo-silanes to the sizing compositions for glass fibers to be used specifically for textile applications can decrease the tensile strength of the strands. This decrease seems to result probably from a degradation by the organo-silane of the ;ntegrity of the strand and of the protection against abrasion. The same phenomenon of destruction of the textile properties can also be observed when, in the sizing from example 1, in place of the organo-silane used, is introduced 0.15% Of ~r aminopropyl-triethoxysilane well known in the technique for sizings for the reenforce-ment of plastic materials.
I~
In another bath, the organo-silane is added to 1/20 of the total volume of water at around 18C with a pH that has been adjusted to 3.5 by acetic acid. The agitation lo is maintained until the hydrolysis of the silane is complete.
The product is thus transferred into the bath already containing the mixture of starch, acrylic copolymer and lubricants. After the addition of the remainder of the water, the pH is adjusted to 7.2 and the temperature controlled at 35C, a temperature which is maintained both for holding the sizing and during application.
The resulting sizing has a viscosity of 10 cPo at 35C and a dry extract of 5.6% by weight, measured after evaporation at 82C for 1 hour and then drying for 10 minutes at 105C. This sizing is applied at a temperature of 35C during the fiberization of standard glass by means of sizing apparatus of the type with a rubberized belt.
In this example, the strands are formed from 9 micron filaments and rolled on their supports during the fiberization operation in order to form reels called "cakes". The quantity of dry sizing deposited on the strand is determined by loss by burning at 625C until there is a constant weight. The first 1,000 meters of strand at the exterior of the cakes presents a dry sizing rate above 0.80% of the weight of the strand and are not used for the final operations, while the rest of the strand possesses a very regular dry sizing rate of ~S.,~
`926 0.75% + 0.05~. The strand is then submitted to a first twisting of 40 turns per meter and the tensile strength is measured in the standard way by the method described by the B.I.S.F.A. (International Bureau for the Standardization of Rayon and Synthetic Fibers). The simple strands, having undergone a twisting of 20 or 40 turns per meter have a tensile strength of 169 kgf/mm2.
Control Example Tl In order to show the increase in tensile strength with the addition of organo-silane, a sizing prepared as described above but not containing organo-silane Y 5987 is applied in the same manner to 9 ~1 m filaments.
The resulting strand possesses a dry sizing rate of 0.74~, that is a rate very near that of example 1, and there is obtained, after the strand has undergone an identical twisting of 20 to 40 turns per meter, a tensile strength of 131 kgf/mm2.
Therefore it may be concluded from the comparison of these results that the introduction in the composition of the organo-silane Y 5987 in a hydrolyzed form increases by 29% the tensile strength of the simple strands.
The comparison of the sized strands shows that the strand with the sizing containing the hydrolyzed organo-silane Y 5987 possesses an improved integrity as compared with the strand coated with the sizing of example Tl, which appears to be attributable to the film forming qualities of this organo-silane.
On the other hand, it is interesting to note that the suitability for the textile operations of 1~ S
warping, pirn winding, and weaving is not completely destroyed with the addition of this organo-silane, contrary to what might be concluded with respect to other organo-silanes such as those employed in example 12 herebelow.
Example 2 A sizing is prepared in which the same components are introduced as in example 1 and in the identical proportions, but the organo-silane Y 5987 is replaced lo by 0.20~ in weight of an organo-silane containing a phenyl radical and two substituted amine groupings of the general formula tIV) in which:
R is a methoxy radical, n = 2, m = 3 Cl CH2 = CH - ~ - CH2 - NH - CCH2)2 - ~H (CH2)3 3 3 The sizing is prepared and applied, according to the same method and the same operatory conditions as those in example 1, to ~ m filaments. The mean dry sizing rate on the strand is 0.78% and the tensile strength obtained with the strand having undergone a first twisting of 20 or 40 turns per meter has a value of 180 kgf/mm2. The gain in tensile strength as compared to the same sizing without organo-silane (example Tl) here represents 37~ and the textile operations of warping and weaving are carried out without any difficulty.
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It is noted, however, that this organo-silane does not improve the integrity of the strands, contrary to the results in example 1.
Example 3 In the sizing composition of example 1, the organo-silane is replaced with 0.15~ of an organo-silane of formula (II) with R = methoxy radical, n = 2, m = 3:
Cl - CH2 - NH - (CH2)2 - NH - ~CH2)3 - Si (OCH3)3 The method for preparing the sizing is the same as that in example 1. The composition presents a dry extract of 4.93~ and the quantity of dry sizing deposited on the strand represents 0.65~ of the weight of the strand.
The tensile strength of the simple strand is raised to ~, 1~ 9~6 195 kgf/mm2, by which there is noted a gain of 49~ as compared with the same sizing without organo-silane (example T1). The textile operations are carried out with this strand without any difficulty, without rupture of the filaments nor tangling of the strand layers.
