CH628917A5 - Deformable sealant, coating composition, adhesive and insulating material - Google Patents

Description

The invention relates to a deformable sealing, coating application conditions that should be as light and quantitative as possible decomposition, adhesive and insulating compound based on 35. Now the strength of the capsule wall is subject

Polymer captolysulfide and / or polymer captolythioether, sometimes difficult to control forces.

containing microencapsulated metal oxide hardener. So the adhesion of the capsule wall material leads to the

Polymer systems based on polymer captolysulfide and polymer solids for a substantial reinforcement of the capsule walls, captopolythioether-based, in the following briefly called polysulfide systems so that the mechanical stability of the microcapsules is so great, are preferably in practice with the help of 40 that in the Forces available in practice, metal oxides or metal oxide-containing preparations, no quantitative destruction of the microcapsules and hence metal oxide hardener for short, hardened. Such Polysul- no complete reactivation of the hardener is possible. fidsystems are mainly used for the production of

Sealing, coating and insulating compounds and of adhesive encapsulation by phase separation, in which the capsules are used, hereinafter referred to as sealing compounds. The 45 wall-serving polymers with the help of another hardening of such polysulfide systems are essentially incompatible polymer, a polymer solution or a chen the 2- and 4-valent oxides of the elements of the II. And IV. Immiscible solvent from its phase excluding main group and the II, IV. and VII. subgroup of the and around the internal phase are used for the micro periodic systems, in particular calcium oxide, encapsulation of metal oxide pigments in practice not a barium oxide, zinc oxide, manganese IV oxide and lead -IV-oxide. This so settable. The sedimentation can then initially be reduced, either as a metal oxide pigment, preferably if the metal oxide particles are suspended in a liquid carrier phase, but in the form of metal oxide pigment / plasticizer pastes, and the carrier phase also counteracts sedimentation over a long period of time. Lead unsolved

In the past, most of these polysulfide systems were still used, but then the above mentioned do not contradict one another or can only be used to a very limited extent as 55 demands on the capsule walls (processing one-component systems, since the catalytic stability in storage and storage; application instability ).

The metal oxide hardener is so high that, due to the high level of this, the following must be observed: The activation of a

Curing speeds insufficient storage stability polymer system containing microcapsules that can be achieved after the. drive the complex coacervation were made

The previous difficulties in producing such metal oxide 60 with the aid of systems catalyzed rapidly curing one-component polysulfide of the microcapsules contained in the polymer system when processing the polymer system were due to the fact that there were no safe pistols which could destroy the microcapsules and their oxygen. and moisture-independent inactivation of the homogeneous distribution of the capsule contents with high-performance hardener until the time of use. Comminution devices have already been equipped or have been proposed with similar devices, this by means of a temporary inactivation device. The disadvantage here is that when the metal oxide hardener is used with the aid of the microencapsulation, the microencapsulation does not result in capsules of uniform size and technology. Microencapsulation is understood to mean a capsule that differs from batch to batch - this is a process by means of which small to the smallest spectrum of substances is obtained.

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ratio the wall thickness increases with decreasing capsule chain mono- and polyhydric alcohols and of phenol diameter. The devices for capsule destruction and its homologues, esters of saturated mono- and polybasic

performance must therefore be oversized, shear aliphatic carboxylic acids with longer-chain alcohol

because only then reproducible properties and sufficient and polyols, higher molecular aromatics and hydroaro-

Adequate economic efficiency is ensured if all microcapacitors, such as. B. diphenyl derivatives, alkylnaphthalenes, anthra-

seln or a constant high proportion are destroyed. This uses zen oil and heavy naphthenic petroleum distillates. In addition, it is assumed that long-chain chlorinated paraf- can be used for the metal oxide pigment / carrier.

fluid systems despite the occasionally high specific fine, chlorohydrin esters and halogen derivatives of diphenyl and

Weight of the metal oxide no sedimentation in the internal of its homologues.

