CN1222174A - Silicon and organic (CO) polymer latex based queous dispersion for preparing silicon elastomer with adjustable translucency - Google Patents

Abstract

The present invention relates to aqueous dispersions based on silicone and organic (co)polymer latexes, which are crosslinked by drying at room temperature to remove water to give elastomers with high mechanical properties and adjustable translucency, characterized in that It does not contain any reinforcing inorganic filler and in that it comprises the following components: (A) based on 100 parts by weight of oil or polymer α, ω-(dihydroxy) polydiorganosiloxane (A1) and 1-100 parts by weight of Oil-in-water emulsions of silicone crosslinking agents (A2) stabilized by at least one surfactant (A3) selected from anionic and nonionic surfactants and mixtures thereof; and having a particle size of 0.1 μm (100 nm) and between 100 μm (100,000 nm); and a dry extract content of at least 60 wt %; (B): 1-100 parts by weight of at least one organic (co)polymer per 100 parts by weight of oil or polymer (A1) Aqueous dispersions of substances having a particle size of 0.01 μm (10 nm) to 10 μm (10,000 nm) and a dry extract content of 10 to 70 wt %; (C) per 100 parts by weight of oil or polymer (A1) , Optionally use 0.01-5 parts by weight of catalytic metal compound for hardening. The dispersion can be used for the preparation of translucent silicone elastomers for the construction industry.

Description

Be used to prepare the water dispersion based on siloxanes and organic (being total to) polymer latex of silicone elastomer with adjustable translucency

The present invention relates to based on silicone compounds with based on the water dispersion of organic (being total to) polymer latex, it can be cross-linked into the elastomerics with adjustable translucency by dry dewatering at normal temperatures.The invention still further relates to its method of preparation and relate to it and in building industry, have the silicone elastomer product of adjustable translucency as the purposes on sealing and weathering resistance mastic coatings, protective cover and the metope external coating (EC) in manufacturing.

Can be cross-linked into the translucency elastomerics is used to prepare building industry and with the water dispersion based on siloxanes of product description is arranged in the prior art already.Therefore, at US-A-4,824, in 890, the water dispersion on basis is the siloxane microemulsion that (i) granularity is lower than 0.15 μ m (150nm), it is that emulsion polymerization by the ring-type polydiorganosiloxane makes, with the colloidal silica of (2i) 5-30 weight part (per 100 parts of siloxane polymers) and (3i) mixture of the dialkyltin dicarboxylates salt catalyst of 1-5 weight part (per 100 parts of siloxane polymers); At EP-A-0,542, in 498, a moisture basis prose style free from parallelism is the water miscible liquid of (i) across-linked siloxane polymer, it is silicone oil and the cross-linking products of organoalkoxysilane in the presence of tin-based catalyst that contains the silanol end group, wherein be lower than 10% the granularity that particle had and be higher than 1 μ m (1000nm), with the specific surfactant of forming by alkylsurfuric acid ammonium salt or an alkali metal salt of (2i) 0.7-2 weight part (per 100 weight part across-linked siloxane polymers) and with use (3i) 2.5-45 weight part (siloxane polymers of per 100 weight parts) for the elastomer product that obtains to have the mechanical property that can be used for building industry be lower than the mixture of the colloidal silica that the water dispersion form of 0.06 μ m (60nm) uses with granularity.

Yet, can be cross-linked into elastomeric these water dispersions of translucency and have some shortcomings, can enumerate following these :-not too enough package stabilities; This is to trend towards obtaining gel because condensation reaction takes place between siloxane polymer and colloidal silica (embodying reactive behavior by its surface hydroxyl) system too early; The level of-translucency mainly is only to regulate by the content of regulating the silicon raw material; Be known that now any variation on silica content will change more elastomeric salient featuress easily significantly, mechanical breaking performance especially, elasticity and adhesivity; Regulating elastomeric translucency therefore can not carry out simultaneously with other salient features of change.

According to the present invention, have now found that a kind of water dispersion:

-it has package stability, because it is raw material such as the colloidal silica that never comprises reactive behavior

Various compositions make and

-to anhydrate by removing, it can be cross-linked into a kind of elastomerics, and this elastomerics has on the one hand can

With its other performance (especially mechanical property) keep the translucency independently regulate with

Although there is not the enhancing mineral filler on the other hand, still have high-mechanical property, make this elastomerics

Be particularly suitable for making the product in the building industry, can replace by the polymer raw material that uses a kind of water dispersion form that is rendered as organic (being total to) polymkeric substance this general type pass through remove the mineral filler of usually using in the water dispersion that the crosslinkable that anhydrates becomes silicone elastomer and obtain.

For the present invention, express phrase " adjustable translucency " and be meant that the level of translucency can easily regulate, in order that cover from opaque fully near transparent high translucent entire area.

The mechanical property that relates in this manual is irrespectively to guarantee the necessary performance of elastomer product of its lining adhesive function with weather condition; Especially can enumerate: secant modulus, elongation at break, breaking tenacity, elasticity and binding property under 100% elongation.

Siloxanes with the use of organic latex already at EP-A-0,410, mention in 899 and be used to improve solids content, the appropriate viscosity that has kept this type aqueous silicone dispersion simultaneously exists to strengthen mineral filler can obtain having high-mechanical property and more opaque Resilient product except that after anhydrating in this dispersion.

Do not had that piece teach literature in the prior art and used polymer raw material according to the inventive subject matter, having with acquisition is the Resilient product of the required adjustable translucency of building industry, need not to use the enhancing mineral filler just to keep the favorable mechanical performance simultaneously.

