CS255390B1 - Polyurethane lubrication for sloping fibers - Google Patents

Abstract

The aqueous compositions contain 0.5 to 5% by weight of the dry matter of the polyurethane emulsion, 0.02 to 1% by weight of aromatic disilanes based on the reaction products of epoxy resin with aminosilane and 0.02 to 1% by weight of acetic or formic acid. Optionally, by adding known aminosilanes, lubricants, wetting agents and antistatic agents, the textile properties of the fibers can be regulated as needed.

Description

The invention relates to polyurethane lubricants for the treatment of glass fibers.

Polyurethane. The emulsions have found wide industrial application for the production of lubricating compositions for the treatment of glass fibers used as reinforcement of plastics, rubbers in the building industry. In particular, the application of such treated fibers is as reinforcement of polyamides (German Patents Nos. 1,922,441, 2,300,368,

No. 426,654, 2,426,657), thermoplastic polyesters (NSR Pat. No. 2,426,656) and polycarbonates (NSR Pat. No. 2,426,655). Various organosilicon compounds are used as binding agents, mainly aminosilanes such as 3-amino-propyltriethoxysilane and epoxysilanes such as 3-glycidoxypropyltrimethoxysilane. As lubricants or wetting agents, various surfactants based on oxyalkylene derivatives, such as oxyethylated fatty acids, alcohols, alkyl phenols and the like, are used. Improvement. properties can be achieved by the addition of epoxy resins, mainly based on bispheinols, either in the form of emulsions or reaction products based thereon (U.S. Pat.

814 592, British Pat. no. 1,522,148). In the case of epoxy resin emulsions, these are hardened as a plasticizer of the polyurethane emulsions unless lubricated in the lubricant. For these reasons, until the epoxy resin is crosslinked, the fibers are so treated separately to produce fabrics and rovings. The toxicity of epoxy resins, especially in contact with the skin, is known and it is difficult to avoid in contact with the skin during handling and use of the lubricant. Brief contact with the skin is usually not harmful, but with frequent personalization, sensitive individuals develop acute eczema at the direct treatment sites. These contact dermatoses often then cause allergic hypersensitivity in individuals, which means that workers must be transferred to another workplace or not come into direct contact with ingredients that have caused them to develop eczema. These problems can be overcome by using epoxy resin-based reaction products by reacting epoxide groups that carry toxic effects. Although it is possible to prepare solid epoxy-based products, these have a thermoplastic character.

These problems can be effectively solved using the lubrication according to the invention.

The present invention provides polyurethane glass fiber lubricants based on 0.5 to 5% by weight of the dry weight of a polyurethane emulsion, 0.02 to 1% by weight of the aromatic disilanes of formula I

OH

I

M [CH 2 CHCH 2 NH 1 (C H 2 Cl 2. NH) x (CH 2) 3 Si (OR 1) 3] 2 (Π where x is an integer O 1, R 1 is methyl or ethyl, M is a structure residue

-θ- <Ο

CHI 3

C 1

CH,

ABOUT-·

n 0 to 1, 0.02 to 1% by weight of formic or acetic acid and the remainder to 100% by weight of water. The improvement of the mechanical properties, in particular of the fiber-reinforced polyamides treated by the inventive lubrication, can be achieved by the addition of aminosilanes of the formula II

NH ₂ (CH ₂ CH ₂ NH) _y (CH 2) 3 Si (OR 2) 3 (II) wherein y is an integer of 0 or 1, R 2 is methyl or ethyl in an amount of 0.02 to 0.6% by weight. If desired to adapt the fiber processing technology and the reinforced plastic production technology, it is possible to control the lubricating and fiber properties by adding 0.05 to 2% by weight of at least one of the group of lubricants, wetting agents, antistatic agents. Depending on the application of the fibers, their polarity can be varied as desired by adding 0.5 to 4.5% by weight of the dry weight of an emulsion of polymers based on vinyl and / or olefinic monomers such as vinyl acetate, styrene, ethylene, acrylic or methacrylic acid and their esters.

Aromatic disllanes based on epoxy resins significantly increase the stiffness and sharpness of the fibers, which is advantageous for their processing into chopped fibers, typically to a length of 3 to 12 mm. They form stable solutions under acidic conditions using formic acid. They are obtainable by reacting a diane-based epoxy resin with an aminosilane such as 3-aminopropyltriethoxysilane or 3- (2-aminoethyl) aminopropyltrimethoxysilane. For the crosslinking of these products, hardeners are not required as in the case of epoxy resins, but only water which is contained in the lubrication.

