CA1191747A - Process for the preparation of coatings - Google Patents
Process for the preparation of coatingsInfo
- Publication number
- CA1191747A CA1191747A CA000420160A CA420160A CA1191747A CA 1191747 A CA1191747 A CA 1191747A CA 000420160 A CA000420160 A CA 000420160A CA 420160 A CA420160 A CA 420160A CA 1191747 A CA1191747 A CA 1191747A
- Authority
- CA
- Canada
- Prior art keywords
- prepolymer
- coating
- mixture
- weight
- isocyanate groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/488—Other macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C04B41/4884—Polyurethanes; Polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
Abstract
PROCESS FOR THE PREPARATION OF COATINGS
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the preparation of coatings using a coating compound based on a system comprising (i) an isocyanate prepolymer based on isophorone diisocyanate and polyalkylene ether polyols having a hydroxyl functionality of 2 to 3 and (ii) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino group.
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the preparation of coatings using a coating compound based on a system comprising (i) an isocyanate prepolymer based on isophorone diisocyanate and polyalkylene ether polyols having a hydroxyl functionality of 2 to 3 and (ii) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino group.
Description
Mo-2447 -1- LeA 21,531 PROCESS FOR THE PREPARATION OF COATINGS
_ FIELD OF THE INVENTION
The invention concerns a process for the preparation of a coating compound and, more particularly, to the preparation of a coating comprising an isocyanate prepolymer.
_CKGROUND OF THE INVENTION
Both rendered and bare building constructions of mineral buildlng materials such as those based on concrete or brick must, in many cases, be covered with a dense, firmly adheringcoating to prevent corrosion of the building materials or of the reinforcing steel. Coatings are also required when chemical attack on the building material is to be expected or where structures such as floors, storage tanks and concrete containers need to be reliably sealed.
The film of coating must have sufficient elasticity to maintain the seal even if cracks form in the substrate, i.e., it should be capable of bridging over the cracks.
The protective function of the coatings is ensured only if the coating films are sufficiently elastic and form a layer of sufficient thickness. These factors have been indicated in the literature (see, for example, "Riss~berbr~ckende Kunststoffbeschichtungen f~r mineralische Baustoffe" by G~nter Rieche, Otto-Graf-Institut Stuttgart, Farbe und Lack, publishers Kurt Vinzenz Verlag, Hanover, Year 85, pages 824-831, 1979).
The coatings are generally required to have a minimum thickness of 0.1 mm and the coating materials should have a rninimum elongation of 100~.
When choosing a coating material, it should be noted that the surfaces to be coated are generally porous and frequently contain a certain quantity of water, the so-called physically associated moisture being assumed to Mo-2447 LeA 21 531-US
~i '7 be approximately 3.5~ by weight. In many cases, especially when applying coa-tlngs outdoors, the water content is found to be conslderably hlgher, and this is bound to lead to interactions with the coating materlal.
Solvent-free polvure-thane systems are the obvious choice for the desired thick-layered elastic coatlngs slnce the polylsocyanates and polyalcohols used as starting ma-terials for the polyurethane coatings can be selected as required to provlde elastic coating fllms of any thickness. Difficulties arise however in that the lsocyanate groups not only react with polyalcohols but also enter lnto competitive reaction with the moisture of the underlylng surface. Thls has the undesirable effect of splitting off carbon dioxide which causes the coating materlal to foam up and form bllsters. Numerous proposals have heen made aimed at the suppression of this undesirable slde reaction. The addition of molecular sieve æeolites has provedto be particularly effective for removing any troublesome water content ln the fillers, pigments or other constituents of the coating materlals so that water derived therefrom will not cause blistering (see, for example, "Polyurethane f~r Beschichtungen und Abdichtungen im Bauwesen", Hermann Gruber, Farbe und Lack, Publishers Verlag Vinzenz, Hanover, Year 80, pages 831-837, 1974).
The "molecular sieve zeolite method" cannot however meet the demands of excessive subsurface moisture with the result that the formation of blisters due to the splitting off of carbon dioxide cannot be prevented with certainty when the coating is applied to moist substrates.
Mo 2447 3~.'7~'7 Thc present illvention provicles a new process for the production of coatings and enables thick, elastic coatings to be applied, in particular to mineral based building materials containing water, which would reliably prevent the undesirable formatlon of blis-ters even in the presence of a high content o subsllr~ace moisture, and for which solvent-free or low solvent co~ting compounds of low viscosity and sufficiently long pot life could be used.
This problem could be solved by the process according to the invention described in detai] below.
SUMMARY OF THE INVENTION
The present invention relates to a process ror the product;on of elastic coatings by coating any substt-ates with a solvent-free or low solvent coating composition, containing, as binder, a two-component system of (i) a polyisocyanate component and (ii) a hardener component, characterized in that (i) has an isocyanate content of from 1 to ~0% by weight and comprises at least one prepolymer containing free iso cyanate groups based on l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohe~ane and one or more poly-alkylene ether polyols having an (average) hydroxyl functionality of from 2 to 3, (ii) comprises to an extent of at least 50 equivalent percent of polyamines selected From the group consisting of a) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in Mo-2447 ," ~
-3a an ortho-position to each amino group and optionally also methyl substituents in further ortho-positions to the amino groups, b) reaction products of such diamines with a sub-equivalent amount of either a prepolymer containing free isocyanate groups based on an organic diisocyanate having a molecular weight of from i68 to 300 and at least one polyalkylene ether polyol having ~0 Mo-2447 i ' 7 ~ i~
an (average) hydroxyl functionality o~ 2 to 3 or oF a mixture of such a pre-polymer ,of up to 500 isocyanate equivalent percents, based on the isocyanate groups of said prepolymer with said cliisoc~anate and c) mixtures of a) and b) and to an extent of up to 50 equivalent percents of dihydric or trihydric alcohols having primary hydroxyl groups and in that (i) and (ii) being used in quantitative proportions corresponding to an NC0/N~2 equivalent ratio in the range of from 0,5:1 to lj5:1.
