Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
  • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences

Definitions

• An emulsion suitable, when diluted, for the hydrophobing of fibrous materials is produced by emulsifying a liquefied water-insoluble wax, fat or silicones with a salt mixture expressed as oxides in aqueous solution and consisting of salts of titanium and zirconium with a monocarboxylic acid with 1 to 4 carbon atoms in a weight ratio when expressed as titanium oxide and zirconium oxide as ranging between 1:0.6 to 1:3, the weight ratio between emulsified substances and metal salts calculated as oxides being between about 120.1 and about 1:03.
• This invention relates to a process of manufacturing concentrated aqueous emulsions and to emulsions which are produced by such process and which are particularly suitable, when diluted, for the hydrophobing of fibrous materials.
• German Patent No. 908,052 describes a process of emulsifying paraffin hydrocarbons, waxes or fats with aqueous solutions of basic aluminum salts, whereby the fats either have an acid value or must be mixed to the extent of about 10% by weight with fatty or waxy acids.
• These emulsions serve essentially for making textiles and other fibrous materials water-repellent. However, they do not resist washing.
• German Patent No. 749,740 describes the use of salts of fourvalent metals, such as zirconium, to produce emulsions which have substantially better wash-resistant hydrophobic effects. It was also suggested to use salts of other fourvalent metals, such as titanium, but such use did not materialize in actual practice, since they have drawbacks which will be set forth hereinafter.
• German specification No. 1,052,943 discloses emulsification of silicons in the same manner with the addition of about 10 to by weight of higher fatty acids, with concentrated aqueous solutions of basic salts of aluminum and/or zirconium, and the use of the emulsions for waterrepellent impregnation.
• wash-resistance is very poor; it is only slightly improved when mixtures of zirconium and aluminum salts are used. Wash resistance is much better when basic zirconium salts are used. Practical experimentation has shown that particularly good water-repellent and wash-resistant effects are produced by emulsions obtained from basic titanium salts. They have various drawbacks, however.
• An object of the present invention is to eliminate these drawbacks of prior art processes and emulsions.
• Another object is to produce with the use of specific mixtures of titanium and zirconium salts, emulsions which when applied to fabrics will impart to them excellent wash resistance (at least as good as that produced with titanium salt alone) and which at the same time can be combined with metal salt catalysts.
• the present invention is based in part on the surprising discovery that emulsions can be produced, the effects of which will be as good as those obtained with titanium salts alone, and which will not have the above-mentioned drawbacks, when aqueous solutions of salts of titanium and zirconium with monocarboxylic acids with 1-4 carbon atoms in a ratio by weight of 1 titanium oxide to 0.6-3.0 zirconium oxide are used for emulsifying water insoluble substances, such as waxes, paraflin, fats or silicones.
• Acetic acid is the preferred choice among salt-forming monocarboxylic acids with 1 to 4 carbon atoms, while the preferred Weight ratio of titanium oxide to zirconium oxide is 1:13.
• the two salts can be dissolved in water separately or as a mixture.
• the aqueous solution can be buffered to a pH value of about 4.5 by the addi tion of alkali salts or ammonium salts of weak acids, such as those of acetates, carbonates or bicarbonates, or it can be converted into a solution of a mixture of basic salts. It can be also produced by dissolving the alcoholates of titanium and zirconium with low monovalent alcohols in water and the addition of an under-stoichiometric amount of the low monocarboxylic acid, especially acetic acid.
• the emulsions of the present invention are produced in their concentrated condition, i.e. they contain about 25 percent by weight, or more, of nonaqueous substances and when used technically they are diluted with several times their quantities of water.
• the weight ratio between emulsified substances and metal salts (calculated as oxides) lies between about 110.1 and about 110.3, particularly at 110.2.
• the emulsions of the different substances can be also produced without the use of 120% aliphatic monocarboxylic acid with at least 12 C-atoms. In all instances it is possible to additionally emulsify organic solvents.
