SK281609B6 - Separable agents and the method of preparation - Google Patents

Abstract

Separating agents produced in the form of aqueous dispersions by dispersing zinc salts of higher fatty acids, inorganic powders (e.g., kaolin, CaCO3, etc.), sodium salt of cellulose ether and glycolic acid or polyvinyl alcohol into water by subsequent hydration and homogenization at 40-70 ° C; which has previously dissolved surfactants (e.g., sodium alkyl sulfate, etc.) and emulsified a concentrated silicone emulsion at 20-80 ° C. After cooling the aqueous dispersions to a temperature of < 50 ° C, an antimicrobial additive (aqueous solution of a mixture of chloro and methyl derivatives of isothiazoline ketones or an emulsion of 2- (thiocyanomethylthio) benzothiazole) was added. Thus, e.g. A 20% aqueous dispersion of the zinc salt separator of higher fatty acids having an average particle size of 8.5 µm which, after dilution with water in a ratio of 1: 10, had a pH of 7.2, a specific conductivity of 1.4 mS.cm -1 and applied to sheets of rubber mixtures and exhibited sufficient separation efficiency. 2% aqueous dispersions prepared from powder formulations by homogenizing the materials in the discontinuous mixer after application to the sheets of rubber mixtures also exhibited sufficient separation efficiency.

Description

Technical field

The invention relates to release agents and a process for the manufacture of powder mixtures and concentrated permanent aqueous dispersions of release agents made on the basis of zinc salts of higher fatty acids, suitable after the addition of water in the form of low concentrated aqueous dispersions for surface treatment of sheets and strips of rubber mixtures or asphalt films.

BACKGROUND OF THE INVENTION

It has been known that in the rubber industry, powdered materials such as chalk, talc, kaolin, zinc stearate, liquid or solid soaps have been used as separating agents for many years in the rubber industry.

Due to the elimination of dustiness in the coating of rubber compositions, the use of a release agent in the form of a low-concentration aqueous dispersion continues to grow, especially in large modern rubber plants, where the rubber mixture is surface treated with the liquid release agent after mixing and before or during the cooling step.

The physico-chemical properties of the metal salts of higher fatty acids - mainly zinc, despite its strong hydrophobic property, predetermine it for surface treatment of vulcanized and unvulcanized rubber mixtures in the form of low-concentrated aqueous dispersions. Wetting of the zinc salt of higher fatty acids with water and the stability of its low and higher concentrated aqueous dispersions can be achieved by suitable selection and concentration of added excipients e.g. surfactants, emulsifiers, etc. By the physicochemical action of these excipients, it is possible to reduce the surface tension at the phase boundary of the dispersing agent and the dispersion medium, thereby achieving targeted steric molecular orientation and micelle formation.

A method for producing permanent aqueous dispersions of carboxylic salts is disclosed in JP 02 215 743 [90 215 743], according to which waterproofing agents for emulsion latexes, lubricants for paper coatings, thickening agents with carboxylic acids having carbon numbers of> 8 with NH ₃ have been prepared. Group II A or II B, Al or their oxides and hydroxides in 40-900 parts water per 100 parts carboxyl salts in the presence of dispersants and vigorous stirring at 100-200 ° C followed by cooling to <100 ° C.

The production of aqueous dispersions of metal salts of higher fatty acids is discussed in patent JP 02 191 531 [2 191 539 A] according to which an aqueous dispersion of superfine metal salts of higher fatty acids having a narrow particle size distribution was obtained by introducing higher fatty acids and metal hydroxide II of the periodic table. to a reaction in water in the presence of a surfactant at a temperature> 100 ° C, preferably 101-160 ° C under pressure with stirring.

A method for preventing the adhesion of unvulcanized rubber compositions is disclosed in JP 57 187 323 [82 187 323], which consists in coating them with a suspension of an inorganic powder (e.g. CaCO ₃ ) having an average particle size of 23 µm coated with a zinc salt of higher fatty acids.

JP 62 119 010 discloses a rubber release agent comprising polymeric hollow spheres having a melting point higher than the vulcanization temperature of the rubber and having an average particle diameter of S 30 µm.