Example 4 A sizing is prepared and applied which is of the same type as that of example 1 but includes 0.15% of an organo-silane of the formula tIII) in which R is a methoxy group and m = 3, that is: ~ -NH - (CH2)3 -Si(OCH3~3.
The quantity of dry sizing deposited on the strands with 9~ m filaments is 0.70% and the tensile strength of the simple strand, having undergone a twisting of 20 or 40 turns per meter, has a value of 165 kgf/mm2.
In this case a gain of 26% in tensile strength is obtained as compared with the strand sized with the composition of example Tl. The final textile transformation operations take place quite normally, without tangling of the strands or rupture of the filaments, and very satis-factory wehs are obtained.
Examples 5 and 6 In the sizing composition for textile strands from example 1, the organo-silane with an organic chain of the polyazamide type (.Y 5987~ is replaced with 0.15 of an organo-silane with a smaller molecular weight, whose polyazamide organic chain responds to the general formula (I) in which:
~' -y = 8.86; R = methoxy radical; n = 2 Rl = R3 = ethylene radical, R2 = hydroxycyclohexyl-ethylene, the cyclohexyl radical being tied to the nitrogen and the ethylene to the silicon atom.
With this organo-silane, sold on the market as Y 5986, Union Carbide, a gain of 21% in the tensile strength is obtained, this strength being raised to 158 kgf/mm2 for a simple strand having a dry sizing rate of 0.72~.
An equivalent gain in the tensile strength as compared with example Tl is also reached by using, under the same conditions (that is in a hydrolyzed form), 0.15%
of a cationic organo-silane, Y 5922 (Union Carbide), with a polyazamide chain responding to the followingcharacteristics:
yx =9.25; R - methoxy radical, n = 2.
Rl = R3 = ethylene radical R2 = propylene radical Example 7 This example relates to a sizing for strands to be used specifically for textile applications and which contains the usual adhesive agents, lubricants and emulsifiers and encompasses, in addition, an organo-silane whose organic chain includes a phenyl radical and two secondary amine groups, one of which is in the form of hydrochlorate.
The sizing has the following composition:
~ of active materials - hybrid corn starch with 60% amylose . . . . . . . . . 3.81 - cationic derivative of corn starch high in amylose . . . . . . . . . . . . . . . . . . . 0.42 - vegetable oil: hydrogenated corn oil . . . . . . . . 1.27 - emulsifier: monooleate of sorbitan polyoxyethylene . . . . . . . . . . . . . . . . 0.13 - cationic lubricant: product of the condensation of pentamine tetraethylene with stearic acid solubilized by acetic acid . . . . . . . . . . . 0.21 - polyethylene glycol, molecular weight = 300 . . . . . . . . . . . . . . . . . . . . . 0.13 - softening agent: polyoxyethylenated nonylphenol (with 9 moles of ethylene oxide). . . 0.02 - organo-silane of formula (IV) with R = methoxy, n = 2, m = 3.
Cl CH2 = CH - ~ - CH2 - NH - (CH2)2 - NH- (CH2)3 - Si(OCH3)3 0.20 - tin tributyl oxide (fungicide) . . . . . . . . . . . . 0.01 - demineralized water . . . . . . . . . . to 100 To prepare this sizing the starches are dispersed in water and preheated to 80C for the preliminary swelling of the starch granules. Then the mixture is baked in a steam oven fed by steam at a pressure of around 7 bars and the temperature upon exit is regulated at about 100C;
under these conditions, there exists a certain portion of incompletely bursted starch granules. The polyethylene glycol and the cationic lubricant, after dilution, are directly introduced into the baked and cooled starch mixture. Another emulsion, consisting of vegetable oil in the presence of a softening agent and of an emulsifier, heated to around 70C, is prepared by the introduction of water and by violent agitation of the solution until there is a phase inversion. After passing through a cone homogenizer the emulsion is then added to the principal mixture and to the fungicide.
112~
In a separate tank, an organo-silane is diluted with demineralized water until a concentration is obtained which is below 3% and agitation is kept up until there is complete hydrolysis of this silane. The product brought to pH = 4.5 is then introduced into the preceding principal mixture and the preparation is brought to its final volume with the addition of the remaining water. The sizing, adjusted to pH = 4.75, must be kept at a temperature of 65C.
The sizing thus obtained presents a dry extract of 6%;
it is applied to the 9 ~m filaments at 65C during fiberization.
The quantity of dry sizing deposited on the strand rises to 1.50% of the weight of the strand. After twisting the strand shows a tensile strength of 192 kgf/mm2.
Control Example T
For a comparison, the same sizing is prepared but without the organo-silane type of component, and this sizing is applied to the filaments under the same conditions in order to form strands identical in yardage.
The resulting strands have a mean dry sizing rate of 1.4% in weight and display a tensile strength of 131 kgf/mm2 after a first twisting.
It may be concluded, therefore, that there is a considerable gain in the tensile strength, reacing 47%
as compared with example T2, which results in noticeable decreases in the number of breaks of the filaments or of the strands in the final textile operations.
