FI58905C - BELAGDA GLASFIBRER - Google Patents

Description

μ Γηί ADVERTISEMENT ςοοπς JUA ^ (11) UTLÄGGNINOSSKRIFT bo? Ub C Patent granted 11 05 lvOl (* 5) Patent rseddelat ^ ^ (51) Kv.ik.3 / int.a.3 C 03 C 25/02 FINLAND —FINLAND (21) fW «llwdt.mu * -Pu« nttnrfknin | 752765 (22) HtkamitpUvI - AniBknbipdtg 03-10.75 (23) Alkupllvt — GIMfhutadag 03-10-75 (41) Tullut | ulklsukil - Bllvlt offantllf OU.OU.76

Patent · and Raklstarihallit · NihUvtkilp ^ j. month | «iwWn date. -

Patent · och reglrteratyrelaen 'Antokin utl «| d och uti.tkriftm pubikend 30.01. Oh

(32) (33) (31) Requested utuolkuui — Bejird priorltet 03-10-7U

USA (US) 5115U7 (Tl) Owens-Coming Fiberglas Corporation, Fiberglas Tower, Toledo,

Ohio U3659, USA (US) (T2) Fred Gerhard Krautz, Newark, Ohio, USA (US) (TU) Oy Kolster Ab (5U) Coated Fiberglass - Belagda glasfibrer

Glass fibers used to reinforce thermoplastics and / or hard plastics are made by drawing glass melt streams until they solidify into filaments, grouping the filaments into a strand, and winding the strand into a package with a rotating mandrel. The fiberglass is easily scratched and broken after being pulled and bent over the guide surfaces. To avoid breaks, in the past the filaments have always been coated in the art immediately after solidification and before the fibers are drawn together into a strand with an aqueous solution of a film former and a lubricant. The lubricant provides lubrication in the wet state between the filaments and between the filament and the guide surfaces over which the filament is pulled. Until now, a combination of a cationic lubricant and a nonionic lubricant has usually been used because the cationic lubricant would not provide proper lubrication of the fiber: * after drying and the nonionic lubricant would not provide lubrication when the fiber is wet. In addition, the lubricants used have hitherto adversely affected the bond between the film-forming polymers and the glass fibers. In addition, lubricants have also adversely affected the bonding of the fiber to the base of the resin or plastic that the fiber is used to reinforce. Therefore, the lubricants used have hitherto been a necessary evil, and in known cases they have reduced or impaired the strength of the reinforced polymers produced. This has been established by preparing the strands with different amounts of lubricant and determining the strength of the laminates obtained; The decrease in strength of the resulting laminate has usually been greater than can be explained by the broken filaments in the Delkäs.

The present invention relates to glass fibers having a coating on their surface comprising a residue obtained from an aqueous composition consisting mainly of an epoxy film former, a silane coupling agent and a cationic lubricant, characterized in that the cationic lubricant is a reaction product of a fatty acid and a secondary amine. , each having at least one OH group, and that the reaction product has a straight chain portion having an ester group on one side of the nitrogen-containing group and two side chains on the other side, each side chain containing at least one OH group.

The new and improved adhesive used in the glass fibers according to the invention contains a substance which not only protects and lubricates the fibers in the wet state, but also protects the fibers in the dried state without reducing or deteriorating the strength of the reinforced polymers obtained with this adhesive, and which substance hopefully increases the strength of the obtained, reinforced, polymeric materials.

Thermoplastic polymers or thermoplastics are the most difficult to reinforce due to their lack of chemical function, and therefore the glass fibers of the invention use a lubricant comprising a thermoplastic polymer and a lubricant that properly lubricates the glass fibers in their wet and dried condition.

The invention is illustrated by the following examples.

Example 1

An adhesive was prepared using as starting materials, the following substances in the following amounts, expressed by weight: 3,5905

Substances Pj i no-oki n FSE-1 epoxy emulsion (55% solids) 12.7

Wyandotte X1042 polyurethane latex (59% solids) 1, f)

Gamma-aminopropyltrimethoxysilane 1.4

Glass lubricant - reaction product of diethanolamine and stearic acid 1.0 Deionized water 83.9

The adhesive was prepared by adding gamma-aminopropyl triine-toxicilane to half of the water with stirring until hydrolysis, and the urethane latex was then added with stirring until the mixture was thoroughly mixed. The epoxy emulsion is then added and mixed thoroughly for 5 minutes. In the second mixing vessel, the glass lubricant is added to 30 parts by weight of water at 48.9 ° C and stirred until this is dissolved. This glass lubricant solution is then added to the masterbatch and mixed until a uniform dispersion is obtained, after which the rest of the water is added.