The polymer beads are of (co) polymer e.g. methyl methacrylate, ethyl methacrylate, (methyl) acrylic acid, etc. and may be partially (1010%) crosslinked by one of the crosslinking agents e.g. ethylene glycol, di (methyl) acrylate, propylene glycol, di (methyl) acrylate. The polymer beads may be in powder form, but are preferably dispersed in water with a nonionic or anionic surfactant (e.g., by addition of alkylphenol products, higher alcohols, aliphatic amines, etc. These separation agents may include an inorganic powder (e.g., chalk, zinc stearate). , a wax (e.g. an aliphatic amide) The release agent has the same release properties as the inorganic powder and is used on the inner tubes of tires.

The advantage of the composition of the powder mixtures and the concentrated permanent aqueous dispersing agent dispersions of the present invention is that sufficient wettability of the zinc salts of higher fatty acids with water has been achieved by optimum concentration and additive composition, antimicrobial stability of concentrated permanent aqueous dispersing agent dispersions. was provided by an effective microbiocide, whereby a suitable application form of release agents with qualitative parameters was achieved for the applicability, in particular, of sheets, bands of rubber mixtures and asphalt films.

The process for preparing the release agents in the form of powder mixtures in the present invention is based on the physicochemical action of the adjuvants on the surface of the powder mixtures and their effect is manifested in the preparation of the low-concentration aqueous dispersions prepared before application. The preparation of the separating agents in the form of powder mixtures is carried out in a discontinuous, continuous or semi-continuous fluidized bed mixer.

The process for preparing the release agents in the form of concentrated, stable aqueous dispersions in the present invention is based on the effective achievement of the physicochemical action of the adjuvants on both the dispersing agent and the dispersing medium, and is feasible in one stage and two stages, thereby shortening the production cycle. Production can be batch and semi-continuous.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The invention is based on the fact that separating agents in the form of powder mixtures and concentrated fixed aqueous dispersions made on the basis of zinc salts of higher fatty acids suitable for the addition of water in the form of low concentrated aqueous dispersions for surface treatment of sheets, bands of rubber mixtures, asphalt films

0.1 to 40 wt. % natural or synthetic aluminosilicates, e.g. % kaolin, bentonite, bleaching clay, clinoptilolite, and / or calcium carbonate, or mixtures thereof, 0.01 to 1.5 wt. % of the sodium salt of higher fatty acids and / or sodium alkyl sulphate, and / or the ethoxylate of higher fatty alcohols,

0.1 to 4 wt. % of higher fatty alcohol ethoxylate e.g. of the Slovasol family,

0.1 to 6 wt. % sodium salt of cellulose ether and glycolic acid and / or polyvinyl alcohol,

0.1 to 2 wt. % antifoam, e.g. a silicone emulsion, polydimethylsiloxane, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and propylene oxide based on a fatty alcohol,

SK 281609-6

0.1 to 2 wt. % aqueous solution of a mixture of chloro- and methyl derivatives of isothiazolinecetones and / or 2- (thiocyanomethylthio) benzothiazole emulsion,

0.1 to 80 wt. % water;

and their preparation in the form of powder mixtures is carried out without the addition of water by homogenizing these substances in a discontinuous, continuous or semi-continuous mixer and subsequently diluted to a working concentration with water only before application;

and their preparation in the form of concentrated, stable aqueous dispersions is carried out by dissolving in a mixed duplicator apparatus the sodium salt of higher fatty acids, and / or sodium alkyl sulfate, and / or ethoxylate of higher fatty alcohols while emulsifying the concentrated silicone emulsion, and / or a polydimethylsiloxane, and / or a copolymer of ethylene oxide and propylene oxide, and / or a copolymer of ethylene oxide and propylene oxide based on higher fatty alcohols and ethoxylate of higher fatty alcohols at a temperature of 20-80 ° C, into which higher zinc salts are dispersed at t <60 ° C fatty acids, and / or natural or synthetic aluminosilicates, and / or calcium carbonate or mixtures thereof, and / or the sodium salt of cellulose ether and glycolic acid, and / or polyvinyl alcohol, the subsequent effective hydration and homogenization of which are effected by stirring at an agitator speed. - 60 rpm in the temperature range of 40-70 ° C for 1-3 hours, to the obtained stable aqueous dispersing agents dispersions, at a temperature of <50 ° C, an aqueous solution of a mixture of chloro and methyl derivatives of isothiazolinecetones and / or an emulsion of 2- (thiocyanomethylthio) benzothiazole further homogenization takes 0.5-2 hours while cooling to 25 ° C;