Phase of the microcapsules occurs, since in the case of mechanical destruction, as carrier liquids for the production of metal oxide disruption of the microcapsules, the carrier liquid is otherwise suitable for practically all liquids which come or go, but the metal oxide pigment is largely on the inside compared to metal oxides or the commercially available metal oxide pig wall of the microcapsules adheres and is therefore miscible and inert in uncontrollable ment / plasticizer pastes and which is removed from the reaction. Another disadvantage of this encapsulation medium can be emulsified without loosening the sealing compound containing microencapsulated metal oxide hardener in that it mixes with them or a polysulphide-based chemical agent consists in the reaction of the material. In addition, the carrier flow-the capsule wall fragments the heterogeneity of this liquid after its release compared to the systems to be hardened is increased. The polysulfide system is appropriately inert and may

The present invention, in contrast, does not adversely affect properties of the hardened sealing, coating, insulating, deformable sealing, coating, adhesive and insulating material and adhesives. The following have proven to be particularly suitable as a carrier mass on the basis of polymer captolysulfide and / liquids: phthalate soft or polymer captolythioether containing micromachers; Halogen paraffins, especially chlorine paraffins; Per-encapsulated metal oxide hardener, according to the invention the fluoropolyether, in particular perfluoropolypropylene oxides; Mass due to the thermal degradation of the microcapsule pan paraffin oils, mineral oils, ester oils and polyphenyl ether oils; Silicons can be heat activated. The micro-25 oils and silanes, in particular mercapto-functional silanes, are advantageous for capsule walls at a temperature of 40-200.degree. B. mercaptopropyltrimethoxysilane. It was found, preferably 80-180 ° C, degradable. Under degradable in the sense that the thermal activation of the invention according to the invention, both a melting or softening sealing compound by microencapsulated, liquid-free metal process with deformation and release of the metal oxide hardener, oxide pigments is quite possible, because by the forced and degradation z . B. with breakup of molecular chains 30 resulting very small microcapsules with given conoder chemical degradation, each with the consequence of the decay of the center to understand an optimal statistical distribution in the sealing microcapsule walls. The microcapsule walls are in bulk.

thereafter produced using a material or the metal oxide pigments or the commercially available metals consist thereof, the heat-mechanical-physical oxide pigment / plasticizer pastes can be homogenized with carrier liquid and / or chemical changes with decomposition of the microcapacities and the resulting metal oxide / Carrier walls suffered. Materials that can be used for the production of a liquid system in a non-aqueous encapsulation-heat-degradable capsule walls are described in the medium by coacervation of film-forming polymeric wall US Pat. No. 3,161,602. materials using temperature or solvent gradients

Microcapsules containing hardeners for the production of metal oxide and / or the action of catalysts and hardeners for the inventive capsules are encapsulated. The sedimentation tendency of the metal oxides in moderate sealant is suitable here for all substances, the film-forming internal phase of the microcapsules can have matching properties by comparison with the internal phase of the density and viscosity of the carrier liquid to the specific or. whose constituents as well as the encapsulated weight and the particle size of the metal oxide pigment are inert and, after their heat dissipation, they are reduced to such an extent that the properties of the sedimentation do not occur even with one-year distribution and re-consolidation.

Do not adversely affect hardened sealant. Preferred As a polymer captolysulfide or thioether, wall materials are suitable for the microcapsules of the compounds according to the invention, such as, for. B. in the following publications sen sealing compound z. B. olefin polymers, in particular are described: DE-AS 1301 577.1495 308.1 545 033, low molecular weight polyethylene and polypropylene; animal, 1 645121, DE-OS 1 645 502.2 054 565.2 062 736.2 103 434. Whole vegetable and mineral waxes, such as tristearin, bees- 50 are generally curable organic liquid bis and Japanese wax and microcrystalline paraffin waxes ; paste-like compounds, the mercapto- and di- or polysulfide-chlorotrifluoroethylene-vinyl fluoride copolymers and reactive or thetheric groups as well as optionally further heterothermoplastic resin / hardener combinations. atoms in the form of silane, ester, imine, urethane, urea