DETAILED DESCRIPTION OF THE INVENTION
Essential to the process of the invention ls the use of new two-component binders consisting of an isocyanate component (i) and a hardener component (ii).
Isocyanate component (i) has an isocyanate content of from 1 to 20% by weight, preferably from 2 to 10~
by weight. Isocyanate component (i) comprises either a prepolymer based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and polyether polyols or polyether polyol mixtures having an (average) OH function-ality of from 2 to 3 and an (average) molecular weight, calculated from the functionality and the hydroxyl content, of from 500 to 4000, preferably from 1000 to 3000, or mixtures of said prepolymer having up to 500, preferably up to 300, isocyanate equivalents percent, based on the isocyanate groups of the prepolymer, with other organic polyisocyanates having aliphatically and/or cycloaliphatically bound isocyanate groups.
Preparation of the isocyanate prepolymers is carried out in a known manner by the reaction of IPDI with subequivalent quantities of polyether polyols or poly-ether polyol mixtures having an (average) hydroxyl functionality of 2 to 3 and an (average) molecular weight, calculated from the hydroxyl functionality and hydroxyl content, of from 500 to 4000, preferably from 1000 to Mo-2447 d' ( ~ ~' _S_~
3000, observing an NCO/O~ equivalent ratio in the range oE from 1.5:1 to 7:1, preferably Erom 2:1 to 4:1. When using an IPDI excess above 2:1 in this reaetion, mixtures of prepolymers with free IPDI are obtained, which are also suitable as isocyanate component for -the process according to the invention. The isocyanate component (i) used in the process according to the invention may also consist of mixtures of prepolymers of the type mentioned above ~ith up to 500 isoeyanate equivalents per-cent, preferably up to 300 isoeyanate equivalents pereent,based on the isocyanate groups of the prepolymer, other organie polyisocyanates having aliphatically and/or cyeloaliphatically bound isoeyanate groups sueh as, for example, 4,4'-diisoeyanato-dieyelohexylmethane, hexamethylene diisoeyanate, tris-(isoeyanatohexyl)-biuret and/or tris-(isoeyanatohexyl)-isocyanurate, but this is less preferred than the use of pure prepolymers or their mixtures with exeess IPDI.
Suitable polyalkylene ether polyols for the preparation of the prepolymers inelude the known compounds used in polyurethane chemistry such as alkoxylation produets, in partieular ethoxylation and/or propoxylation products of di- and/or trifunctional starter molecules sueh as water, ethylene glycol, 1,2-dihydroxypropane, trimethylolpropane or glycerol. Polyether polyol mixtures, obtained by the alkoxylation of starting mixtures having an average hydroxyl functionality of 2 to 3 and containing compounds with more than 3 hydroxyl groups (such as pentaerythritol) may also be used.
PreEerred polyether polyols include polypropylene glycol and/or propoxylated trimethylolpropane within the above-mentioned (average) molecular weight range.
Mo~2447 Ihe hr-~rclener component (:ii) whlch IS essentlal to th:is invention May be a) at least one dLprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino ~roup and optionally also me-thyl subs-tituents in other ortho-positions to the amino groups. These compounds have a molecular weight of from 178 to 346. Typical examples oE such aromatic diamines include l-methyl-3,5-diethyl-2,a-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 10 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3',5'-tetraethyl-4, 4'-diamino-diphenylmethane, 3,5,3',5'-tetraisopropyl-4, 4 ' -diamino-diphenylmethane, 3, 5-diethyl-3',5'-diisoproPyl-4, 4 ' -diamino-diphenylmethane and any mixtures of such diamines.
r, The hardener component ( ii ) which is essential to this invention may also be b ) the reaction product of at least one such aromatic diamine wi th a subequivalent amount of a NCO-prepolymer or with a mlxture of NCO-pre-polymer with up to 500 equivalent percents, based on the isocyanate groups of the NCO-prepolymer of an organic diisocyanate having a molecular weight ?~ f From 168 to 300. The NCO-prepolymer may be the reaction product of a polyether polyol or polyether polyol mixture of the kind disclosed herein-before with any organic diisocyanate having a molecular weight of from 168 to 300 such as hexamethylene diisocyanate, IPDI, 2,4- and/or 2,6-diisocyanato toluene , 4, 4 ' -diisocyanato-diphenylmethane or 4, 4 ' -di-~5 isocyanato-dicyclohexane observing an NCO/OH equivalent ratio in the range of from 1,5:1 to 7:1, preferably from 2:1 to 4:1. If an excess greater than 2:1 is used a mixture of prepolymer with the diisocyanate is formed. The reaction product of the diamine with the NCO-prepolymer resp. mixture of NCO-prepolymer with -.n diisocyanate is preferably obtained by simply bringing the re-actants together at room temperature at an equivalent ratio between amino groups and NCO-groups of from 1, 5 :1 to 20 :1 ore-ferably of from 3:1 to 8:1. This can be done in the presence of additives which are inert towards amino and isocyanate groups ~:~ and which are commonly used in coating compositions. After combi-nation of the reactants the mixtures are stored at room temperature until the reaction is completed (e.g. from 10 to 30 minutes). If an excess oF amine is used which is greater than 2:1 mixtures c) of free amine and reaction product are obtained which may be used as compo-nent ( i i ) .