and their preparation in the form of concentrated, stable aqueous dispersions is carried out by dissolving and emulsifying in a separate stirred duplicator device, the contents of which are pumped into a second stirred duplicator device, in which dispersion, hydration, homogenization and antimicrobial protection are performed.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

34.74 kg of zinc salts of higher fatty acids, 1.01 kg of ethoxylate of higher fatty alcohols and 0.25 kg of sodium alkyl sulfate were homogenized in a 0.2 m ³ fluidized bed mixer for 0.3 h.

The pulverulent release agent so produced was characterized by an average particle size of 8.3 µm. The 2% aqueous dispersion of the pulverulent separation agent had the following physicochemical parameters: pH-specific conductivity stability after 1 hour. stability after 48 hours

= 8.10 = 0.83 mS.cm ^-1 = 75 vol. % = 30 vol. %

Example 2

The powder mixture of the release agent was prepared according to the procedure of Example 1 having the following composition: zinc salt of higher fatty acids 57.50 wt. % kaolin 40.00 wt. % higher fatty alcohol ethoxylate 2.00 wt. % sodium alkyl sulfate 0.50 wt. %

The separating agent powder mixture had an average particle size of 8.9 µm. The 2% aqueous dispersion of the release agent powder mixture had the following physicochemical parameters:

pH-specific conductivity stability after 1 hour stability after 48 hours

Example 3

1.7 kg of higher fatty acid sodium salt was dissolved in a 1.5 m ³ stirred duplicator apparatus in 733.31 demi water and emulsified with 8 kg of silicone emulsion and 12 kg of higher fatty alcohol ethoxylate at 75 ° C to which 222 kg of zinc salts of higher fatty acids, 16 kg of sodium cellulose ether and glycolic acid were dispersed for 1.5 hours at 40 ° C. Hydration and homogenization was carried out at 60 ° C for 3 hours with slow stirring at a stirrer speed of 60 rpm. The concentrated, stable aqueous dispersion of the release agent thus prepared was stabilized antimicrobially at 40 ° C by the addition of 7 kg of a concentrated emulsion of 2- (thiocyanomethylthio) benzothiazole while homogenizing until it cooled to 25 ° C. The obtained concentrated, stable aqueous dispersion of the release agent was characterized by an average particle size of 8.0 µm.

After further dilution with water at a ratio of 1:12, the low concentration aqueous dispersion of the separating agent obtained had the following physicochemical parameters: pH value = 8.68 specific conductivity = 2.4 mS.cm ¹ stability for 1 hour. = 45 vol. % stability after 48 hours = 20 vol. %

75.1 wt. %

0.1 wt. %

0.2 wt. %

0.5 wt. %

22.0 wt. %

1.9 wt. %

Example 4

A concentrated, stable aqueous dispersion of the release agent was prepared according to the procedure of Example 1 according to the following composition: demi water sodium salt of higher fatty acids silicone emulsion ethoxylate of higher fatty alcohols zinc salt of higher fatty acids polyvinyl alcohol aqueous solution of a mixture of chloro- and methyl derivatives of isothiazolinecetones 0.2 wt. %

The obtained concentrated, stable aqueous dispersion of the release agent had an average particle size of 9.1 µm. Following a 1: 10 dilution with water, the low concentration aqueous dispersion of the release agent had the following physicochemical parameters: pH value = 7.13 specific conductivity = 0.84 mS.cm ^-1 stability for 1 hour. = 22 vol. % stability after 48 hours = 20 vol. %

69.1 wt. %

0.1 wt. %

0.2 wt. %

0.8 wt. %

7.5 wt. %

Example 5

A concentrated, stable aqueous dispersion of the release agent was prepared according to the procedure described in Example 3 with the following composition: demi water sodium alkyl sulfate sodium silicone emulsion ethoxylate of higher fatty alcohols kaolin

2816 zinc salt of higher fatty acids 22.0 wt. % aqueous solution of a mixture of chloro-and methyl derivatives of isothiazoline ketones 0.2 wt. %

The obtained concentrated stable aqueous dispersion of the scavenger had an average particle size of 8.2 µm.