Contain metal oxide hardeners in the sense of the present inventions and carbonyl groups.

are z. B. Metal oxide pigments and metal oxide pigment / 55 As encapsulation medium, all liquids can be used as plasticizer pastes, but preferably metal oxide / carrier, in which the internal phase does not dissolve or liquid preparations that are used using inert ones with those of the internal phase or the components of which do not enter into carrier liquids from the metal oxide pigments or the chemical reaction. These are e.g. B. aliphatic and metal oxide pigment / plasticizer pastes were prepared. alicyclic hydrocarbons; perfluorinated cyclic ether; The metal oxides are, in particular, the metal oxides of the egg 60 perfluorinated polyether; perfluorinated trialkylamines; Silicone oils, elements of the II. And IV. Main group as well as the II, IV. And VII. Especially those derived from methyl-phenyl or diphe sub-group of the periodic system, namely calcium oxide, nyl-silane diols. Depending on whether the coacervation by barium oxide, zinc oxide, manganese IV oxide and lead IV oxide uses temperature gradients, solvent gradients or polyre. action is brought about are dependent on the properties of the

As a plasticizer, all substances can be encapsulated with a plastic encapsulation medium in relation to the wall material.

appropriate effect can be used that neither with the metal- different demands.

oxide pigment still react with the carrier liquid. The activation temperature of the plasticizers of this type according to the invention are: phosphoric acid ester sealing compounds is, for example, 40-200 ° C., preferably

628 917 4

80-180 ° C, and the melting point or softening point - much less restrictions than when using the interval or the chemical degradation areas of the capsule - the unprotected metal oxide hardener. The invented

wall material of the microcapsules. Micro-encapsulated metal oxide

Formation of certain mixtures of fusible wall material hardener can also occasionally cocatalysts and / or lien, such as. B. microcrystalline paraffin waxes and Vinylhar's accelerators for the curing of the polymer system and / or zen can contain wall materials with defined softening substances to prevent sedimentation.

point and thus polymer systems with a defined activation. The production of the sealing compound according to the invention can be produced at temperature. When choosing the wall mat - by incorporating the microcapsules according to the known method

rials must be taken into account that with higher melting wall driving, z. B. with the help of planetary mixers. The materials, including metal oxide pigment carrier liquids and microcapsules, can be used both before and after incorporation.

Encapsulation media with a correspondingly high boiling point of the additives can be incorporated. When manufacturing

must be used in order to rule out malfunctions of highly viscous or pasty sealants and / or the genes caused by the vapor pressure of these components during the coacervation. However, use of larger microcapsules has proven to be sensible. proven to be expedient, the microcapsules in the liquid poly

To incorporate with the micro-encapsulated sealing compound according to the invention and then add the additives

rare metal oxide hardener, whereby the capsule walls are made of thermoplastic and / or the microcapsules are made of mixable materials before incorporation, destruction of lubricants must be treated. Such sealing compounds of the microcapsule walls do not mechanically meet the requirements for storage-stable, easily activated and excluded. fast curing metal oxide hardenable and vulcanizable

The thermal activation of the sealing one-component systems according to the invention.

mass can be without and with simultaneous and / or subsequent. The invention will be made in the following with examples of the mechanical homogenization. In the microencapsulation of the metal oxide hardener and of the sealing compound according to the invention, the relatively small embodiments of the sealing compound according to the invention can be used

Thermal conductivity explained when using microencapsulated.