-6a-The hardener component (ii.) may also comprise up to 50 equivalent percents, based on all the isocyanate reactive groups present in ~he mixture of dihydric or trihydric, preferably dihydric alcohols having primary hydroxyl groups, e.g., ethylene glycol, diethylene glycol, trie~hylene glycol or other polyether polyols of ~he above-mentioned functionality containing (primary) hydroxyethyl end groups and having an (average) molecu-lar weight of up to 6000. The use of hardener mixtures of this ~ype is, however, less preferred than the use of pure aromatic diamines or diamine mixtures.
Components (i) and (ii) which are essential to this invention are used in such quantities when carrying out the process according to the invention that the equivalent ratio of isocyanate groups of component ~i) to amino groups of component (ii) is in the range of from 0~5:1 to 1.5:1, preferably from 0.9:1 to 1.1:1.
Mo-2447 `1~.
, ~ i , 71'1~7 When using the less preferred mixtures men-tioned above as hardener componen-t (ii~, the NCO/NH2 equivalent ratio is preferably kept below 1:1, the ratio being dependent on the proportion of polyol component, in the hardener mixture, so that the total ratio of iso-cyanate groups to all isocyanate reactive groups is approximately in the range of 0.9:1 to l.l:l.
It is frequently advantageous if, in addition to the binder components (i) and (ii), there are incorporated, in the coating compounds to be used according to the invention, from 0.1 to 5% by weiyht, preferably from 0~5 to 2% by weight, of organic, preferably cycloaliphatic carboxylic acid anhydrides, in particular dicarboxylic acid anhydrides such as hexahydrophthalic acid anhydride or methyl hexahydrophthalic acid anhydride, which results in a marked improvement in the rate of hardening without adversely affecting the pot life of the coating compounds.
The coating compounds to be used according to the invention may also contain the usual auxiliary agents and additives employed in coating technology.
Thus, the coating compounds may contain, for example, up to 15% by weight, based on the total weight of coating compounds, of conventional lacquer solvents such as toluene, xylene, butylacetate and/or ethylene glycol monoethylether acetate although the use of solvent-free coating compounds is preferred according to the invention.
Other auxiliary agents and additives which may optionally be used include, e.g., pigments, fillers plastizisers such as 3a e.g. coal tar and levelling agents. It is generally not necessary to add the usual catalysts which accelerate isocyanate addition reactions since the coating compounds to be used according to the invention have a sufficiently high reactivity in the absence of such catalysts.
Mo-2447 The coating compounds having the compositlon described above and to be used according to the invention generally have a viscosity at 23C of from 1000 to 20,000 mPa.s and a pot life of approximately 5 to 60 minutes.
They may be used by the usual methods of coating technology for coating any substrates. The preferred field of application of the coating compounds to be used according to the invention is the coating of mineral building materials which are frequently moist, e.g., the coating of concrete constructions or of brick work.
The special advantage of the process according to the invention lies in the fact that when coating such moist mineral substrates, highly elastic, homogeneous coatings, i.e., coatings free from blisters are obtained. The process according to the invention is suitable, in parti-cular, for the production of thick coatings on such substrates, i.e., coatings having a dry film thickness of from 0.2 to 5 mm.
The process according to the invention is further illustrated in the following examples.
EXA~IPLES
The following isocyanate components are used in the examples given below:
Isocyanate component A:
. .
1000 g of isophorone diisocyanate are added to 4000 g of a polypropylene glycol ether having an average molecular weight of 2000 obtained by the propoxylation of 1,2-dihydroxypropane, and the mixture is reacted at 100C
to produce a mixture of prepolymers and free IPDI corres-ponding to the above-mentioned starting materials and containing isocyanate groups amounting to an isocyanate content of 4% by weight. The mixture obtained is a clear liquid having a viscosity of 5 Pas/23C. The mixture Mo-2447 '7'~7 ~ 9_ contains no ~el parti`cles and is suitable for use as isocyanate component for a solvent-free coating compound.
Isocyanate component B: (Comparison) 750 y of 2,4-diisocyanatotoluene are added to 4000 g of a polypropylene glycol ether having an average molecular weight of 3000 which has been obtained by the propo~ylation of trimethylolpropane, and the components are reacted -together at 100C to produce an isocyana-te prepolymer having an isocyanate content of 10 3.5%. A clear liquid having a viscosity of 8 Pas/23C
is obtained.
A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip off, a mixture of 200 g of isocyanate component A and 13.5 g of 1-methyl-3,5-diethyl-2,4-diaminobenzene is poured over the panel. The mixture has a working lifeof ca. 30 minutes which is sufficient for practical purposes, and hardens on the moist surface to form a coating covering over the cracks without forming blisters or other structural irregularities.
The followillg mechanical properties characterize the coating:
Elongation at break according to DIN 53 455 800%
30 Tensile strength according to DIN 53 455 24 N/mm Tear propagation resistance according to DIN 53 515 30 N/mm2 This example illustrates the accelerating effect of a carboxylic acid anhydride on the complete process of hardening of the coating of Example 1. The amount of acid anhydride was varied from 0.2 to 1.0, based on the whole mixture. As a measure of the speed of hardening, the Shore hardness is determined 5 hours after application of the coating compound. The results are shown in the following Table.
Mo-2447 Working time and Shore hardness A determined as functions of the amount of methylhexahydrophthalic acid anhydride added.
Working timeShore A hardness 5 7 Addition _(minutes) _after 5 hours 0.0 30 15 0.2 27 36 0.4 25 50 0.6 23 54 0.8 22 60 1.0 20 62 As may be seen from the figures, the speed o~
hardening is doubled and the pot life is insubstantially reduced by the addition of 0.2%.