Example 8 While using the same operating conditions as in the preceding example, a sizing is prepared having the following composition:
% of active materials - hybrid corn starch with 60% amylose 3.81 - cationic derivative of corn starch high in amylose . . . . . . . . . . . . 0.42 - acrylonitrile, acrylamide and acrylic acid, acrylic copolymer in the respective proportions of 40%, 55%, 5% . . . . . . . 0.42 - hydrogenated corn oil . . . . . . . . . . 0.50 - emulsifier: sorbitan polyoxyethylene lo monooleate . . . . . . . . . . . . . . . 0.13 - cationic lubricant: product of the condensation of tetraethylene pentamine with stearic acid solubilized with acetic acid . . . . . . . 0.21 - polyethylene glycol, molecular weight = 300 0.13 - softening agent: nonylphenol polyoxyethylene with 9 moles ethylene oxide . . . . . . . . . 0.02 - organo-silane of formula (II) with R = methoxy, n = 2, m = 3:
Cl ~ - CH2 - NH - (CH2)2 - NH (CH2)3 3 3 0.15 - demineralized water . . . . . . . . . . . . . to 100 The acrylic copolymer, neutralized to pH = 7 by an equimolecular mixture of triethanolamine and sodium hydroxide, is introduced into the demineralized water brought to 75C in order to form a 10% solution. After agitation to a point when a clear and transparent liquid is obtained, it is cooled with the addition of water until the temperature is 65C. The copolymer in solution is then added to the starch mixture, baked and cooled as in example 7, before the addition of the polyethylene glycol and other components.
4~6 This sizing has a dry extract rate of 4.69%. It is applied at a temperature of 65C during the fiberization operation and, thus, strands are obtained with a sizing rate of 1.53~. The strands display, after a twisting of 20 to 40 turns per meter, a tensile strength of 195 kgf/mm .
Example 9 The organo-silane in example 8 is replaced with 0.15% of an organo-silane with a chain of the polyazamide o ( T 5987 Union Carbide) type. The sizing applied at a temperature of 65C results in strands possessing a dry sizing rate of 1.50% in weight. These strands, after twisting of 20 or 40 turns per meter, have a tensile strength of 171 kgf/mm2.
The strands sized with this composition have a better appearance than those in example 8, probably because of the improvement in their integrity brought about by the presence of organo-silane Y 5987. The final textile operations are carried out w;thout any rupture of the strands, thus leading to better fabrication yields.
Example 10 % of active materials - hybrid corn starch with 60% amylose 3.81 - cationic derivative of corn starch high in amylose ............................. 0.42 - acrylonitrile, acrylamide and acrylic acid copolymer in the respective proportions of 40%, 55%, 5% ................. 0.30 - hydrogenated corn oil ....................... 1.27 - emulsifier: sorbitan polyoxyethylene monooleate................................... o.l3 - cationic lubricant: product of the condensation of tetraethylene pentamine with stearic acid solubilized by acetic acid 0.21 2~
- polyethylene glycol, molecular weight = 300 . . . . . . . . . . . . . . . . . . . . . . 0.13 - softening agent: polyoxyethylenated nonyl-phenol (with 9 moles of ethylene oxide). . . . . . 0.02 - organo-silanes:
- glycidyl-oxypropyl-trimethoxysilane . . . . . 0.10 - silane with a polyazamide organic chain Y 5987 (Union Carbide) . . . . . . . . . . 0.10 This sizing composition is obtained under the same lo conditions as those for the sizings in examples 8 and 9 which only contain a single organo-silane. The two organo-silanes are introduced one after the other, after hydrolysis, into a mixture already containing the other products.
The final composition is applied to the 9~ m filaments at a temperature of 65C during the fiberization opera-tion. The dry sizing rate on the strands formed by the union of the filaments is 1.40%, and after a first twisting of 40 turns per meter, these strands possess a tensile strength of 176 kgf/mm2. As compared with strands sized with a similar composition not including organo-silane, the tensile strength is improved by 34%.
Respecting the textile operations, it is noted that the presence of these two silanes in combination in the sizing composition further facilitates warping.
Example 11 A sizing composition is prepared which is similar to that in example 7 and according to the same method i ;g~
and with the same operating conditions, but the organo-silane is replaced with the following mixture of two organo-silanes:
- 0.10% of glycidyl-oxypropyl-trimethoxysilane - 0.10% of N-vinyl-toluyl-ethyl-diamine-propyl-trimethoxy-silane (formula (IV):
Cl CH2 = CH - ~ - CH2 - NH - (CH2)2 - N~ - (CH2)3 3 3 The strands have a dry sizing rate of 1.41% of the weight of the strand and the tensile strength reaches 190 kgf/mm2, which represents a gain of 45~ as compared with the strands coated with the same sizing not containing this organo-silane, that is the composition of example T2. The strands sized with this composition behave as satisfactorily during the standard textile operations as they do in example 7.