• the emulsions of the present invention are used for making textiles and other fibrous materials waterrepellent, their advantages are that they produce very good results and that the treated materials have excellent stability against chemical cleaning and washing with soap. The results are better than those produced by emulsions made solely with zirconium salts. As compared to emulsions made solely from titanium salts, they have the advantage that they produce stable treating baths with salts of two-valent metals, which are used as hardening agents for synthetic resin precondensates. With reference to silicone emulsions there is the additional advantage that very good results are produced even when an organopolysiloxane is emulsified which does not have a splittable hydrogen atom.
• organopolysiloxanes When organopolysiloxanes are emulsified in accordance with the process of the present invention, they can be indicated by the general formula wherein R or R are hydrogen, an alkyl, aryl, cycloalkyl, or acyl residue, x+y is a number between 1.5 and 3 and n is a number higher than 1.
• EXAMPLE 1 80 kg. technical zirconium tetraacetate (35-37% ZrO are dissolved in 550 1. water and 80 kg. titanium tetraacetate (26% TiO are added while stirring to the solution. A warm solution of 6070 C. is thus produced. 20 kg. lignite wax acid (acid number 135; melting point 80 C.) molten in 170 kg. paraflin (M.P. 5055) are slowly added in a turbornixer to the solution. After adding 260 1. water the resulting product is circulated through a homogenizing machine and is cooled while the stirring is continued. A very fine-particled liquid emulsion is produced which keeps very well in storage.
• a hath made from this emulsion produces upon textiles the same excellent water-repellent effects as an emulsion made only with titanium tetraacetate, but contrary to the latter, it remains completely stable with salts of two-valent metals which are used as hardening catalysts jointly with heat-hardening synthetic resin precondensates.
• EXAMPLE 2 50 kg. titanium tetraacetate are dissolved along with 30 kg. zirconium tetraacetate in 250 1. water. After heating to 6070 C. another solution is added in a turbomixer which has also been brought to 60 C. and which consists of 84 kg. parafiin (M.P. 50-55 3.5 technical stearic acid (A.N. 206, M.P. 65) and 7.5 kg. lignite Wax acid (A.N. 90, M.P. 80) in 101. benzene (boiling point about 120 to 140 C.). After adding 60 1. water the resulting product is advantageously additionally homogenized.
• a turbomixer which has also been brought to 60 C. and which consists of 84 kg. parafiin (M.P. 50-55 3.5 technical stearic acid (A.N. 206, M.P. 65) and 7.5 kg. lignite Wax acid (A.N. 90, M.P. 80) in 101.
• the emulsion consists of very fine particles and can be diluted with water in any proportion. When diluted it is compatible in an excellent manner with synthetic resin precondensates and their metal salt catalysts and when used by itself or in combination with synthetic resins it produces better hydrophobic effects than a corresponding emulsion made with zirconium salt.
• EXAMPLE 3 60 kg. zirconium tetraacetate are dissolved in 400 1. water and 25 kg. ammonium acetate are added. Immediately thereafter 30 kg. titanium tetraacetate are dissolved therein, the solution is heated to 60-70 C. and a liquefied mixture of 170 kg. paraffin (M.P. 60 C.) and 30 kg. lignite wax acid (A.N. 135, M.P. 80) is introduced with forceful stirring. After adding 300 1. water the emulsion is homogenized and stirred until cool. Instead of the acetates equivalent amounts of formiates may be used. The emulsions thus produced have properties similar to those set forth in the preceding examples.
• EXAMPLE 4 55 kg. zirconium tetraacetate, 27 kg. ammonium bicarbonate and 50 kg. titanium tetraacetate are dissolved in 388 1. water at 60 C. A solution is stirred into it with the use of a quick stirrer, consisting of 250 kg. dimethyl siloxane (viscosity 750 cst., SiO content and 25 kg. oleic acid mixed with 36 kg. perchloroethylene and 114 kg. toluene; the emulsion which is thus produced is diluted with 520 1. water and finally is homogenized in a high pressure machine.
• a quick stirrer consisting of 250 kg. dimethyl siloxane (viscosity 750 cst., SiO content and 25 kg. oleic acid mixed with 36 kg. perchloroethylene and 114 kg. toluene; the emulsion which is thus produced is diluted with 520 1. water and finally is homogenized in a high pressure machine.