More particularly, the present invention relates to based on siloxanes with based on the water dispersion of organic (being total to) polymkeric substance, it is cross-linked into the elastomerics with high-mechanical property and adjustable translucency by dry at normal temperatures except that anhydrating, it is characterized in that it does not contain any enhancing mineral filler and is that it comprises following component: (A): based on 100 weight part oil or α, ω-(dihydroxyl) polydiorganosiloxane polymkeric substance (A1) and based on the emulsion oil-in-water of the organosilicon cross-linking agent (A2) of 1-100 weight part, this emulsion:

Live by at least a surface that is selected from negatively charged ion and nonionogenic tenside and its mixture

Property agent (A3) is stablized,

Granularity 0.1 μ m (100nm) and 100 μ m (100,000nm) between,

Solids content is 60wt% at least; (B): per 100 weight part oil or polymkeric substance (A1), the water dispersion of at least a organic (being total to) polymkeric substance of 1-100 weight part, this dispersion has

0.01 μ m (10nm)-10 μ m (10, the 000nm) granularity between;

Solids content between 10-70wt%; (C) optional use, per 100 weight part oil or polymkeric substance (A1), the catalytic metal curing compound of 0.01-5 weight part; This water dispersion has solids content and is 60wt% at least; The translucency of the elastomer product for preparing is regulated in the preparation process of water dispersion, and method is that following parameters is adjusted to needed value: the size of the polymer beads in latex (B); Or form the refractive index of the polymkeric substance of this latex (B), the chemical constitution of organic by changing (being total to) polymkeric substance; Or simultaneously, above-mentioned two kinds of parameters, i.e. size and refractive index.

Final water dispersion is by thoroughly mixing all its components simply, obtaining making at the homogeneous dispersion that does not have shelf-stable under the situation of air.

Skilled person in the art knows, at continuum [in this case, by removing the silicone matrix anhydrate the crosslinked back of phase (A) is obtained] in particle [in this case, polymer beads in the latex (B)] scattering force, it controls elastomeric opaqueness (being inversely proportional to its translucency), descends along with following parameter:

-particle size and

-the difference of refractive index between particle and continuum.

This instruction is according to Rayleigh scattering rule, and this rule is expressed scattering force Pd by following equation:

Pd=2.67x ⁴[(m ²-1)/(m ²+ 2)] ²X=2 π r/ λ wherein, wherein r=particulate mean radius and λ=light wavelength, and m=n1/n2, the wherein refractive index of n1=particulate refractive index and n2=continuum.

Emulsion (A):

Oil or polymkeric substance (A1):

α, ω-(dihydroxyl) polydiorganosiloxane must have 100mPa.s at least under 25 ℃, and preferably at least 50, the viscosity of 000mPa.s.

The reason of this respect is that viscosity is higher than 50,000mPa.s, and the elastomerics that acquisition has a series of suitable mechanical is especially with regard to extension at break and breaking tenacity.

Also have, viscosity is high more, and mechanical property is preserved more in elastomeric weathering process.

Preferred viscosities of the present invention is 50,000 and 1,500, between the 000mPa.s (25 ℃).

Viscosity described here is the kinetic viscosity under 25 ℃; It is by using the Brookfield viscometer to measure according to the explanation of the AFNOR standard NFT76102 in May nineteen eighty-two.

α, the organic radical of ω-(dihydroxyl) polydiorganosiloxane contain the monovalence alkyl of 6 carbon atoms at the most, and be optional by cyano group or fluorine replacement.According to they in Industrial products the easily property obtained and the general substituting group that uses is a methyl, ethyl, propyl group, phenyl, vinyl and 3,3,3-trifluoro propyl.Generally, these groups of at least 80% (by number) are methyl.

Linking agent (A2):

As previously discussed, use the linking agent of organosilicon character.The catalogue of the linking agent of being recommended sees hereinafter-in the middle of them each, under the prerequisite of the character of considering the linking agent that uses-at the accurate consumption of recommendation in the emulsion (A) to express with respect to the oil of per 100 weight parts or the parts by weight for the polymkeric substance (A1):

The organosilicon acid esters (organosiliconate) of 1-15 part;

The silsesquioxane of 1-100 part (silsesquioxane) resin microemulsion, according to US-A-3,355,406 and US-A-3,433,780 both instructions;

The lower molecular weight reactive behavior silicone resin that contains alkoxyl group and acyloxy of 5-100 part;

The high molecular weight silicone resin of the toluene insoluble of 5-100 part;

The per molecule of 5-100 part contains at least two different units and the hydroxyl silicone resin of hydroxy radical content (by weight) between 0.1-10%, and this unit is selected from those with following structural formula: R ₃SiO _0.5(M), R ₂SiO (D), RSiO _1.5(T) and SiO ₂(Q), R mainly is C ₁-C ₆Alkyl, vinyl or 3,3,3-trifluoro propyl.In the middle of these resins, introduce, can mention resin M Q, MDQ, TD and MTD with their former state or with the water miscible liquid form;

1-20 part have a formula R _aSiX _4-aSilane, wherein R is an any monovalent organic radical, especially methyl or vinyl, a is 1 or 0, but X is condensation and/or hydrolyzable group, is preferably selected from alkoxyl group, acyloxy, ketoimine oxygen base, alkylamino, amido and alkenyl oxy and its various possible mixed groups.When X was alkoxyl group, according to EP-A-0,259,734 instruction needed to add the 2-amino-2-methyl propyl alcohol as stablizer.

Employed linking agent (A2) is the hydroxyl silicone resin of mentioning just now of 5-100 part preferably.

Tensio-active agent (A3):

In the context of the present invention, employed tensio-active agent comprises anion surfactant, and they are selected from, for example, alkali-metal alkylbenzene sulfonate, alkyl-sulphate, sulfated alkyl ether, alkyl aryl ether sulfate and dioctylsulfosuccinat salt and their mixture.The preferred anionic surfactants tensio-active agent is alkali-metal many benzene sulfonates.