This result is surprising because it was noted else-where that the use in this composition of ~-glycidoxypropyl-trimethoxysilane alone has a tendency to degrade the ability of the strand to withstand the textile operations.
On the contrary, this example shows that this detrimental effect is nullified by the presence of 0.1% of N-vinyl-toluyl-ethyl-diamine-propyl-tirmethoxysilane which carries with it the strong tensile strength value.
Example 12 In the sizing from example 1 the organo-silane is replaced with 0.15% of an organo-silane of the formula:
O - NH - CH2 - CH2 - NH - (CH2)3 3 3 ~4~
This organo-silane is used in the prior art in compositions with a starch base for the coating of glass fibers to be used for reenforcing plastic material in the form of webs such as described in the French Patent 2,259,127.
The sizing is applied at 35C and a strand is obtained having a dry sizing rate of 0.70~. After twist-ing, it is noted that the tensile strength of the strands only reached 100 kgf/mm2, a value below that obtained with the same sizing not containing organo-silane (example Tl).
This example shows that the addition of organo-silanes to the sizing compositions for glass fibers to be used specifically for textile applications can decrease the tensile strength of the strands. This decrease seems to result probably from a degradation by the organo-silane of the ;ntegrity of the strand and of the protection against abrasion. The same phenomenon of destruction of the textile properties can also be observed when, in the sizing from example 1, in place of the organo-silane used, is introduced 0.15% Of ~r aminopropyl-triethoxysilane well known in the technique for sizings for the reenforce-ment of plastic materials.
I~
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Aqueous composition for the coating of glass fibers, characterized in that it comprises:
- 0.5 to 15% in weight of at least one starch, - 0.05 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic,aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 to 6 m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
- 0.5 to 15% in weight of at least one starch, - 0.05 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic,aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 to 6 m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
2. Aqueous sizing for the coating of glass fibers according to claim 1, characterized in that it contains up to 7% of supplementary film forming materials and/or up to 1% of another organo-silane.
3. Aqueous sizing according to claim 1, charac-terized in that it comprises:
- 0.5 to 10% in weight of modified starch, - 0.1 to 5% of acrylic polymer, - 1 to 5% of emulsified, non-ionic lubricant(s), - 0.2 to 2% of polyethylene wax, - 0.03 to 0.6% of a cationic emulsifier for polyethylene wax, - 0.1 to 2% of the organo-silane.
- 0.5 to 10% in weight of modified starch, - 0.1 to 5% of acrylic polymer, - 1 to 5% of emulsified, non-ionic lubricant(s), - 0.2 to 2% of polyethylene wax, - 0.03 to 0.6% of a cationic emulsifier for polyethylene wax, - 0.1 to 2% of the organo-silane.
4. Aqueous sizing according to claim 1, charac-terized in that the at least one organo-silane is selected from the general formulas II and IV.
5. Aqueous sizing for coating glass fibers according to claim 1, characterized in that it contains at least one of the organo-silanes of the following formulas:
in which n equals 2 or 3, m is 1 to 4.
in which n equals 2 or 3, m is 1 to 4.
6. Aqueous composition for the coating of glass fibers according to claim 1 characterized in that it contains at least one organo-silane of the general formulas:
(II) in which n is 2 to 6, m is 1 to 10, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, (III) in which: m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, (IV) in which: n is 2 to 6, m is 1 to 10, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
(II) in which n is 2 to 6, m is 1 to 10, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, (III) in which: m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, (IV) in which: n is 2 to 6, m is 1 to 10, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
7. Aqueous sizing according to claim 1, charac-terized in that it comprises:
- 0.5 to 10% in weight of modified starch, - 0.1 to 5% of acrylic polymer, - 1 to 5% of emulsified, non-ionic lubricant(s), - 0.2 to 2% of polyethylene wax, - 0.03 to 0.6% of a cationic emulsifier for polyethylene wax, - 0.1 to 2% of at least one organo-silane of the general formulas (II), (III), and (IV).
- 0.5 to 10% in weight of modified starch, - 0.1 to 5% of acrylic polymer, - 1 to 5% of emulsified, non-ionic lubricant(s), - 0.2 to 2% of polyethylene wax, - 0.03 to 0.6% of a cationic emulsifier for polyethylene wax, - 0.1 to 2% of at least one organo-silane of the general formulas (II), (III), and (IV).