The above adhesive was applied to type 816 E glass fibers having a diameter of 0.00089 to 0.0152 mm during molding using a belt-type applicator, whereby the moistened filament is wound into a package at a speed of 1080 m / min and the package is dried for 24 hours in a heated oven 129 ° C. The fibers thus prepared have a coating comprising about 0.5% by weight of the coated fiber. The coated strands are chopped to lengths of about 6.35 mm. Thirty parts of these coated, short fibers are then placed in a tumbler mixer along with 70 parts of nylon 66 having a melt index of 2.0 and a molecular weight of about 100,000. This mixture is then placed in a National Rubber type extruder with a 2.5 mm screw. which is electrically heated to 282 ° C, after which the mixture is compressed into cylindrical rods with a diameter of 3.18 mm, which are then fed to a Cumberland-type baller to obtain 6.35 mm long balls. These spheres, in turn, are fed into an injection molding machine heated to 288 ° C, and the material is injection molded into a specimen in accordance with ASTM D-633, which is in the shape of a corpuscle and which, when cooled to room temperature and tested in accordance with in a tensile strength test machine, broke, 2 when a force corresponding to 1760 kg / cm was applied to the test piece. The modulus of elasticity of the material was 1.2 x 10.

By way of comparison and thus not in accordance with the invention, the glass fibers were terminated with an adhesive previously known in the art having the following composition: * 58905

Substances Printing parts

Polyvinyl acetate (55% solids)

Gamma-aminopropyltrimethoxysilane 1, 4

Polyoxyethylene monooleate 1.0 The fibers coated with this material in Example 1 give the following. 2 using only the tensile strengths of 1410 kg / cm with the same fiber load as mentioned above. This polyvinyl acetate adhesive has been selected for comparison because polyvinyl acetate is known to have good wetting and binding properties on the surface of glass fibers and has long been an accepted standard material.

Example 2

The procedure of Example 1 was repeated using the adhesive of Example 1 except that no glass lubricant was used, and the fibers were prepared at a reduced speed of 610 m / min and with great care. The obtained specimen had a tensile strength 2 of only 1550 kg / cm and the filament did not have lubricating properties such that it could be used on a commercial scale.

Example 3

The procedure of Example 1 was repeated except that the amount of lubricant was reduced to 0.5 parts by weight. The obtained test piece 2 had a breaking strength of 1720 kg / cm.

Example 4

The procedure of Example 1 was repeated except that the polyurethane emulsion was omitted. The breaking strength of the test piece thus prepared was substantially the same as that of the test piece of Example 1.

Example 5

The procedure of Example 1 was repeated except that the amount of glass lubricant was added to 2%. The tensile strength of the test piece 2 thus obtained was 1720 kg / cm.

Example 6

The procedure of Example 1 was repeated except that n-beta- (aminoethyl) gamma-aminopropyltrimethoxysilane was used as the binder instead of gamma-aminopropyltrimethoxysilane.

2 The tensile strength of the test piece thus obtained was about 1760 kg / cm.

5 58905

Example 7

The procedure of Example 1 was repeated except that an adhesive having the following composition was used:

Substances Printing parts

Water-soluble epoxy resin of formula 2.0 FSE-1 epoxy emulsion (55% solids) 13.0

Gamma-aminopropyltrimethoxysilane, glass binder 1.0

Deionized water 90.0

The water-soluble epoxy resin had the following formula:

HO-CH2-CH2? H Γ CH3? H

HO-CH-CH> -CH2-CH-CH2 + - ° - <X ^ O-CH2-CH-CH2-22 L CH3. J n «CH- OH _ 0 oin -O-Q> - ^ - O-CH2-CH-CH2 --- O-CH2-CH2 --- O-C- (CH2) 7-CH = CH- (CH 2) 7 CH 3

ch3 L J X

The adhesive was prepared by adding half the water-soluble epoxy resin with a sufficient amount of acetic acid to dissolve the substance. The glass binder was added and mixed thoroughly. The epoxy emulsion was then added and mixed thoroughly for 5 minutes. In another mixing vessel, the glass lubricant was added to 30 parts by weight of water at 48.9 ° C and stirred until dissolved. The glass lubricant solution was then added to the main mixture and stirred until a uniform dispersion was obtained, after which the rest of the water was added.