Employed tensio-active agent also can be a non-ionic type; For example can mention alkoxylated fatty acid, the poly-alkoxylation alkylphenol, the poly-alkoxylation Fatty Alcohol(C12-C14 and C12-C18), poly-alkoxylation or bound to polyglycerol fatty amide, bound to polyglycerol salmefamol and alcohols, the ethylene oxide/propylene oxide segmented copolymer, the polydiorganosiloxane that contains the siloxy units of carrying ethylene oxide chain or propylene oxide chain, and alkyl glucoside, alkyl polyglucoside, sucrose ether (sucroether), sucrose ester (sucroester), sucroglyceride (sucroglyceride), sorbitan ester, the ethoxylated compound of these sugar derivativess and these surfactant mixtures.Preferred nonionic is poly-alkoxylation alkylphenol and poly-alkoxylation Fatty Alcohol(C12-C14 and C12-C18).

As preferred examples, can use preferred nonionic and a kind of (or multiple) preferred anionic surfactants surfactant mixtures.

Function as the character that needs emulsive silicone oil or polymkeric substance (A1) comes the option table surface-active agent, separately or with form of mixtures; The general HLB that selects about 11-15 contains α with emulsification, oil of ω-(dihydroxyl) polydiorganosiloxane or polymkeric substance (A1).

The preparation of latex A:

In order to prepare latex A, can use the emulsion polymerisation process that directly obtains emulsion (A).In addition, this method makes to have the very full-bodied α of containing, and the emulsion (A) of ω-(dihydroxyl) polydiorganosiloxane easily obtains.

According to this method, the emulsion oil-in-water of siloxanes phase is that the anionic polymerization by the oil (A1) with low viscosity (in the 100mPa.s-1000mPa.s scope) prepares, this polyreaction is chosen wantonly in the presence of linking agent (A2) and is carried out, according to another kind of method, also can after polyreaction, add linking agent (A2).This anionic polymerisation process is described in U.S. Pat-A-2, and 891,920 and US-A-3 especially, in 294,725 (the enumerating as a reference).The polymkeric substance that is obtained is stablized in the negatively charged ion mode by means of tensio-active agent, according to US-A-3, and 294,725 instruction, this tensio-active agent is an alkali metal salt of aromatic hydrocarbyl sulfonic acid preferably, and free acid also can be used as polymerizing catalyst.

Preferred catalyzer and tensio-active agent are Witco 1298 Soft Acid and its an alkali metal salt, especially its sodium salt.Can also choose wantonly and add other negatively charged ion or nonionogenic tenside.Yet this interpolation is dispensable because according to US-A-3,294,725 instruction, in and the amount of the resulting anion surfactant of sulfonic acid be enough to make polymer emulsion stable.This consumption generally is lower than 3%, preferred 1.5% of emulsion (A) weight.

Yet, according to the present invention, preferably use prepolymerized α, ω-(dihydroxyl) polydiorganosiloxane begins, in the presence of linking agent (A2), put it in the water miscible liquid then, make this emulsion-stabilizing with negatively charged ion and/or nonionogenic tenside simultaneously, the method well-known and that describe in detail in the literature according to those skilled persons in the art (referring to, for example, patent FR-A-2,064,563, FR-A-2,094,322, FR-A-2,114,230 and EP-A-0,169,098).

According to this method, by simple stirring with α, ω-(dihydroxyl) polydiorganosiloxane polymkeric substance (A1) mixes with linking agent (A2) with negatively charged ion and/or nonionogenic tenside (A3), this tensio-active agent might be an aqueous solution form, if need, add water then, then by allowing mixture make it to change into meticulous and uniform emulsion through the standard colloidal mill.So the abrasive substance that obtains can be chosen the water dilution with suitable additional content wantonly.Therefore obtain shelf-stable by negatively charged ion or the stable emulsion (A) of nonionogenic tenside.

By emulsion polymerization or by siloxane polymer (A1) being put into the prepared emulsion of emulsion (A) is that solids content is greater than or equal to 60wt% and preferred emulsion oil-in-water between 80-98wt%.

Should be noted that, viscosity is higher than 30,000mPa.s very heavy-gravity siloxane polymer (A1) can be ideally by using the in addition emulsification of the described method of WO-A-94/09058 (enumerating as a reference), the feature of this method is very accurately to control the ratio of water and siloxanes viscosity mutually.

All or part of that makes emulsion (A) by the emulsion polymerization technology or by preferred emulsifying technology do not break away from spirit of the present invention, this emulsion polymerization or this emulsification be directly in the presence of latex (B) with whole or some component (A1) and (A2) begin to carry out.

The dispersion of latex (B)

Latex (B):

Latex (B) is that the aqeous suspension of the polymer beads that made by emulsion (being total to) polymerisation process from polymerisable organic monomer forms.

Main polymerisable monomer is made up of at least a main monomer that is selected from vinylbenzene (a), divinyl (b), acrylate (c) and vinyl nitrile (d).Term acrylate is represented vinylformic acid and methacrylic acid and C ₁-C ₁₂Alkanol, preferred C ₁-C ₈The ester class of alkanol, as methyl acrylate, ethyl propenoate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA and Propenoic acid, 2-methyl, isobutyl ester.

Vinyl nitrile comprises those that contain 3-12 carbon atom, especially vinyl cyanide and methacrylonitrile.

Vinylbenzene can partly or entirely replace with alpha-methyl styrene or Vinyl toluene.