8. Method for fabricating glass fibers by mechanical attenuation at high speed of molten glass threads according to which a sizing or an oversizing is deposited on the filaments, characterized in that the aqueous sizing composition deposited on the filaments, expressed in weight percentages of active materials, comprises the following:
- 0.5 to 15% in weight of at least one starch, - 0.5 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 to 6 m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
- 0.5 to 15% in weight of at least one starch, - 0.5 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 to 6 m is 1 to 10 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
9. Aqueous composition for the coating of glass fibers characterized in that it comprises:
- 0.5 to 15% in weight of at least one starch, - 0.05 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 or 3 m is 1 to 4 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
- 0.5 to 15% in weight of at least one starch, - 0.05 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 or 3 m is 1 to 4 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
10. Method for fabricating glass fibers by mechanical attenuation at high speed of molten glass threads according to which a sizing or an oversizing is deposited on the filaments, characterized in that the aqueous sizing composition deposited on the filaments, expressed in weight percentages of active materials, comprises the following:
- 0.5 to 15% in weight of at least one starch, - 0.5 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 or 3 m is 1 to 4 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
- 0.5 to 15% in weight of at least one starch, - 0.5 to 5% of non-ionic lubricant, - 0.03 to 2% of cationic lubricant, - 0.02 to 1% of emulsifier, - 0.1 to 2% of at least one organo silane selected from the group consisting of (A) (I) in which:
? is 0.5 to 15; n is 2 to 6, R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical, R1 and R3 are divalent alkylene radicals containing 1 to 3 carbon atoms, and R2 represents a substituted or non-substituted divalent cycloaliphatic, aromatic, or aliphatic radical; or (B) (II) (C) (III) (D) (IV) in which: n is 2 or 3 m is 1 to 4 R is a methoxy, ethoxy, propoxy, n-butoxy or .beta.-methoxyethoxy radical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7701386 | 1977-01-19 | ||
| FR7701386A FR2377982A1 (en) | 1977-01-19 | 1977-01-19 | COMPOSITIONS FOR COATING FIBERS OF GLASS AND FIBERS SO OBTAINED |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1124926A true CA1124926A (en) | 1982-06-01 |
Family
ID=9185655
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000295264A Expired CA1121530A (en) | 1977-01-19 | 1978-01-19 | Method and composition for coating glass fibers and the fibers obtained |
| CA295,290A Expired CA1124926A (en) | 1977-01-19 | 1978-01-19 | Composition and method for coating glass fibers and the fibers obtained |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000295264A Expired CA1121530A (en) | 1977-01-19 | 1978-01-19 | Method and composition for coating glass fibers and the fibers obtained |
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| Country | Link |
|---|---|
| US (2) | US4246145A (en) |
| JP (2) | JPS5390496A (en) |
| AT (2) | AT370390B (en) |
| BE (2) | BE863030A (en) |
| CA (2) | CA1121530A (en) |
| DE (2) | DE2802243A1 (en) |
| DK (2) | DK25578A (en) |
| ES (2) | ES466111A1 (en) |
| FI (2) | FI62524C (en) |
| FR (1) | FR2377982A1 (en) |
| GB (2) | GB1590051A (en) |
| IE (2) | IE46373B1 (en) |
| IT (2) | IT1093251B (en) |
| LU (2) | LU78889A1 (en) |
| MX (1) | MX147370A (en) |
| NL (2) | NL7800593A (en) |
| NO (2) | NO150726C (en) |
| SE (2) | SE426052B (en) |
| TR (2) | TR19555A (en) |
| YU (1) | YU10178A (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3021030A (en) * | 1958-09-26 | 1962-02-13 | Automatic Canteen Co | Vending devices |
| US4241136A (en) * | 1979-03-05 | 1980-12-23 | Owens-Corning Fiberglas Corporation | Glass fiber size composition and process |
| JPS5669244A (en) * | 1979-11-07 | 1981-06-10 | Fuji Fiber Glass Kk | Composition for sizing fiber used in friction material |
| US4286999A (en) * | 1980-03-04 | 1981-09-01 | Raybestos-Manhattan, Inc. | Method of improving properties of ceramic fibers |