After dilution with water at a ratio of 1: 15, the low concentration aqueous dispersion of the release agent had the following physicochemical parameters: pH-specific conductivity stability for 1 hour. stability after 48 hours

= 7.49 = 0.85 mS.cm ^-1 = 32 vol. % = 25 vol. %

65.0 wt. %

1.0 wt. %

0.4 wt. %

15.5 wt. %

17.4 wt. %

Example 6

A concentrated, stable aqueous dispersion of the release agent was prepared according to the procedure of Example 3 having the following composition: demi water higher fatty alcohol ethoxylate copolymer of ethylene oxide and propylene oxide based on higher fatty alcohols bleaching earth zinc salt of higher fatty acids emulsion of 2- (thiocyanomethylthio) benzothiothiazolylthio weight. %

The obtained concentrated, stable aqueous dispersion of the release agent had an average particle size of 12.5 µm.

After dilution with water at a ratio of 1:17, the low concentration aqueous dispersion of the release agent had the following physicochemical parameters: pH-specific conductivity stability for 1 hour. stability after 48 hours

= 9.67 = 0.69 mS.cm ^-1 = 35 vol. % = 20 vol. %

Example Ί

A concentrated, stable aqueous dispersion of the release agent was prepared in two stages, in the first stage in a 800 L stirred duplicator apparatus in 784.4 L of demi water, 0.6 kg of sodium higher fatty acid was dissolved and emulsified 2 kg of silicone emulsion and 9 kg of higher fatty alcohol oxyethylate at 75 ° C for 0.5 h. The contents of the boiler were transferred to a 1.5 m ³ stirred duplicator. The dispersion of 180 kg of zinc salts of higher fatty acids, 12 kg of sodium cellulose ether and glycolic acid for 1 hour was carried out at 40 ° C. Hydration and homogenization of the mixture took 2.5 hours at 60 ° C. The antimicrobial protection of the thus produced concentrated, stable aqueous dispersion of the release agent was ensured by the addition of 2 kg of an aqueous solution of a mixture of chloro- and methyl derivatives of isothiazoline ketones at 40 ° C, while homogenization was continued until it cooled to 25 ° C. The obtained concentrated stable aqueous dispersion of the release agent had an average particle size of 8.5 µm. After dilution with water at a ratio of 1: 10, the low concentration aqueous dispersion of the release agent had the following physicochemical parameters:

pH-specific conductivity = 7.2 = 1.4 mS.cm ^-1 stability for 1 hour. = 40 vol. % stability after 48 hours = 28 vol. %

Example 8

A concentrated, stable aqueous dispersion of the release agent was prepared according to the procedure described in Example 6, the composition of the components being as follows: demi water 64.19 wt. % sodium alkyl sulphate 0.01 wt. % copolymer of ethylene oxide and propylene oxide based on higher fatty alcohols 0.30 wt. % higher fatty alcohol ethoxylate 1.00 wt. % clinoptilolite 20.00 wt. % zinc salt of higher fatty acids 14.00 wt. % sodium salt of cellulose ether and glycolic acid 0.50 wt. % emulsion of 2- (thiocyanomethylthio) benzothiazole 0.70 wt. %

The obtained concentrated, stable aqueous dispersion of the release agent had an average particle size of 10.5 µm.

After dilution with water at a ratio of 1: 17, the low concentrated aqueous dispersion of the release agent had the following physicochemical parameters: pH-value conductivity stability for 1 hour stability for 48 hours.