• This emulsion consists of fine particles, keeps Well in storage and can be easily diluted with water.
• very good results are obtained, which can not be produced by an emulsion made solely from basic zirconium acetate.
• EXAMPLE 6 35 kg. zirconium tetraformiate (about 44% ZrO are dissolved in 270 1. water while heating to 60 to 70 C., then 27 kg. ammonium bicarbonate and finally 50 kg. technical titanium tetraformiate (about 40% TiO are dissolved; with the use of a centrifugal mixer 80 kg. of a methyl hydrosiloxane are stirred in, which is blocked endwise by phenyl-diethylsiloxy groups, with a viscosity of 100 cst. at 25 C., and which is mixed with 10 kg. molten stearic acid; the preemulsion which is thus produced is diluted with 80 1. Warm water and finally homogenized. This emulsion is also stable and when diluted produces good water repellent effects which withstand cleaning.
• EXAMPLE 7 37 kg. titanium tetraacetate (26% TiO 75 kg. zirconium tetraacetate (36% ZrO and 31 kg. ammonium acetate are dissolved in 500 l. warm water; a molten mixture is stirred in, consisting of 200 kg. of a liquid mixed polymer (viscosity 350 cst.) composed of diand trirncthylsiloxane units, and 20 kg. mineral wax (acidity 90).
• EXAMPLE 8 kg. of an aqueous zirconium acetate solution (26% zirconium oxide and 43% acetic acid) are mixed with 117 kg. of an aqueous titanium acetate solution (17% titanium dioxide and 45% acetic acid) and are diluted with a solution of 48 kg. urea and 5 kg. ammonium bicarbonate in 550 1. water.
• To this solution which is maintained at 60 C. are slowly stirred in by the use of a quick stirrer kg. paraffin (melting point 58 to 60) which have been heated to 80 to 90 C.
• the emulsion which is thus produced is diluted with 210 1. Warm water of 60 C. and is finally homogenized.
• This emulsion is very stable in concentrated as well as diluted state and produces better water-repellent effects upon a cotton fabric than an emulsion made only from a zirconium salt. Its compatibility with magnesium salts or similar salts of two-valent metals, which are used jointly with synthetic resin precondensates as hardening means, is very good.
• EXAMPLE 9 A very useful emulsion can be produced under the same conditions and with the same relative amounts as set forth in Example 4, but leaving out 25 kg. oleic acid. The properties of such emulsion are to a great extent the same as those of the emulsion which was made with the addition of oleic acid.
• a diluted emulsion produced by emulsifying a liquefied water-insoluble substance selected from the class consisting of waxes, solid to liquid natural and synthetic fats and silicones with an aqueous .solution of salts of titanium and zirconium mixed in a weight ratio when expressed as titanium oxide and zirconium oxide as ranging between 1:06 to 1:3 with a monocarboxylic acid with l to 4 carbon atoms, the weight ratio between the emulsified substance and metal salts calculated as oxides being substantially between 1:0.l and 1:0.3.
• a process of manufacturing concentrated aqueous acid-reacting emulsions which comprises emulsifying of a liquefied water-insoluble substance selected from the class consisting of waxes, solid to liquid natural and synthetic fats and silicones with a salt mixture expressed as oxides in aqueous solution, wherein said salt mixture consists of salts of titanium and zirconium with a monocarboxylic acid with 1 to 4 carbon atoms in a weight ratio when expressed as titanium oxide and zirconium oxide as ranging between 1:06 to 1:3, the weight ratio between the emulsified substance and metal salts calculated as oxides being substantially between 110.1 and 1:0.3.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Colloid Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=27209575

Family Applications (1)

Country Status (8)

Cited By (1)

Families Citing this family (1)

Citations (4)

Family Cites Families (1)

• 1965
  • 1965-01-16 DE DE19651719407 patent/DE1719407A1/de active Pending
  • 1965-05-07 DE DEC35781A patent/DE1285441B/de active Pending
  • 1965-10-29 DE DE19651469313 patent/DE1469313A1/de active Pending
  • 1965-12-14 CH CH1719765A patent/CH464233A/de unknown
  • 1965-12-28 US US517081A patent/US3466178A/en not_active Expired - Lifetime
  • 1965-12-29 SE SE16929/65A patent/SE304279B/xx unknown
• 1966
  • 1966-01-10 FR FR45376A patent/FR1463367A/fr not_active Expired
  • 1966-01-13 NL NL6600451A patent/NL6600451A/xx unknown
  • 1966-01-14 BE BE675117D patent/BE675117A/xx unknown
  • 1966-01-14 GB GB1925/66A patent/GB1139362A/en not_active Expired

Patent Citations (4)

Also Published As

Similar Documents