Except above-mentioned principal monomer (a)-(d), also might allow in these main monomers some with at least a other ethylenically unsaturated monomer or the compound of 40wt% (with respect to monomeric gross weight) carry out copolymerization at the most, these monomers or compound are selected from: (e): the vinyl ester of carboxylic acid, as vinyl-acetic ester, branched paraffin carboxylic acid's vinyl acetate (vinylversatate) or propionate; (f): unsaturated list of olefinic or dicarboxylic acid, as vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or fumaric acid; (g): the above dicarboxylic acid of in (f), mentioning and the mono alkyl ester of the alkanol that contains 1-4 carbon atom and the derivative of its N-replacement; (h): unsaturated carboxylic acid amides, as acrylamide, Methacrylamide, N-methylol (methalol)-acrylamide or Methacrylamide; (i): contain sulfonic olefinic type monomers and its ammonium salt or an alkali metal salt, vinyl sulfonic acid for example, vinylbenzenesulfonic acid, α-acrylamido-methyl propane sulfonic acid or methacrylic acid 2-sulfo group-ethylidene ester; (j): the ethylenically unsaturated monomer class that contains amino or nitrogenous heterocyclic radical of the second month in a season, uncle or season, vinyl pyridine for example, vinyl imidazole, (methyl) acrylic-amino alkyl esters and aminoalkyl group (methyl) acrylic amide, as acrylic or methacrylic acid dimethylaminoethyl ester, acrylic or methacrylic acid di-t-butyl amino-ethyl ester, the dimethylamino methyl acrylamide or-Methacrylamide, and amphoteric ion type monomer class, as vinylformic acid sulfo group propyl group (dimethyl) aminopropyl ester; (k): (methyl) vinylformic acid and the ester class that preferably contains the alkanediol of 2-8 carbon atom, as list (methyl) vinylformic acid glycol ester, single (methyl) vinylformic acid hydroxy-propyl ester or single (methyl) vinylformic acid 1, the 4-butanediol ester, and the monomer class that contains two polymerisable double bonds, as Ethylene glycol dimethacrylate.

Except above-mentioned monomer (e)-(k); also might use a small amount of (0.1-5wt%; with respect to monomeric gross weight) the unsaturated olefinic monomer class with crosslinkable character; as (methyl) glycidyl acrylate (l) or vinyl and acryl (acrylic) silane (m), as vinyltrimethoxy silane and vinyltriethoxysilane.

Except above-mentioned monomer (e)-(m); that also might use 40wt% (with respect to the gross weight of ethylenically unsaturated monomer or compound) at the most carries at least one olefinic unsaturated functional group (for example vinyl or (methyl) acryl functional group); this functional group can add optional at least a monomer (e)-(m) reaction and the functional organo-siloxanes (n) of optional at least one other reactive functional (for example epoxide functional groups or hydroxyl functional group) through free radical approach and at least a ethylenically unsaturated monomer (a)-(d).(especially referring to EP-A-0,635,526).

As the dispersion of using in the present invention (B), especially can mention and containing from those of monomer (a), (c) and the homopolymer that (e) obtains.

As copolymer emulsion (B), especially can mention the latex that contains the multipolymer that obtains from following monomer :-at least a monomer (a), at least a monomer (d) and at least a monomer (f);-at least a monomer (a) and at least a monomer (c);-at least two kinds of monomers of different nature (c);-at least a monomer (c) and at least a monomer (f);-at least a monomer (c), at least a monomer (e) and at least a monomer (g);-at least a monomer (c) and at least a monomer (e);-at least a monomer (c) and at least a monomer (m).

According to aforementioned Rayleigh scattering rule, for given siloxane latex, will observe, the elastomeric translucency that contains polymer raw material [this raw material is the polymer beads of the latex (B) of granularity between for example 0.01 μ m (10nm) and 0.06 μ m (60nm) in this case] always is higher than and contains same but have obviously the more elastomeric translucency of the polymer raw material of volume particle size (promptly being higher than 0.06 μ m (60nm)) in this case.Also can observe,,, promptly always can improve translucency greatly by the chemical constitution that changes described polymkeric substance suitably by reducing the refractive index of stock polymer for particulate intended size in the polymer raw material (little or big).

According to the preferred embodiments of the invention, the elastomerics that can in medium paramount scope, regulate for translucency, use has the latex (B) of following parameter :-granularity is between 0.01 μ m (10nm)-0.08 μ m (80nm), preferably between 0.02 μ m (20nm)-0.06 μ m (60nm), and-solids content is between 10-50wt%.

According to preferred embodiment, for realizing above-mentioned translucency purpose, use latex (B), this latex has small grain size and above specified solids content and contains following vinylformic acid (being total to) polymkeric substance :-the acrylate homopolymer that obtains from monomer (c), with-partly or entirely (be selected from monomer (f) from Acrylic Acid Monomer (c) or from least a monomer (c) and another kind of at least Acrylic Acid Monomer, (methyl) vinylformic acid for example, monomer (h), for example acrylic acid derivative, and monomer (k)) multipolymer of Huo Deing.

For part from Acrylic Acid Monomer (c) or (c)+(f) and/or (h) and/or the multipolymer that (k) obtains, the consumption of Acrylic Acid Monomer is in (with respect to monomeric gross weight) between the 70%-99% (wt) and preferably between 80%-99% (wt) (with respect to monomeric gross weight).

Much less, the mechanical property of latex (B) depends on the monomer that is selected to prepare them to a great extent.The polymkeric substance that constitutes latex (B) can have glass transition temperature Tg-70 ℃ and+230 ℃ between.

According to embodiment of the present invention even preferred, employed water dispersion (B) is the above latex that defines in the narration of so-called " more preferably " embodiment, wherein the part acrylic polymkeric substance have glass transition temperature Tg+50 ℃ and+130 ℃ between.The selection of these Tg values makes might obtain the highest enhancing efficient (better value being arranged for fracture property).

The polymkeric substance of forming latex (B) has general refractive index n in the 1.34-1.60 scope.This index is to be calculated by following simplification Gladstone-Dale relational expression: Wherein xi and ni represent the volume fraction of each component of polymkeric substance and refractive index (referring to polymer handbook, 1989, VI/452-VI/461 page or leaf) respectively.