The invention is further illustrated by way of examples.

Example 1

200 g of acetic acid and 30 l of water are added to the stirrer boilers. 60 g of 3-aminopropyltriethoxysinate and 140 g of aromatic disilane of the general formula ## STR2 ## where x is 0, R1 ethyl, having an average molecular weight of 822, are added with stirring. After dissolution, 200 g of a lubricant composed of 15.9% by weight of aminoamides of oleic acid and diethylenetriamine, 3.7% by weight of oleic acid, 4.4% by weight of acetic acid, 6.0% by weight of oxyethylated coconut oil fatty acids with 10 moles of ethylene oxide and 70% by weight of water. The composition is diluted with water to a volume of 60, 6 kg of polyurethane emulsion (33% dry weight) is added and made up to a volume of 100 L with water. m ^_1 . The fibers treated with this lubrication are suitable for the production of roving coils used as reinforcement for thermoplastics, especially polyamide.

Example 2

The lubrication was prepared as in Tab Lubrication according to Example 1 bulk density (kg.m ^-3 j 0.29

Example 5

To 1 L of water was added 15 g of acetic acid, 12.5 g of 3- (2-aminoethyl) amino-propyltrimethoxysilane and 12.5 g of the aromatic disilane of the above formula wherein x is 1, R 1 methyl, with an average molecular weight of 824. After mixing 750 g of polyurethane emulsion (33% dry weight) was added and the composition made up to a volume of 5 L with water. The prepared lubrication is suitable for treating chopped fibers using electrostatic neutralizer mowers.

Example 6

Lubricant composition as in Example 5, except that 20 g of Example 1 was added thereto, except that 200 g of aromatic disilane alone was used as the binding agent.

Example 3

The lubrication is prepared as in Example 1, except that 100 g of 3- (2-aminoethyl) amino-propyltrimethoxysin and 100 g of aromatic disilane of the above general formula wherein x is 1, R 1 methyl, of average molecular weight are used as the coupling agent. weight 824.

Example 4

For comparison, no lubrication was prepared as in Example 1, using a known binding agent, i. j. 200 g of 3-aminopropyltriethoxysilane. Lubrications according to Examples 1 to 4 were used to treat glass fibers, the strand of which consisted of 200 elementary strands having an average thickness of 15 microns. After drying the fibers at 125 ° C for 6 h, the effect of silanes on the properties of the fibers was evaluated by determining the bulk density after being chopped to a length of 6 min. The results obtained are shown in the table.

I k a

3 4

0.29 0.32 0.26 thousand of a coconut 3-bis (2-hydroxyethylamino) 2-hydroxypropyl ester of a coconut oil fatty acid.

Example 7

Lubricant composition as in Example 3, except that 3 kg of vinyl acetate-vinyl chloride copolymer emulsion was added thereto. The treatment has good textile properties and the fiber treated with this mixture can be processed); into various forms. The use of the aromatic dislants according to the invention, besides having a positive effect on the textile properties of the fibers, also makes it possible to actually reduce the costs of producing these compositions, since organosilicon compounds are the most cost-effective item.

SUBJECT

Claims (4)

SUBJECT Polyurethane lubricants for the treatment of glass fibers, characterized in that they consist of 0.5 to 5% by weight of dry matter OH BACKGROUND OF THE INVENTION 0.02 to 1% by weight of aromatic disilanes of general formula I M [CH 2 CHCH 2 NH (CH 2 CH 2 NH), (CH 2) 3 Si (OR 1) 3] 2 (I) wherein x is an integer of 0 or 1, R 1 is methyl or ethyl, M is 0 to 1, 0.02 to 1% formic acid or acetic acid and the remainder up to 100% by weight of water. 2. Polyurethane lubrication according to claim 1, characterized in that they contain amino silanes of the general formula II NH 2 (CH ₂ CH ₂ NH) _y (CH 2) 3 Si (OR 2) 3 (Π) wherein y is an integer of 0 or 1, R 2 is methyl or ethyl in an amount of 0.02 to 0.6% by weight. 3. Polyurethane lubricants according to items 1 and 2, characterized in that they contain from 0.05 to 2% by weight of at least one additive from the group of lubricants, wetting agents, antistatic agents. 4. Polyurethane lubricants according to claim 1, characterized in that they contain from 0.5 to 4.5% by weight of emulsion dry matter of polymers based on vinyl and / or olefinic monomers, such as vinyl acetate, styrene, ethylene, acrylic or methacrylic acid and their esters. Severography, n. p. zflvod 7, Mn »t Price 2,40 KCs