The above adhesive was applied to the glass fibers using the method of Example 1 except that the fibers were prepared at 610 m / min and dried for 2H hours in a heated oven at 129 ° C. The fibers thus prepared had a coating comprising about 1.0% by weight of the coated fiber. The coated fiber was chopped to lengths of about 3.18 mm. These fibers gave when. they were tested as described in Example 1, on a test piece, 1 · / 2 with a breaking strength of 1760 kg / cm in the base weight of nylon 66.

6 58905

For comparison and thus not in accordance with the invention, the above-described method was repeated except that the glass lubricant was omitted, and the test piece thus prepared had a breaking strength of about 1480 kg / 2 cm.

Example 8

The procedure of Example 7 was repeated except that the glass binder was omitted, and the test piece thus prepared had a breaking strength of about 1410 kg / cm 2.

Example 9

The procedure of Example 7 was repeated except that the base mass used in the manufacture of the canine-shaped specimens was, instead of nylon 66, nylon 612 having a molecular weight. ? the weight was 150,000. The tensile strength of these specimens was 1900 kg / cm.

Example 10

The procedure of Example 1 was repeated except that polycarbonate having a Molecular Weight of 150,000 and a Melt Index of 2 was used instead of the base mass of nylon 66. In addition, the operating temperature of the extruder was 299 ° C and the working temperature of the injection molding machine was 304 ° C. The amount of chopped glass fibers used was only 20% of the polycarbonate-glass fiber mixture, and the breaking strength of the test piece 2 was measured to be 1200 kg / cm. By way of comparison and thus not in accordance with the invention, the refractive index of test pieces prepared in the same manner except that the glass fibers contained the previously known polyvinyl acetate adhesive is only 984 kg / cm.

Example 11

The procedure of Example 1 is repeated except that nylon 66 was replaced by a polybutylene glycol-terephthalate polyester having a molecular weight of 180,000 and a melt index of 3 and prepared by reacting 1 mole of polybutylene glycol with 1 mole of terephthalate.

with formic acid, and an extrusion temperature of 249 ° C is used

and a molding temperature of 254 ° C. The tensile strength 2 of the test piece thus prepared was 1340 kg / cm, while the tensile strength of the same material reinforced with the previously known polyvinyl acetate adhesive-treated glass fibers 2 was only 914 kg / cm.

7 58905

Example 12 99.5 parts of the nylon 66 used according to Example 1 are mixed with 0.5 part of the reaction product of diethanolamine and stearic acid from the mold as a release agent. Dog bone shaped specimens are prepared using the method described in Example 1, and these specimens are easily removed from the mold and have as good or slightly better breaking strength than specimens made of nylon 66 alone. It is apparent that any by-product of a fatty acid and a secondary amine having two organic side chains, each having a carbon to oxygen ratio of up to 4: 1 and each having at least one OH group, acts as a mold release agent for thermoplastic polymers, and when used as such, they are effective in amounts of 0.1% -2% by molding weight.

Example 13

The procedure of Example 1 was repeated except that a polyester emulsion was used instead of the epoxy film formers of Example 7. The polyester was prepared by reacting 1 mole of ortho-phthalic acid and 1 mole of succinic acid and 2.4 moles of propylene glycol until the acid number was 30-35. An emulsion was prepared from the following substances in amounts by weight:

Substances Weight%

The polyester 47.5 described above

Xylene 5.3

Diacetone alcohol 10.6

Wyandotte Chem. C/o. Pluronic L101 2.6

Wyandotte Chem. C/o. Pluronic P105 7.8

Water 26.8

An emulsion was prepared by diluting the polyester with xylene. The pluronic substances were dissolved in diacetone alcohol and the solution was added to the polyester solution. Water was then added with slow stirring until the inversion point was reached. The rest of the water was then added and mixed thoroughly. The polyester emulsion thus obtained, when used instead of epoxies, gave essentially the same results as the substances of Example 7.

8 58905

Example 14

The procedure of Example 1 is repeated except that 1.25% of the reaction product of butylethyl, 2,2'-dihydroxyamine and oleic acid replaced the lubricant of Example 1, wherein the test piece has substantially the same properties.

Example 15

The procedure of Example 14 is repeated except that the lubricant is the reaction product of butylethyl, 3,2'-dihydroxyamine and geranium, and the test piece has substantially the same breaking strength as in Example 1.

Example 16

The procedure of Example 1 is repeated except that the lubricant is the reaction product of dibutylethyl-2,2 ', 2 "-trihydroxyamine and palmitic acid, and the test piece has substantially the same breaking strength as the test piece of Example 1.