According to highly preferred embodiment of the present invention, employed water dispersion (B) is that above " even the more preferably latex that defines in " the embodiment, wherein the index n of polymkeric substance is between 1.34-1.50 so-called.

According to different embodiments of the present invention, the elastomerics that can in the certain numerical value scope, regulate for translucency, this numerical range is significantly less than the front with regard to the cited medium paramount numerical range of the preferred embodiment of the invention, uses the latex (B) meet the following conditions :-its granularity is between just above the value-10 μ m of 0.08 μ m (80nm) and preferably between the value-2 μ m just above 0.08 μ m (80nm); And solid content is between 30%-70% (weight); With-it contains above vinylformic acid (being total to) polymkeric substance that defines in so-called " more preferably " embodiment.

According to difference of the present invention and embodiment preferred, employed water dispersion (B) is the above latex that defines in so-called " difference " embodiment, wherein the part acrylic polymkeric substance have glass transition temperature Tg+50 ℃ and+130 ℃ between.

According to different and preferred embodiment, employed water dispersion (B) is the above latex that defines in so-called " different and preferred " embodiment, and the index n of its polymkeric substance is between 1.34-1.50.

The preparation of latex (B):

The skilled person knows how to prepare latex (B) in the art.The method that the water dispersion of several preparation organic polymers is arranged; Obtain dispersion by the following method :-by in emulsion, carrying out Raolical polymerizable;-react by the direct polymerization of corresponding monomeric microemulsion;-by emulsification and evaporating solvent: this method is polymkeric substance is dissolved in a kind of water unmixability solvent that boiling point is lower than water, then with polymers soln emulsification in water, removes by evaporation then and desolvates;-by in non-solvent, precipitating: this method is to be settled out polymkeric substance then with in the water-soluble miscible solvent of polymkeric substance from water;-by condensing: this method is, begins with homogeneous phase solution, obtains to be separated by changing physical factor such as pH value or temperature, therefore forms gel phase (being rich in polymkeric substance).

Dropping on the method that being preferred in the scope of the invention prepare latex (B) is the method for the Raolical polymerizable in emulsion.

As for latex (B) with small grain size between 0.01 μ m (10nm)-0.08 μ m (80nm), they use in a preferred embodiment of the invention, they are to prepare by preferred free radical polymerization reaction method, this method is described in EP-A-0, in 644,205 (the enumerating as a reference), this method comprise with monomer gradually increment introduce in the water-containing reacting medium, introduce simultaneously, also optional in the mode of increment gradually, radical initiator.

Metal-cured compound (C)

Compound (C), especially for some linking agent (A2) as silicon ester, can choose use wantonly, but recommend use (C) in the present invention.

Catalytic metal curing compound (C) mainly is the carboxylate salt and the halogenide of the metal selected from lead, zinc, zirconium, titanium, iron, tin, barium, calcium and manganese.

Component (C) is the catalytic tin compound preferably, is generally organic tin salt, preferably introduces with the water miscible liquid form.Spendable organic tin salt specifically describes writing books＜siloxanes chemistry and technology at Noll 〉, academic press (Academic Press) (1968), 337 pages.If need, this emulsion can be stablized with for example polyvinyl alcohol.

The reaction product of alkyl silicate or aryl trialkoxy silane and dibutyltin diacetate salt also can be used, as belgian patent BE-A-842, described in 305.

Preferred pink salt is the two inner complex (EP-A-0 of tin, 147,323 and EP-A-0,235,049), dicarboxylic acid two organic tin salts and especially two branched paraffin carboxylic acid's dibutyl pink salts or dioctyl pink salt (English Patent GB-A-1,289,900), dibutyltin diacetate salt or dioctyl pink salt and dibutyl tin laurate salt or dioctyl pink salt.Per 100 parts (A1) uses 0.01-3, the metal-cured compound (C) of preferred 0.05-2 part.

The additive that other is optional:

Also can comprise one or more additives according to water dispersion of the present invention, for example, especially: (D): randomly, the oil of per 100 weight parts or polymkeric substance (A1), the tackiness agent of 0.1-20 weight part; (E): randomly, the oil of per 100 weight parts or polymkeric substance (A1), the nonionic of 0.1-5 weight part, negatively charged ion or positively charged ion organic silicon surfactant; (F): randomly, at least a compound of significant quantity, these compounds are selected from anti-mycotic agent, defoamer, frostproofer such as ethylene glycol and propylene glycol and thixotropic agent such as carboxymethyl cellulose and xanthene glue.

Preferably; tackiness agent (D) is selected from silicoorganic compound, and this compound carries the organic group of the group replacement of (1) being selected and the hydrolysable group that (2) are connected in Siliciumatom from amino, urea groups, isocyanide acyl group, epoxy group(ing), alkenyl, isocyanuric acid ester group, hydantoyl and thiol esters group.

For example purposes, can mention silicoorganic compound (D) (having attached the patent No. of describing them) corresponding to following formula:

EP-A-0?074?001H ₂N-CH ₂-CH ₂-HN-CH ₂-CH(CH ₃)-COO(CH ₂) ₃-Si(OCH ₃) ₃

DE-A-3?304?182

US-A-4?356?116

US-A-4?273?698

EP-A-0?031?996

(C ₂H ₅O) ₃Si(CH ₂) ₃NHCO-CH=CH-COOH

US-A-4?466?739

US-A-4?115?356

FR-A-2?259?833

Preferably, organic silicon surfactant (E) is selected from that (reagent of this type is with trade(brand)name Tegopren with oxyethane or propylene oxide chain, 30,58 or 70 types, available from Goldschmidt company), or with salifiable amino (reagent of this type also with trade(brand)name Tegopren 69 types available from Goldschmidt company), or with the metal sulfamate alkali (for this reason referring to writing books: surface phenomena in water-based paint and the printing technology and additive; M.K.Sharma compiles, and Plenum press, New York, 1991, the 73-82 page or leaf, it described the reagent of this type) in addition functionalized organopolysiloxane.