EXAMPLE 3 (Comparison) A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip off, a mixture of 200 g of isocyanate component B, 11.5 g of triethylene glycol, 5 g of zeolite powder as drying agent and 0.05 g of dibutyl tin dilaurate is poured over the panel. The mixture remains in a workable condition for ca. 60 minutes but compared with Example 1 it hardens with the formation of a large number of blisters and is unsuitable for use as a coating required to bridge over the cracks.
Although the invention has been described in detail in the foregoing for the purpose of illustration it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2447 ,;, . .. ~
d ~
Example 4 100 9 of isocyanate component A is admixed with a separate mixture which has been obtained by mixing 100 9 of coal tar, 50 9 o~ aluminum silicate, 10 9 of 1-methyl-3,5-diethyl-2,4-diamino-benzene and 25 9 of isocyanate 5 component B and storage of the reaction mixture for 30 minutes.
A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip o~F above reaction mixture is poured over the panel. The mixture remains in a workable condition for abou~ 90 minutes and hardens without formation of any blisters. The following mechanical properties characterise the coating:
Elongation at break according to DIN 53455 70D Do tensile strength according to DIN 53455 5 N/mm tear propagation resistance according to DIn 53515 15 N/mm
_ FIELD OF THE INVENTION
The invention concerns a process for the preparation of a coating compound and, more particularly, to the preparation of a coating comprising an isocyanate prepolymer.
_CKGROUND OF THE INVENTION
Both rendered and bare building constructions of mineral buildlng materials such as those based on concrete or brick must, in many cases, be covered with a dense, firmly adheringcoating to prevent corrosion of the building materials or of the reinforcing steel. Coatings are also required when chemical attack on the building material is to be expected or where structures such as floors, storage tanks and concrete containers need to be reliably sealed.
The film of coating must have sufficient elasticity to maintain the seal even if cracks form in the substrate, i.e., it should be capable of bridging over the cracks.
The protective function of the coatings is ensured only if the coating films are sufficiently elastic and form a layer of sufficient thickness. These factors have been indicated in the literature (see, for example, "Riss~berbr~ckende Kunststoffbeschichtungen f~r mineralische Baustoffe" by G~nter Rieche, Otto-Graf-Institut Stuttgart, Farbe und Lack, publishers Kurt Vinzenz Verlag, Hanover, Year 85, pages 824-831, 1979).
The coatings are generally required to have a minimum thickness of 0.1 mm and the coating materials should have a rninimum elongation of 100~.
When choosing a coating material, it should be noted that the surfaces to be coated are generally porous and frequently contain a certain quantity of water, the so-called physically associated moisture being assumed to Mo-2447 LeA 21 531-US
~i '7 be approximately 3.5~ by weight. In many cases, especially when applying coa-tlngs outdoors, the water content is found to be conslderably hlgher, and this is bound to lead to interactions with the coating materlal.
Solvent-free polvure-thane systems are the obvious choice for the desired thick-layered elastic coatlngs slnce the polylsocyanates and polyalcohols used as starting ma-terials for the polyurethane coatings can be selected as required to provlde elastic coating fllms of any thickness. Difficulties arise however in that the lsocyanate groups not only react with polyalcohols but also enter lnto competitive reaction with the moisture of the underlylng surface. Thls has the undesirable effect of splitting off carbon dioxide which causes the coating materlal to foam up and form bllsters. Numerous proposals have heen made aimed at the suppression of this undesirable slde reaction. The addition of molecular sieve æeolites has provedto be particularly effective for removing any troublesome water content ln the fillers, pigments or other constituents of the coating materlals so that water derived therefrom will not cause blistering (see, for example, "Polyurethane f~r Beschichtungen und Abdichtungen im Bauwesen", Hermann Gruber, Farbe und Lack, Publishers Verlag Vinzenz, Hanover, Year 80, pages 831-837, 1974).
The "molecular sieve zeolite method" cannot however meet the demands of excessive subsurface moisture with the result that the formation of blisters due to the splitting off of carbon dioxide cannot be prevented with certainty when the coating is applied to moist substrates.
Mo 2447 3~.'7~'7 Thc present illvention provicles a new process for the production of coatings and enables thick, elastic coatings to be applied, in particular to mineral based building materials containing water, which would reliably prevent the undesirable formatlon of blis-ters even in the presence of a high content o subsllr~ace moisture, and for which solvent-free or low solvent co~ting compounds of low viscosity and sufficiently long pot life could be used.
This problem could be solved by the process according to the invention described in detai] below.
SUMMARY OF THE INVENTION
The present invention relates to a process ror the product;on of elastic coatings by coating any substt-ates with a solvent-free or low solvent coating composition, containing, as binder, a two-component system of (i) a polyisocyanate component and (ii) a hardener component, characterized in that (i) has an isocyanate content of from 1 to ~0% by weight and comprises at least one prepolymer containing free iso cyanate groups based on l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohe~ane and one or more poly-alkylene ether polyols having an (average) hydroxyl functionality of from 2 to 3, (ii) comprises to an extent of at least 50 equivalent percent of polyamines selected From the group consisting of a) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in Mo-2447 ," ~
-3a an ortho-position to each amino group and optionally also methyl substituents in further ortho-positions to the amino groups, b) reaction products of such diamines with a sub-equivalent amount of either a prepolymer containing free isocyanate groups based on an organic diisocyanate having a molecular weight of from i68 to 300 and at least one polyalkylene ether polyol having ~0 Mo-2447 i ' 7 ~ i~
an (average) hydroxyl functionality o~ 2 to 3 or oF a mixture of such a pre-polymer ,of up to 500 isocyanate equivalent percents, based on the isocyanate groups of said prepolymer with said cliisoc~anate and c) mixtures of a) and b) and to an extent of up to 50 equivalent percents of dihydric or trihydric alcohols having primary hydroxyl groups and in that (i) and (ii) being used in quantitative proportions corresponding to an NC0/N~2 equivalent ratio in the range of from 0,5:1 to lj5:1.