Example 17

The procedure of Example 1 is repeated except that the lubricant is the reaction product of di-2-hydrindindyl-1,1'-dihydroxyamine and stearin-day, and the test piece has substantially the same properties as the test piece of Example 1.

, Example 18

The procedure of Example 1 is repeated except that the lubricant is the reaction product of dipropyl-3,3'-diallyloxy-2,2'-dihydroxyamine and stearic acid, and the test piece has substantially the same properties as the test piece of Example 1.

Example 19

The procedure of Example 1 is repeated except that the lubricant is the reaction product of diisopropanolamine and stearic acid, and the test piece has substantially the same properties as the test piece of Example 1.

Example 20

The procedure of Example 1 is repeated except that the lubricant is the ethylene oxide addition product of the lubricant of Example 1. This adduct has an average of 4 ethylene oxide groups per molecule in the hydroxyl-containing side chains of the amine, which 58905 amine is reacted with stearic acid. The test pieces thus obtained have essentially the same properties as the test pieces according to Example 1.

From the above information, it is apparent that there is an interaction between the lubricants and film formers used in accordance with the present invention that provides improved lubrication and protection during the wet and dry stages of filament fabrication and handling, while providing improved bonding effect to coated glass fibers and base polymer. between which the fibers are reinforced. It is found that the lubricant is a reaction product of a fatty acid and a secondary amine, the secondary amine having two side chains each having at least one OH group. The amine nitrogen and OH groups produce a strong hydrophilic radical capable of dissolving the fatty acid. These soluble side chains may comprise hydrocarbon fractions, provided that they also comprise at least one oxygen atom relative to an oxygen atom for each group of 4 carbon atoms.

Thus, the improved lubricating portion of the adhesive compositions of the invention comprises a molecule having a single fatty acid chain that forms an ester with an amine hydrogen. the other half forms two amine nitrogen side chain, each of which has an OH function. It is known that glass fibers, when wetted with water, retain a layer of water on the surface of the glass, which tends to be rich in OH groups. The lubricant of the invention differs from most lubricants previously known in the art in that the lubricant is linear in nature with OH groups on one side of the amine nitrogen and with a fatty acid radical moiety on the opposite side of the amine nitrogen. Nitrogen becomes cationic in the adhesive mixture and is attracted by the surface of the glass, causing the OH-containing chains to protrude into the aqueous layer on the surface of the glass fibers and the fatty acid radicals extending substantially perpendicularly tightly trapped against them. In most previously known adhesive compositions, cationic lubricants, especially if they are not linear, may be uniformly on the glass to prevent other molecules from binding to the glass surface. In the adhesive composition of the invention, the lubricants are believed to form a coating, with the fatty acid portions of the molecules extending parallel to each other from the glass surface to provide a substantial coating thickness on the glass surface with the molecular lubricant components facing outward. The fibers are therefore completely separated by coatings with a substantially lubricating surface. Even after the fibers have dried, it becomes apparent that at least some of the cationic lubricant remains to lubricate the surface of the glass.

However, when the coated fibers are embedded in a plastic or resin base mass, including a thermoplastic base mass, the lubricant molecules are removed from the glass and disperse between the polymer chains. Since the lubricant used according to the invention has two side chains, each of which has at least one OH group, these side chains are able to provide a hydrogen bond to the polar components in the polymer base mass. Because there are two OH groups, one on each side chain, one side chain is capable of binding to another polymer molecule, while the other side chain is capable of hydrogen bonding to an adjacent polymer molecule. This function is believed to be responsible for the increase in strength it imparts to the polymer base mass. Because the lubricant molecules are predominantly linear, the fatty acid radical moiety or lubricating moiety is able to settle between the polymer chains to act as a harmless plasticizer, which in some cases can reduce the brittleness of the polymer base mass.

As noted above, side chains containing OH groups can be of considerable length provided that they contain at least one oxygen atom for each group of four carbon atoms. Since this oxygen atom is also capable of hydrogen bonding and is also able to affect water solubility, additional oxygen atoms replace the hydrophobic nature of carbon atoms. In this regard, reversible ethylene oxide groups are a preferred chain extender, and it is believed that a small increase in flexibility is achieved as the length of the hydrophilic side chains increases.