The preparation of water dispersion of the present invention

In order to prepare water dispersion of the present invention, suggestion at first joins dispersion (B) in the emulsion (A) under the situation of stirring at room, add metallic curing catalyst (C) (randomly with water dispersion or emulsion form) and optional additive (D), (E) and/or (F) then.What should remind is, might having the lower section or carrying out the emulsion polymerization or the emulsification of emulsion (A) fully in dispersion (B).

The pH value of water dispersion can be acid, neutral or alkaline.Yet suggestion is adjusted to the pH value of dispersion with strong organic bases or preferred strong inorganic base (trolamine and preferably sodium hydroxide and potassium hydroxide) and is higher than 7, preferably the value between 8-13.

The final dispersion that is obtained is by homogenizing, and the degassing then is in the wrapping material of pack into then impermeable atmosphericoxygen and water vapor.

Component (A), (B), (C) and optional (D), (E) and/or (F) mixed, their consumption should make the solids content of final emulsion equal 60wt% at least, preferably between 80-95wt%.

In order to measure solids content, the 2g dispersion is put into the aluminum crucible of having weighed, in dry air round-robin baking oven, heated 3 hours down at 50 ℃.After cooling, crucible weighed again and to measure the percentage ratio of the material that remains from initial 2g, it has represented solids content.

According to a preferred version, after having prepared dispersion of the present invention, it at room temperature experiences a maturation stage of several hours-several days.

This maturation stage is to leave standstill dispersion simply under the situation that is not having atmosphericoxygen before the use.

Can in building industry, be used to prepare translucency silicone elastomer product according to dispersion of the present invention, especially the external coating (EC) of the sealing of building surface and weathering resistance mastic coatings and water repellency coating or the metope that contacts with atrocious weather is with dispersion/m of for example 20-100g ²The such amount in processed surface use.

The following examples are used for illustrating the present invention but are not to limit its scope.

Embodiment 1 (contrast is used)

Emulsion (A) is to prepare by introduce following component in having 5 liters of Meili mixing machines that impact arm: 1000g's is 80 25 ℃ of following viscosity, the α of 000mPa.s, ω-(dihydroxyl) polydimethyl siloxane oil; The CH that the 60g former state is introduced by 62wt% ₃SiO _1.5(the CH of unit and 24wt% ₃) ₂(the CH of SiO unit and 14wt% ₃) ₃SiO _0.5Unit hydroxyl silicone resin that form, that contain the 0.5wt% hydroxyl; This resin dissolves in the toluene and has molecular weight about 1000 and CH ₃/ Si mol ratio is 1.5; The Genapol X080 of 45g by the sale of Hoechst company, it is a nonionogenic tenside, i.e. poly-alkoxylation (having about 8 ethylene oxide units) Fatty Alcohol(C12-C14 and C12-C18) (containing 13 carbon atoms); Water with 35g.

The final mixture that is obtained was by homogenizing 180 minutes.

It is that 0.5 μ m (500nm) and solids content are 96.9wt% that the latex A that obtains like this has mean particle size.

In same mixing machine, following composition is introduced in the emulsion (A), stirred 10 minutes for each additive: solids content is the water dispersion of 43.6% precipitated chalk, composed of the following components: the precipitated chalk of 280g, mean particle size is 0.07 μ m (70nm), be that volume is equal to particulate volume in the polymer raw material of embodiment below, 13g contains the dispersion agent of aqueous solution form of 40wt% sodium polyacrylate and the water of 323g; The water miscible liquid of the Bis(lauroyloxy)dioctyltin salt that contains 38wt% of 10g, this pink salt is stablized with the polyvinyl alcohol of 5wt% (with respect to pink salt); With the solids content of 22g be 50% potassium hydroxide aqueous solution.

Final dispersion have the pH value be 12 and solids content be 81.3wt%.

After storing 4 days, the preparation sample is to be used for measuring following described various performances: the mechanical property of fracture and elasticity aspect:

Dispersion is coated on the teflon plate to obtain the thick film of 2.5mm, then in 7 days (23 ℃ ± 2 ℃ of temperature of air-conditioning room's inner drying with scraper; Relative humidity: 55% ± 5%).

The test piece H2 that downcuts from desciccator diaphragm is measured following performance: extension at break (EB is measured in the explanation according to AFNOR standard T-46002, %) and breaking tenacity (BS, MPa), measure the elasticity (E of mastic coatings by the relaxation test under the following condition, %): sample 100% elongation under 300mm/min speed, extended sample subsequently lax 15 minutes.By equation 100 (1-C ₁₅/ C ₀) evaluation elasticity (%), wherein C ₀And C ₁₅Be sample (C when stopping to extend ₀) and after 15 minutes (C ₁₅) constraint that met with.Elastic evaluation is carried out average 3 samples.

Translucency:

The dispersion of packing in the dark flat crucible of 4mm and this molectron are in 10 days (23 ℃ ± 2 ℃ of temperature of air-conditioning room's inner drying; Relative humidity: 55% ± 5%).

By sample for the contrast gradient of black and white background than (CR %) comes the translucency of working sample.The machine of the same title of selling with Datacolor Machine company under following illumination condition is measured this ratio: the diffused light photograph, use the brightness C of anti-UV and anti-dazzle spectral filter ₁₀Translucency is to be estimated than CR=Y black background/Y white background * 100 (%) by contrast gradient, and promptly CR/100 is by the ratio that is placed on the elastomer sample Y (green glow) of the trichromatic coordinates of the light of reflection under 90 ℃ on the black and white background respectively.