DETAILED DESCRIPTION OF THE INVENTION
Essential to the process of the invention ls the use of new two-component binders consisting of an isocyanate component (i) and a hardener component (ii).
Isocyanate component (i) has an isocyanate content of from 1 to 20% by weight, preferably from 2 to 10~
by weight. Isocyanate component (i) comprises either a prepolymer based on 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and polyether polyols or polyether polyol mixtures having an (average) OH function-ality of from 2 to 3 and an (average) molecular weight, calculated from the functionality and the hydroxyl content, of from 500 to 4000, preferably from 1000 to 3000, or mixtures of said prepolymer having up to 500, preferably up to 300, isocyanate equivalents percent, based on the isocyanate groups of the prepolymer, with other organic polyisocyanates having aliphatically and/or cycloaliphatically bound isocyanate groups.
Preparation of the isocyanate prepolymers is carried out in a known manner by the reaction of IPDI with subequivalent quantities of polyether polyols or poly-ether polyol mixtures having an (average) hydroxyl functionality of 2 to 3 and an (average) molecular weight, calculated from the hydroxyl functionality and hydroxyl content, of from 500 to 4000, preferably from 1000 to Mo-2447 d' ( ~ ~' _S_~
3000, observing an NCO/O~ equivalent ratio in the range oE from 1.5:1 to 7:1, preferably Erom 2:1 to 4:1. When using an IPDI excess above 2:1 in this reaetion, mixtures of prepolymers with free IPDI are obtained, which are also suitable as isocyanate component for -the process according to the invention. The isocyanate component (i) used in the process according to the invention may also consist of mixtures of prepolymers of the type mentioned above ~ith up to 500 isoeyanate equivalents per-cent, preferably up to 300 isoeyanate equivalents pereent,based on the isocyanate groups of the prepolymer, other organie polyisocyanates having aliphatically and/or cyeloaliphatically bound isoeyanate groups sueh as, for example, 4,4'-diisoeyanato-dieyelohexylmethane, hexamethylene diisoeyanate, tris-(isoeyanatohexyl)-biuret and/or tris-(isoeyanatohexyl)-isocyanurate, but this is less preferred than the use of pure prepolymers or their mixtures with exeess IPDI.
Suitable polyalkylene ether polyols for the preparation of the prepolymers inelude the known compounds used in polyurethane chemistry such as alkoxylation produets, in partieular ethoxylation and/or propoxylation products of di- and/or trifunctional starter molecules sueh as water, ethylene glycol, 1,2-dihydroxypropane, trimethylolpropane or glycerol. Polyether polyol mixtures, obtained by the alkoxylation of starting mixtures having an average hydroxyl functionality of 2 to 3 and containing compounds with more than 3 hydroxyl groups (such as pentaerythritol) may also be used.
PreEerred polyether polyols include polypropylene glycol and/or propoxylated trimethylolpropane within the above-mentioned (average) molecular weight range.
Mo~2447 Ihe hr-~rclener component (:ii) whlch IS essentlal to th:is invention May be a) at least one dLprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino ~roup and optionally also me-thyl subs-tituents in other ortho-positions to the amino groups. These compounds have a molecular weight of from 178 to 346. Typical examples oE such aromatic diamines include l-methyl-3,5-diethyl-2,a-diaminobenzene, l-methyl-3,5-diethyl-2,6-diaminobenzene, 10 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3',5'-tetraethyl-4, 4'-diamino-diphenylmethane, 3,5,3',5'-tetraisopropyl-4, 4 ' -diamino-diphenylmethane, 3, 5-diethyl-3',5'-diisoproPyl-4, 4 ' -diamino-diphenylmethane and any mixtures of such diamines.
r, The hardener component ( ii ) which is essential to this invention may also be b ) the reaction product of at least one such aromatic diamine wi th a subequivalent amount of a NCO-prepolymer or with a mlxture of NCO-pre-polymer with up to 500 equivalent percents, based on the isocyanate groups of the NCO-prepolymer of an organic diisocyanate having a molecular weight ?~ f From 168 to 300. The NCO-prepolymer may be the reaction product of a polyether polyol or polyether polyol mixture of the kind disclosed herein-before with any organic diisocyanate having a molecular weight of from 168 to 300 such as hexamethylene diisocyanate, IPDI, 2,4- and/or 2,6-diisocyanato toluene , 4, 4 ' -diisocyanato-diphenylmethane or 4, 4 ' -di-~5 isocyanato-dicyclohexane observing an NCO/OH equivalent ratio in the range of from 1,5:1 to 7:1, preferably from 2:1 to 4:1. If an excess greater than 2:1 is used a mixture of prepolymer with the diisocyanate is formed. The reaction product of the diamine with the NCO-prepolymer resp. mixture of NCO-prepolymer with -.n diisocyanate is preferably obtained by simply bringing the re-actants together at room temperature at an equivalent ratio between amino groups and NCO-groups of from 1, 5 :1 to 20 :1 ore-ferably of from 3:1 to 8:1. This can be done in the presence of additives which are inert towards amino and isocyanate groups ~:~ and which are commonly used in coating compositions. After combi-nation of the reactants the mixtures are stored at room temperature until the reaction is completed (e.g. from 10 to 30 minutes). If an excess oF amine is used which is greater than 2:1 mixtures c) of free amine and reaction product are obtained which may be used as compo-nent ( i i ) .