metal oxide hardener in the case of meltable capsule walls 25

by melting the capsule walls a very even- Example 1: Microencapsulation of lead IV oxide:

progressive hardening can be achieved. To avoid 300 g of lead-I V-oxide pigment, 300 g of phthalate - an inhomogeneity or anisotropy - are used in the hardened product to soften the plasticizer, which at 25 ° C has a density Ô2s = 1.069-1.076 g / ml, especially with fast-curing or with, with the help of a stirrer equipped with a so-called friction-relatively low-temperature activatable products, pasted and rubbed for homogenization massive microcapsules with diameters smaller than 200 µm, rubbed twice on the three-roll mill. The wipers are preferably used smaller than 50 | xm in order to have a very good flow behavior and also to avoid differences in concentration local to length. Storage no separation of the components. 600 g of this

The thermal activation of the sealing PbCh paste according to the invention is encapsulated as follows:

In practice, mass is predominantly carried out under simultaneous> 5 In a 5 liter reactor, in which all with the encapsulation

and / or subsequent mechanical homogenization of the parts that come into contact with the medium are teflonized,

Components. Depending on the capsule wall material, the capsule becomes 3.6 liters of the inert liquid fluorine compound FC43

wall in the polymer was first thermally degraded and the 3M company used the encapsulation medium at 97-99 ° C

then the liquid wall material and the metal oxide are heated. In another container, a phase relationship

or the metal oxide composition on mechanical 40 nis PR = 3: 1 corresponding to 200 g wall material, consisting of

Paths homogeneously distributed in the polymer, or the capsule wall in an emulsifiable polyethylene wax with a medium one

The polymer initially softened to such an extent that the molecular weight Mr. 3000 and a softening point EP

sufficient sufficient low forces are sufficient to = 94 ° C, z. B. "Epolene" HCE from Eastman Chemical to release internal phase and melted homogeneous products or Hoechst wax PAD 521 in the polymer. Now distribute. To homogenize the 45 according to the invention, 600 g of the PbCh- prepared as described above are

Sealant after or during the thermal degradation of the paste with stirring in the encapsulation medium to a partial

Capsule walls suffice for simple, low shear forces with an emulsified diameter of 50-500 | j.m. After the above, occasionally heated devices such. B. after-resulting dispersion has reached a temperature of tete screw conveyor etc. 97-99 ° C, the molten wall material

The activatability of the sealing compound according to the invention is added with stirring and the temperature is slowly reduced.

is also reduced within certain limits by the capsule spectra, whereby the encapsulation takes place. The system has approx. 20 ° C

and the phase relationships of the microcapsules contained, the microcapsules are separated by filtration, influenced. In microencapsulation, one understands that with l, l, 2-trifluoro-l, 2,2-trichloroethane («Frigen» 133; Kp =

Phase ratio PR the mass ratio of the internal phase (47.6 ° C) washed and dried at T = 30 ° C in an air stream,

to the wall material phase. With decreasing phase shift 55

For a given capsule diameter, Ratnis takes the mechanical example 2: Microencapsulation of zinc oxide:

see stability of the microcapsules. The risk of involuntary 300 g zinc oxide pigment and 350 g chlorinated paraffin (dîo = 1.42-

gene destruction of the microcapsules during production and 1.43 g / ml; t | 2o = 40 000 mPa.s) using a friction disc

Storage of the sealing compound according to the invention and their adapted to achieve the optimal statistical distribution

Hardening decreases. The sealing compound according to the invention contains eo of the pigment in the carrier liquid twice on a three-roller

For example, microcapsules with a phase ratio of zenstuhl rubbed off and encapsulated as follows: In a 5 liter

1: 1 to 40: 1, preferably from 2: 1 to 14: 1, and a capsule reactor according to Example 1, 2.8 liters of FG43 are introduced,

diameter of 5-2000 | i, m, preferably 10 to 200 [im. heated to a temperature 3-5 ° C above the melting

The sealing compound according to the invention can be the usual point of the wall material to be used, and therein

Supplements such as fillers, dyes, viscosity regulators, vulcanized 87.5 g CaO paste by stirring to a particle diameter, auxiliaries, plasticizers, adhesion promoters, etc. contain about 200-1000 (emulsified. After the dispersion th. By the Micro-encapsulation of the metal oxide hard-molded, 37.5 g Ù 30% of which is slightly above the tester subject to the sealant with respect to the additives melting point heated wall material, a mixture of