Binding property

After 23 ℃ ± 2 ℃ of temperature and 55% ± 5% time drying of relative humidity 7 days, on the transparent glass carrier by the wide 180 ° of T stripping tests of filming of the 25mm of mastic coatings with the elastomeric binding property of the speed evaluation of 50mm/min (A, newton).

The polyamide fabric of filming in such a way with the big order number of nylon-66 of mastic coatings strengthens: what deposition 1.5mm was thick first films, and sprawls the polymeric amide wire rod in the above; Use the 2.5mm scraper on this molectron, to deposit the second layer of siloxanes water dispersion, and then obtain mastic coatings-polymeric amide-mastic coatings sandwich structural body.

The performance of all measurements is listed in the following table II.

Embodiment 2-7 (according to the present invention)

Carry out this method according to described in the embodiment 1, just have fine-grained latex (B) with 300g now and replace the calcium carbonate water dispersion.

The characteristic of employed nano level latex (nanolatex):

The table I

Embodiment	Form (wt%)	Solids content (wt%)	Mean particle size nm	???Tg(℃) ????(2)	? n ?(3)
						???MMA???STY??BuA???MAA??VTEO
	?2						????90????0????0?????10????0	????30	????40	????114	?1.493
?3		????35????0????55????10????0	????30	????40	????1	?1.480
	?4						????0?????0????90????10????0	????30	????40	????-42	?1.472
?5		????100???0????0?????0?????0	????30	????40	????105	?1.489
	?6						????95????0????0?????0?????5	????30	????40	????105	?1.489

(1) MMA=methyl methacrylate; STY=vinylbenzene; The BuA=butyl acrylate; The MAA=methacrylic acid; The VTEO=vinyltriethoxysilane; (2) Tg is the explanation according to AFNOR standard T51-5077, is measured by dsc (or DSC).(3) (be total to) the refractive index n of polymkeric substance: according to the Index for Calculation of Gladstone-Dale addition rule: n polystyrene=1.591 from homopolymer, n polyacrylic acid=1.527, n polymethylmethacrylate=1.485, n butyl polyacrylate=1.4666.

The general method of preparation nano level latex:

With the 3g Sodium Lauryl Sulphate BP/USP, the aqueous solution that 240.3g water and 0.5g contain the 30wt% ammonium persulphate joins the 1 liter of stainless steel reactor that agitator is housed and is used for the water cycle chuck of temperature in the conditioned reaction device successively.Reactor content was adjusted to 90 ℃ temperature then, continued to add the mixture of 100g ethylenically unsaturated monomer then through 2 hours time.Dispersion is cooled then and filters.

Obtaining solids content 30wt% and mean particle size is the pewter latex of 0.04 μ m (40nm).

The final dispersion of the embodiment 2-7 that is obtained have the pH value be 12 and solids content be 81.3%.

Be listed in the table below in the II with nano level latex enhanced elastomeric properties and with the performance of the reference elasticity body of carbonate:

The table II

	????CR ???(％)	????EB ???(％)	?????BS ???(MPa)	??????E ????(％)	?????A ????(N)
						Embodiment 1 (contrast)	????100	????935	????0.75	????26.5	????0.1
Embodiment 2	????93.0	????930	????0.89	????29.2	????0.5
						Embodiment 3	????88.6	????675	????0.50	????21.3	????0.1
Embodiment 4	????76.3	????640	????0.33	????26.8	????0.1
						Embodiment 5	????87.9	????935	????0.51	????30.6	????10
Embodiment 6	????90.0	????730	????0.77	????42.9	????15

With compare with carbonate enhanced elastomerics, have quite the mechanical property of (if not better words) and significantly higher translucency arranged with nano level latex enhanced elastomerics.

Claims (18)