| US4358502A (en) * | 1981-12-14 | 1982-11-09 | Owens-Corning Fiberglas Corporation | Glass fiber mat for reinforcing polyamides |
| US4374177A (en) * | 1981-12-24 | 1983-02-15 | Ppg Industries, Inc. | Aqueous sizing composition for glass fibers and sized glass fibers for thermoplastic reinforcement |
| US4626289A (en) * | 1982-09-24 | 1986-12-02 | Ppg Industries, Inc. | Treated glass fibers and aqueous dispersion and nonwoven mat of glass fibers |
| US4473618A (en) * | 1983-05-13 | 1984-09-25 | Owens-Corning Fiberglas Corporation | Chrome-free sizing composition containing titanium acetyl acetonate for glass fiber gun roving |
| US4487797A (en) * | 1983-12-01 | 1984-12-11 | Ppg Industries, Inc. | Glass fibers to reinforce polymeric materials |
| WO1986001811A1 (en) * | 1984-09-24 | 1986-03-27 | Owens-Corning Fiberglas Corporation | Chrome-free sizing for glass fiber gun roving |
| US4855341A (en) * | 1985-03-21 | 1989-08-08 | Owens-Corning Fiberglas Corporation | High-strength magnesium aluminosilicate glass fibers having size coating of epoxy resin with methacryloxyalkyl and aminoalkyl silanes |
| US4637956A (en) * | 1985-03-29 | 1987-01-20 | Ppg Industries, Inc. | Sized glass fibers and reinforced polymers containing same |
| US4749614A (en) * | 1986-04-10 | 1988-06-07 | International Business Machines Corporation | Process for coating fibers, use thereof, and product |
| EP0304837B1 (en) * | 1987-08-28 | 1993-12-01 | Ppg Industries, Inc. | Chemically treated fibers and method of preparing and method of using to reinforce polymers |
| US4824877A (en) * | 1988-02-02 | 1989-04-25 | Dow Corning Corporation | High polymer content silicone emulsions |
| CA1339475C (en) * | 1988-07-05 | 1997-09-23 | Ppg Industries Ohio, Inc. | Chemical treatment for fibers and reinforcement for polymer matrices resulting in good solvent resistance |
| US5141802A (en) * | 1988-07-15 | 1992-08-25 | Ppg Industries, Inc. | Chemically treated shapes, fillers and reinforcement for polymer matrices |
| US4927869A (en) * | 1988-09-15 | 1990-05-22 | Ppg Industries, Inc. | Chemically treated glass fibers for reinforcing polymers |
| FR2638448B1 (en) * | 1988-10-27 | 1992-08-21 | Saint Gobain Isover | BINDER AND BONDING THEREOF FOR MINERAL FIBERS |
| GB8829405D0 (en) * | 1988-12-16 | 1989-02-01 | Cerestar Holding Bv | Process for the manufacture of mineral fibre compositions |
| US5085938A (en) * | 1989-11-29 | 1992-02-04 | Ppg Industries, Inc. | Chemically treated fibers and method of preparing and method of using to reinforce polymers |
| JPH09500661A (en) * | 1992-01-30 | 1997-01-21 | ピーピージー インダストリーズ インコーポレーテッド | Starch oil sizing composition and glass fibers treated with the composition |
| US5405895A (en) * | 1992-07-30 | 1995-04-11 | Industrial Technology Research Institute | Surface treating compositions and methods of preparation and use in treating long glass fibers |
| DE4233021A1 (en) * | 1992-10-01 | 1994-04-07 | Huels Chemische Werke Ag | Organosilane polycondensates |
| JP2734345B2 (en) * | 1993-08-24 | 1998-03-30 | 新神戸電機株式会社 | Method for producing glass fiber nonwoven fabric for laminate and method for producing laminate |
| FR2727972B1 (en) * | 1994-12-13 | 1997-01-31 | Vetrotex France Sa | SIZING COMPOSITION FOR GLASS WIRES, PROCESS USING THIS COMPOSITION AND RESULTING PRODUCTS |
| FR2772369B1 (en) * | 1997-12-17 | 2000-02-04 | Vetrotex France Sa | SIZING COMPOSITION FOR GLASS WIRES, PROCESS USING THIS COMPOSITION AND RESULTING PRODUCTS |
| DE19846099C2 (en) | 1998-10-07 | 2000-08-24 | Bayer Ag | Amine functional urea alkoxy silanes, a process for their preparation and their use |
| US6228281B1 (en) * | 1998-10-30 | 2001-05-08 | Owens Corning Fiberglas Technology | Sizing for glass fibers having low nonionic and cationic lubricant content |
| US6551707B1 (en) * | 1998-10-30 | 2003-04-22 | Owens Corning Fiberglas Technology, Inc. | Mixed lubricant sizing |
| JP4576692B2 (en) * | 2000-10-02 | 2010-11-10 | 日東紡績株式会社 | Glass fiber sizing agent, glass fiber bundle coated with the sizing agent, and phenol resin containing the glass fiber bundle |
| US6479454B1 (en) | 2000-10-05 | 2002-11-12 | Ecolab Inc. | Antimicrobial compositions and methods containing hydrogen peroxide and octyl amine oxide |
| US8062746B2 (en) * | 2003-03-10 | 2011-11-22 | Ppg Industries, Inc. | Resin compatible yarn binder and uses thereof |