-6a-The hardener component (ii.) may also comprise up to 50 equivalent percents, based on all the isocyanate reactive groups present in ~he mixture of dihydric or trihydric, preferably dihydric alcohols having primary hydroxyl groups, e.g., ethylene glycol, diethylene glycol, trie~hylene glycol or other polyether polyols of ~he above-mentioned functionality containing (primary) hydroxyethyl end groups and having an (average) molecu-lar weight of up to 6000. The use of hardener mixtures of this ~ype is, however, less preferred than the use of pure aromatic diamines or diamine mixtures.
Components (i) and (ii) which are essential to this invention are used in such quantities when carrying out the process according to the invention that the equivalent ratio of isocyanate groups of component ~i) to amino groups of component (ii) is in the range of from 0~5:1 to 1.5:1, preferably from 0.9:1 to 1.1:1.
Mo-2447 `1~.
, ~ i , 71'1~7 When using the less preferred mixtures men-tioned above as hardener componen-t (ii~, the NCO/NH2 equivalent ratio is preferably kept below 1:1, the ratio being dependent on the proportion of polyol component, in the hardener mixture, so that the total ratio of iso-cyanate groups to all isocyanate reactive groups is approximately in the range of 0.9:1 to l.l:l.
It is frequently advantageous if, in addition to the binder components (i) and (ii), there are incorporated, in the coating compounds to be used according to the invention, from 0.1 to 5% by weiyht, preferably from 0~5 to 2% by weight, of organic, preferably cycloaliphatic carboxylic acid anhydrides, in particular dicarboxylic acid anhydrides such as hexahydrophthalic acid anhydride or methyl hexahydrophthalic acid anhydride, which results in a marked improvement in the rate of hardening without adversely affecting the pot life of the coating compounds.
The coating compounds to be used according to the invention may also contain the usual auxiliary agents and additives employed in coating technology.
Thus, the coating compounds may contain, for example, up to 15% by weight, based on the total weight of coating compounds, of conventional lacquer solvents such as toluene, xylene, butylacetate and/or ethylene glycol monoethylether acetate although the use of solvent-free coating compounds is preferred according to the invention.
Other auxiliary agents and additives which may optionally be used include, e.g., pigments, fillers plastizisers such as 3a e.g. coal tar and levelling agents. It is generally not necessary to add the usual catalysts which accelerate isocyanate addition reactions since the coating compounds to be used according to the invention have a sufficiently high reactivity in the absence of such catalysts.
Mo-2447 The coating compounds having the compositlon described above and to be used according to the invention generally have a viscosity at 23C of from 1000 to 20,000 mPa.s and a pot life of approximately 5 to 60 minutes.
They may be used by the usual methods of coating technology for coating any substrates. The preferred field of application of the coating compounds to be used according to the invention is the coating of mineral building materials which are frequently moist, e.g., the coating of concrete constructions or of brick work.
The special advantage of the process according to the invention lies in the fact that when coating such moist mineral substrates, highly elastic, homogeneous coatings, i.e., coatings free from blisters are obtained. The process according to the invention is suitable, in parti-cular, for the production of thick coatings on such substrates, i.e., coatings having a dry film thickness of from 0.2 to 5 mm.
The process according to the invention is further illustrated in the following examples.
EXA~IPLES
The following isocyanate components are used in the examples given below:
Isocyanate component A:
. .
1000 g of isophorone diisocyanate are added to 4000 g of a polypropylene glycol ether having an average molecular weight of 2000 obtained by the propoxylation of 1,2-dihydroxypropane, and the mixture is reacted at 100C
to produce a mixture of prepolymers and free IPDI corres-ponding to the above-mentioned starting materials and containing isocyanate groups amounting to an isocyanate content of 4% by weight. The mixture obtained is a clear liquid having a viscosity of 5 Pas/23C. The mixture Mo-2447 '7'~7 ~ 9_ contains no ~el parti`cles and is suitable for use as isocyanate component for a solvent-free coating compound.
Isocyanate component B: (Comparison) 750 y of 2,4-diisocyanatotoluene are added to 4000 g of a polypropylene glycol ether having an average molecular weight of 3000 which has been obtained by the propo~ylation of trimethylolpropane, and the components are reacted -together at 100C to produce an isocyana-te prepolymer having an isocyanate content of 10 3.5%. A clear liquid having a viscosity of 8 Pas/23C
is obtained.
A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip off, a mixture of 200 g of isocyanate component A and 13.5 g of 1-methyl-3,5-diethyl-2,4-diaminobenzene is poured over the panel. The mixture has a working lifeof ca. 30 minutes which is sufficient for practical purposes, and hardens on the moist surface to form a coating covering over the cracks without forming blisters or other structural irregularities.
The followillg mechanical properties characterize the coating:
Elongation at break according to DIN 53 455 800%
30 Tensile strength according to DIN 53 455 24 N/mm Tear propagation resistance according to DIN 53 515 30 N/mm2 This example illustrates the accelerating effect of a carboxylic acid anhydride on the complete process of hardening of the coating of Example 1. The amount of acid anhydride was varied from 0.2 to 1.0, based on the whole mixture. As a measure of the speed of hardening, the Shore hardness is determined 5 hours after application of the coating compound. The results are shown in the following Table.
Mo-2447 Working time and Shore hardness A determined as functions of the amount of methylhexahydrophthalic acid anhydride added.
Working timeShore A hardness 5 7 Addition _(minutes) _after 5 hours 0.0 30 15 0.2 27 36 0.4 25 50 0.6 23 54 0.8 22 60 1.0 20 62 As may be seen from the figures, the speed o~
hardening is doubled and the pot life is insubstantially reduced by the addition of 0.2%.