95% by weight of paraffin wax and 5% by weight of ethylene-vinyl acetate copolymer (“Elvax” 150 from Du Pont) were added and distributed in the form of fine droplets by stirring, whereupon the encapsulation by coating the dispersed internal phase with the still liquid Coacervate occurs. Now the temperature is slowly lowered to approx. 20 ° C, the goacervate solidifying to form a self-supporting capsule wall structure. At this temperature, stirring is continued for about 2 hours to bring the internal phase to the ambient temperature before isolating the microcapsules. The microcapsules are then filtered off, washed with “Frigen” 113 and dried at T = 30 ° C in an air stream.

Example 3: Microencapsulation of manganese IV oxide:

The encapsulation of manganese IV oxide pigment takes place in a 5 liter encapsulation reactor equipped with two agitators, in which all parts that come into contact with the encapsulation medium are teflonized. The two independently adjustable agitators consist of a three-bladed agitator, which is arranged concentrically above the reactor floor, and a four-bladed agitator, which is adjustable in height in the upper third of the encapsulation medium and is offset by 30 ° from the lower agitator.

For encapsulation, 3.2 liters of FC-43 are placed in the reactor and, at room temperature, 37.5 g of “Karagami wax” from Concord Chemical Co. or Hoechst-Wachs RT are added in powder form at room temperature, the speed of the lower agitator being lower than the one above. Now the mixture is heated with constant stirring until the wall material is in liquid form. 87.5 g of MnCh pigment are then added to this dispersion, corresponding to an internal phase of 70% by weight. The pigment particles are distributed homogeneously via the speed of the agitator arranged at the top, while at the same time the speed of the lower agitator is reduced to such an extent that this just prevents the setting of vertical particle size gradients. After coacervation has taken place, the temperature is slowly lowered to approx. 20 ° C while stirring, whereby self-supporting, mechanically stable capsule walls are formed. The microcapsules are separated by filtration, washed with «Frigen» 111 and then dried in an air stream at T = 30 ° C.

Example 4: Gray one-component sealant

Composition:% by weight

Polysulfide 5300 (Sekisui) 27.7 5 "Rhenoblend" M 102 (Rhein-Chemie Rheinau GmbH) 25.25

Phthalate plasticizer 2.25

Titanium dioxide 12.25

Chalk, of course 10.10

Chalk, filled 6.00

Carbon black 0.25

Adhesive resin 1.75

Viscosity regulator 1.20

Sulfur 0.05

Lead IV oxide microcapsules 13.00

Manufacturing

The Pb02-containing microcapsules produced according to Example 1 are separated with “Rhenoblend” M 102, one in chlo628917

cured diphenyl-dissolved butyl rubber, carefully pasted and this paste only worked in when the remaining separately pasted components are homogenized. The incorporation takes place with the help of a planetary mixer. The sealing compound according to the invention can be stored for one year and can be activated purely thermally at T = 100 ° C.

Example 5: Gray one-component sealant

Composition:

Component A:% by weight

Polsulfide S 340 (Sekisui) 47.50

Plasticizer 17.40

Talc 7.00

Chalk 9.60

Titanium dioxide 14.20

Soot 0.30

Adhesive resin 2.40

Viscosity regulator 1.56

Sulfur 0.04 component B:

Manganese IV oxide microcapsules 50.00

Plasticizer 50.00

Manufacturing

To produce the one-component sealing compound according to the invention, components A and B are homogenized on their own, component A is introduced and component B is incorporated, so that a mixing ratio of 12: 1 to 14: 1 is present. When incorporating the Mn02 microcapsules contained in component B, produced according to Example 3, no precautionary measures need to be taken, since the internal phase of these microcapsules consists only of the solid MnC> 2 pigment.