| EP1747176A2 (en) * | 2004-05-17 | 2007-01-31 | PPG Industries Ohio, Inc. | Sizing compositions for glass fibers and sized fiber glass products |
| DE102004025767A1 (en) | 2004-05-26 | 2005-12-22 | Degussa Ag | Stable solutions of N-substituted aminopolysiloxanes, their preparation and use |
| US20080085388A1 (en) * | 2006-09-26 | 2008-04-10 | Intertape Polymer Corp. | Filament reinforced tapes useful as underwater pipe wrap |
| JP4887323B2 (en) * | 2007-05-22 | 2012-02-29 | 三洋化成工業株式会社 | Fiber sizing agent |
| DE202008015660U1 (en) | 2008-11-26 | 2009-03-12 | S.D.R. Biotec Verfahrenstechnik Gmbh | Aqueous textile sizing for the treatment of R, E, ECR and S glass fibers |
| DE102008059046B4 (en) | 2008-11-26 | 2013-08-22 | S.D.R. Biotec Verwaltungs GmbH | Aqueous textile sizing for the treatment of R, E, ECR and S glass fibers and their use |
| US20140290534A1 (en) * | 2013-03-14 | 2014-10-02 | Ppg Industries Ohio, Inc. | Sizing Compositions For Glass Fibers And Sized Fiber Glass Products |
| ES2763932T3 (en) | 2017-10-18 | 2020-06-01 | Evonik Operations Gmbh | A colorless composition containing 3- (N-vinylbenzyl-2-aminoethyl) aminopropyltrimethoxysilane and methanol, a procedure for its production and use |
| DE102018208691A1 (en) | 2018-01-31 | 2019-08-01 | Evonik Degussa Gmbh | Special composition of organofunctional alkoxysilanes and their use |
| EP3611236B1 (en) | 2018-08-17 | 2020-09-30 | Evonik Operations GmbH | An aqueous, storage-stable composition containing n-benzyl substituted n- (2-aminoethyl)-3-aminopropylsiloxane-hydrochlorides, method for their preparation and their use |
| EP3708569A1 (en) | 2019-03-11 | 2020-09-16 | Evonik Operations GmbH | A voc free aqueous and shelf-stable n-vinylbenzylaminalkyl-functional siloxanol and method for producing the same |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1080964B (en) * | 1954-12-08 | 1960-05-05 | Owens Corning Fiberglass Corp | Process for changing the surface properties of glass fibers, thin flexible glass films or the like. |
| US3097963A (en) * | 1959-03-30 | 1963-07-16 | Owens Corning Fiberglass Corp | Sized glass fibers and composition |
| US3252825A (en) * | 1959-09-14 | 1966-05-24 | Owens Corning Fiberglass Corp | Process of coating glass fibers with hydrolyzed condensation product of amino silane and copolymerizable monomer |
| US3207623A (en) * | 1960-07-25 | 1965-09-21 | Owens Corning Fiberglass Corp | Sized glass fiber |
| BE631196A (en) * | 1962-04-18 | |||
| US3252278A (en) * | 1962-08-22 | 1966-05-24 | Owens Corning Fiberglass Corp | Elastomeric-glass fiber products and process |
| US3284179A (en) * | 1963-01-02 | 1966-11-08 | Pittsburgh Plate Glass Co | Method of forming glass fibers |
| FR1391278A (en) | 1963-03-21 | 1965-03-05 | Pittsburgh Plate Glass Co | Glass fiber reinforced phenolic resins |
| NL302973A (en) * | 1963-03-21 | 1900-01-01 | ||
| FR2007727B1 (en) * | 1968-05-03 | 1973-03-16 | Ppg Industries Inc | |
| US3702276A (en) * | 1969-01-13 | 1972-11-07 | Owens Corning Fiberglass Corp | Method of making high impact strength glass fiber-plastic composites |
| US3819675A (en) * | 1969-05-15 | 1974-06-25 | Dow Corning | Cationic unsaturated amine-functional silane coupling agents |
| US3734763A (en) * | 1969-05-15 | 1973-05-22 | Dow Corning | Cationic unsaturated amine-functional silane coupling agents |
| CA939378A (en) | 1969-05-15 | 1974-01-01 | Edwin P. Plueddemann | Cationic unsaturated amine-functional silane coupling agents |
| US3775074A (en) * | 1970-11-02 | 1973-11-27 | Owens Corning Fiberglass Corp | Method and apparatus for processing glass and forming fibers therefrom |
| AU467618B2 (en) | 1971-06-01 | 1975-12-04 | Owens-Corning Fiberglas Corporation | Sizing composition for glass fibers |
| BE787378A (en) | 1971-08-10 | 1973-02-09 | Ppg Industries Inc | COMPATIBLE TWO-COMPONENT POLYESTER - EPOXY SIZING PRODUCTS, FOR FIBERGLASS |
| BE793680A (en) | 1972-01-07 | 1973-07-04 | Johns Manville | AQUEOUS COMPOSITION OF GLASS FIBER PRIMER CONTAINING UETHANE LATEX AS A FILM FORMER |
| US3746738A (en) * | 1972-03-28 | 1973-07-17 | Union Carbide Corp | Silicon containing polyazimides |
| DE2224729A1 (en) | 1972-05-20 | 1973-11-29 | Owens Corning Fiberglass Corp | METHOD AND DEVICE FOR PRODUCING AND COATING GLASS FIBERS |