EXAMPLE 3 (Comparison) A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip off, a mixture of 200 g of isocyanate component B, 11.5 g of triethylene glycol, 5 g of zeolite powder as drying agent and 0.05 g of dibutyl tin dilaurate is poured over the panel. The mixture remains in a workable condition for ca. 60 minutes but compared with Example 1 it hardens with the formation of a large number of blisters and is unsuitable for use as a coating required to bridge over the cracks.
Although the invention has been described in detail in the foregoing for the purpose of illustration it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2447 ,;, . .. ~
d ~
Example 4 100 9 of isocyanate component A is admixed with a separate mixture which has been obtained by mixing 100 9 of coal tar, 50 9 o~ aluminum silicate, 10 9 of 1-methyl-3,5-diethyl-2,4-diamino-benzene and 25 9 of isocyanate 5 component B and storage of the reaction mixture for 30 minutes.
A concrete panel measuring 50 x 20 x 1.5 cm is immersed in water and after it has been left to allow the water to drip o~F above reaction mixture is poured over the panel. The mixture remains in a workable condition for abou~ 90 minutes and hardens without formation of any blisters. The following mechanical properties characterise the coating:
Elongation at break according to DIN 53455 70D Do tensile strength according to DIN 53455 5 N/mm tear propagation resistance according to DIn 53515 15 N/mm
Claims (4)
1. A process for the production of elastic coatings by coating any substrates with a solvent-free or low solvent coating composition, containing, as binder, a two-component system of (1) a polyisocyanate component and (ii) a hardener component, characterized in that (i) has an isocyanate content of from 1 to 20% by weight and comprises of at least one prepolymer containing free isocyanate groups based on l-isocyanato-3,3,5-tri-methyl-5-isocyanatomethylcyclohexane and one or more polyalkylene ether polyols having an (average) hydroxyl functionality of from 2 to 3, (ii) comprises to an extent of at least 50 equivalent percent of polyamines selected from the group consisting of (a) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino group and optionally also methyl substituents in further ortho-positions to the amino groups, (b) reaction products of such diamines with a sub-equivalent amount of either a prepolymer containing free isocyanate groups based on an organic diisocyanate having a molecular weight of from 168 to 300 and at least one polyalkylene ether polyol having an (average) hydroxyl functionality of 2 to 3 or of a mixture \
of such a prepolymer with up to 500 iso-cyanate equivalent percent, based on the isocyanate groups of said prepolymer, of said diisocyanate and (c) mixtures of (a) and (b) and to an extent of up to 50 equivalent percent of dihydric or tri-hydric alcohols having primary hydroxyl groups and in that (i) and (ii) being used in quantitative proportions corresponding to an NCO/NH2 equivalent ratio in the range of from 0.5:1 to 1.5:1.
of such a prepolymer with up to 500 iso-cyanate equivalent percent, based on the isocyanate groups of said prepolymer, of said diisocyanate and (c) mixtures of (a) and (b) and to an extent of up to 50 equivalent percent of dihydric or tri-hydric alcohols having primary hydroxyl groups and in that (i) and (ii) being used in quantitative proportions corresponding to an NCO/NH2 equivalent ratio in the range of from 0.5:1 to 1.5:1.
2. The process of Claim 1, further charac-terized in that from 0.1 to 5% by weight, based on the sum of (i)+(ii), of a carboxylic acid anhydride are incorporated in said coating composition.
3. The process of claim 1 wherein said low solvent coating composition contains up to 15% of lacquer solvents, said percent being relative to the weight of the coating.
4. A process for coating moist concrete comprising preparing a mixture of (i) a polyisocyanate component and (ii) a hardener component wherein (i) has an isocyanate content of from 1 to 20% by weight and comprises of at least one prepolymer containing free isocyanate groups based on l-isocyanato-3,3,5-tri-methyl-5-isocyanatomethylcyclohexane and one or more polyalkylene ether polyols having an (average) hydroxyl functionality of from 2 to 3, and wherein (ii) comprises to an extent of at least 50 equivalent percent of polyamines selected from the group consisting of (a) at least one diprimary aromatic diamine having at least one alkyl substituent with 2 to 3 carbon atoms in an ortho-position to each amino group and optionally also methyl substituents in further ortho-positions to the amino groups, (b) reaction products of such diamines with a subequivalent amount of either a pre-polymer containing free isocyanate groups based on an organic diisocyanate having a molecular weight of from 168 to 300 and at least one polyalkylene ether polyol having an (average) hydroxyl functionality of 2 to 3 or of a mixture of such a prepolymer with up to 500 iso-cyanate equivalent percent, based on the isocyanate groups of said prepolymer, of said diisocyanate and (c) mixtures of (a) and (b) and to an extent of up to 50 equivalent percent of dihydric or tri-hydric alcohols having primary hydroxyl groups and wherein (i) and (ii) are used in quantitative proportions corresponding to an NCO/NH2 equivalent ratio in the range of from 0.5:1 to 1.5:1, and applying said mixture to the moist concrete surface before it has reacted sufficiently to have lost its fluidity.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823203490 DE3203490A1 (en) | 1982-02-03 | 1982-02-03 | METHOD FOR PRODUCING COVERS |