= 9.85 = 0.56 mS.cm ^-1 = 28 vol. % = 20 vol. %

77.50 wt. %

0.10 wt. %

0.40 wt. %

0.80 wt. %

15.00 wt. %

5.00 wt. %

Example 9

A concentrated, stable aqueous dispersion of the release agent was prepared according to the procedure of Example 6 with the following composition of components: demi water sodium higher fatty acids silicone emulsion higher fatty alcohol ethoxylate zinc higher fatty acids calcium carbonate sodium cellulose ether glycolic acid 1.00 wt. . % aqueous solution of a mixture of chloro- and methyl derivatives of isothiazoline ketones 0.20 wt. %

The obtained concentrated, stable aqueous dispersion of the release agent had an average particle size of 7.8 µm.

After diluting with water at a ratio of 1:11, the low concentration aqueous dispersion of the release agent had the following physicochemical parameters: pH-specific conductivity stability for 1 hour. stability after 48 hours

= 9.4 = 1.15 mS.cm ^-1 = 56 vol. % = 30 vol. %

Industrial usability

Separating agents in the form of powder mixtures and concentrated permanent aqueous dispersions made on the basis of zinc salts of higher fatty acids after addition of water in the form of low concentrated aqueous dispersions are suitable for surface treatment of various forms of rubber mixtures as well as bituminous foils ensuring their separability even after prolonged stacking storage.

Claims (4)

PATENT CLAIMS 1. Separating agents in the form of powder mixtures and concentrated fixed aqueous dispersions made on the basis of zinc salts of higher fatty acids, suitable for the addition of water in the form of low-concentrated aqueous dispersions for surface treatment of sheets, bands of rubber mixtures, asphalt foils, 0.1 to 40 wt. % natural or synthetic aluminosilicates, e.g. % of kaolin, bentonite, bleaching clay, clinoptilolite, and / or calcium carbonate, or mixtures thereof, from 0.01 to 1.5 wt. % of a sodium salt of higher fatty acids, and / or sodium alkyl sulfate, and / or higher fatty alcohol ethoxylate, from 0.1 to 4 wt. % of higher fatty alcohol ethoxylate e.g. from the Slovasol family, from 0.1 to 6 wt. % sodium salt of cellulose ether and glycolic acid and / or polyvinyl alcohol from 0.1 to 2 wt. % defoamer. e.g. a silicone emulsion, a polydimethylsiloxane, a copolymer of ethylene oxide and propylene oxide, a copolymer of ethylene oxide and propylene oxide based on a fatty alcohol, from 0.1 to 2 wt. % of an aqueous solution of a mixture of chlorine methyl isothiazoline ketone derivatives and / or 2- (thiocyanomethylthio) benzothiazole emulsion and from 0.1 to 80 wt. % water. Method for the production of separating agents in the form of powder mixtures of the composition according to claim 1, characterized in that the powder mixture without the addition of water is prepared by homogenizing these substances in a discontinuous, continuous or semi-continuous mixer and subsequently diluted with water until working. . Method for the production of the release agents in the form of concentrated, stable aqueous dispersions of the composition according to claim 1, characterized in that the sodium salt of higher fatty acids and / or sodium alkyl sulphate and / or ethoxylate of higher fatty alcohols is dissolved in the mixed duplicator apparatus. a concentrated silicone emulsion, and / or polydimethylsiloxane, and / or a copolymer of ethylene oxide and propylene oxide and / or a copolymer of ethylene oxide and propylene oxide based on higher fatty alcohols and ethoxylate of higher fatty alcohols at a temperature of 20-80 ° C to which at t <60 ° C disperse the zinc salts of higher fatty acids and / or natural or synthetic aluminosilicates and / or calcium carbonate or mixtures thereof, and / or the sodium salt of cellulose ether and glycolic acid, and / or polyvinyl alcohol, the subsequent effective hydration and homogenization of which is stirred 30 - 60 rpm. in the temperature range of 40-70 ° C for 1-3 hours, an aqueous solution of a mixture of chloro- and methyl derivatives of isothiazoline ketones and / or an emulsion is added to the obtained stable aqueous dispersing agents dispersions at a temperature of <50 ° C 2- (thiocyanomethylthio) benzothiazole, whose further homogenization takes 0.5-2 hours while cooling to 25 ° C. The method of claim 3, wherein the dissolution and emulsification is carried out in a separate stirred duplicator device, the contents of which are pumped into a second stirred duplicator device, in which dispersion, hydration, homogenization and antimicrobial protection are carried out.