The lubricants used in accordance with the present invention can thus be characterized as esters formed, for example, by the reaction of a fatty acid with a secondary amine having two hydrophilic side chains, each containing at least one OH group. These side chains are hydrophilic if they contain at least one oxygen atom for each group of 4 carbon atoms. According to one embodiment of such substances, the length of the hydrophilic side chains can be increased by reacting the alcohol radicals with ethylene oxide, as is known. Because lubricant molecules have a tendency to associate with polymers, it is believed that the lubricant molecules move away from the glass surface and disperse through the deposited polymers during molding, thus allowing the polymer to enter the surface of the glass materials therein. Thus, it can be seen that the lubricants of the invention in a way make a "convex gig" from the position and action they perform in the wet state of the fibers, to the position and action they perform when they are bonded to the polymer base mass. It is very unusual that a lubricant can actually increase the strength of the bond between the polymer base mass and the glass fibers, and the lubricants used according to the invention are able to achieve this result with any base mass, whether based on thermoplastic or hard plastic. In addition, higher strength is obtained whether or not a glass binder is used, but in preferred embodiments where the highest strength is desired, silane-type glass binders are used, and in particular cationic silanes having a nitrogen-containing organic group. The amount of silanes used is not critical, as the efficiency generally increases in proportion to the amount used until the amounts increase to about 5% of the adhesive.

Preferred adhesive compositions generally comprise the following materials, the amounts being expressed in parts by weight.

Substances Printing parts

Film-forming polymers 2-12

Silane type glass binder 0.1 to 5.0

Cationic lubricant as defined above 0.1 to 5.0

Water 78 -97.8

Preferred film formers for use in the adhesives of the invention are epoxy polymers, especially bisphenol type A, and polyurethanes. The remaining oxirane groups of the epoxy polymers can form a good bond with the OH groups of the lubricant and are catalyzed by the amine nitrogen. In addition, they have good glass wetting properties. In this regard, benzene rings of 12,590,905 of bisphenol A are preferred. Urethanes, if any isocyanate groups remain, are also able to react with the 0H groups of the lubricant, and are also cationic and have good glass wetting properties. As stated above, polyesters can be used because they contain polar oxygen either as ester groups or as acids or hydroxyl groups.

When using adhesive compositions to coat glass to reinforce nylon, the following compositions prove to be most preferred:

Substances Printing parts

Epoxy emulsion solids 5.0 to 12.0

Polyurethane latex solids 0-7.0

Silane type glass binder 0.1 to 5.0

The lubricant described above is 0.1 to 5.0

Water the rest

A particularly preferred mixture is as follows:

Substances Printing parts

Bisphenol A type epoxy polymer film former emulsified particles 7.00

Polyurethane film former 0.50

Gamma-aminopropyltrialkoxysilane 1.40

Cationic lubricant 0.50

Although the invention has been described in a remarkably simple manner, it is not intended to be limited to the specific embodiments shown and described herein, but to encompass all novel applications and modifications thereof which fall within the scope of one skilled in the art to which the invention pertains.

Claims (9)

13 58905 Glass fibers having a coating on their surface comprising a residue obtained from an aqueous composition consisting essentially of an epoxy film former, a silane coupling agent and a cationic lubricant, characterized in that the cationic lubricant is a reaction product of a fatty acid and a secondary amine having two is at least one OH group, and that the reaction product has a straight-chain moiety in which the nitrogen-containing group has an ester group on one side and two side chains on the other side, each side chain containing at least one OH group. Glass fibers according to Claim 1, characterized in that the secondary amine is a dialkanolamine. Glass fibers according to Claim 1, characterized in that the secondary amine is an ethylene oxide addition compound of diethanolamine. Glass fibers according to claim 1, characterized in that the cationic lubricant is present in the aqueous composition in an amount of about 0.1 to 5 parts by weight. Glass fibers according to Claim 1, characterized in that the cationic lubricant is the reaction product of butylethyl 2,2-dihydroxyamine and oleic acid. Glass fibers according to Claim 1, characterized in that the cationic lubricant is the reaction product of butylethyl-3,2-dihydroxyamine and polaronic acid. Glass fibers according to Claim 1, characterized in that the cationic lubricant is a reaction product of dibutylethyl-2,2-2-trihydroxyamine and palmitic acid. Glass fibers according to Claim 1, characterized in that the cationic lubricant is the reaction product of di-2-hydrindyl-1,1-dihydroxyamine and stearic acid. Glass fibers according to Claim 1, characterized in that the cationic lubricant is the reaction product of dipropyl-3,3-diallyloxy-2,2-dihydroxyamine and stearic acid.