| DEP3203490.3 | 1982-02-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1191747A true CA1191747A (en) | 1985-08-13 |
Family
ID=6154596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000420160A Expired CA1191747A (en) | 1982-02-03 | 1983-01-25 | Process for the preparation of coatings |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4463126A (en) |
| EP (1) | EP0085365B1 (en) |
| JP (1) | JPS58134160A (en) |
| AT (1) | ATE19862T1 (en) |
| CA (1) | CA1191747A (en) |
| DE (2) | DE3203490A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4546167A (en) * | 1984-07-30 | 1985-10-08 | American Cyanamid Company | P-TMXDI Polyurethane elastomers with good compression set properties |
| US4616043A (en) * | 1985-04-26 | 1986-10-07 | Thermocell Development, Ltd. | Aliphatic polyurethane sprayable coating compositions and method of preparation |
| US4581433A (en) * | 1985-04-29 | 1986-04-08 | Mobay Corporation | Elastomer polyurethane-polyurea coatings based on bis(4-isocyanatocyclohexyl)methane |
| DE3610729A1 (en) * | 1986-03-29 | 1987-10-01 | Bayer Ag | METHOD FOR PRODUCING THIXOTROPIC BINDERS, THE BINDERS AVAILABLE BY THIS PROCESS, AND THE USE THEREOF FOR PRODUCING COATING AND SEALING AGENTS |
| US5236994A (en) * | 1991-03-28 | 1993-08-17 | Miles Inc. | Process for sealing and/or priming concrete with aqueous polyisocyanate dispersions and the concrete obtained by this process |
| US5128433A (en) * | 1991-06-04 | 1992-07-07 | Polytek Development Corp. | Thixotropic polymer compositions and process for use thereof |
| DE4217023A1 (en) * | 1992-05-22 | 1993-11-25 | Bayer Ag | Use of alkylthio-substituted aromatic diamines from hardeners for polyisocyanates in coating compositions or joint casting compounds |
| FR2691995B1 (en) * | 1992-06-04 | 1994-09-02 | Smac Acieroid | Roof waterproofing coating and its manufacturing process. |
| JP3957779B2 (en) * | 1995-12-28 | 2007-08-15 | 保土谷化学工業株式会社 | Room temperature curing type polyurethane coating material |
| JP3835858B2 (en) * | 1996-06-28 | 2006-10-18 | 保土谷化学工業株式会社 | Method for producing polyurethane coating material |
| DE10246707A1 (en) * | 2002-10-07 | 2004-04-15 | Bayer Ag | Two-component systems for the production of elastic coatings |
| DE102005047562A1 (en) * | 2005-10-04 | 2007-04-05 | Bayer Materialscience Ag | Two-component coating system for production of flexible coatings on various substrates, contains a polyisocyanate prepolymer with allophanate-linked polyether groups and an aminofunctional polyaspartate ester as hardener |
| BRPI0906909A2 (en) * | 2008-04-09 | 2015-07-21 | Dow Global Technologies Inc | Polyurethane elastomer, article and method for forming a polyurethane elastometer. |
| DE102008024352A1 (en) | 2008-05-20 | 2009-11-26 | Bayer Materialscience Ag | polyurea |
| DE102009007228A1 (en) | 2009-02-03 | 2010-08-05 | Bayer Materialscience Ag | coatings |
| DE102009007194A1 (en) | 2009-02-03 | 2010-08-05 | Bayer Materialscience Ag | Flexible coatings |
| CN102311700A (en) * | 2010-06-29 | 2012-01-11 | 拜耳材料科技(中国)有限公司 | Aliphatic Polyurea paint, preparation method and application thereof |
| DE102010031682A1 (en) | 2010-07-20 | 2012-01-26 | Bayer Materialscience Ag | Binder combinations for constructive drinking water pipe coatings |
| JP6735598B2 (en) * | 2016-05-02 | 2020-08-05 | アイシーケイ株式会社 | Fast-curing urethane waterproof material composition and construction method |
| JP6839947B2 (en) * | 2016-09-14 | 2021-03-10 | アイシーケイ株式会社 | Fast-curing two-component urethane waterproof material composition and its manufacturing method |
| JP7173849B2 (en) * | 2018-12-03 | 2022-11-16 | コニシ株式会社 | Concrete piece spalling prevention method |
| JP7398208B2 (en) * | 2019-05-21 | 2023-12-14 | コニシ株式会社 | Method to prevent concrete pieces from falling off |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1240654B (en) * | 1965-05-14 | 1967-05-18 | Bayer Ag | Process for the production of crosslinked plastics using the isocyanate polyaddition process |
| FR2178757B2 (en) * | 1972-04-05 | 1974-08-02 | Pechiney Ugine Kuhlmann | |
| US4218543A (en) * | 1976-05-21 | 1980-08-19 | Bayer Aktiengesellschaft | Rim process for the production of elastic moldings |
| DE2622951B2 (en) * | 1976-05-21 | 1979-09-06 | Bayer Ag, 5090 Leverkusen | Process for the production of elastic shaped bodies |
-
1982
- 1982-02-03 DE DE19823203490 patent/DE3203490A1/en not_active Withdrawn
-
1983
- 1983-01-21 EP EP83100511A patent/EP0085365B1/en not_active Expired
- 1983-01-21 AT AT83100511T patent/ATE19862T1/en not_active IP Right Cessation
- 1983-01-21 DE DE8383100511T patent/DE3363558D1/en not_active Expired
- 1983-01-25 CA CA000420160A patent/CA1191747A/en not_active Expired
- 1983-01-27 US US06/461,339 patent/US4463126A/en not_active Expired - Lifetime
- 1983-02-03 JP JP58015552A patent/JPS58134160A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0085365B1 (en) | 1986-05-21 |
| US4463126A (en) | 1984-07-31 |
| JPS58134160A (en) | 1983-08-10 |
| DE3203490A1 (en) | 1983-08-11 |
| ATE19862T1 (en) | 1986-06-15 |
| DE3363558D1 (en) | 1986-06-26 |
| EP0085365A1 (en) | 1983-08-10 |
| JPH0262594B2 (en) | 1990-12-26 |
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