1. Aqueous dispersions based on siloxane and organic (co)polymers, which are cross-linked by drying at room temperature to remove water into elastomers with high mechanical properties and adjustable translucency, characterized in that they do not Contains any reinforcing inorganic filler and in that it includes the following components: (A): based on 100 parts by weight of oil or α, ω-(dihydroxy) polydiorganosiloxane polymer (A1) and based on 1-100 parts by weight of An oil-in-water emulsion of a silicone crosslinker (A2), which: ·Consisting of at least one surfactant selected from anionic and nonionic surfactants and mixtures thereof Active agent (A3) to stabilize, ·Particle size between 0.1μm (100nm) and 100μm (100,000nm), A solids content of at least 60% by weight; (B): per 100 parts by weight of oil or polymer (A1), 1-100 parts by weight of an aqueous dispersion of at least one organic (co)polymer having Particle size between 0.01μm (10nm) and 10μm (10,000nm); A solids content between 10-70% by weight; (C) optionally used, per 100 parts by weight of oil or polymer (A1), 0.01-5 parts by weight of a catalytic metal curing compound; the aqueous dispersion has a solids content is at least 60% by weight; the translucency of the elastomer product to be prepared is adjusted during the preparation of the aqueous dispersion by adjusting the following parameters to the desired values: the size of the polymer particles in the latex (B) ; or the refractive index of the polymers that make up the latex (B), by changing the chemical composition of the organic (co)polymer; or simultaneously, the above two parameters, namely size and refractive index. 2. Dispersion according to claim 1, characterized in that the α,ω-(dihydroxy)polydiorganosiloxanes (A1) must have a viscosity of at least 50,000 mPa.s at 25°C and in that the siloxanes An organic group is a monovalent hydrocarbon group containing up to 6 carbon atoms, optionally substituted by cyano or fluorine. 3. Dispersion according to claim 1 or 2, characterized in that the crosslinking agent (A2) is selected from the group consisting of: organosilicates; microemulsion resins of silsesquioxane resins; containing alkoxy and acyloxy groups low molecular weight reactive siloxane resins; toluene-insoluble high molecular weight siloxane resins; hydroxy siloxane resins containing at least two different units per molecule and a hydroxyl content (by weight) between 0.1-10% , the unit is selected from those having the following structural formula: R ₃ SiO _0.5 (M), R ₂ SiO (D), RSiO _1.5 (T) and SiO ₂ (Q), R is mainly C ₁ -C ₆ alkyl, ethylene or 3,3,3-trifluoropropyl; Silanes of the formula R _a SiX _4-a , wherein R is a monovalent organic group, especially methyl or vinyl, a is 1 or 0, and X is condensable And/or hydrolyzable groups are preferably selected from alkoxy, acyloxy, ketiminooxy, alkylamino, amido and alkenyloxy groups and various possible mixed groups thereof. 4. Dispersion according to any one of claims 1-3, characterized in that the aqueous dispersion (B) is an aqueous dispersion containing an organic (co)polymer selected from the group consisting of styrene (a), butadiene (b), acrylate (c) and vinylnitrile (d) at least one main monomer (co)polymerization obtained, it is also possible to make these main monomers (a) - some of (d) are copolymerized with up to 40% by weight (relative to the total weight of monomers) of at least one other monomer or unsaturated compound selected from: (e): carboxylic acids (f): ethylenically unsaturated mono- and dicarboxylic acids; (g): combinations of dicarboxylic acids mentioned above in (f) with alkanols containing 1 to 4 carbon atoms Alkyl esters, and their N-substituted derivatives; (h): unsaturated carboxamides; (i): olefinic monomers containing sulfonic acid groups and their ammonium or alkali metal salts; (j): containing secondary , tertiary or quaternary amino or nitrogen-containing heterocyclic ethylenically unsaturated monomers, and zwitterionic monomers; (k): (meth)acrylic acid and preferably alkane containing 2-8 carbon atoms Esters of diols, and monomers containing two polymerizable double bonds; (l): glycidyl methacrylate; (m): vinyl or acryloyl silane; (n): carrying at least one Polyorganosiloxanes functionalized with ethylenically unsaturated functional groups capable of reacting with another ethylenically unsaturated monomer via a free radical pathway. 5. Dispersion according to any one of claims 1-4, characterized in that in order to prepare elastomers whose translucency can be adjusted in the range of medium to high values, the latex (B) used has : - particle size between 0.01 μm (10 nm) and 0.08 μm (80 nm), and - solids content in the range 10-50 wt%. 6. Dispersion according to claim 5, characterized in that the aqueous dispersion or latex (B) contains - a homopolymer of acrylic acid obtained from monomer (c), and - a copolymer obtained partly or wholly from acrylic monomers (c) or from at least one monomer (c) and at least one other acrylic monomer, the copolymer obtained from the monomers (f) , such as (meth)acrylic acid, monomers (h), such as acrylic acid derivatives, and monomers (k); and for parts from acrylic monomers (c) or (c)+(f) and/or (h ) and/or (k) obtained copolymer, the consumption of acrylic acid monomer is between 70%-99% (wt) relative to the total weight of the monomer. 7. Dispersion according to claim 6, characterized in that the aqueous dispersion (B) contains an acrylic organic (co)polymer having a glass transition temperature Tg between +50°C and +130°C. 8. Dispersion according to claim 7, characterized in that the aqueous dispersion (B) contains an acrylic organic (co)polymer with a Tg between +50° C. and +130° C. and a refractive index n between 1.34 and 1.50 between. 9. The aqueous dispersion according to any one of claims 1-3, characterized in that, in order to prepare elastomers whose translucency can be adjusted within a certain value range, the value range is lower than that stated in claim 5. In the medium to high range of values, latex (B) is used which: - has a particle size between values just above 0.08 μm (80 nm) - 10 μm; and has a solids content between 30% and 70% by weight and - it contains the acrylic (co)polymer as defined in claim 6 above. 10. The aqueous dispersion according to claim 9, characterized in that the aqueous dispersion (B) contains an acrylic organic (co)polymer having a glass transition temperature Tg between +50°C and +130°C. 11. The aqueous dispersion according to claim 10, characterized in that the aqueous dispersion (B) contains an acrylic organic (co)polymer having a Tg between +50° C. and +130° C. and a refractive index n between 1.34 and Between 1.50. 12. Aqueous dispersion according to any one of claims 5-8, characterized in that latex B has a particle size between 0.02 [mu]m (20 nm) and 0.06 [mu]m (60 nm). 13. Aqueous dispersion according to any one of claims 9-11, characterized in that the particle size of latex B is between a value just above 0.08 [mu]m (80 nm) - 2 [mu]m. 14. Aqueous dispersion according to any one of claims 1-13, characterized in that: • the solids content of the emulsion (A) is 80-98% by weight; • the solids content of the final aqueous dispersion is 80-95% by weight. 15. Aqueous dispersion according to any one of claims 1-14, characterized in that the metal compound (C) is an organotin salt in the form of an aqueous emulsion. 16. Process for the preparation of aqueous dispersions as defined in claims 1-15, characterized in that the dispersion (B) is first added to the emulsion (A) at room temperature and subsequently the metal curing catalyst (C) is added, the Catalyst (C) optionally takes the form of an aqueous dispersion or emulsion, with addition of optional additives. 17. Process according to claim 16, characterized in that the pH of the final aqueous dispersion is adjusted to a value above 7 by adding a strong inorganic base. 18. Use of an aqueous dispersion as defined in any one of claims 1 to 16 in the construction industry for the preparation of translucent siloxanes consisting of sealing and weather-resistant mastics, protective paints and topcoats for walls The use of alkane elastic products.