Example 6: White one-component system

Composition:% by weight

Polysulfide LP 33 (Thiokol) 20.00

"Rhenoblend" M 103 9.00

"Rhenoblend" M 212 5.00

Phthalate plasticizer 9.30

Chalk, of course 17.00

Chalk, filled 8.00

Aluminum calcium silicate 8.00

Titanium dioxide 5.00

Adhesive resin 2.50

Viscosity regulator 2.00

Xylene 3.00

Halogenated hydrocarbon plasticizer 5.00

"Rhenosorb" C (Rhein-Chemie Rheinau GmbH) 2.00

Zinc oxide microcapsules 4.20

Manufacturing

The ZnO-containing microcapsules produced according to Example 2 are successively pasted into "Rhenoblend" M 212 (chloroprene rubber in phthalate) and "Rhenoblend" M 103 (butyl rubber in chlorinated diphenyl), and this paste is separated into the separately homogenized mass from the rest Components carefully incorporated using a planetary mixer. The one-component system manufactured in this way is stable in storage for over a year even at high relative air humidity.

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Claims (6)

628917 2 PATENT CLAIMS encased in a closed self-supporting envelope 1. Deformable sealing, coating, adhesive and insulating can be. mass based on polymer captolysulfide and / prerequisite for successful use of micro- or polymer captolythioether with a content of metal-encapsulated metal oxides as hardener for polymer systems are oxide hardeners in the form of microcapsules, characterized on the one hand by mechanically sufficiently stable and diffusion-tight net that the mass through thermal degradation of the microcapsule capsule walls to ensure sufficient stability in the case of single walls can be activated by the fact that the capsule wall in polymer systems and a high storage stability in the heat guarantee physical or chemical changes and, on the other hand, suffer simple, largely disintegrate. quantitative releasability of the capsule contents for activation 2. Composition according to claim 1, characterized in that 10 of the polymer system. Some catalytically active metal oxides, the microcapsule walls at a temperature of 40 to or metal oxide pigment / carrier liquid systems can be heat-degradable at 200 ° C., preferably 80 to 180 ° C. be encapsulated by complex coacervation. Doing so 3. Mass according to claim 1 or 2, characterized in an aqueous, preferably acidic medium from two colloid-that the microcapsules metal oxide from the class formed from the one coacervate, which after its solidification, the oxides of the metals of the II. And IV. Main group as well as the II., 5 forms later self-supporting capsule wall. A prerequisite for IV. And VII. Subgroup of the periodic system, the microencapsulation in the aqueous medium is that it is preferably selected from calcium oxide, barium oxide, zinc oxide, manganese metal oxide pigment or the metal oxide pigment / carrier liquid IV oxide and lead IV oxide Contain metal oxide. system is so hydrophobicized before encapsulation, 4. Composition according to one of claims 1 to 3, characterized in that, despite the basic or amphoteric properties, the microcapsules, in addition to the metal oxides, do not undergo hydrolysis in the encapsulation. Contain at least one carrier liquid on this hardener. As an older invention suggests, the cat- 5. Mass according to one of claims 1 to 4, characterized in that the lytic activity of the metal oxides is characterized by the encapsulation that the microcapsules do not impair a capsule diameter. have from 5-2000 µm, preferably from 10-200 µm. The release of the metal oxide hardener from the microcap 6. mass according to one of claims 1 to 5, can be 25 in this case, however, only by the mechanical Zergek characterizes that the mass ratio of the internal phase disruption of the capsule wall, so that formulated with the wall material phase of the microcapsules 1: 1 to 40: 1, preferred 1-component systems can only be activated mechanically, for example 2: 1 to 14: 1. However, the mechanical release is problematic in that the microcapacitors containing the metal oxide hardener 30 on the one hand must be mechanically sufficiently stable in order to B. not be destroyed when incorporated into the polymer system already with the release of the metal oxide hardener and under storage and transport conditions, on the other hand under