| US3884886A (en) * | 1973-01-15 | 1975-05-20 | Dow Corning | Cationic unsaturated amine-functional silane coupling agents |
| US3946132A (en) * | 1973-01-26 | 1976-03-23 | Ppg Industries, Inc. | Tire cord containing glass fibers sized with a starch based size |
| US3944707A (en) * | 1973-04-02 | 1976-03-16 | Owens-Corning Fiberglas Corporation | Glass fibers coated with compositions containing complex organo silicon compounds |
| US3869308A (en) * | 1973-04-27 | 1975-03-04 | Ppg Industries Inc | Forming size for glass fibers and resulting product |
| US3870547A (en) | 1974-01-24 | 1975-03-11 | Owens Corning Fiberglass Corp | Starch coated fibers for embedding in resin matrix forming materials and composites so formed |
| US4014726A (en) * | 1974-03-18 | 1977-03-29 | Owens-Corning Fiberglas Corporation | Production of glass fiber products |
| US3946131A (en) * | 1974-05-06 | 1976-03-23 | Owens-Corning Fiberglas Corporation | Glass fibers coated with silicon containing aminimide compounds |
| US4039716A (en) * | 1974-09-20 | 1977-08-02 | Owens-Corning Fiberglas Corporation | Resin coated glass fibers and method of producing same through use of an aqueous silane-containing sizing composition whereby hydrolysis and polymerization of the silane is inhibited |
| GB1522148A (en) * | 1974-10-03 | 1978-08-23 | Owens Corning Fiberglass Corp | Glass fibres coated with a size which provides forming and bonding properties |
| US3936285A (en) * | 1974-10-07 | 1976-02-03 | Ppg Industries, Inc. | Glass fiber sizing method |
| US4056651A (en) * | 1975-03-18 | 1977-11-01 | United Technologies Corporation | Moisture and heat resistant coating for glass fibers |
| US3997306A (en) * | 1975-03-31 | 1976-12-14 | Ppg Industries, Inc. | Glass fiber sizing composition for the reinforcement of resin matrices and method of using same |
-
1977
- 1977-01-19 FR FR7701386A patent/FR2377982A1/en active Granted
-
1978
- 1978-01-11 GB GB1066/78A patent/GB1590051A/en not_active Expired
- 1978-01-11 GB GB1065/78A patent/GB1597991A/en not_active Expired
- 1978-01-16 FI FI780128A patent/FI62524C/en not_active IP Right Cessation
- 1978-01-16 MX MX172061A patent/MX147370A/en unknown
- 1978-01-16 FI FI780127A patent/FI62523C/en not_active IP Right Cessation
- 1978-01-17 TR TR19555A patent/TR19555A/en unknown
- 1978-01-17 TR TR19715A patent/TR19715A/en unknown
- 1978-01-17 SE SE7800559A patent/SE426052B/en not_active IP Right Cessation
- 1978-01-17 YU YU00101/78A patent/YU10178A/en unknown
- 1978-01-17 SE SE7800558A patent/SE426051B/en not_active IP Right Cessation
- 1978-01-18 IE IE117/78A patent/IE46373B1/en unknown
- 1978-01-18 DK DK25578A patent/DK25578A/en not_active Application Discontinuation
- 1978-01-18 NO NO780182A patent/NO150726C/en unknown
- 1978-01-18 US US05/870,508 patent/US4246145A/en not_active Expired - Lifetime
- 1978-01-18 NL NL7800593A patent/NL7800593A/en not_active Application Discontinuation
- 1978-01-18 NL NL7800594A patent/NL7800594A/en not_active Application Discontinuation
- 1978-01-18 ES ES466111A patent/ES466111A1/en not_active Expired
- 1978-01-18 DK DK25678A patent/DK25678A/en not_active Application Discontinuation
- 1978-01-18 US US05/870,507 patent/US4244844A/en not_active Expired - Lifetime
- 1978-01-18 LU LU78889A patent/LU78889A1/en unknown
- 1978-01-18 LU LU78890A patent/LU78890A1/en unknown
- 1978-01-18 BE BE184413A patent/BE863030A/en not_active IP Right Cessation
- 1978-01-18 ES ES466110A patent/ES466110A1/en not_active Expired
- 1978-01-18 NO NO780181A patent/NO150008C/en unknown
- 1978-01-18 BE BE184412A patent/BE863029A/en not_active IP Right Cessation
- 1978-01-18 IE IE116/78A patent/IE46309B1/en unknown
- 1978-01-19 IT IT789428A patent/IT1093251B/en active
- 1978-01-19 AT AT0040378A patent/AT370390B/en not_active IP Right Cessation
- 1978-01-19 DE DE19782802243 patent/DE2802243A1/en active Granted
- 1978-01-19 CA CA000295264A patent/CA1121530A/en not_active Expired
- 1978-01-19 DE DE19782802242 patent/DE2802242A1/en active Granted
- 1978-01-19 IT IT9429/78A patent/IT1093252B/en active
- 1978-01-19 JP JP378078A patent/JPS5390496A/en active Granted
- 1978-01-19 AT AT0040278A patent/AT370389B/en not_active IP Right Cessation
- 1978-01-19 CA CA295,290A patent/CA1124926A/en not_active Expired
- 1978-01-19 JP JP377978A patent/JPS5394696A/en active Granted
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